TW201840907A - Electrolysis electrode, layered body, wound body, electrolytic cell, method for manufacturing electrolytic cell, method for renewing electrode, method for renewing layered body, and method for manufacturing wound body - Google Patents

Electrolysis electrode, layered body, wound body, electrolytic cell, method for manufacturing electrolytic cell, method for renewing electrode, method for renewing layered body, and method for manufacturing wound body Download PDF

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TW201840907A
TW201840907A TW107109914A TW107109914A TW201840907A TW 201840907 A TW201840907 A TW 201840907A TW 107109914 A TW107109914 A TW 107109914A TW 107109914 A TW107109914 A TW 107109914A TW 201840907 A TW201840907 A TW 201840907A
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electrode
electrolysis
electrolytic cell
anode
cathode
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TWI694174B (en
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船川明恭
角佳典
蜂谷敏徳
古池潤
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日商旭化成股份有限公司
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Priority claimed from JP2018053149A external-priority patent/JP7072413B2/en
Priority claimed from JP2018053145A external-priority patent/JP7109220B2/en
Priority claimed from JP2018053139A external-priority patent/JP7073152B2/en
Priority claimed from JP2018053146A external-priority patent/JP7075792B2/en
Priority claimed from JP2018053217A external-priority patent/JP7058152B2/en
Priority claimed from JP2018053231A external-priority patent/JP7075793B2/en
Priority claimed from JP2018053144A external-priority patent/JP7104533B2/en
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/091Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
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    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00Diaphragms; Spacing elements
    • C25B13/02Diaphragms; Spacing elements characterised by shape or form
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    • C25B13/00Diaphragms; Spacing elements
    • C25B13/04Diaphragms; Spacing elements characterised by the material
    • C25B13/08Diaphragms; Spacing elements characterised by the material based on organic materials
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    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
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    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D1/08Perforated or foraminous objects, e.g. sieves

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Abstract

The present invention relates to an electrolysis electrode, a layered body, a wound body, an electrolytic cell, a method for manufacturing an electrolytic cell, a method for renewing an electrode, a method for renewing a layered body, and a method for manufacturing a wound body. The electrolysis electrode pertaining to an embodiment of the present invention has a mass per unit area of 48 mg/cm2 or less and an applied force per nit mass/unit area of 0.08 N/mg.cm2 or greater.

Description

電解用電極、積層體、捲繞體、電解槽、電解槽之製造方法、電極之更新方法、積層體之更新方法、及捲繞體之製造方法Electrolytic electrode, laminated body, wound body, electrolytic cell, electrolytic cell manufacturing method, electrode renewal method, laminated body renewal method, and wound body manufacturing method

本發明係關於一種電解用電極、積層體、捲繞體、電解槽、電解槽之製造方法、電極之更新方法、積層體之更新方法、及捲繞體之製造方法。The present invention relates to a method for manufacturing an electrode for electrolysis, a laminate, a wound body, an electrolytic cell, an electrolytic cell, a method for updating an electrode, a method for updating a laminated body, and a method for manufacturing a wound body.

於食鹽水等鹼金屬氯化物水溶液之電性分解及水之電性分解(以下稱為「電解」)中,利用使用具備隔膜、更具體而言為離子交換膜或微多孔膜之電解槽之方法。該電解槽於較多情形時於其內部具備多個串聯連接之電解池。將隔膜介置於各電解池之間而進行電解。於電解池中,將具有陰極之陰極室與具有陽極之陽極室介隔間隔壁(背面板)或經由壓製壓力、藉由螺栓緊固等獲得之推壓而背對背配置。 目前用於該等電解槽之陽極、陰極係藉由焊接、折入等方法而固定於電解池之各陽極室、陰極室,其後,保管並向顧客處輸送。另一方面,隔膜係於其本身單獨捲繞於氯乙烯(vinyl chloride)製之管等之狀態下保管並向顧客處輸送。於顧客處將電解池排列於電解槽之架上,將隔膜夾於電解池之間而組裝電解槽。由此實施電解池之製造及顧客處之電解槽之組裝。作為可應用於此種電解槽之結構物,於專利文獻1、2中揭示有隔膜與電極成為一體之結構物。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開昭58-048686 [專利文獻2]日本專利特開昭55-148775For the electrolytic decomposition of an aqueous solution of an alkali metal chloride such as saline and the electrolytic decomposition of water (hereinafter referred to as "electrolysis"), an electrolytic cell having a separator, more specifically, an ion exchange membrane or a microporous membrane is used method. In many cases, the electrolytic cell is provided with multiple electrolytic cells connected in series inside. The separator is interposed between each electrolytic cell to perform electrolysis. In the electrolytic cell, a cathode chamber having a cathode and an anode chamber having an anode are arranged back-to-back through a partition wall (back panel) or a push obtained by pressing pressure, bolt fastening, or the like. The anodes and cathodes currently used in these electrolytic cells are fixed to the anode and cathode chambers of the electrolytic cell by welding, folding in, etc., and thereafter, they are stored and transported to customers. On the other hand, the separator is stored in a state where it is wound around a tube made of vinyl chloride, and is transported to a customer. The electrolytic cell is arranged on the rack of the electrolytic cell at the customer, and the diaphragm is sandwiched between the electrolytic cells to assemble the electrolytic cell. In this way, the manufacture of the electrolytic cell and the assembly of the electrolytic cell at the customer are carried out. As a structure applicable to such an electrolytic cell, Patent Documents 1 and 2 disclose structures in which a separator and an electrode are integrated. [Prior Art Literature] [Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open Sho 58-048686 [Patent Literature 2] Japanese Patent Laid-Open Sho 55-148775

[發明所欲解決之問題] 若啟動電解運轉並持續,則因各種要因,各零件劣化,電解性能降低,而於某一時點將各零件更換。藉由將隔膜從電解池之間抽出,並插入新隔膜,而可將隔膜簡單地更新。另一方面,由於陽極或陰極係被固定於電解池,因此存在產生如下非常繁雜之作業之課題:於電極更新時,從電解槽取出電解池,將其搬出至專用之更新工場,解除焊接等之固定並剝離取下舊電極後,設置新電極,藉由焊接等方法將其固定並搬運至電解工場,移回至電解槽。此處,考慮將專利文獻1、2所記載之藉由熱壓接使隔膜與電極成為一體之結構物用於上述更新,但該結構物即使於實驗室等級能夠相對較容易地製造,符合實際之商業尺寸之電解池(例如,縱1.5 m、橫3 m)進行製造並不容易。又,電解性能(電解電壓、電流效率、苛性鈉中食鹽濃度等)、耐久性顯著較差,於隔膜與界面之電極上會產生氯氣或氫氣,因此若長期用於電解,則會完全剝離,實用上無法使用。 本發明係鑒於上述先前技術所具有之課題而完成者,其目的在於提供以下之電解用電極、積層體、捲繞體、電解槽、電解槽之製造方法、電極之更新方法、積層體之更新方法、及捲繞體之製造方法。 (第1目的) 本發明之目的之一在於提供一種輸送或操作變得容易、能夠大幅地簡化啟動新品之電解槽時或更新劣化之電極時之作業、進而亦能夠維持或提高電解性能之電解用電極、積層體及捲繞體。 (第2目的) 本發明之目的之一在於提供一種能夠提高電解槽中之電極更新時之作業效率、進而更新後亦能夠表現出優異之電解性能之積層體。 (第3目的) 基於上述第2目的以外之另一觀點,本發明之目的之一在於提供一種能夠提高電解槽中之電極更新時之作業效率、進而更新後亦能夠表現出優異之電解性能之積層體。 (第4目的) 本發明之目的之一在於提供一種電解性能優異並且能夠防止隔膜之損傷之電解槽、電解槽之製造方法及積層體之更新方法。 (第5目的) 本發明之目的之一在於提供一種能夠提高電解槽中之電極更新時之作業效率的電解槽之製造方法、電極之更新方法、及捲繞體之製造方法。 (第6目的) 基於上述第5目的以外之另一觀點,本發明之目的之一在於提供一種能夠提高電解槽中之電極更新時之作業效率的電解槽之製造方法。 (第7目的) 基於上述第5及第6目的以外之另一觀點,本發明之目的之一在於提供一種能夠提高電解槽中之電極更新時之作業效率的電解槽之製造方法。 [解決問題之技術手段] 本發明者等人為了達成第1目的而反覆進行銳意研究,結果發現,藉由製作每單位面積之質量較小、能夠以較弱之力與離子交換膜及微多孔膜等隔膜或劣化之電極接著之電解用電極,輸送、操作變得容易,能夠大幅地簡化啟動新品之電解槽時或更新劣化之零件時之作業,進而,與先前技術之電解性能相比,能夠大幅地提高性能。又,能夠使其電解性能與更新作業繁雜之先前之電解池的電解性能相同或有所提高,從而完成本發明。 即,本發明包含以下。 [1]一種電解用電極,其每單位面積之質量為48 mg/cm2 以下,每單位質量·單位面積所承受之力為0.08 N/mg・cm2 以上。 [2]如[1]所記載之電解用電極,其中上述電解用電極包含電解用電極基材及觸媒層,電解用電極基材之厚度為300 μm以下。 [3]如[1]或[2]所記載之電解用電極,其中藉由以下之方法(3)所測得之比率為75%以上。 [方法(3)] 將於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之膜(170 mm見方)與電解用電極樣品(130 mm見方)依序加以積層。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電解用電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,1分鐘後測定於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之膜與電解用電極樣品密接之部分之面積的比率(%)。 [4]如[1]至[3]中任一項所記載之電解用電極,其係多孔結構,開孔率為5~90%。 [5]如[1]至[4]中任一項所記載之電解用電極,其係多孔結構,開孔率為10~80%。 [6]如[1]至[5]中任一項所記載之電解用電極,其中電解用電極之厚度為315 μm以下。 [7]如[1]至[6]中任一項所記載之電解用電極,其中藉由以下之方法(A)對電解用電極進行測定而獲得之值為40 mm以下。 [方法(A)] 於溫度23±2℃、相對濕度30±5%之條件下,將積層離子交換膜與上述電解用電極而成之樣品捲繞並固定於外徑f32 mm之氯乙烯製芯材之曲面上,靜置6小時後將該電解用電極分離並載置於水平之板,測定此時該電解用電極之兩端部之垂直方向之高度L1 及L2 ,以該等之平均值作為測定值。[8]如[1]至[7]中任一項所記載之電解用電極,其中將上述電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時之通氣阻力為24 kPa・s/m以下。 [9]如[1]至[8]中任一項所記載之電解用電極,其中電極含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 [10]一種積層體,其含有如[1]至[9]中任一項所記載之電解用電極。 [11]一種捲繞體,其含有如[1]至[9]中任一項所記載之電解用電極、或如[10]所記載之積層體。 本發明者等人為了達成第2目的而反覆進行銳意研究,結果發現,藉由具備離子交換膜及微多孔膜等隔膜或劣化之既有電極等饋電體及以較弱之力與其進行接著之電極的積層體,輸送、操作變得容易,能夠大幅地簡化啟動新品之電解槽時或更新劣化之零件時之作業,進而,亦能夠維持或提高電解性能,從而完成本發明。 即,本發明包含以下之態樣。 [2-1] 一種積層體,其具備 電解用電極、及 與上述電解用電極相接之隔膜或饋電體, 針對上述隔膜或饋電體之上述電解用電極之每單位質量·單位面積所承受之力未達1.5 N/mg・cm2 。[2-2] 如[2-1]所記載之積層體,其中針對上述隔膜或饋電體之上述電解用電極之每單位質量·單位面積所承受之力超過0.005 N/mg・cm2 。 [2-3] 如[2-1]或[2-2]所記載之積層體,其中上述饋電體為金屬絲網、金屬不織布、沖孔金屬、多孔金屬、或發泡金屬。 [2-4] 如[2-1]至[2-3]中任一項所記載之積層體,其具有含有親水性氧化物粒子與導入有離子交換基之聚合物之混合物的層作為上述隔膜之至少一表面層。[2-5] 如[2-1]至[2-4]中任一項所記載之積層體,其中於上述電解用電極與上述隔膜或饋電體之間介置液體。 本發明者等人為了達成第3目的而反覆進行銳意研究,結果發現,藉由局部固定有隔膜與電解用電極之積層體,能夠解決上述課題,從而完成本發明。 即,本發明包含以下之態樣。 [3-1] 一種積層體,其具有 隔膜、及 固定於上述隔膜之表面之至少一區域之電解用電極, 上述隔膜之表面中之上述區域之比率超過0%且未達93%。[3-2] 如[3-1]所記載之積層體,其中上述電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。 [3-3] 如[3-1]或[3-2]所記載之積層體,其中於上述區域,上述電解用電極之至少一部分貫通上述隔膜而被固定。 [3-4] 如[3-1]至[3-3]中任一項所記載之積層體,其中於上述區域,上述電解用電極之至少一部分位於上述隔膜之內部而被固定。 [3-5] 如[3-1]至[3-4]中任一項所記載之積層體,其進而具有用以將上述隔膜與上述電解用電極加以固定之固定用構件。 [3-6] 如[3-5]所記載之積層體,其中上述固定用構件之至少一部分從外部將上述隔膜與上述電解用電極固持。 [3-7] 如[3-5]或[3-6]所記載之積層體,其中上述固定用構件之至少一部分藉由磁力將上述隔膜與上述電解用電極加以固定。 [3-8] 如[3-1]至[3-7]中任一項所記載之積層體,其中上述隔膜包含於表面層含有有機樹脂之離子交換膜,且 上述有機樹脂存在於上述區域。 [3-9] 如[3-1]至[3-8]中任一項所記載之積層體,其中上述隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之EW之第2離子交換樹脂層。 [3-10] 如[3-1]至[3-8]中任一項所記載之積層體,其中上述隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之官能基之第2離子交換樹脂層。 本發明者等人為了達成第4目的而反覆進行銳意研究,結果發現,藉由將隔膜與電解用電極之積層體之至少一部分夾持於陽極側墊片及陰極側墊片,能夠解決上述課題,從而完成本發明。 即,本發明包含以下之態樣。 [4-1] 一種電解槽,其具備 陽極、 支持上述陽極之陽極框、 配置於上述陽極框上之陽極側墊片、 與上述陽極相對向之陰極、 支持上述陰極之陰極框、 配置於上述陰極框上且與上述陽極側墊片相對向之陰極側墊片、及 配置於上述陽極側墊片與上述陰極側墊片之間之隔膜與電解用電極之積層體,且 上述積層體之至少一部分由上述陽極側墊片及上述陰極側墊片所夾持, 將上述電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時之通氣阻力為24 kPa・s/m以下。[4-2] 如[4-1]所記載之電解槽,其中上述電解用電極之厚度為315 μm以下。 [4-3] 如[4-1]或[4-2]所記載之電解槽,其中藉由以下之方法(A)對上述電解用電極進行測定而獲得之值為40 mm以下。 [4-方法(A)] 於溫度23±2℃、相對濕度30±5%之條件下,將積層離子交換膜與上述電解用電極而成之樣品捲繞並固定於外徑f32 mm之氯乙烯製芯材之曲面上,靜置6小時後將該電解用電極分離並載置於水平之板,測定此時該電解用電極之兩端部之垂直方向之高度L1 及L2 ,以該等之平均值作為測定值。[4-4] 如[4-1]至[4-3]中任一項所記載之電解槽,其中上述電解用電極之每單位面積之質量為48 mg/cm2 以下。 [4-5] 如[4-1]至[4-4]中任一項所記載之電解槽,其中上述電解用電極之每單位質量·單位面積所承受之力超過0.005 N/mg・cm2 。 [4-6] 如[4-1]至[4-5]中任一項所記載之電解槽,其中上述積層體之最外周緣位於較上述陽極側墊片及陰極側墊片之最外周緣更靠通電面方向外側之位置。[4-7] 如[4-1]至[4-6]中任一項所記載之電解槽,上述電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。 [4-8] 如[4-1]至[4-7]中任一項所記載之電解槽,其中於上述積層體中,上述電解用電極之至少一部分貫通上述隔膜而被固定。 [4-9] 如[4-1]至[4-7]中任一項所記載之電解槽,其中於上述積層體中,上述電解用電極之至少一部分位於上述隔膜之內部而被固定。 [4-10] 如[4-1]至[4-9]中任一項所記載之電解槽,其中於上述積層體中進而具有用以將上述隔膜與上述電解用電極加以固定之固定用構件。 [4-11] 如[4-10]所記載之電解槽,其中於上述積層體中,上述固定用構件之至少一部分貫通上述隔膜與上述電解用電極而加以固定。 [4-12] 如[4-10]或[4-11]所記載之電解槽,其中於上述積層體中,上述固定用構件含有可溶於電解液之可溶材料。 [4-13] 如[4-10]至[4-12]中任一項所記載之電解槽,其中於上述積層體中,上述固定用構件之至少一部分從外部將上述隔膜與上述電解用電極固持。 [4-14] 如[4-10]至[4-13]中任一項所記載之電解槽,其中於上述積層體中,上述固定用構件之至少一部分藉由磁力將上述隔膜與上述電解用電極加以固定。 [4-15] 如[4-1]至[4-14]中任一項所記載之電解槽,其中上述隔膜包含於表面層含有有機樹脂之離子交換膜,且 於上述有機樹脂中固定有上述電解用電極。 [4-16] 如[4-1]至[4-15]中任一項所記載之電解槽,其中上述隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之EW之第2離子交換樹脂層。 [4-17] 一種如[4-1]至[4-16]中任一項所記載之電解槽之製造方法, 其具有於上述陽極側墊片與陰極側墊片之間夾持上述積層體之步驟。 [4-18] 一種如[4-1]至[4-16]中任一項所記載之電解槽中之積層體之更新方法,其具有 藉由將上述積層體從上述陽極側墊片及上述陰極側墊片分離而將該積層體從電解槽取出之步驟;及 於上述陽極側墊片與陰極側墊片之間夾持新的上述積層體之步驟。 本發明者等人為了達成第5目的而反覆進行銳意研究,結果發現,藉由使用電解用電極或該電解用電極與新隔膜之積層體之捲繞體,能夠解決上述課題,從而完成本發明。 即,本發明包含以下之態樣。 [5-1] 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽配置電解用電極或該電解用電極與新隔膜之積層體而製造新電解槽之方法,並且 使用上述電解用電極或上述積層體之捲繞體。 [5-2] 如[5-1]所記載之電解槽之製造方法,其具有將上述電解用電極或上述積層體保持為捲繞狀態而獲得上述捲繞體之步驟(A)。[5-3] 如[5-1]或[5-2]所記載之電解槽之製造方法,其具有解除上述捲繞體之捲繞狀態之步驟(B)。 [5-4] 如[5-3]所記載之電解槽之製造方法,其具有於上述步驟(B)後於上述陽極及上述陰極之至少一者之表面上配置上述電解用電極或上述積層體之步驟(C)。 [5-5] 一種電極之更新方法,其係用以藉由使用電解用電極而更新既有之電極之方法,並且 使用上述電解用電極之捲繞體。 [5-6] 如[5-5]所記載之電極之更新方法,其具有將上述電解用電極保持為捲繞狀態而獲得上述捲繞體之步驟(A')。 [5-7] 如[5-5]或[5-6]所記載之電極之更新方法,其具有解除上述電解用電極之捲繞狀態之步驟(B')。 [5-8] 如[5-7]所記載之電極之更新方法,其具有於上述步驟(B')後於既有電極之表面上配置上述電解用電極之步驟(C')。 [5-9] 一種捲繞體之製造方法,其係用以更新具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽的捲繞體之製造方法,並且 具有將電解用電極或該電解用電極與新隔膜之積層體捲繞而獲得上述捲繞體之步驟。 本發明者等人為了達成第6目的而反覆進行銳意研究,結果發現,藉由將電解用電極與新隔膜於該隔膜不熔融之溫度下進行一體化,可解決上述課題,從而完成本發明。 即,本發明包含以下之態樣。 [6-1] 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽配置積層體而製造新電解槽之方法,並且具有 藉由將電解用電極與新隔膜於該隔膜不熔融之溫度下進行一體化,而獲得上述積層體之步驟(A);及 於上述步驟(A)後將既有電解槽中之上述隔膜更換為上述積層體之步驟(B)。[6-2] 如[6-1]所記載之電解槽之製造方法,其中上述一體化係於常壓下進行。 本發明者等人為了達成第7目的而反覆進行銳意研究,結果發現,藉由電解槽架內之操作,能夠解決上述課題,從而完成本發明。 即,本發明包含以下之態樣。 [7-1] 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、固定於上述陽極與上述陰極之間之隔膜、以及支持上述陽極、上述陰極及上述隔膜之電解槽架的既有電解槽配置包含電解用電極及新隔膜之積層體而製造新電解槽之方法,並且具有: 於上述電解槽架內解除上述隔膜之固定之步驟(A);及 於上述步驟(A)後將上述隔膜與上述積層體交換之步驟(B)。[7-2] 如[7-1]所記載之電解槽之製造方法,其中上述步驟(A)係藉由使上述陽極及上述陰極分別沿該等之排列方向滑動而進行。 [7-3] 如[7-1]或[7-2]所記載之電解槽之製造方法,其係於上述步驟(B)後,藉由來自上述陽極及上述陰極之按壓,而將上述積層體固定於上述電解槽架內。 [7-4] 如[7-1]至[7-3]中任一項所記載之電解槽之製造方法,其中於上述步驟(B)中,於上述積層體不熔融之溫度下將該積層體固定於上述陽極及上述陰極之至少一者之表面上。[7-5] 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、固定於上述陽極與上述陰極之間之隔膜、以及支持上述陽極、上述陰極及上述隔膜之電解槽架的既有電解槽配置電解用電極而製造新電解槽之方法,並且具有: 於上述電解槽架內解除上述隔膜之固定之步驟(A);及 於上述步驟(A)後,於上述隔膜與上述陽極或上述陰極之間配置上述電解用電極之步驟(B')。 [發明之效果] (1)根據本發明之電解用電極,輸送或操作變得容易,能夠大幅地簡化啟動新品之電解槽時或更新劣化之電極時之作業,進而亦能夠維持或提高電解性能。 (2)根據本發明之積層體,能夠提高電解槽中之電極更新時之作業效率,進而更新後亦能夠表現出優異之電解性能。 (3)根據本發明之積層體,基於上述(2)以外之另一觀點,能夠提高電解槽中之電極更新時之作業效率,進而更新後亦能夠表現出優異之電解性能。 (4)根據本發明之電解槽,電解性能優異,並且能夠防止隔膜之損傷。 (5)根據本發明之電解槽之製造方法,能夠提高電解槽中之電極更新時之作業效率。 (6)根據本發明之電解槽之製造方法,基於上述(5)以外之另一觀點,能夠提高電解槽中之電極更新時之作業效率。 (7)根據本發明之電解槽之製造方法,基於上述(5)及(6)以外之另一觀點,能夠提高電解槽中之電極更新時之作業效率。[Problems to be Solved by the Invention] When the electrolytic operation is started and continued, due to various factors, each part is deteriorated, and the electrolytic performance is reduced. Therefore, each part is replaced at a certain point. The diaphragm can be simply renewed by withdrawing the diaphragm from between the electrolytic cells and inserting a new diaphragm. On the other hand, since the anode or cathode system is fixed to the electrolytic cell, there is a problem that a very complicated operation occurs: when the electrode is renewed, the electrolytic cell is taken out from the electrolytic cell, and it is moved out to a dedicated renewal workshop, and welding is cancelled. After the old electrode is fixed and peeled off, a new electrode is set, and it is fixed and transported to the electrolytic plant by welding and other methods, and then returned to the electrolytic cell. Here, it is considered that the structure in which the separator and the electrode are integrated by thermal compression bonding described in Patent Documents 1 and 2 is used for the above-mentioned update. However, the structure can be relatively easily manufactured even in a laboratory level, which is in line with the actual situation. It is not easy to manufacture a commercial size electrolytic cell (e.g., 1.5 m in length and 3 m in width). In addition, the electrolytic performance (electrolytic voltage, current efficiency, salt concentration in caustic soda, etc.) and durability are significantly inferior. Chlorine or hydrogen gas is generated on the electrodes of the separator and the interface. Therefore, if it is used for electrolysis for a long time, it will completely peel off. Is not available. The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a method for manufacturing an electrode for electrolysis, a laminate, a wound body, an electrolytic cell, an electrolytic cell, a method for updating an electrode, and an update of a laminated body. A method and a method for manufacturing a wound body. (First object) One of the objects of the present invention is to provide an electrolytic solution that can be easily transported or operated, can greatly simplify the operation when starting a new electrolytic cell or renews a deteriorated electrode, and can also maintain or improve electrolytic performance. Use electrodes, laminates and wound bodies. (Second Object) One of the objects of the present invention is to provide a laminated body capable of improving the working efficiency when the electrodes in the electrolytic cell are renewed and further exhibiting excellent electrolytic performance after the renewal. (Third Object) Based on another aspect other than the second object described above, one object of the present invention is to provide an electrode which can improve the working efficiency when the electrode in the electrolytic cell is renewed, and can further exhibit excellent electrolytic performance after the renewal. Laminated body. (Fourth Object) One of the objects of the present invention is to provide an electrolytic cell having excellent electrolytic performance and capable of preventing damage to a separator, a method for manufacturing the electrolytic cell, and a method for updating a laminated body. (Fifth Object) It is an object of the present invention to provide a method for manufacturing an electrolytic cell, a method for updating an electrode, and a method for manufacturing a wound body, which can improve work efficiency when the electrode in the electrolytic cell is renewed. (Aim 6) Based on another viewpoint other than the aforesaid fifth object, one object of the present invention is to provide a method for manufacturing an electrolytic cell capable of improving the working efficiency when the electrodes in the electrolytic cell are renewed. (Aim 7) Based on another viewpoint other than the above-mentioned objects 5 and 6, it is an object of the present invention to provide a method for producing an electrolytic cell capable of improving the working efficiency when the electrodes in the electrolytic cell are renewed. [Technical means to solve the problem] The present inventors and the like have made intensive studies repeatedly in order to achieve the first objective, and found that by making the mass per unit area smaller, the ion exchange membrane and microporosity can be used with a weaker force. Membrane diaphragms or degraded electrodes followed by electrolytic electrodes can be easily transported and operated, which greatly simplifies operations when starting new electrolytic cells or updating degraded parts, and compared with the electrolytic performance of the prior art, Can greatly improve performance. In addition, the electrolytic performance can be made the same as or improved by the electrolytic performance of the previous electrolytic cell, which has been complicated for the renewal operation, thereby completing the present invention. That is, the present invention includes the following. [1] An electrode for electrolysis, wherein the mass per unit area is 48 mg / cm 2 or less, and the force per unit mass and unit area is 0.08 N / mg · cm 2 or more. [2] The electrode for electrolysis according to [1], wherein the electrode for electrolysis includes an electrode substrate for electrolysis and a catalyst layer, and a thickness of the electrode substrate for electrolysis is 300 μm or less. [3] The electrode for electrolysis according to [1] or [2], wherein the ratio measured by the following method (3) is 75% or more. [Method (3)] A film coated with inorganic particles and a binding agent (170 mm square) and an electrode sample for electrolysis (130 mm square) were sequentially coated on both sides of a film of a perfluorocarbon polymer introduced with an ion exchange group. Laminate. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body is placed on the curved surface of a polyethylene pipe (145 mm in outer diameter) so that the sample of the electrode for electrolysis in the laminated body becomes the outer side. The laminated body and the tube were sufficiently impregnated with pure water to remove excess water adhering to the surface of the laminated body and the tube. After 1 minute, the two sides of the membrane of the perfluorocarbon polymer introduced with the ion-exchange group were coated with inorganic substances. The ratio (%) of the area of the portion of the film of particles and binder to the portion of the electrode electrode for electrolytic contact. [4] The electrode for electrolysis according to any one of [1] to [3], which has a porous structure and an open porosity of 5 to 90%. [5] The electrode for electrolysis according to any one of [1] to [4], which has a porous structure and an open porosity of 10 to 80%. [6] The electrode for electrolysis according to any one of [1] to [5], wherein the thickness of the electrode for electrolysis is 315 μm or less. [7] The electrode for electrolysis according to any one of [1] to [6], wherein a value obtained by measuring the electrode for electrolysis by the following method (A) is 40 mm or less. [Method (A)] Under the conditions of a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, a sample formed by laminating an ion exchange membrane and the above-mentioned electrode for electrolysis was wound and fixed to a vinyl chloride product having an outer diameter of f32 mm. On the curved surface of the core material, after standing for 6 hours, the electrode for electrolysis was separated and placed on a horizontal plate. At this time, the vertical heights L 1 and L 2 of both ends of the electrode for electrolysis were measured. The average value is used as the measured value. [8] The electrode for electrolysis according to any one of [1] to [7], wherein the size of the electrode for electrolysis is 50 mm × 50 mm and the temperature is 24 ° C., the relative humidity is 32%, and the piston is The ventilation resistance at a speed of 0.2 cm / s and a ventilation volume of 0.4 cc / cm 2 / s is 24 kPa · s / m or less. [9] The electrode for electrolysis according to any one of [1] to [8], wherein the electrode contains at least one element selected from the group consisting of nickel (Ni) and titanium (Ti). [10] A laminated body comprising the electrode for electrolysis according to any one of [1] to [9]. [11] A wound body comprising the electrode for electrolysis according to any one of [1] to [9], or the laminated body according to [10]. The present inventors have conducted diligent research in order to achieve the second object, and as a result, they have found that a power source such as an ion-exchange membrane and a microporous membrane or a deteriorated existing electrode and the like are adhered to it with a weak force. The laminated body of the electrode can be easily transported and operated, which can greatly simplify the operation when starting a new electrolytic cell or updating a deteriorated part, and also can maintain or improve the electrolytic performance, thereby completing the present invention. That is, the present invention includes the following aspects. [2-1] A laminated body comprising an electrode for electrolysis, and a separator or a power supply body connected to the electrode for electrolysis, and the unit / mass per unit area of the electrode for electrolysis of the separator or power supply body is The force was less than 1.5 N / mg · cm 2 . [2-2] The laminated body according to [2-1], wherein the force per unit mass and unit area of the above-mentioned electrolytic electrode for the separator or the power feeder exceeds 0.005 N / mg · cm 2 . [2-3] The laminated body according to [2-1] or [2-2], wherein the power feeder is a metal wire mesh, a metal non-woven fabric, a punched metal, a porous metal, or a foamed metal. [2-4] The laminated body according to any one of [2-1] to [2-3], which has a layer containing a mixture of hydrophilic oxide particles and a polymer having an ion exchange group introduced therein as the above At least one surface layer of the separator. [2-5] The multilayer body according to any one of [2-1] to [2-4], wherein a liquid is interposed between the electrode for electrolysis and the separator or the power supply body. The inventors of the present invention have made intensive studies repeatedly in order to achieve the third object, and as a result, they have found that the above-mentioned problems can be solved by a laminated body in which a separator and an electrode for electrolysis are locally fixed, thereby completing the present invention. That is, the present invention includes the following aspects. [3-1] A laminated body comprising a separator and an electrode for electrolysis fixed to at least one area of a surface of the separator, and a ratio of the area in the surface of the separator exceeds 0% to less than 93%. [3-2] The laminated body according to [3-1], wherein the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, and Ni , Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La , Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy, at least one catalyst component in the group. [3-3] The laminated body according to [3-1] or [3-2], in which at least a part of the electrode for electrolysis penetrates the separator and is fixed in the region. [3-4] The laminated body according to any one of [3-1] to [3-3], wherein at least a part of the electrode for electrolysis is located inside the separator and is fixed in the region. [3-5] The laminated body according to any one of [3-1] to [3-4], further comprising a fixing member for fixing the separator and the electrode for electrolysis. [3-6] The laminated body according to [3-5], wherein at least a part of the fixing member holds the separator and the electrode for electrolysis from outside. [3-7] The laminated body according to [3-5] or [3-6], wherein at least a part of the fixing member fixes the separator and the electrode for electrolysis by magnetic force. [3-8] The laminated body according to any one of [3-1] to [3-7], wherein the separator is included in an ion exchange membrane containing an organic resin in a surface layer, and the organic resin is present in the region . [3-9] The laminated body according to any one of [3-1] to [3-8], wherein the separator includes a first ion exchange resin layer and an EW different from the first ion exchange resin layer The second ion exchange resin layer. [3-10] The laminated body according to any one of [3-1] to [3-8], wherein the separator includes a first ion exchange resin layer and has a different function from the first ion exchange resin layer Based second ion exchange resin layer. The present inventors have made intensive research in order to achieve the fourth object, and as a result, have found that the above-mentioned problem can be solved by sandwiching at least a part of a laminate of a separator and an electrode for electrolysis between an anode-side gasket and a cathode-side gasket. To complete the present invention. That is, the present invention includes the following aspects. [4-1] An electrolytic cell comprising an anode, an anode frame supporting the anode, an anode-side gasket disposed on the anode frame, a cathode opposite to the anode, a cathode frame supporting the cathode, and disposed on the A cathode-side gasket on the cathode frame and facing the anode-side gasket, and a laminated body of a separator and an electrode for electrolysis disposed between the anode-side gasket and the cathode-side gasket, and at least the laminated body is at least A part is sandwiched between the anode-side gasket and the cathode-side gasket. The size of the electrode for electrolysis is 50 mm × 50 mm, and the temperature is 24 ° C, the relative humidity is 32%, and the piston speed is 0.2 cm / s. When the ventilation volume is 0.4 cc / cm 2 / s, the ventilation resistance is 24 kPa · s / m or less. [4-2] The electrolytic cell according to [4-1], wherein the thickness of the electrode for electrolysis is 315 μm or less. [4-3] The electrolytic cell according to [4-1] or [4-2], wherein the value obtained by measuring the above-mentioned electrode for electrolysis by the following method (A) is 40 mm or less. [4-Method (A)] Under the conditions of a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, a sample formed by laminating an ion exchange membrane and the above-mentioned electrode for electrolysis was wound and fixed to chlorine with an outer diameter of f32 mm. On the curved surface of the ethylene core material, after standing for 6 hours, the electrode for electrolysis was separated and placed on a horizontal plate. At this time, the vertical heights L 1 and L 2 of both ends of the electrode for electrolysis were measured. These average values are used as measured values. [4-4] The electrolytic cell according to any one of [4-1] to [4-3], wherein the mass per unit area of the electrode for electrolysis is 48 mg / cm 2 or less. [4-5] The electrolytic cell according to any one of [4-1] to [4-4], wherein the force per unit mass and unit area of the electrode for electrolysis described above exceeds 0.005 N / mg · cm 2 . [4-6] The electrolytic cell according to any one of [4-1] to [4-5], wherein the outermost peripheral edge of the laminated body is located more than the outermost periphery of the anode-side gasket and the cathode-side gasket The edge is located further outside the direction of the current-carrying surface. [4-7] The electrolytic cell according to any one of [4-1] to [4-6], wherein the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, At least one catalyst component in the group consisting of O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy. [4-8] The electrolytic cell according to any one of [4-1] to [4-7], wherein in the multilayer body, at least a part of the electrode for electrolysis passes through the separator and is fixed. [4-9] The electrolytic cell according to any one of [4-1] to [4-7], in the laminated body, at least a part of the electrode for electrolysis is located inside the separator and is fixed. [4-10] The electrolytic cell according to any one of [4-1] to [4-9], further including a fixing member for fixing the separator and the electrode for electrolysis in the laminated body. member. [4-11] The electrolytic cell according to [4-10], wherein in the laminated body, at least a part of the fixing member penetrates the separator and the electrolytic electrode and is fixed. [4-12] The electrolytic cell according to [4-10] or [4-11], wherein in the laminated body, the fixing member contains a soluble material that is soluble in an electrolytic solution. [4-13] The electrolytic cell according to any one of [4-10] to [4-12], wherein in the laminated body, at least a part of the fixing member externally connects the diaphragm and the electrolytic device. Electrode hold. [4-14] The electrolytic cell according to any one of [4-10] to [4-13], wherein in the laminated body, at least a part of the fixing member is configured to electrolyze the diaphragm and the electrolysis by magnetic force. Fix it with electrodes. [4-15] The electrolytic cell according to any one of [4-1] to [4-14], wherein the separator includes an ion exchange membrane containing an organic resin in a surface layer, and is fixed to the organic resin The electrode for electrolysis. [4-16] The electrolytic cell according to any one of [4-1] to [4-15], wherein the separator includes a first ion exchange resin layer and has an EW different from the first ion exchange resin layer The second ion exchange resin layer. [4-17] A method for manufacturing an electrolytic cell according to any one of [4-1] to [4-16], which comprises sandwiching the laminate between the anode-side gasket and the cathode-side gasket Body steps. [4-18] A method for updating a laminated body in an electrolytic cell according to any one of [4-1] to [4-16], which comprises removing the laminated body from the anode-side gasket and A step of separating the cathode-side gasket and removing the laminated body from the electrolytic cell; and a step of sandwiching the new laminated body between the anode-side gasket and the cathode-side gasket. The present inventors have made earnest researches repeatedly in order to achieve the fifth object, and as a result, they have found that the above problems can be solved by using an electrode for electrolysis or a wound body of a laminate of the electrode for electrolysis and a new separator, thereby completing the present invention . That is, the present invention includes the following aspects. [5-1] A method for manufacturing an electrolytic cell, which is used to arrange electrolysis for an existing electrolytic cell provided with an anode, a cathode opposite to the anode, and a separator disposed between the anode and the cathode. A method for manufacturing a new electrolytic cell by using an electrode or a laminate of the electrode for electrolysis and a new separator, and using the electrode for electrolysis or a wound body of the laminate. [5-2] The method for producing an electrolytic cell according to [5-1], comprising the step (A) of obtaining the wound body by maintaining the electrode for electrolysis or the laminated body in a wound state. [5-3] The method for producing an electrolytic cell according to [5-1] or [5-2], which includes a step (B) of releasing the winding state of the wound body. [5-4] The method for manufacturing an electrolytic cell according to [5-3], which comprises, after the step (B), disposing the electrode for electrolysis or the laminate on the surface of at least one of the anode and the cathode. System step (C). [5-5] A method for updating an electrode, which is a method for updating an existing electrode by using an electrode for electrolysis, and using the wound body of the above electrode for electrolysis. [5-6] The method for updating an electrode according to [5-5], which comprises the step (A ') of maintaining the electrode for electrolysis in a wound state to obtain the wound body. [5-7] The method for updating an electrode according to [5-5] or [5-6], which includes a step (B ') of releasing the winding state of the electrode for electrolysis. [5-8] The method for updating an electrode according to [5-7], which comprises the step (C ') of disposing the electrode for electrolysis on a surface of an existing electrode after the step (B'). [5-9] A method for manufacturing a wound body, which is used to update a wound body of an existing electrolytic cell provided with an anode, a cathode opposite to the anode, and a separator disposed between the anode and the cathode The manufacturing method further includes a step of winding the electrode for electrolysis or a laminate of the electrode for electrolysis and a new separator to obtain the wound body. The present inventors have made earnest researches repeatedly in order to achieve the sixth object, and as a result, they have found that the above-mentioned problems can be solved by integrating the electrode for electrolysis and a new separator at a temperature at which the separator does not melt, thereby completing the present invention. That is, the present invention includes the following aspects. [6-1] A method for manufacturing an electrolytic cell, which is configured to arrange a laminated body with an existing electrolytic cell provided with an anode, a cathode opposite to the anode, and a separator disposed between the anode and the cathode. The method for manufacturing a new electrolytic cell has a step (A) of obtaining the above-mentioned laminated body by integrating the electrode for electrolysis and the new separator at a temperature at which the separator does not melt; and after the above step (A) Step (B) of replacing the separator in the existing electrolytic cell with the laminated body. [6-2] The method for manufacturing an electrolytic cell according to [6-1], wherein the integration is performed under normal pressure. The inventors of the present invention made intensive studies repeatedly in order to achieve the seventh object, and as a result, found that the above problems can be solved by the operation in the electrolytic cell rack, and the present invention has been completed. That is, the present invention includes the following aspects. [7-1] A method for manufacturing an electrolytic cell, which is configured to support the anode, the cathode, and the cathode by providing an anode, a cathode opposite to the anode, a separator fixed between the anode and the cathode, and The existing electrolytic cell rack of the above-mentioned diaphragm has a method for manufacturing a new electrolytic cell by disposing a laminated body including electrodes for electrolysis and a new diaphragm, and has the step (A) of releasing the fixation of the diaphragm in the electrolytic cell rack; And step (B) of exchanging the diaphragm and the laminated body after the step (A). [7-2] The method for manufacturing an electrolytic cell according to [7-1], wherein the step (A) is performed by sliding the anode and the cathode in the arrangement direction, respectively. [7-3] The method for manufacturing an electrolytic cell according to [7-1] or [7-2], which is performed after the above step (B), and the above is pressed by the anode and the cathode. The laminated body is fixed in the electrolytic cell rack. [7-4] The method for producing an electrolytic cell according to any one of [7-1] to [7-3], wherein in the step (B), the step is performed at a temperature at which the laminated body does not melt. The laminated body is fixed on the surface of at least one of the anode and the cathode. [7-5] A method for manufacturing an electrolytic cell, which is configured to support an anode, the cathode, and a cathode by providing an anode, a cathode facing the anode, a separator fixed between the anode and the cathode, The method for producing a new electrolytic cell by disposing the electrolytic cell with the existing electrolytic cell in the electrolytic cell rack of the above diaphragm includes: a step (A) of releasing the fixation of the diaphragm in the electrolytic cell rack; and in the above step (A) Then, a step (B ') of disposing the electrode for electrolysis between the separator and the anode or the cathode. [Effects of the Invention] (1) According to the electrode for electrolysis of the present invention, it is easy to transport or operate, which can greatly simplify the operation when starting a new electrolytic cell or renewing a deteriorated electrode, and can also maintain or improve the electrolytic performance. . (2) According to the laminated body of the present invention, it is possible to improve the working efficiency when the electrodes in the electrolytic cell are renewed, and further, they can exhibit excellent electrolytic performance after the renewal. (3) According to the laminated body of the present invention, based on another viewpoint other than the above (2), it is possible to improve the working efficiency when the electrodes in the electrolytic cell are renewed, and further, they can exhibit excellent electrolytic performance after the renewal. (4) The electrolytic cell of the present invention has excellent electrolytic performance and can prevent damage to the separator. (5) According to the manufacturing method of the electrolytic cell of the present invention, it is possible to improve the work efficiency when the electrodes in the electrolytic cell are renewed. (6) According to the manufacturing method of the electrolytic cell of the present invention, based on another viewpoint other than the above (5), it is possible to improve the work efficiency when the electrodes in the electrolytic cell are renewed. (7) According to the manufacturing method of the electrolytic cell of the present invention, based on another viewpoint other than the above (5) and (6), it is possible to improve the work efficiency when the electrodes in the electrolytic cell are updated.

以下,關於本發明之實施形態(以下亦稱為本實施形態),視需要一邊參照圖式一邊逐個對<第1實施形態>~<第7實施形態>進行詳細說明。以下之實施形態係用以說明本發明之例示,本發明並不限定於以下之內容。又,隨附圖式係表示實施形態之一例者,形態並不限定於此進行解釋。本發明可於其主旨之範圍內適當地變形而實施。再者,只要無特別說明,則圖式中上下左右等位置關係係基於圖式所示之位置關係。圖式之尺寸及比率並不限於所圖示者。 <第1實施形態> 此處,一邊參照圖1~21一邊對本發明之第1實施形態進行詳細說明。 [電解用電極] 第1實施形態(以下於<第1實施形態>之項中簡稱為「本實施形態」)之電解用電極可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力,進而,就經濟性之觀點而言,每單位面積之質量為48 mg/cm2 以下。又,就上述方面而言,較佳為30 mg/cm2 以下,進而較佳為20 mg/cm2 以下,進而,就合併操作性、接著性及經濟性之綜合性之觀點而言,較佳為15 mg/cm2 以下。下限值並無特別限定,例如為1 mg/cm2 左右。 上述每單位面積之質量例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則每單位面積之質量有變小之傾向,若減小開孔率,則每單位面積之質量有變大之傾向。 本實施形態之電解用電極就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力之觀點而言,每單位質量·單位面積所承受之力為0.08 N/(mg・cm2 )以上。又,就上述方面而言,較佳為0.1 N/(mg・cm2 )以上,更佳為0.14 N/(mg・cm2 )以上,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理更容易之觀點而言,進而較佳為0.2 N/(mg・cm2 )以上。上限值並無特別限定,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 若本實施形態之電解用電極為彈性變形區域較廣之電極,則就可獲得更良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有更良好之接著力之觀點而言,電解用電極之厚度較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,於本實施形態中,所謂「彈性變形區域較廣」意指將電解用電極捲繞而製成捲繞體,解除捲繞狀態後不易產生由捲繞引起之翹曲。又,所謂電解用電極之厚度於包含下文所述之觸媒層之情形時,係指合併電解用電極基材與觸媒層之厚度。藉由本實施形態之電解用電極,如上所述,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力,能夠與離子交換膜或微多孔膜等隔膜進行一體化而使用。因此,於更新電極時,無需伴隨將固定於電解池之電極剝離等繁雜之更換貼附作業,而可藉由與隔膜之更新相同之簡單之作業更新電極,因此作業效率大幅提高。又,即使於在新品之電解池僅設置有饋電體之情形時(即,設置有無觸媒層之電極),亦可僅藉由將本實施形態之電解用電極貼附於饋電體而使其作為電極發揮作用,因此亦可大幅地減少觸媒塗層,或者甚至無觸媒塗層。 進而,藉由本實施形態之電解用電極,能夠使電解性能與新品時之性能相同或有所提高。 本實施形態之電解用電極例如可以捲繞於氯乙烯製之管等之狀態(滾筒狀等)進行保管、向顧客處輸送等,操作大幅地變得容易。 承受力可藉由以下之方法(i)或(ii)進行測定,詳細而言,如實施例所記載。關於承受力,藉由方法(i)之測定所獲得之值(亦稱為「承受力(1)」)與藉由方法(ii)之測定所獲得之值(亦稱為「承受力(2)」)可相同亦可不同,但任一值均為0.08 N/(mg・cm2 )以上。 上述承受力例如可藉由適當調整下文所述之開孔率、電極之厚度、算術平均表面粗糙度等而設為上述範圍。更具體而言,例如,若增大開孔率,則承受力有變小之傾向,若減小開孔率,則承受力有變大之傾向。 [方法(i)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方)、於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方,關於此處所謂離子交換膜之詳細如實施例所記載)及電解用電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。再者,噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.7 μm。算術平均表面粗糙度(Ra)之具體之算出方法如實施例所記載。 於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電解用電極樣品以10 mm/分鐘沿垂直方向上升,測定電解用電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電解用電極樣品與離子交換膜之重疊部分之面積、及與離子交換膜重疊部分之電解用電極樣品之質量,而算出每單位質量·單位面積所承受之力(1)(N/mg・cm2 )。 藉由方法(i)獲得之每單位質量·單位面積所承受之力(1)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,為0.08 N/(mg・cm2 )以上,較佳為0.1 N/(mg・cm2 )以上,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理更容易之觀點而言,更佳為0.2 N/(mg・cm2 )以上。上限值並無特別限定,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 若本實施形態之電解用電極滿足承受力(1),則例如能夠與離子交換膜或微多孔膜等隔膜進行一體化而使用,因此於更新電極時,無需藉由焊接等方法固定於電解池之陰極及陽極之更換貼附作業,作業效率大幅提高。又,藉由將本實施形態之電解用電極用作與離子交換膜一體化而成之電極,能夠使電解性能與新品時之性能相同或有所提高。 於出貨新品之電解池時,先前對固定於電解池之電極施加有觸媒塗層,但僅藉由使未形成有觸媒塗層之電極與本實施形態之電解用電極組合,而可用作電極,因此能夠大幅地減少用以形成觸媒塗層之製造步驟或觸媒之量或者甚至不存在該等。觸媒塗層大幅減少或不存在之先前之電極與本實施形態之電解用電極電性連接,而可使其作為用以流通電流之饋電體發揮功能。 [方法(ii)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方,與上述方法(i)相同之鎳板)與電解用電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電解用電極樣品以10 mm/分鐘沿垂直方向上升,測定電解用電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電解用電極樣品與鎳板之重疊部分之面積、及與鎳板重疊部分中之電解用電極樣品之質量,算出每單位質量•單位面積之接著力(2)(N/mg・cm2 )。 藉由方法(ii)獲得之每單位質量·單位面積所承受之力(2)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,為0.08 N/(mg・cm2 )以上,較佳為0.1 N/(mg・cm2 )以上,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理更容易之觀點而言,更佳為0.14 N/(mg・cm2 )以上。上限值並無特別限定,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 若本實施形態之電解用電極滿足承受力(2),則例如可以捲繞於氯乙烯製之管等之狀態(滾筒狀等)進行保管、向顧客處輸送等,操作大幅地變得容易。又,藉由對劣化之電極貼附本實施形態之電解用電極,能夠使電解性能與新品時之性能相同或有所提高。 於本實施形態中,存在於離子交換膜或微多孔膜等隔膜與電解用電極、或者饋電體(劣化之電極或未形成有觸媒塗層之電極)與電解用電極之間之液體只要為水、有機溶劑等產生表面張力者,則可使用任意液體。液體之表面張力越大,對隔膜與電解用電極、或金屬板與電解用電極之間承受之力越大,因此較佳為表面張力較大之液體。作為液體,可列舉如下者(括號內之數值係該液體之表面張力)。 己烷(20.44 mN/m)、丙酮(23.30 mN/m)、甲醇(24.00 mN/m)、乙醇(24.05 mN/m)、乙二醇(50.21 mN/m)、水(72.76 mN/m) 若為表面張力較大之液體,則隔膜與電解用電極、或者金屬多孔板或金屬板(饋電體)與電解用電極成為一體(成為積層體),電極更新變得容易。隔膜與電解用電極、或者金屬多孔板或金屬板(饋電體)與電解用電極之間之液體為藉由表面張力而互相貼附之程度之量即可,其結果為液體量較少,因此即使於將該積層體設置於電解池後混入至電解液中,亦不會對電解本身造成影響。 就實用上之觀點而言,作為液體,較佳為使用乙醇、乙二醇、水等表面張力為20 mN/m至80 mN/m之液體。尤佳為水或將苛性鈉、氫氧化鉀、氫氧化鋰、碳酸氫鈉、碳酸氫鉀、碳酸鈉、碳酸鉀等溶解於水中製成鹼性之水溶液。又,亦可使該等液體含有界面活性劑而調整表面張力。藉由含有界面活性劑,隔膜與電解用電極、或金屬板與電解用電極之接著性發生變化,而可調整操作性。作為界面活性劑,並無特別限制,可使用離子性界面活性劑、非離子性界面活性劑之任一種。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。該電解用電極基材之厚度(量規厚度)並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折,大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 本實施形態之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,藉由以下之方法(2)所測得之比率較佳為90%以上,更佳為92%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為95%以上。上限值為100%。 [方法(2)] 依序積層離子交換膜(170 mm見方)與電解用電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電解用電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑280 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電解用電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折之觀點而言,藉由以下之方法(3)所測得之比率較佳為75%以上,更佳為80%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為90%以上。上限值為100%。 [方法(3)] 依序積層離子交換膜(170 mm見方)與電解用電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電解用電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電解用電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力,防止電解中產生之氣體滯留之觀點而言,較佳為多孔結構,且其開孔率或空隙率為5~90%以下。開孔率更佳為10~80%以下,進而較佳為20~75%。 再者,所謂開孔率係每單位體積之開孔部之比率。開孔部亦根據考慮至次微米級抑或僅考慮目視可見之開口而有各種算出方法。於本實施形態中,藉由根據電極之量規厚度、寬度、長度之值算出體積V,進而對重量W進行實測,而利用下述之式算出開孔率A。 A=(1-(W/(V×ρ))×100 ρ係電極之材質之密度(g/cm3 )。例如於鎳之情形時為8.908 g/cm3 ,於鈦之情形時為4.506 g/cm3 。開孔率之調整係藉由如下方法進行適當調整:若為沖孔金屬,則變更每單位面積沖裁金屬之面積;若為多孔金屬,則變更SW(短徑)、LW(長徑)、進給之值;若為絲網,則變更金屬纖維之線徑、網眼數;若為電成形,則變更所使用之光阻之圖案;若為不織布,則變更金屬纖維直徑及纖維密度;若為發泡金屬,則變更用以使空隙形成之模板等。 本實施形態中之電解用電極就操作性之觀點而言,藉由以下之方法(A)所測得之值較佳為40 mm以下,更佳為29 mm以下,進而較佳為10 mm以下,進而更佳為6.5 mm以下。再者,具體之測定方法如實施例所記載。 [方法(A)] 於溫度23±2℃、相對濕度30±5%之條件下,將積層離子交換膜與上述電解用電極而成之樣品捲繞並固定於外徑f32 mm之氯乙烯製芯材之曲面上,靜置6小時後將該電解用電極分離並載置於水平之板,測定此時該電解用電極之兩端部之垂直方向之高度L1 及L2 ,以該等之平均值作為測定值。本實施形態中之電解用電極較佳為將該電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時(以下亦稱為「測定條件1」)之通氣阻力(以下亦稱為「通氣阻力1」)為24 kPa・s/m以下。通氣阻力較大意指空氣難以流動,指密度較高之狀態。於該狀態下,電解之產物停留於電極中,反應基質難以擴散至電極內部,因此有電解性能(電壓等)變差之傾向。又,有膜表面之濃度提高之傾向。具體而言,有陰極面苛性濃度提高而陽極面鹽水之供給性降低之傾向。其結果為,由於產物以高濃度滯留於隔膜與電極相接之界面,因此有導致隔膜之損傷,亦導致陰極面上之電壓上升及膜損傷、陽極面上之膜損傷之傾向。於本實施形態中,為了防止該等異常,較佳為將通氣阻力設為24 kPa・s/m以下。就上述同樣之觀點而言,更佳為未達0.19 kPa・s/m,進而較佳為0.15 kPa・s/m以下,進而更佳為0.07 kPa・s/m以下。 再者,於本實施形態中,若通氣阻力大至一定程度以上,則於陰極之情形時有電極中產生之NaOH滯留於電極與隔膜之界面而成為高濃度之傾向,於陽極之情形時有鹽水供給性降低而鹽水濃度成為低濃度之傾向,就將可能因此種滯留產生之對隔膜之損傷防患於未然之方面而言,較佳為未達0.19 kPa・s/m,更佳為0.15 kPa・s/m以下,進而較佳為0.07 kPa・s/m以下。 另一方面,於通氣阻力較低之情形時,由於電極之面積變小,因此有電解面積變小而電解性能(電壓等)變差之傾向。於通氣阻力為零之情形時,由於未設置電解用電極,因此有饋電體作為電極發揮功能而電解性能(電壓等)顯著變差之傾向。就該方面而言,作為通氣阻力1而特定出之較佳之下限值並無特別限定,較佳為超過0 kPa・s/m,更佳為0.0001 kPa・s/m以上,進而較佳為0.001 kPa・s/m以上。 再者,通氣阻力1就其測定法方面而言,若為0.07 kPa・s/m以下,則存在無法獲得充分之測定精度之情形。就該觀點而言,相對於通氣阻力1為0.07 kPa・s/m以下之電解用電極,亦可實現藉由以下之測定方法(以下亦稱為「測定條件2」)獲得之通氣阻力(以下亦稱為「通氣阻力2」)之評價。即,通氣阻力2係將電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度2 cm/s及通氣量4 cc/cm2 /s之情形時之通氣阻力。 具體之通氣阻力1及2之測定方法如實施例所記載。 上述通氣阻力1及2例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則有通氣阻力1及2變小之傾向,若減小開孔率,則有通氣阻力1及2變大之傾向。 以下,對本實施形態之電解用電極之一形態進行說明。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。觸媒層如下所述,可包含複數層,亦可為單層結構。 如圖1所示,本實施形態之電解用電極100具備電解用電極基材10、及被覆電解用電極基材10之兩表面之一對第一層20。第一層20較佳為將電解用電極基材10整體被覆。藉此,電極之觸媒活性及耐久性變得容易提高。再者,亦可僅於電解用電極基材10之一表面積層第一層20。 又,如圖1所示,第一層20之表面可由第二層30所被覆。第二層30較佳為將第一層20整體被覆。又,第二層30可僅積層於第一層20之一表面。 (電解用電極基材) 作為電解用電極基材10,並無特別限定,例如可使用鎳、鎳合金、不鏽鋼、進而以鈦等為代表之閥金屬(valve metal)。較佳為含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。即,較佳為電解用電極基材含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 於在高濃度之鹼性水溶液中使用不鏽鋼之情形時,若考慮到鐵及鉻溶出、及不鏽鋼之導電性為鎳之1/10左右,則較佳為使用含有鎳(Ni)之基材作為電解用電極基材。 又,電解用電極基材10於在接近飽和之高濃度之食鹽水中於氯氣產生環境中使用之情形時,材質亦較佳為耐蝕性較高之鈦。 電解用電極基材10之形狀並無特別限定,可根據目的選擇合適之形狀。作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。其中,較佳為沖孔金屬或多孔金屬。再者,所謂電成形係將照相製版與電鍍法組合而製作精密之圖案之金屬薄膜的技術。其係藉由光阻於基板上形成圖案,對未受到光阻保護之部分實施電鍍而獲得金屬薄膜之方法。 關於電解用電極基材之形狀,根據電解槽中之陽極與陰極之距離而有適宜之規格。並無特別限定,於陽極與陰極具有有限之距離之情形時,可使用多孔金屬、沖孔金屬形狀,於離子交換膜與電極相接之所謂零間距電解槽之情形時,可使用編織細線而成之編織網、發泡金屬、金屬不織布、多孔金屬、沖孔金屬、金屬多孔箔等。 作為電解用電極基材10,可列舉:金屬箔、金屬絲網、金屬不織布、沖孔金屬、多孔金屬或發泡金屬。 作為加工為沖孔金屬、多孔金屬前之板材,較佳為經壓延成形之板材、電解箔等。電解箔較佳為進而作為後處理而藉由與母材相同之元素實施鍍覆處理,於表面形成凹凸。 又,電解用電極基材10之厚度如上文所述,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於電解用電極基材中,較佳為藉由在氧化環境中將電解用電極基材進行退火而緩和加工時之殘留應力。又,為了提高與被覆於電解用電極基材之表面之觸媒層之密接性,較佳為使用鋼砂、氧化鋁砂等於上述表面形成凹凸,其後藉由酸處理而增加表面積。較佳為藉由與基材相同之元素實施鍍覆處理,增加表面積。 為了使第一層20與電解用電極基材10之表面密接,較佳為對電解用電極基材10進行增大表面積之處理。作為增大表面積之處理,可列舉使用鋼線粒(cut wire shot)、鋼砂、氧化鋁砂等之噴擊處理、使用硫酸或鹽酸之酸處理、利用與基材相同元素之鍍覆處理等。基材表面之算術平均表面粗糙度(Ra)並無特別限定,較佳為0.05 μm~50 μm,更佳為0.1~10 μm,進而較佳為0.1~5 μm。 繼而,對使用本實施形態之電解用電極作為食鹽電解用陽極之情形進行說明。 (第一層) 於圖1中,作為觸媒層之第一層20含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物。作為釕氧化物,可列舉RuO2 等。作為銥氧化物,可列舉IrO2 等。作為鈦氧化物,可列舉TiO2 等。第一層20較佳為含有釕氧化物及鈦氧化物之兩種氧化物,或含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物。藉此,第一層20成為更穩定之層,進而,與第二層30之密接性亦進一步提高。 於第一層20含有釕氧化物及鈦氧化物之兩種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為1~9莫耳,更佳為1~4莫耳。藉由將兩種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之銥氧化物較佳為0.2~3莫耳,更佳為0.3~2.5莫耳。又,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為0.3~8莫耳,更佳為1~7莫耳。藉由將三種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有選自釕氧化物、銥氧化物及鈦氧化物中之至少兩種氧化物之情形時,該等氧化物較佳為形成固溶體。藉由形成氧化物固溶體,電解用電極100表現出優異之耐久性。 除了上述組成以外,只要含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物,則可使用各種組成者。例如,亦可使用稱為DSA(註冊商標)之含有釕、銥、鉭、鈮、鈦、錫、鈷、錳、鉑等之氧化物塗層作為第一層20。 第一層20無需為單層,亦可包含複數層。例如,第一層20可包含含有三種氧化物之層與含有兩種氧化物之層。第一層20之厚度較佳為0.05~10 μm,更佳為0.1~8 μm。 (第二層) 第二層30較佳為含有釕與鈦。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較佳為含有氧化鈀、氧化鈀與鉑之固溶體或鈀與鉑之合金。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較厚者能夠維持電解性能之時間變長,就經濟性之觀點而言,較佳為0.05~3 μm之厚度。 繼而,對使用本實施形態之電解用電極作為食鹽電解用陰極之情形進行說明。 (第一層) 作為觸媒層之第一層20之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬、及該等金屬之氧化物或氫氧化物。 於含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少一種之情形時,較佳為鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金含有鉑、鈀、銠、釕、銥中之至少一種鉑族金屬。 作為鉑族金屬,較佳為含有鉑。 作為鉑族金屬氧化物,較佳為含有釕氧化物。 作為鉑族金屬氫氧化物,較佳為含有釕氫氧化物。 作為鉑族金屬合金,較佳為含有鉑與鎳、鐵、鈷之合金。 較佳為進而視需要含有鑭系元素之氧化物或氫氧化物作為第二成分。藉此,電解用電極100表現出優異之耐久性。 作為鑭系元素之氧化物或氫氧化物,較佳為含有選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑中之至少1種。 較佳為進而視需要含有過渡金屬之氧化物或氫氧化物作為第三成分。 藉由添加第三成分,電解用電極100能夠表現出更優異之耐久性,降低電解電壓。 作為較佳之組合之例,可列舉:僅釕、釕+鎳、釕+鈰、釕+鑭、釕+鑭+鉑、釕+鑭+鈀、釕+鐠、釕+鐠+鉑、釕+鐠+鉑+鈀、釕+釹、釕+釹+鉑、釕+釹+錳、釕+釹+鐵、釕+釹+鈷、釕+釹+鋅、釕+釹+鎵、釕+釹+硫、釕+釹+鉛、釕+釹+鎳、釕+釹+銅、釕+釤、釕+釤+錳、釕+釤+鐵、釕+釤+鈷、釕+釤+鋅、釕+釤+鎵、釕+釤+硫、釕+釤+鉛、釕+釤+鎳、鉑+鈰、鉑+鈀+鈰、鉑+鈀+鑭+鈰、鉑+銥、鉑+鈀、鉑+銥+鈀、鉑+鎳+鈀、鉑+鎳+釕、鉑與鎳之合金、鉑與鈷之合金、鉑與鐵之合金等。 於不含鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之情形時,觸媒之主成分較佳為鎳元素。 較佳為含有鎳金屬、氧化物、氫氧化物中之至少1種。 作為第二成分,可添加過渡金屬。作為所添加之第二成分,較佳為含有鈦、錫、鉬、鈷、錳、鐵、硫、鋅、銅、碳中之至少一種元素。 作為較佳之組合,可列舉:鎳+錫、鎳+鈦、鎳+鉬、鎳+鈷等。 視需要可於第一層20與電解用電極基材10之間設置中間層。藉由設置中間層,能夠提高電解用電極100之耐久性。 作為中間層,較佳為對第一層20與電解用電極基材10之兩者具有親和性者。作為中間層,較佳為鎳氧化物、鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物。作為中間層,可藉由將含有形成中間層之成分之溶液進行塗佈、燒成而形成,亦可於空氣環境中在300~600℃之溫度下對基材實施熱處理而形成表面氧化物層。除此以外,可藉由熱熔射法、離子鍍敷法等已知之方法形成。 (第二層) 作為觸媒層之第一層30之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬、及該等金屬之氧化物或氫氧化物。可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。作為第二層所含之元素之較佳之組合例,有第一層中所列舉之組合等。第一層與第二層之組合可為組成相同而組成比不同之組合,亦可為組成不同之組合。 作為觸媒層之厚度,較佳為將所形成之觸媒層及中間層累加而成之厚度為0.01 μm~20 μm。若為0.01 μm以上,則能夠作為觸媒充分發揮功能。若為20 μm以下,則從基材脫落之情況較少,能夠形成牢固之觸媒層。更佳為0.05 μm~15 μm。更佳為0.1 μm~10 μm。進而較佳為0.2 μm~8 μm。 作為電極之厚度、即電解用電極基材與觸媒層之合計之厚度,就電極之操作性之方面而言,較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,電極之厚度可藉由利用電子數顯厚度計(Digimatic Thickness Gauge)(Mitutoyo股份有限公司,最少顯示0.001 mm)進行測定而求出。電解用電極基材之厚度係與電極之厚度同樣地進行測定。觸媒層之厚度可藉由電極之厚度減去電解用電極基材之厚度而求出。 (電解用電極之製造方法) 其次,對電解用電極100之製造方法之一實施形態進行詳細說明。 於本實施形態中,藉由利用氧環境下之塗膜之燒成(熱分解)、或離子鍍敷、鍍覆、熱熔射等方法於電解用電極基材上形成第一層20、較佳為第二層30,可製造電解用電極100。其中,由於熱分解法、鍍覆法、離子鍍敷法能夠抑制電解用電極基材之變形,並且形成觸媒層,故而較佳。進而加入生產性之觀點,進而較佳為鍍覆法、熱分解法。此種本實施形態之製造方法能夠實現電解用電極100之較高之生產性。具體而言,於熱分解法中,藉由塗佈含有觸媒之塗佈液之塗佈步驟、乾燥塗佈液之乾燥步驟、進行熱分解之熱分解步驟,而於電解用電極基材上形成觸媒層。此處所謂熱分解意指對成為前驅物之金屬鹽進行加熱而分解為金屬或金屬氧化物與氣體狀物質。根據所使用之金屬種類、鹽之種類、進行熱分解之環境等,分解產物有所不同,但於氧化性環境下多數金屬有容易形成氧化物之傾向。於電解用電極之工業性之製造工藝中,熱分解通常於空氣中進行,多數情形時形成金屬氧化物或金屬氫氧化物。 (陽極之第一層之形成) (塗佈步驟) 第一層20係將溶解有釕、銥及鈦中之至少一種金屬之鹽的溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之釕、銥及鈦之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材100後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (陽極之第二層之形成) 第二層30係視需要而形成,例如將含有鈀化合物及鉑化合物之溶液或含有釕化合物及鈦化合物之溶液(第二塗佈液)塗佈於第一層20上後,於氧氣之存在下進行熱分解而獲得。 (利用熱分解法之陰極之第一層之形成) (塗佈步驟) 第一層20係將溶解有各種組合之金屬鹽之溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之金屬之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及乙醇、丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材10後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步長時間燒成後,於350℃~650℃之範圍內進行1分鐘~90分鐘之加熱,則能夠進一步提高第一層20之穩定性。 (中間層之形成) 中間層係視需要而形成,例如將含有鈀化合物或鉑化合物之溶液(第二塗佈液)塗佈於基材上後,於氧氣之存在下進行熱分解而獲得。或者,亦可不塗佈溶液而僅於300℃~580℃之範圍內將基材加熱1分鐘~60分鐘,藉此於基材表面形成氧化鎳中間層。 (利用離子鍍敷之陰極之第一層之形成) 第一層20亦可藉由離子鍍敷而形成。 作為一例,可列舉將基材固定於腔室內並對金屬釕靶照射電子束之方法。所蒸發之金屬釕粒子於腔室內之電漿中帶正電,而沈積於帶負電之基板上。電漿環境為氬氣、氧氣,釕係以釕氧化物之形式沈積於基材上。 (利用鍍覆之陰極之第一層之形成) 第一層20亦可藉由鍍覆法而形成。 作為一例,若使用基材作為陰極,於含有鎳及錫之電解液中實施電解鍍覆,則可形成鎳與錫之合金鍍覆。 (利用熱熔射之陰極之第一層之形成) 第一層20亦可藉由熱熔射法而形成。 作為一例,藉由將氧化鎳粒子電漿熔射於基材上,而可形成混合有金屬鎳與氧化鎳之觸媒層。 本實施形態之電解用電極能夠與離子交換膜或微多孔膜等隔膜進行一體化而使用。因此,可用作膜一體電極,無需更新電極時之陰極及陽極之更換貼附作業,作業效率大幅提高。 本實施形態之電解用電極藉由與離子交換膜或微多孔膜等隔膜形成積層體,製成隔膜與電極之一體物,而能夠使電解性能與新品時之性能相同或有所提高。該隔膜只要可與電極製成積層體,則無特別限定,以下進行詳細說明。 [離子交換膜] 離子交換膜具有含有具有離子交換基之烴系聚合物或含氟系聚合物之膜本體、與設置於該膜本體之至少一面上之塗佈層。又,塗佈層含有無機物粒子與結合劑,塗佈層之比表面積為0.1~10 m2 /g。該結構之離子交換膜於電解中所產生之氣體對電解性能之影響較少,能夠發揮出穩定之電解性能。 上述離子交換膜具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層之任一者。就強度及尺寸穩定性之觀點而言,較佳為進而具有強化芯材。 以下於塗佈層之說明之欄對無機物粒子及結合劑進行詳細說明。 圖2係表示離子交換膜之一實施形態之剖面模式圖。離子交換膜1具有:膜本體10,其含有具有離子交換基之烴系聚合物或含氟系聚合物;以及塗佈層11a及11b,其等形成於膜本體10之兩面。 於離子交換膜1中,膜本體10具備磺酸層3與羧酸層2,藉由強化芯材4強化強度及尺寸穩定性。離子交換膜1由於具備磺酸層3與羧酸層2,因此可作為離子交換膜而適宜地使用。 再者,離子交換膜亦可僅具有磺酸層及羧酸層之任一者。又,離子交換膜未必由強化芯材所強化,強化芯材之配置狀態亦不限定於圖2之例。 (膜本體) 首先,對構成離子交換膜1之膜本體10進行說明。 膜本體10只要為具有使陽離子選擇性地透過之功能且含有具有離子交換基之烴系聚合物或含氟系聚合物者即可,其構成或材料並無特別限定,可適當選擇適宜者。 膜本體10中之具有離子交換基之烴系聚合物或含氟系聚合物例如可由具有可藉由水解等成為離子交換基之離子交換基前驅物之烴系聚合物或含氟系聚合物獲得。具體而言,例如使用主鏈包含氟化烴、具有可藉由水解等轉換為離子交換基之基(離子交換基前驅物)作為懸垂側鏈且能夠熔融加工之聚合物(以下視情形稱為「含氟系聚合物(a)」)製作膜本體10之前驅物後,將離子交換基前驅物轉換為離子交換基,藉此可獲得膜本體10。 含氟系聚合物(a)例如可藉由使選自下述第1群之至少一種單體與選自下述第2群及/或下述第3群之至少一種單體進行共聚合而製造。又,亦可藉由選自下述第1群、下述第2群、及下述第3群之任一群之1種單體之均聚而製造。 作為第1群之單體,例如可列舉氟乙烯化合物。作為氟乙烯化合物,例如可列舉:氟乙烯、四氟乙烯、六氟丙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、全氟烷基乙烯醚等。尤其是於將離子交換膜用作鹼電解用膜之情形時,氟乙烯化合物較佳為全氟單體,較佳為選自由四氟乙烯、六氟丙烯、全氟烷基乙烯醚所組成之群中之全氟單體。 作為第2群之單體,例如可列舉具有可轉換為羧酸型離子交換基(羧酸基)之官能基之乙烯系化合物。作為具有可轉換為羧酸基之官能基之乙烯系化合物,例如可列舉以CF2 =CF(OCF2 CYF)s -O(CZF)t -COOR表示之單體等(此處,s表示0~2之整數,t表示1~12之整數,Y及Z各自獨立地表示F或CF3 ,R表示低級烷基。低級烷基例如為碳數1~3之烷基)。 該等中,較佳為以CF2 =CF(OCF2 CYF)n -O(CF2 )m -COOR表示之化合物。此處,n表示0~2之整數,m表示1~4之整數,Y表示F或CF3 ,R表示CH3 、C2 H5 、或C3 H7 。 再者,於將離子交換膜用作鹼電解用陽離子交換膜之情形時,較佳為至少使用全氟化合物作為單體,但由於酯基之烷基(參照上述R)於水解時從聚合物喪失,因此烷基(R)亦可不為全部氫原子被取代為氟原子之全氟烷基。 作為第2群之單體,於上述中,更佳為下述所表示之單體。 CF2 =CFOCF2 -CF(CF3 )OCF2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )2 COOCH3 、 CF2 =CF[OCF2 -CF(CF3 )]2 O(CF2 )2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )3 COOCH3 、 CF2 =CFO(CF2 )2 COOCH3 、 CF2 =CFO(CF2 )3 COOCH3 。 作為第3群之單體,例如可列舉具有可轉換為磺酸型離子交換基(磺酸基)之官能基之乙烯系化合物。作為具有可轉換為磺酸基之官能基之乙烯系化合物,例如較佳為以CF2 =CFO-X-CF2 -SO2 F表示之單體(此處,X表示全氟伸烷基)。作為該等之具體例,可列舉下述所表示之單體等。 CF2 =CFOCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、 CF2 =CF(CF2 )2 SO2 F、 CF2 =CFO[CF2 CF(CF3 )O]2 CF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF2 OCF3 )OCF2 CF2 SO2 F。 該等中,更佳為CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、及CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F。 由該等單體獲得之共聚物可藉由針對氟乙烯之均聚及共聚合所開發之聚合法、尤其是對四氟乙烯所使用之通常之聚合方法而製造。例如,於非水性法中,可使用全氟烴、氯氟碳等不活性溶劑,於全氟碳過氧化物或偶氮化合物等自由基聚合起始劑之存在下,於溫度0~200℃、壓力0.1~20 MPa之條件下進行聚合反應。 於上述共聚合中,上述單體之組合之種類及其比率並無特別限定,根據欲對所獲得之含氟系聚合物賦予之官能基之種類及量選擇確定。例如於製成僅含有羧酸基之含氟系聚合物之情形時,從上述第1群及第2群分別選擇至少1種單體進行共聚合即可。又,於製成僅含有磺酸基之含氟系聚合物之情形時,從上述第1群及第3群之單體中分別選擇至少1種單體進行共聚合即可。進而,於製成具有羧酸基及磺酸基之含氟系聚合物之情形時,從上述第1群、第2群及第3群之單體中分別選擇至少1種單體進行共聚合即可。於該情形時,藉由使包含上述第1群及第2群之共聚物與包含上述第1群及第3群之共聚物分開進行聚合,其後加以混合亦可獲得目標之含氟系聚合物。又,各單體之混合比率並無特別限定,於增加每單位聚合物之官能基之量之情形時,增加選自上述第2群及第3群之單體之比率即可。 含氟系共聚物之總離子交換容量並無特別限定,較佳為0.5~2.0 mg當量/g,更佳為0.6~1.5 mg當量/g。此處,所謂總離子交換容量係指相對於單位重量之乾燥樹脂之交換基之當量,可藉由中和滴定等進行測定。 於離子交換膜1之膜本體10中,積層有含有具有磺酸基之含氟系聚合物之磺酸層3與含有具有羧酸基之含氟系聚合物之羧酸層2。藉由製成此種層結構之膜本體10,能夠進一步提高鈉離子等陽離子之選擇性透過性。 於將離子交換膜1配置於電解槽之情形時,通常以磺酸層3位於電解槽之陽極側、羧酸層2位於電解槽之陰極側之方式配置。 磺酸層3較佳為由電阻較低之材料構成,就膜強度之觀點而言,較佳為其膜厚厚於羧酸層2。磺酸層3之膜厚較佳為羧酸層2之2~25倍,更佳為3~15倍。 羧酸層2較佳為即使膜厚較薄亦具有較高之陰離子排斥性者。此處所謂陰離子排斥性係指阻礙陰離子對離子交換膜1之滲入或透過之性質。為了提高陰離子排斥性,有效的是對磺酸層配置離子交換容量較小之羧酸層等。 作為磺酸層3所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F作為第3群之單體所獲得之聚合物。 作為羧酸層2所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF2 )O(CF2 )2 COOCH3 作為第2群之單體所獲得之聚合物。 (塗佈層) 離子交換膜於膜本體之至少一面上具有塗佈層。又,如圖2所示,於離子交換膜1中,於膜本體10之兩面上分別形成有塗佈層11a及11b。 塗佈層含有無機物粒子與結合劑。 無機物粒子之平均粒徑更佳為0.90 μm以上。若無機物粒子之平均粒徑為0.90 μm以上,則不僅極大地提高對氣體附著之耐久性,而且極大地提高對雜質之耐久性。即,藉由增大無機物粒子之平均粒徑,並且滿足上述比表面積之值,可獲得尤其顯著之效果。為了滿足此種平均粒徑與比表面積,較佳為不規則狀之無機物粒子。可使用藉由熔融獲得之無機物粒子、藉由原石粉碎獲得之無機物粒子。較佳可適宜地使用藉由原石粉碎獲得之無機物粒子。 又,無機物粒子之平均粒徑可設為2 μm以下。若無機物粒子之平均粒徑為2 μm以下,則能夠防止因無機物粒子而損傷膜。無機物粒子之平均粒徑更佳為0.90~1.2 μm。 此處,平均粒徑可藉由粒度分佈計(「SALD2200」島津製作所)進行測定。 無機物粒子之形狀較佳為不規則形狀。對雜質之耐性進一步提高。又,無機物粒子之粒度分佈較佳為較寬。 無機物粒子較佳為含有選自由週期表第IV族元素之氧化物、週期表第IV族元素之氮化物、及週期表第IV族元素之碳化物所組成之群中之至少一種無機物。就耐久性之觀點而言,更佳為氧化鋯之粒子。 該無機物粒子較佳為藉由將無機物粒子之原石粉碎所製造之無機物粒子,或以藉由將無機物粒子之原石熔融並加以精製而粒子之直徑一致之球狀之粒子作為無機物粒子。 作為原石粉碎方法,並無特別限定,可列舉:球磨機、珠磨機、膠體磨機、錐形磨機、盤磨機、輪輾機、磨粉機、錘磨機、造粒機、VSI磨機(vertical shaft impactor mill,立軸式衝擊磨機)、威利磨機(Wiley mill)、輥磨機、噴射磨機等。又,較佳為粉碎後將其洗淨,作為此時之洗淨方法,較佳為酸處理。藉此,能夠減少附著於無機物粒子之表面之鐵等雜質。 塗佈層較佳為含有結合劑。結合劑係將無機物粒子保持於離子交換膜之表面、形成塗佈層之成分。就對電解液或電解之產物之耐性之觀點而言,結合劑較佳為含有含氟系聚合物。 作為結合劑,就對電解液或電解之產物之耐性、及對離子交換膜之表面之接著性之觀點而言,更佳為具有羧酸基或磺酸基之含氟系聚合物。於在含有具有磺酸基之含氟聚合物之層(磺酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有磺酸基之含氟系聚合物。又,於在含有具有羧酸基之含氟聚合物之層(羧酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有羧酸基之含氟系聚合物。 塗佈層中,無機物粒子之含量較佳為40~90質量%,更佳為50~90質量%。又,結合劑之含量較佳為10~60質量%,更佳為10~50質量%。 離子交換膜中之塗佈層之分佈密度較佳為每1 cm2 為0.05~2 mg。又,於離子交換膜於表面具有凹凸形狀之情形時,塗佈層之分佈密度較佳為每1 cm2 為0.5~2 mg。 作為形成塗佈層之方法,並無特別限定,可使用公知之方法。例如可列舉藉由噴射等塗佈將無機物粒子分散於含有結合劑之溶液中而成之塗佈液之方法。 (強化芯材) 離子交換膜較佳為具有配置於膜本體之內部之強化芯材。 強化芯材係強化離子交換膜之強度或尺寸穩定性之構件。藉由將強化芯材配置於膜本體之內部,尤其能夠將離子交換膜之伸縮控制為所需之範圍。該離子交換膜於電解時等不會伸縮為必要程度以上,而能夠長期維持優異之尺寸穩定性。 強化芯材之構成並無特別限定,例如可將稱為強化紗之紗進行紡紗而形成。此處所謂強化紗係構成強化芯材之構件,指能夠對離子交換膜賦予所需之尺寸穩定性及機械強度且於離子交換膜中能夠穩定地存在之紗。藉由使用將該強化紗紡紗而成之強化芯材,能夠對離子交換膜賦予更優異之尺寸穩定性及機械強度。 強化芯材及其所使用之強化紗之材料並無特別限定,較佳為對酸或鹼等具有耐性之材料,就需要長期之耐熱性、耐化學品性之方面而言,較佳為包含含氟系聚合物之纖維。 作為強化芯材所使用之含氟系聚合物,例如可列舉:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、四氟乙烯-六氟丙烯共聚物、三氟氯乙烯-乙烯共聚物及偏二氟乙烯聚合物(PVDF)等。該等中,尤其是就耐熱性及耐化學品性之觀點而言,較佳為使用包含聚四氟乙烯之纖維。 強化芯材所使用之強化紗之紗直徑並無特別限定,較佳為20~300丹尼,更佳為50~250丹尼。紡織密度(每單位長度之織入根數)較佳為5~50根/英吋。作為強化芯材之形態,並無特別限定,例如可使用織布、不織布、針織布等,較佳為織布之形態。又,使用織布之厚度較佳為30~250 μm、更佳為30~150 μm者。 織布或針織布可使用單絲、複絲或該等之紗線、切膜絲(slit yarn)等,紡織方法可使用平織、紗羅組織、針織、凸條組織、縐條紋薄織(seersucker)等各種紡織方法。 膜本體中之強化芯材之紡織方法及配置並無特別限定,可考慮離子交換膜之大小或形狀、離子交換膜所需之物性及使用環境等適當設為適宜之配置。 例如,可沿膜本體之特定之一方向配置強化芯材,就尺寸穩定性之觀點而言,較佳為沿特定之第一方向配置強化芯材,且沿大致垂直於第一方向之第二方向配置其他強化芯材。藉由在膜本體之縱向膜本體之內部以大致成一列之方式配置複數個強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。例如,較佳為於膜本體之表面織入沿縱向配置之強化芯材(縱紗)與沿橫向配置之強化芯材(橫紗)之配置。就尺寸穩定性、機械強度及製造容易性之觀點而言,更佳為製成使縱紗與橫紗一上一下交替織入而紡織之平紋織物、或一邊撚轉2根經紗一邊與橫紗交織之紗羅組織物、於每2根或數根並紗配置之縱紗中織入相同數量之橫紗而紡織之斜紋織物(twill weave)等。 尤佳為沿離子交換膜之MD方向(縱向(Machine Direction)方向)及TD方向(橫向(Transverse Direction)方向)之兩方向配置強化芯材。即,較佳為沿MD方向與TD方向平織。此處,所謂MD方向係指於下文所述之離子交換膜之製造步驟中搬送膜本體或各種芯材(例如,強化芯材、強化紗、下文所述之犧牲紗等)之方向(行進方向),所謂TD方向係指大致垂直於MD方向之方向。此外,將沿MD方向紡織之紗稱為MD紗,將沿TD方向紡織之紗稱為TD紗。通常電解所使用之離子交換膜係矩形,長度方向為MD方向、寬度方向為TD方向之情況較多。藉由織入作為MD紗之強化芯材與作為TD紗之強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。 強化芯材之配置間隔並無特別限定,可考慮離子交換膜所需之物性及使用環境等適當設為適宜之配置。 強化芯材之開口率並無特別限定,較佳為30%以上,更佳為50%以上且90%以下。開口率就離子交換膜之電化學性質之觀點而言,較佳為30%以上,就離子交換膜之機械強度之觀點而言,較佳為90%以下。 所謂強化芯材之開口率係指膜本體之任一表面之面積(A)中離子等物質(電解液及其所含之陽離子(例如,鈉離子))能夠通過之表面之總面積(B)之比率(B/A)。所謂離子等物質能夠通過之表面之總面積(B)可指於離子交換膜中陽離子或電解液等不被離子交換膜所含之強化芯材等阻斷之區域之總面積。 圖3係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。圖3係將離子交換膜之一部分放大而僅圖示該區域內之強化芯材21及22之配置,其他構件省略圖示。 藉由從由沿縱向配置之強化芯材21與沿橫向配置之強化芯材22所圍成之亦包括強化芯材之面積在內之區域的面積(A)減去強化芯材之總面積(C),可求出上述區域之面積(A)中離子等物質能夠通過之區域之總面積(B)。即,開口率可藉由下述式(I)求出。 開口率=(B)/(A)=((A)-(C))/(A) …(I) 於強化芯材中,就耐化學品性及耐熱性之觀點而言,尤佳之形態係含有PTFE之帶狀紗線或高配向單絲。具體而言,更佳為如下強化芯材,其係使用將包含PTFE之高強度多孔質片材切為帶狀而成之帶狀紗線、或包含PTFE之高度配向之單絲之50~300丹尼且紡織密度為10~50根/英吋之平紋織物,其厚度為50~100 μm之範圍。含有該強化芯材之離子交換膜之開口率進而較佳為60%以上。 作為強化紗之形狀,可列舉圓紗、帶狀紗等。 (連通孔) 離子交換膜較佳為於膜本體之內部具有連通孔。 所謂連通孔係指能夠成為電解時產生之離子或電解液之流路之孔。又,所謂連通孔係形成於膜本體內部之管狀之孔,藉由下文所述之犧牲芯材(或犧牲紗)溶出而形成。連通孔之形狀或直徑等可藉由選擇犧牲芯材(犧牲紗)之形狀或直徑進行控制。 藉由在離子交換膜形成連通孔,於電解時能夠確保電解液之移動性。連通孔之形狀並無特別限定,根據下文所述之製法,可製成連通孔之形成所使用之犧牲芯材之形狀。 連通孔較佳為以交替通過強化芯材之陽極側(磺酸層側)與陰極側(羧酸層側)之方式形成。藉由設為該結構,於強化芯材之陰極側形成有連通孔之部分,通過充滿連通孔之電解液所輸送之離子(例如,鈉離子)亦能夠流至強化芯材之陰極側。其結果為,由於陽離子之流動未被遮蔽,因此能夠進一步降低離子交換膜之電阻。 連通孔可僅沿構成離子交換膜之膜本體之特定之一方向形成,就發揮出更穩定之電解性能之觀點而言,較佳為沿膜本體之縱向與橫向之兩方向形成。 [製造方法] 作為離子交換膜之適宜之製造方法,可列舉具有以下之(1)步驟~(6)步驟之方法。 (1)步驟:製造具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之含氟系聚合物之步驟。 (2)步驟:藉由視需要至少織入複數個強化芯材與具有溶於酸或鹼之性質且形成連通孔之犧牲紗而獲得於鄰接之強化芯材彼此之間配置有犧牲紗之補強材之步驟。 (3)步驟:將具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之上述含氟系聚合物進行膜化之步驟。 (4)步驟:視需要將上述補強材埋入至上述膜中而獲得內部配置有上述補強材之膜本體之步驟。 (5)步驟:將(4)步驟中獲得之膜本體進行水解之步驟(水解步驟)。 (6)步驟:於(5)步驟中獲得之膜本體設置塗佈層之步驟(塗佈步驟)。 以下,對各步驟進行詳細說明。 (1)步驟:製造含氟系聚合物之步驟 於(1)步驟中,使用上述第1群~第3群所記載之原料之單體製造含氟系聚合物。為了控制含氟系聚合物之離子交換容量,於形成各層之含氟系聚合物之製造中調整原料之單體之混合比即可。 (2)步驟:補強材之製造步驟 所謂補強材係紡織強化紗之織布等。藉由將補強材埋入至膜內而形成強化芯材。於製成具有連通孔之離子交換膜時,亦將犧牲紗一起織入至補強材中。該情形時之犧牲紗之混織量較佳為補強材整體之10~80質量%,更佳為30~70質量%。藉由織入犧牲紗,亦能夠防止強化芯材之脫線。 犧牲紗係於膜之製造步驟或電解環境下具有溶解性者,可使用嫘縈、聚對苯二甲酸乙二酯(PET)、纖維素及聚醯胺等。又,亦較佳為具有20~50丹尼之粗細程度、包含單絲或複絲之聚乙烯醇等。 再者,於(2)步驟中,可藉由調整強化芯材或犧牲紗之配置而控制開口率或連通孔之配置等。 (3)步驟:膜化步驟 於(3)步驟中,使用擠出機將上述(1)步驟中獲得之含氟系聚合物進行膜化。膜可為單層結構,亦可如上所述為磺酸層與羧酸層之2層結構,亦可為3層以上之多層結構。 作為膜化之方法,例如可列舉以下者。 分別將具有羧酸基之含氟聚合物、具有磺酸基之含氟聚合物分開進行膜化之方法。 藉由共擠出將具有羧酸基之含氟聚合物與具有磺酸基之含氟聚合物製成複合膜之方法。 再者,膜可分別為複數片。又,將異種之膜共擠出有助於提高界面之接著強度,故而較佳。 (4)步驟:獲得膜本體之步驟 於(4)步驟中,藉由將(2)步驟中獲得之補強材埋入至(3)步驟中獲得之膜之內部,而獲得內有補強材之膜本體。 作為膜本體之較佳之形成方法,可列舉:(i)藉由共擠出法將位於陰極側之具有羧酸基前驅物(例如,羧酸酯官能基)之含氟系聚合物(以下將包含其之層稱為第一層)與具有磺酸基前驅物(例如,磺醯氟官能基)之含氟系聚合物(以下將包含其之層稱為第二層)進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將補強材、第二層/第一層複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法;(ii)區別於第二層/第一層複合膜,預先將具有磺酸基前驅物之含氟系聚合物(第三層)單獨進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將第三層膜、強化芯材、包含第二層/第一層之複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法。 此處,將第一層與第二層共擠出有助於提高界面之接著強度。 又,於減壓下進行一體化之方法與加壓壓製法相比,具有補強材上之第三層之厚度變大之特徵。進而,由於將補強材固定於膜本體之內面,因此具有能夠充分保持離子交換膜之機械強度之性能。 再者,此處所說明之積層之變化係一例,可考慮所需之膜本體之層構成或物性等,適當選擇適宜之積層圖案(例如,各層之組合等)後進行共擠出。 再者,為了進一步提高離子交換膜之電性能,亦可於第一層與第二層之間進一步介置包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層,或使用包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層代替第二層。 第四層之形成方法可為分開製造具有羧酸基前驅物之含氟系聚合物與具有磺酸基前驅物之含氟系聚合物後加以混合之方法,亦可為使用將具有羧酸基前驅物之單體與具有磺酸基前驅物之單體共聚合而成者之方法。 於將第四層製成離子交換膜之構成之情形時,可將第一層與第四層之共擠出膜加以成形,第三層及第二層與其分開單獨進行膜化,藉由上文所述之方法進行積層,亦可將第一層/第四層/第二層之3層一次共擠出而進行膜化。 於該情形時,所擠出之膜行進之方向為MD方向。由此可將含有具有離子交換基之含氟系聚合物之膜本體形成於補強材上。 又,離子交換膜較佳為於包含磺酸層之表面側具有包含具有磺酸基之含氟聚合物之突出的部分、即凸部。作為形成此種凸部之方法,並無特別限定,可採用於樹脂表面形成凸部之公知之方法。具體而言,例如可列舉對膜本體之表面實施壓紋加工之方法。例如,於將上述複合膜與補強材等進行一體化時,藉由使用預先經壓紋加工之脫模紙,可形成上述凸部。於藉由壓紋加工形成凸部之情形時,凸部之高度或配置密度之控制可藉由控制所轉印之壓紋形狀(脫模紙之形狀)而進行。 (5)水解步驟 於(5)步驟中,進行將(4)步驟中獲得之膜本體水解而將離子交換基前驅物轉換為離子交換基之步驟(水解步驟)。 又,於(5)步驟中,藉由利用酸或鹼將膜本體所含之犧牲紗溶解去除,可於膜本體形成溶出孔。再者,犧牲紗亦可不完全溶解去除,而殘留於連通孔中。又,殘留於連通孔中之犧牲紗可於將離子交換膜供於電解時藉由電解液溶解去除。 犧牲紗係於離子交換膜之製造步驟或電解環境下對酸或鹼具有溶解性者,藉由使犧牲紗溶出而於該部位形成連通孔。 (5)步驟可將(4)步驟中獲得之膜本體浸漬於含有酸或鹼之水解溶液中進行。作為該水解溶液,例如可使用含有KOH與DMSO(Dimethyl sulfoxide,二甲基亞碸)之混合溶液。 該混合溶液較佳為含有2.5~4.0 N之KOH,且含有25~35質量%之DMSO。 作為水解之溫度,較佳為70~100℃。溫度越高,可使視厚度更厚。更佳為75~100℃。 作為水解之時間,較佳為10~120分鐘。時間越長,可使視厚度更厚。更佳為20~120分鐘。 此處,對藉由溶出犧牲紗而形成連通孔之步驟進一步詳細地說明。圖4(a)、(b)係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 於圖4(a)、(b)中,僅圖示強化紗52、犧牲紗504a及由犧牲紗504a形成之連通孔504,膜本體等其他構件省略圖示。 首先,將於離子交換膜中構成強化芯材之強化紗52與於離子交換膜中用以形成連通孔504之犧牲紗504a製成針織織入補強材。然後,於(5)步驟中藉由使犧牲紗504a溶出而形成連通孔504。 藉由上述方法,根據於離子交換膜之膜本體內如何配置強化芯材、連通孔而調整強化紗52與犧牲紗504a之針織織入方法即可,因此較簡便。 於圖4(a)中,例示於紙面沿縱向與橫向之兩方向將強化紗52與犧牲紗504a織入之平織之補強材,可視需要變更補強材中之強化紗52與犧牲紗504a之配置。 (6)塗佈步驟 於(6)步驟中,製備含有藉由原石粉碎或原石熔融獲得之無機物粒子與結合劑之塗佈液,將塗佈液塗佈於(5)步驟中獲得之離子交換膜之表面並加以乾燥,藉此可形成塗佈層。 作為結合劑,較佳為將具有離子交換基前驅物之含氟系聚合物水解於含有二甲基亞碸(DMSO)及氫氧化鉀(KOH)之水溶液中之後,浸漬於鹽酸中將離子交換基之抗衡離子置換為H+ 而成之結合劑(例如,具有羧基或磺基之含氟系聚合物)。藉此,變得容易溶解於下文所述之水或乙醇中,故而較佳。 將該結合劑溶解於混合水與乙醇而成之溶液中。再者,水與乙醇之較佳之體積比為10:1~1:10,更佳為5:1~1:5,進而較佳為2:1~1:2。藉由球磨機使無機物粒子分散於由此獲得之溶解液中而獲得塗佈液。此時,亦可藉由調整分散時之時間、旋轉速度而調整粒子之平均粒徑等。再者,無機物粒子與結合劑之較佳之調配量如上文所述。 塗佈液中之無機物粒子及結合劑之濃度並無特別限定,較佳為製成稀薄之塗佈液。藉此,能夠均勻地塗佈於離子交換膜之表面。 又,於使無機物粒子分散時,亦可將界面活性劑添加於分散液中。作為界面活性劑,較佳為非離子系界面活性劑,例如可列舉日油股份有限公司製造之HS-210、NS-210、P-210、E-212等。 藉由利用噴射塗佈或滾筒塗敷將所獲得之塗佈液塗佈於離子交換膜表面而可獲得離子交換膜。 [微多孔膜] 作為本實施形態之微多孔膜,只要如上文所述,可與電解用電極製成積層體,則無特別限定,可應用各種微多孔膜。 本實施形態之微多孔膜之氣孔率並無特別限定,例如可設為20~90,較佳為30~85。上述氣孔率例如可藉由下述之式算出。 氣孔率=(1-(乾燥狀態之膜重量)/(由根據膜之厚度、寬度、長度算出之體積與膜素材之密度所算出之重量))×100 本實施形態之微多孔膜之平均孔徑並無特別限定,例如可設為0.01 μm~10 μ,較佳為0.05 μm~5 μm。上述平均孔徑例如係沿厚度方向將膜垂直切斷,藉由FE-SEM(field emission-scanning electron microscope,場發射掃描式電子顯微鏡)觀察切斷面。對所觀察之孔之直徑測定100點左右並求出平均值,藉此可求出平均孔徑。 本實施形態之微多孔膜之厚度並無特別限定,例如可設為10 μm~1000 μm,較佳為50 μm~600 μm。上述厚度例如可使用測微計(Mitutoyo股份有限公司製造)等進行測定。 作為如上所述之微多孔膜之具體例,可列舉Agfa公司製造之Zirfon Perl UTP 500(於本實施形態中亦稱為Zirfon膜)、國際公開第2013-183584號說明書、國際公開第2016-203701號說明書等所記載者。 [積層體] 本實施形態之積層體具備本實施形態之電解用電極及與上述電解用電極相接之隔膜或饋電體。由於以上述方式構成,因此本實施形態之積層體能夠提高電解槽中之電極更新時之作業效率,進而於更新後亦能夠表現出優異之電解性能。 即,藉由本實施形態之積層體,於更新電極時,無需伴隨剝離固定於電解池之電極等繁雜之作業,藉由如與隔膜之更新相同之簡單之作業即可更新電極,因此作業效率大幅提高。 進而,藉由本發明之積層體,對於電解性能,能夠維持新品時之性能或有所提高。又,即使於在新品之電解池僅設置有饋電體之情形時(即,設置有無觸媒層之電極),亦可僅藉由將本實施形態之電解用電極貼附於饋電體而使其作為電極發揮作用,因此亦可大幅地減少觸媒塗層或者甚至無觸媒塗層。 本實施形態之積層體例如可以捲繞於氯乙烯製之管等之狀態(滾筒狀等)進行保管、向顧客處輸送等,操作大幅地變得容易。 再者,作為本實施形態中之饋電體,可應用劣化之電極(即既有電極)或未形成有觸媒塗層之電極等下文所述之各種基材。 於本實施形態之積層體中,針對上述隔膜或饋電體之上述電解用電極之每單位質量·單位面積所承受之力較佳為0.08 N/(mg・cm2 )以上,更佳為0.1 N/(mg・cm2 )以上,進而較佳為0.14 N/(mg・cm2 )以上,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理更容易之觀點而言,進而更佳為0.2 N/(mg・cm2 )以上。上限值並無特別限定,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 [捲繞體] 本實施形態之捲繞體包含本實施形態之電解用電極、或本實施形態之積層體。即,本實施形態之捲繞體係將本實施形態之電解用電極、或本實施形態之積層體捲繞而成者。如本實施形態之捲繞體般,藉由將本實施形態之電解用電極、或本實施形態之積層體進行捲繞並減小尺寸,能夠進一步提高操作性。 [電解槽] 本實施形態之電解槽包含本實施形態之電解用電極。以下,以使用離子交換膜作為隔膜進行食鹽電解之情形為例,對電解槽之一實施形態進行詳細說明。 [電解池] 圖5係電解池1之剖面圖。 電解池1具備陽極室10、陰極室20、設置於陽極室10及陰極室20之間之間隔壁30、設置於陽極室10之陽極11、及設置於陰極室20之陰極21。視需要亦可具備具有基材18a與形成於該基材18a上之逆向電流吸收層18b且設置於陰極室內之逆向電流吸收體18。屬於1個電解池1之陽極11及陰極21互相電性連接。換言之,電解池1具備如下陰極結構體。陰極結構體40具備陰極室20、設置於陰極室20之陰極21、及設置於陰極室20內之逆向電流吸收體18,逆向電流吸收體18如圖9所示具有基材18a與形成於該基材18a上之逆向電流吸收層18b,陰極21與逆向電流吸收層18b電性連接。陰極室20進而具有集電體23、支持該集電體之支持體24、及金屬彈性體22。金屬彈性體22係設置於集電體23及陰極21之間。支持體24係設置於集電體23及間隔壁30之間。集電體23經由金屬彈性體22而與陰極21電性連接。間隔壁30經由支持體24而與集電體23電性連接。因此,間隔壁30、支持體24、集電體23、金屬彈性體22及陰極21係電性連接。陰極21及逆向電流吸收層18b係電性連接。陰極21及逆向電流吸收層可直接連接,亦可經由集電體、支持體、金屬彈性體或間隔壁等而間接連接。陰極21之表面整體較佳為由用於還原反應之觸媒層所被覆。又,電性連接之形態可為分別直接將間隔壁30與支持體24、支持體24與集電體23、集電體23與金屬彈性體22安裝,並且於金屬彈性體22上積層陰極21之形態。作為將該等各構成構件互相直接安裝之方法,可列舉焊接等。又,亦可將逆向電流吸收體18、陰極21、及集電體23總稱為陰極結構體40。 圖6係電解槽4內鄰接之2個電解池1之剖面圖。圖7表示電解槽4。圖8表示組裝電解槽4之步驟。如圖6所示,將電解池1、陽離子交換膜2、電解池1依序串聯排列。於電解槽內鄰接之2個電解池中之一電解池1之陽極室與另一電解池1之陰極室之間配置離子交換膜2。即,電解池1之陽極室10及與其鄰接之電解池1之陰極室20係由陽離子交換膜2隔開。如圖7所示,電解槽4包含介隔離子交換膜2而串聯連接之複數個電解池1。即,電解槽4係具備串聯配置之複數個電解池1、及配置於鄰接之電解池1之間之離子交換膜2的複極式電解槽。如圖8所示,電解槽4係藉由介隔離子交換膜2將複數個電解池1串聯配置並利用壓製器5連結而組裝。 電解槽4具有連接於電源之陽極端子7與陰極端子6。於電解槽4內串聯連結之複數個電解池1中位於最靠端之電解池1之陽極11係電性連接於陽極端子7。於電解槽4內串聯連結之複數個電解池2中位於陽極端子7之相反側之端之電解池的陰極21係電性連接於陰極端子6。電解時之電流從陽極端子7側起,經過各電解池1之陽極及陰極而流向陰極端子6。再者,可於連結之電解池1之兩端配置僅具有陽極室之電解池(陽極終端池)與僅具有陰極室之電解池(陰極終端池)。於該情形時,將陽極端子7連接於配置於其一端之陽極終端池,將陰極端子6連接於配置於另一端之陰極終端池。 於進行鹽水之電解之情形時,向各陽極室10供給鹽水,向陰極室20供給純水或低濃度之氫氧化鈉水溶液。各液體係從電解液供給管(圖中省略)起,經過電解液供給軟管(圖中省略)而向各電解池1供給。又,電解液及電解之產物係由電解液回收管(圖中省略)所回收。於電解中,鹽水中之鈉離子從一電解池1之陽極室10起,通過離子交換膜2,向旁邊之電解池1之陰極室20移動。由此電解中之電流沿將電解池1串聯連結之方向流通。即,電流係經由陽離子交換膜2而從陽極室10流向陰極室20。伴隨鹽水之電解,於陽極11側產生氯氣,於陰極21側產生氫氧化鈉(溶質)與氫氣。 (陽極室) 陽極室10具有陽極11或陽極饋電體11。於將本實施形態之電解用電極插入陽極側之情形時,11作為陽極饋電體發揮功能。於不將本實施形態之電解用電極插入陽極側之情形時,11作為陽極發揮功能。又,陽極室10較佳為具有向陽極室10供給電解液之陽極側電解液供給部、配置於陽極側電解液供給部之上方且以與間隔壁30大致平行或傾斜之方式配置之擋板、及配置於擋板之上方且從混入有氣體之電解液中分離氣體之陽極側氣液分離部。 (陽極) 於不將本實施形態之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極11。作為陽極11,可使用所謂DSA(註冊商標)等金屬電極。所謂DSA係藉由以釕、銥、鈦作為成分之氧化物被覆表面之鈦基材之電極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極饋電體) 於將本實施形態之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極饋電體11。作為陽極饋電體11,可使用所謂DSA(註冊商標)等金屬電極,亦可使用未形成有觸媒塗層之鈦。又,亦可使用使觸媒塗層厚度變薄之DSA。進而,亦可使用使用過之陽極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極側電解液供給部) 陽極側電解液供給部係向陽極室10供給電解液者,其連接於電解液供給管。陽極側電解液供給部較佳為配置於陽極室10之下方。作為陽極側電解液供給部,例如可使用表面形成有開口部之管(分散管)等。該管更佳為以沿陽極11之表面平行於電解池之底部19之方式配置。該管係連接於向電解池1內供給電解液之電解液供給管(液供給噴嘴)。從液供給噴嘴供給之電解液藉由管被搬送至電解池1內,從設置於管之表面之開口部向陽極室10之內部供給。藉由將管以沿陽極11之表面平行於電解池之底部19之方式配置,能夠將電解液均勻地供給至陽極室10之內部,故而較佳。 (陽極側氣液分離部) 陽極側氣液分離部較佳為配置於擋板之上方。於電解中,陽極側氣液分離部具有將氯氣等產生氣體與電解液分離之功能。再者,只要無特別說明,則所謂上方意指圖5之電解池1中之上方向,所謂下方意指圖5之電解池1中之下方向。 電解時,若電解池1中產生之產生氣體與電解液成為混相(氣液混相)而被排出至系外,則存在因電解池1內部之壓力變動導致產生振動而引起離子交換膜之物理破損之情形。為了抑制該情形,較佳為於本實施形態之電解池1中設置用以將氣體與液體分離之陽極側氣液分離部。較佳為於陽極側氣液分離部設置用以消除氣泡之消泡板。藉由在氣液混相流通過消泡板時氣泡破裂,而可分離為電解液與氣體。其結果為,能夠防止電解時之振動。 (擋板) 擋板較佳為配置於陽極側電解液供給部之上方,且以與間隔壁30大致平行或傾斜之方式配置。擋板係控制陽極室10之電解液之流動之間隔板。藉由設置擋板,可使電解液(鹽水等)於陽極室10內部循環,使其濃度變得均勻。為了引起內部循環,擋板較佳為以將陽極11附近之空間與間隔壁30附近之空間隔開之方式配置。就該觀點而言,擋板較佳為以與陽極11及間隔壁30之各表面相對向之方式設置。於由擋板分隔之陽極附近之空間,藉由進行電解,電解液濃度(鹽水濃度)降低,又,產生氯氣等產生氣體。藉此,於由擋板分隔之陽極11附近之空間與間隔壁30附近之空間產生氣液之比重差。利用該情況,能夠促進陽極室10中之電解液之內部循環,使陽極室10之電解液之濃度分佈變得更均勻。 再者,於圖5並未圖示,但亦可於陽極室10之內部另行設置集電體。作為該集電體,亦可設為與下文所述之陰極室之集電體相同之材料或構成。又,於陽極室10中,亦可使陽極11本身作為集電體發揮功能。 (間隔壁) 間隔壁30係配置於陽極室10與陰極室20之間。間隔壁30有時亦稱為間隔件,係將陽極室10與陰極室20進行劃分者。作為間隔壁30,可使用作為電解用之間隔件所公知者,例如可列舉於陰極側焊接包含鎳之板、於陽極側焊接包含鈦之板之間隔壁等。 (陰極室) 陰極室20於將本實施形態之電解用電極插入陰極側之情形時,21作為陰極饋電體發揮功能,於不將本實施形態之電解用電極插入陰極側之情形時,21作為陰極發揮功能。於具有逆向電流吸收體之情形時,陰極或陰極饋電體21與逆向電流吸收體係電性連接。又,陰極室20較佳為與陽極室10同樣,亦具有陰極側電解液供給部、陰極側氣液分離部。再者,構成陰極室20之各部位中,關於與構成陽極室10之各部位相同者省略說明。 (陰極) 於不將本實施形態之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極21。陰極21較佳為具有鎳基材與被覆鎳基材之觸媒層。作為鎳基材上之觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬、及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD(chemical vapor deposition,化學氣相沈積)、PVD(physical vapor deposition,物理氣相沈積)、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可視需要對陰極21實施還原處理。再者,作為陰極21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陰極饋電體) 於將本實施形態之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極饋電體21。可對陰極饋電體21被覆觸媒成分。該觸媒成分可為原本用作陰極而殘存者。作為觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬、及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。再者,作為陰極饋電體21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 又,饋電體21可使用未形成有觸媒塗層之鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (逆向電流吸收層) 可選擇具有較上文所述之陰極之觸媒層用元素的氧化還原電位更低之氧化還原電位之材料作為逆向電流吸收層之材料。例如可列舉鎳或鐵等。 (集電體) 陰極室20較佳為具備集電體23。藉此,集電效果提高。於本實施形態中,集電體23較佳為多孔板,且以與陰極21之表面大致平行之方式配置。 作為集電體23,例如較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。集電體23可為該等金屬之混合物、合金或複合氧化物。再者,集電體23之形狀只要為作為集電體發揮功能之形狀,則可為任意形狀,可為板狀、網狀。 (金屬彈性體) 藉由在集電體23與陰極21之間設置金屬彈性體22,將串聯連接之複數個電解池1之各陰極21壓抵於離子交換膜2,各陽極11與各陰極21之間之距離變短,可降低對串聯連接之複數個電解池1整體施加之電壓。藉由電壓降低,可降低消耗電量。又,藉由設置金屬彈性體22,於將含有本發明之電解用電極之積層體設置於電解池時,藉由金屬彈性體22之壓抵壓,可將該電解用電極穩定地維持於起始位置。 作為金屬彈性體22,可使用螺旋彈簧、線圈等彈簧構件、緩衝性之墊等。作為金屬彈性體22,可考慮壓抵離子交換膜之應力等而適當採用適宜者。可將金屬彈性體22設置於陰極室20側之集電體23之表面上,亦可設置於陽極室10側之間隔壁之表面上。通常以陰極室20小於陽極室10之方式劃分兩室,因此就框體之強度等觀點而言,較佳為將金屬彈性體22設置於陰極室20之集電體23與陰極21之間。又,金屬彈性體23較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。 (支持體) 陰極室20較佳為具備將集電體23與間隔壁30電性連接之支持體24。藉此,能夠效率良好地流通電流。 支持體24較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。又,作為支持體24之形狀,只要為能夠支持集電體23之形狀,則可為任意形狀,可為棒狀、板狀或網狀。支持體24例如為板狀。複數個支持體24係配置於間隔壁30與集電體23之間。複數個支持體24係以各自之面互相平行之方式排列。支持體24係以大致垂直於間隔壁30及集電體23之方式配置。 (陽極側墊片、陰極側墊片) 陽極側墊片較佳為配置於構成陽極室10之框體表面。陰極側墊片較佳為配置於構成陰極室20之框體表面。1個電解池所具備之陽極側墊片及與其鄰接之電解池之陰極側墊片以夾持離子交換膜2之方式將電解池彼此連接(參照圖5、6)。藉由該等墊片,於介隔離子交換膜2將複數個電解池1串聯連接時,能夠對連接處賦予氣密性。 所謂墊片係將離子交換膜與電解池之間密封者。作為墊片之具體例,可列舉中央形成有開口部之邊框狀之橡膠製片等。對於墊片要求對腐蝕性之電解液或所產生之氣體等具有耐性而可長期使用。因此,就耐化學品性或硬度之方面而言,通常可使用乙烯-丙烯-二烯橡膠(EPDM橡膠)、乙烯-丙烯橡膠(EPM橡膠)之硫化物或過氧化物交聯物等作為墊片。又,視需要亦可使用以聚四氟乙烯(PTFE)或四氟乙烯-全氟烷基乙烯醚共聚物(PFA)等氟系樹脂被覆與液體相接之區域(接液部)之墊片。該等墊片只要以不妨礙電解液之流動之方式分別具有開口部即可,其形狀並無特別限定。例如沿構成陽極室10之陽極室框或構成陰極室20之陰極室框之各開口部之周緣,藉由接著劑等貼附邊框狀之墊片。此外,於例如介隔離子交換膜2連接2個電解池1之情形時(參照圖6),介隔離子交換膜2將貼附有墊片之各電解池1緊固即可。藉此,能夠抑制電解液、因電解而產生之鹼金屬氫氧化物、氯氣、氫氣等漏至電解池1之外部之情況。 (離子交換膜2) 作為離子交換膜2,如上述離子交換膜之項所記載。 (水電解) 本實施形態之進行水電解之情形時之電解槽係具有將上述進行食鹽電解之情形時之電解槽中之離子交換膜變更為微多孔膜之構成者。又,於所供給之原料為水之方面與上述進行食鹽電解之情形時之電解槽不同。關於其他構成,進行水電解之情形時之電解槽亦可採用與進行食鹽電解之情形時之電解槽相同之構成。於食鹽電解之情形時,由於在陽極室產生氯氣,因此陽極室之材質使用鈦,於水電解之情形時,由於在陽極室僅產生氧氣,因此可使用與陰極室之材質相同者。例如可列舉鎳等。又,陽極塗層適宜為產生氧氣用之觸媒塗層。作為觸媒塗層之例,可列舉鉑族金屬及過渡金屬族之金屬、氧化物、氫氧化物等。例如可使用鉑、銥、鈀、釕、鎳、鈷、鐵等元素。 <第2實施形態> 此處,一邊參照圖22~42一邊對本發明之第2實施形態進行詳細說明。 [積層體] 第2實施形態(以下於<第2實施形態>之項中簡稱為「本實施形態」)之積層體具備電解用電極、及與上述電解用電極相接之隔膜或饋電體,針對上述隔膜或饋電體之上述電解用電極之每單位質量·單位面積所承受之力未達1.5 N/mg・cm2 。由於以上述方式構成,因此本實施形態之積層體能夠提高電解槽中之電極更新時之作業效率,進而更新後亦能夠表現出優異之電解性能。 即,藉由本實施形態之積層體,於更新電極時,無需伴隨剝離固定於電解池之既有電極等繁雜之作業,藉由如與隔膜之更新相同之簡單之作業即可更新電極,因此作業效率大幅提高。 進而,藉由本發明之積層體,對於電解性能,能夠維持新品時之性能或有所提高。因此,固定於先前之新品之電解池且作為陽極、陰極發揮功能之電極僅作為饋電體發揮功能即可,能夠大幅地減少觸媒塗層或者甚至無觸媒塗層。 本實施形態之積層體例如可以捲繞於氯乙烯製之管等之狀態(滾筒狀等)進行保管、向顧客處輸送等,操作大幅地變得容易。 再者,作為本實施形態中之饋電體,可應用劣化之電極(即既有電極)、或未形成有觸媒塗層之電極等下文所述之各種基材。 又,本實施形態之積層體只要具有上述構成,則可為一部分具有固定部者。即,於本實施形態之積層體具有固定部之情形時,將不具有該固定部之部分供於測定,所獲得之電解用電極之每單位質量·單位面積所承受之力未達1.5 N/mg・cm2 即可。 [電解用電極] 本實施形態之電解用電極就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、饋電體(劣化之電極及未形成有觸媒塗層之電極)等具有良好之接著力之觀點而言,每單位質量·單位面積所承受之力未達1.5 N/mg・cm2 ,較佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而較佳為1.1 N/mg・cm2 以下,進而較佳為1.10 N/mg・cm2 以下,更佳為1.0 N/mg・cm2 以下,進而更佳為1.00 N/mg・cm2 以下。 就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/mg・cm2 以上,進而更佳為0.14 N/(mg・cm2 )以上。就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.2 N/(mg・cm2 )以上。 上述承受力例如可藉由適當調整下文所述之開孔率、電極之厚度、算術平均表面粗糙度等而設為上述範圍。更具體而言,例如,若增大開孔率,則承受力有變小之傾向,若減小開孔率,則承受力有變大之傾向。 又,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力之觀點,進而就經濟性之觀點而言,較佳為每單位面積之質量為48 mg/cm2 以下,更佳為30 mg/cm2 以下,進而較佳為20 mg/cm2 以下,進而,就合併操作性、接著性及經濟性之綜合性之觀點而言,較佳為15 mg/cm2 以下。下限值並無特別限定,例如為1 mg/cm2 左右。 上述每單位面積之質量例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則每單位面積之質量有變小之傾向,若減小開孔率,則每單位面積之質量有變大之傾向。 承受力可藉由以下之方法(i)或(ii)進行測定,詳細而言,如實施例所記載。關於承受力,藉由方法(i)之測定所獲得之值(亦稱為「承受力(1)」)與藉由方法(ii)之測定所獲得之值(亦稱為「承受力(2)」)可相同亦可不同,但任一值均未達1.5 N/mg・cm2 。 [方法(i)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方)、於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方,關於此處所謂離子交換膜之詳細如實施例所記載)及電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。再者,噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.5~0.8 μm。算術平均表面粗糙度(Ra)之具體之算出方法如實施例所記載。 於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與離子交換膜之重疊部分之面積、及與離子交換膜重疊部分之電極樣品之質量,而算出每單位質量·單位面積所承受之力(1)(N/mg・cm2 )。 藉由方法(i)獲得之每單位質量·單位面積所承受之力(1)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,未達1.5 N/mg・cm2 ,較佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下,進而較佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,更佳為1.0 N/mg・cm2 以下,進而更佳為1.00 N/mg・cm2 以下。又,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 ),更佳為0.2 N/(mg・cm2 )以上。 若本實施形態之電解用電極滿足承受力(1),則例如可與離子交換膜或微多孔膜等隔膜或饋電體進行一體化(即製成積層體)使用,因此於更新電極時,無需藉由焊接等方法固定於電解池之陰極及陽極之更換貼附作業,作業效率大幅提高。又,藉由將本實施形態之電解用電極用作與離子交換膜或微多孔膜或饋電體進行一體化而成之積層體,而能夠使電解性能與新品時之性能相同或有所提高。 於出貨新品之電解池時,先前對固定於電解池之電極施加有觸媒塗層,但僅藉由使未形成有觸媒塗層之電極與本實施形態之電解用電極組合,而可用作電極,因此能夠大幅地減少用以形成觸媒塗層之製造步驟或觸媒之量或者甚至不存在該等。觸媒塗層大幅減少或不存在之先前之電極與本實施形態之電解用電極電性連接,而可使其作為用以流通電流之饋電體發揮功能。 [方法(ii)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方,與上述方法(i)相同之鎳板)與電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與鎳板之重疊部分之面積、及與鎳板重疊部分中之電極樣品之質量,而算出每單位質量•單位面積之接著力(2)(N/mg・cm2 )。 藉由方法(ii)獲得之每單位質量·單位面積所承受之力(2)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,未達1.5 N/mg・cm2 ,較佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下,進而較佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,更佳為1.0 N/mg・cm2 以下,進而更佳為1.00 N/mg・cm2 以下。就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 )以上。 若本實施形態之電解用電極滿足承受力(2),則例如可以捲繞於氯乙烯製之管等之狀態(滾筒狀等)進行保管、向顧客處輸送等,操作大幅地變得容易。又,藉由對劣化之既有電極貼附本實施形態之電解用電極而製成積層體,能夠使電解性能與新品時之性能相同或有所提高。 若本實施形態之電解用電極為彈性變形區域較廣之電極,則就可獲得更良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有更良好之接著力之觀點而言,電解用電極之厚度較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,於本實施形態中,所謂「彈性變形區域較廣」意指將電解用電極捲繞而製成捲繞體,解除捲繞狀態後不易產生由捲繞引起之翹曲。又,所謂電解用電極之厚度於包含下文所述之觸媒層之情形時,係指合併電解用電極基材與觸媒層之厚度。本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。該電解用電極基材之厚度(量規厚度)並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折,大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於本實施形態中,較佳為於離子交換膜或微多孔膜等隔膜與電極、或者劣化之既有電極或未形成有觸媒塗層之電極等金屬多孔板或金屬板(即饋電體)與電解用電極之間介置液體。該液體只要為水、有機溶劑等產生表面張力者,則可使用任意液體。液體之表面張力越大,對隔膜與電解用電極、或者金屬多孔板或金屬板與電解用電極之間承受之力越大,因此較佳為表面張力較大之液體。作為液體,可列舉如下者(括號內之數值係該液體於20℃下之表面張力)。 己烷(20.44 mN/m)、丙酮(23.30 mN/m)、甲醇(24.00 mN/m)、乙醇(24.05 mN/m)、乙二醇(50.21 mN/m)水(72.76 mN/m) 若為表面張力較大之液體,則隔膜與電解用電極、或者金屬多孔板或金屬板(饋電體)與電解用電極成為一體(成為積層體),電極更新變得容易。隔膜與電解用電極、或者金屬多孔板或金屬板(饋電體)與電解用電極之間之液體為藉由表面張力而互相貼附之程度之量即可,其結果為液體量較少,因此即使於將該積層體設置於電解池後混入至電解液中,亦不會對電解本身造成影響。 就實用上之觀點而言,作為液體,較佳為使用乙醇、乙二醇、水等表面張力為24 mN/m至80 mN/m之液體。尤佳為水或將苛性鈉、氫氧化鉀、氫氧化鋰、碳酸氫鈉、碳酸氫鉀、碳酸鈉、碳酸鉀等溶解於水中製成鹼性之水溶液。又,亦可使該等液體含有界面活性劑而調整表面張力。藉由含有界面活性劑,隔膜與電解用電極、或者金屬多孔板或金屬板(饋電體)與電解用電極之接著性發生變化,而可調整操作性。作為界面活性劑,並無特別限制,可使用離子性界面活性劑、非離子性界面活性劑之任一種。 本實施形態之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力之觀點而言,藉由以下之方法(2)所測得之比率較佳為90%以上,更佳為92%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為95%以上。上限值為100%。 [方法(2)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑280 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折之觀點而言,藉由以下之方法(3)所測得之比率較佳為75%以上,更佳為80%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為90%以上。上限值為100%。 [方法(3)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,防止電解中產生之氣體滯留之觀點而言,較佳為多孔結構,且其開孔率或空隙率為5~90%以下。開孔率更佳為10~80%以下,進而較佳為20~75%。 再者,所謂開孔率係每單位體積之開孔部之比率。開孔部亦根據考慮至次微米級抑或僅考慮目視可見之開口而有各種算出方法。於本實施形態中,藉由根據電極之量規厚度、寬度、長度之值算出體積V,進而對重量W進行實測,而利用下述之式算出開孔率A。 A=(1-(W/(V×ρ))×100 ρ係電極之材質之密度(g/cm3 )。例如於鎳之情形時為8.908 g/cm3 ,於鈦之情形時為4.506 g/cm3 。開孔率之調整係藉由如下方法進行適當調整:若為沖孔金屬,則變更每單位面積沖裁金屬之面積;若為多孔金屬,則變更SW(短徑)、LW(長徑)、進給之值;若為絲網,則變更金屬纖維之線徑、網眼數;若為電成形,則變更所使用之光阻之圖案;若為不織布,則變更金屬纖維直徑及纖維密度;若為發泡金屬,則變更用以使空隙形成之模板等。 本實施形態中之電解用電極就操作性之觀點而言,藉由以下之方法(A)所測得之值較佳為40 mm以下,更佳為29 mm以下,進而較佳為10 mm以下,進而更佳為6.5 mm以下。再者,具體之測定方法如實施例所記載。 [方法(A)] 於溫度23±2℃、相對濕度30±5%之條件下,將積層離子交換膜與上述電解用電極而成之樣品捲繞並固定於外徑f32 mm之氯乙烯製芯材之曲面上,靜置6小時後將該電解用電極分離並載置於水平之板,測定此時該電解用電極之兩端部之垂直方向之高度L1 及L2 ,以該等之平均值作為測定值。本實施形態中之電解用電極較佳為將該電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時(以下亦稱為「測定條件1」)之通氣阻力(以下亦稱為「通氣阻力1」)為24 kPa・s/m以下。通氣阻力較大意指空氣難以流動,指密度較高之狀態。於該狀態下,電解之產物停留於電極中,反應基質難以擴散至電極內部,因此有電解性能(電壓等)變差之傾向。又,有膜表面之濃度提高之傾向。具體而言,有陰極面苛性濃度提高而陽極面鹽水之供給性降低之傾向。其結果為,由於產物以高濃度滯留於隔膜與電極相接之界面,因此有導致隔膜之損傷,亦導致陰極面上之電壓上升及膜損傷、陽極面上之膜損傷之傾向。於本實施形態中,為了防止該等異常,較佳為將通氣阻力設為24 kPa・s/m以下。就上述同樣之觀點而言,更佳為未達0.19 kPa・s/m,進而較佳為0.15 kPa・s/m以下,進而更佳為0.07 kPa・s/m以下。 再者,於本實施形態中,若通氣阻力大至一定程度以上,則於陰極之情形時有電極中產生之NaOH滯留於電極與隔膜之界面而成為高濃度之傾向,於陽極之情形時有鹽水供給性降低而鹽水濃度成為低濃度之傾向,就將可能因此種滯留產生之對隔膜之損傷防患於未然之方面而言,較佳為未達0.19 kPa・s/m,更佳為0.15 kPa・s/m以下,進而較佳為0.07 kPa・s/m以下。 另一方面,於通氣阻力較低之情形時,由於電極之面積變小,因此有電解面積變小而電解性能(電壓等)變差之傾向。於通氣阻力為零之情形時,由於未設置電解用電極,因此有饋電體作為電極發揮功能而電解性能(電壓等)顯著變差之傾向。就該方面而言,作為通氣阻力1而特定出之較佳之下限值並無特別限定,較佳為超過0 kPa・s/m,更佳為0.0001 kPa・s/m以上,進而較佳為0.001 kPa・s/m以上。 再者,通氣阻力1就其測定法方面而言,若為0.07 kPa・s/m以下,則存在無法獲得充分之測定精度之情形。就該觀點而言,相對於通氣阻力1為0.07 kPa・s/m以下之電解用電極,亦可實現藉由以下之測定方法(以下亦稱為「測定條件2」)獲得之通氣阻力(以下亦稱為「通氣阻力2」)之評價。即,通氣阻力2係將電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度2 cm/s及通氣量4 cc/cm2 /s之情形時之通氣阻力。 具體之通氣阻力1及2之測定方法如實施例所記載。 上述通氣阻力1及2例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則有通氣阻力1及2變小之傾向,若減小開孔率,則有通氣阻力1及2變大之傾向。本實施形態之電解用電極如上所述,針對隔膜或饋電體之上述電解用電極之每單位質量·單位面積所承受之力未達1.5 N/mg・cm2 。由此,本實施形態之電解用電極藉由以適度之接著力與隔膜或饋電體(例如,電解槽中之既有之陽極或陰極等)相接,而可構成與隔膜或饋電體之積層體。即,無需藉由熱壓接等繁雜之方法將隔膜或饋電體與電解用電極牢固地接著,例如即使藉由如源自離子交換膜或微多孔膜等隔膜可含之水分之表面張力的相對較弱之力亦接著而成為積層體,因此無論為何種規模均可容易地構成積層體。進而,此種積層體表現出優異之電解性能,因此本實施形態之積層體適於電解用途,例如,可尤佳地用於與電解槽之構件或該構件之更新相關之用途。 以下,對本實施形態之電解用電極之一形態進行說明。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。觸媒層如下所述,可包含複數層,亦可為單層結構。 如圖22所示,本實施形態之電解用電極100具備電解用電極基材10、及被覆電解用電極基材10之兩表面之一對第一層20。第一層20較佳為將電解用電極基材10整體被覆。藉此,電解用電極之觸媒活性及耐久性變得容易提高。再者,亦可僅於電解用電極基材10之一表面積層第一層20。 又,如圖22所示,第一層20之表面可由第二層30所被覆。第二層30較佳為將第一層20整體被覆。又,第二層30可僅積層於第一層20之一表面。 (電解用電極基材) 作為電解用電極基材10,並無特別限定,例如可使用鎳、鎳合金、不鏽鋼、或以鈦等為代表之閥金屬,較佳為含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 於在高濃度之鹼性水溶液中使用不鏽鋼之情形時,若考慮到鐵及鉻溶出、及不鏽鋼之導電性為鎳之1/10左右,則較佳為使用含有鎳(Ni)之基材作為電解用電極基材。 又,電解用電極基材10於在接近飽和之高濃度之食鹽水中於氯氣產生環境中使用之情形時,材質亦較佳為耐蝕性較高之鈦。 電解用電極基材10之形狀並無特別限定,可根據目的選擇合適之形狀。作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。其中,較佳為沖孔金屬或多孔金屬。再者,所謂電成形係將照相製版與電鍍法組合而製作精密之圖案之金屬薄膜的技術。其係藉由光阻於基板上形成圖案,對未受到光阻保護之部分實施電鍍而獲得金屬薄膜之方法。 關於電解用電極基材之形狀,根據電解槽中之陽極與陰極之距離而有適宜之規格。並無特別限定,於陽極與陰極具有有限之距離之情形時,可使用多孔金屬、沖孔金屬形狀,於離子交換膜與電極相接之所謂零間距電解槽之情形時,可使用編織細線而成之編織網、金屬絲網、發泡金屬、金屬不織布、多孔金屬、沖孔金屬、金屬多孔箔等。 作為電解用電極基材10,可列舉:金屬多孔箔、金屬絲網、金屬不織布、沖孔金屬、多孔金屬或發泡金屬。 作為加工為沖孔金屬、多孔金屬前之板材,較佳為經壓延成形之板材、電解箔等。電解箔較佳為進而作為後處理而藉由與母材相同之元素實施鍍覆處理,於單面或兩面形成凹凸。 又,電解用電極基材10之厚度如上文所述,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於電解用電極基材中,較佳為藉由在氧化環境中將電解用電極基材進行退火而緩和加工時之殘留應力。又,為了提高與被覆於電解用電極基材之表面之觸媒層之密接性,較佳為使用鋼砂、氧化鋁粉等於上述表面形成凹凸,其後藉由酸處理而增加表面積。或者,較佳為藉由與基材相同之元素實施鍍覆處理,增加表面積。 為了使第一層20與電解用電極基材10之表面密接,較佳為對電解用電極基材10進行增大表面積之處理。作為增大表面積之處理,可列舉使用鋼線粒、鋼砂、氧化鋁砂等之噴擊處理、使用硫酸或鹽酸之酸處理、利用與基材相同元素之鍍覆處理等。基材表面之算術平均表面粗糙度(Ra)並無特別限定,較佳為0.05 μm~50 μm,更佳為0.1~10 μm,進而較佳為0.1~8 μm。 繼而,對使用本實施形態之電解用電極作為食鹽電解用陽極之情形進行說明。 (第一層) 於圖22中,作為觸媒層之第一層20含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物。作為釕氧化物,可列舉RuO2 等。作為銥氧化物,可列舉IrO2 等。作為鈦氧化物,可列舉TiO2 等。第一層20較佳為含有釕氧化物及鈦氧化物之兩種氧化物,或含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物。藉此,第一層20成為更穩定之層,進而,與第二層30之密接性亦進一步提高。 於第一層20含有釕氧化物及鈦氧化物之兩種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為1~9莫耳,更佳為1~4莫耳。藉由將兩種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之銥氧化物較佳為0.2~3莫耳,更佳為0.3~2.5莫耳。又,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為0.3~8莫耳,更佳為1~7莫耳。藉由將三種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有選自釕氧化物、銥氧化物及鈦氧化物中之至少兩種氧化物之情形時,該等氧化物較佳為形成固溶體。藉由形成氧化物固溶體,電解用電極100表現出優異之耐久性。 除了上述組成以外,只要含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物,則可使用各種組成者。例如,亦可使用稱為DSA(註冊商標)之含有釕、銥、鉭、鈮、鈦、錫、鈷、錳、鉑等之氧化物塗層作為第一層20。 第一層20無需為單層,亦可包含複數層。例如,第一層20可包含含有三種氧化物之層與含有兩種氧化物之層。第一層20之厚度較佳為0.05~10 μm,更佳為0.1~8 μm。 (第二層) 第二層30較佳為含有釕與鈦。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較佳為含有氧化鈀、氧化鈀與鉑之固溶體或鈀與鉑之合金。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較厚者能夠維持電解性能之時間變長,就經濟性之觀點而言,較佳為0.05~3 μm之厚度。 繼而,對使用本實施形態之電解用電極作為食鹽電解用陰極之情形進行說明。 (第一層) 作為觸媒層之第一層20之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。 於含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少一種之情形時,較佳為鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金含有鉑、鈀、銠、釕、銥中之至少一種鉑族金屬。 作為鉑族金屬,較佳為含有鉑。 作為鉑族金屬氧化物,較佳為含有釕氧化物。 作為鉑族金屬氫氧化物,較佳為含有釕氫氧化物。 作為鉑族金屬合金,較佳為含有鉑與鎳、鐵、鈷之合金。 較佳為進而視需要含有鑭系元素之氧化物或氫氧化物作為第二成分。藉此,電解用電極100表現出優異之耐久性。 作為鑭系元素之氧化物或氫氧化物,較佳為含有選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑中之至少1種。 較佳為進而視需要含有過渡金屬之氧化物或氫氧化物作為第三成分。 藉由添加第三成分,電解用電極100能夠表現出更優異之耐久性,降低電解電壓。 作為較佳之組合之例,可列舉:僅釕、釕+鎳、釕+鈰、釕+鑭、釕+鑭+鉑、釕+鑭+鈀、釕+鐠、釕+鐠+鉑、釕+鐠+鉑+鈀、釕+釹、釕+釹+鉑、釕+釹+錳、釕+釹+鐵、釕+釹+鈷、釕+釹+鋅、釕+釹+鎵、釕+釹+硫、釕+釹+鉛、釕+釹+鎳、釕+釹+銅、釕+釤、釕+釤+錳、釕+釤+鐵、釕+釤+鈷、釕+釤+鋅、釕+釤+鎵、釕+釤+硫、釕+釤+鉛、釕+釤+鎳、鉑+鈰、鉑+鈀+鈰、鉑+鈀+鑭+鈰、鉑+銥、鉑+鈀、鉑+銥+鈀、鉑+鎳+鈀、鉑+鎳+釕、鉑與鎳之合金、鉑與鈷之合金、鉑與鐵之合金等。 於不含鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之情形時,觸媒之主成分較佳為鎳元素。 較佳為含有鎳金屬、氧化物、氫氧化物中之至少1種。 作為第二成分,可添加過渡金屬。作為所添加之第二成分,較佳為含有鈦、錫、鉬、鈷、錳、鐵、硫、鋅、銅、碳中之至少一種元素。 作為較佳之組合,可列舉:鎳+錫、鎳+鈦、鎳+鉬、鎳+鈷等。 視需要可於第一層20與電解用電極基材10之間設置中間層。藉由設置中間層,能夠提高電解用電極100之耐久性。 作為中間層,較佳為對第一層20與電解用電極基材10之兩者具有親和性者。作為中間層,較佳為鎳氧化物、鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物。作為中間層,可藉由將含有形成中間層之成分之溶液進行塗佈、燒成而形成,亦可於空氣環境中在300~600℃之溫度下對基材實施熱處理而形成表面氧化物層。除此以外,可藉由熱熔射法、離子鍍敷法等已知之方法形成。 (第二層) 作為觸媒層之第一層30之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。作為第二層所含之元素之較佳之組合例,有第一層中所列舉之組合等。第一層與第二層之組合可為組成相同而組成比不同之組合,亦可為組成不同之組合。 作為觸媒層之厚度,較佳為將所形成之觸媒層及中間層累加而成之厚度為0.01 μm~20 μm。若為0.01 μm以上,則能夠作為觸媒充分發揮功能。若為20 μm以下,則從基材脫落之情況較少,能夠形成牢固之觸媒層。更佳為0.05 μm~15 μm。更佳為0.1 μm~10 μm。進而較佳為0.2 μm~8 μm。 作為電解用電極之厚度、即電解用電極基材與觸媒層之合計之厚度,就電解用電極之操作性之方面而言,較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,電極之厚度可藉由利用電子數顯厚度計(Mitutoyo股份有限公司,最少顯示0.001 mm)進行測定而求出。電解用電極基材之厚度可與電解用電極之厚度同樣地進行測定。觸媒層之厚度可藉由電解用電極之厚度減去電解用電極基材之厚度而求出。 (電解用電極之製造方法) 其次,對電解用電極100之製造方法之一實施形態進行詳細說明。 於本實施形態中,藉由利用氧環境下之塗膜之燒成(熱分解)、或離子鍍敷、鍍覆、熱熔射等方法於電解用電極基材上形成第一層20、較佳為第二層30,可製造電解用電極100。此種本實施形態之製造方法能夠實現電解用電極100之較高之生產性。具體而言,藉由塗佈含有觸媒之塗佈液之塗佈步驟、乾燥塗佈液之乾燥步驟、進行熱分解之熱分解步驟,而於電解用電極基材上形成觸媒層。此處所謂熱分解意指對成為前驅物之金屬鹽進行加熱而分解為金屬或金屬氧化物與氣體狀物質。根據所使用之金屬種類、鹽之種類、進行熱分解之環境等,分解產物有所不同,但於氧化性環境下多數金屬有容易形成氧化物之傾向。於電極之工業性之製造工藝中,熱分解通常於空氣中進行,多數情形時形成金屬氧化物或金屬氫氧化物。 (陽極之第一層之形成) (塗佈步驟) 第一層20係將溶解有釕、銥及鈦中之至少一種金屬之鹽的溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之釕、銥及鈦之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材100後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (第二層之形成) 第二層30係視需要而形成,例如將含有鈀化合物及鉑化合物之溶液或含有釕化合物及鈦化合物之溶液(第二塗佈液)塗佈於第一層20上後,於氧氣之存在下進行熱分解而獲得。 (利用熱分解法之陰極之第一層之形成) (塗佈步驟) 第一層20係將溶解有各種組合之金屬鹽之溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之金屬之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材10後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (中間層之形成) 中間層係視需要而形成,例如將含有鈀化合物或鉑化合物之溶液(第二塗佈液)塗佈於基材上後,於氧氣之存在下進行熱分解而獲得。或者,亦可不塗佈溶液,而僅加熱基材,藉此於基材表面形成氧化鎳中間層。 (利用離子鍍敷之陰極之第一層之形成) 第一層20亦可藉由離子鍍敷而形成。 作為一例,可列舉將基材固定於腔室內並對金屬釕靶照射電子束之方法。所蒸發之金屬釕粒子於腔室內之電漿中帶正電,而沈積於帶負電之基板上。電漿環境為氬氣、氧氣,釕係以釕氧化物之形式沈積於基材上。 (利用鍍覆之陰極之第一層之形成) 第一層20亦可藉由鍍覆法而形成。 作為一例,若使用基材作為陰極,於含有鎳及錫之電解液中實施電解鍍覆,則可形成鎳與錫之合金鍍覆。 (利用熱熔射之陰極之第一層之形成) 第一層20亦可藉由熱熔射法而形成。 作為一例,藉由將氧化鎳粒子電漿熔射於基材上,而可形成混合有金屬鎳與氧化鎳之觸媒層。 本實施形態之電解用電極能夠與離子交換膜或微多孔膜等隔膜進行一體化而使用。因此,可用作膜一體電極,無需更新電極時之陰極及陽極之更換貼附作業,作業效率大幅提高。 又,藉由與離子交換膜或微多孔膜等隔膜之一體電極,能夠使電解性能與新品時之性能相同或有所提高。 以下,對離子交換膜進行詳細說明。 [離子交換膜] 離子交換膜具有含有具有離子交換基之烴系聚合物或含氟系聚合物之膜本體、與設置於該膜本體之至少一面上之塗佈層。又,塗佈層含有無機物粒子與結合劑,塗佈層之比表面積為0.1~10 m2 /g。該結構之離子交換膜於電解中所產生之氣體對電解性能之影響較少,能夠發揮出穩定之電解性能。 上述所謂導入有離子交換基之全氟碳聚合物之膜係具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層之任一者。就強度及尺寸穩定性之觀點而言,較佳為進而具有強化芯材。 以下於塗佈層之說明之欄對無機物粒子及結合劑進行詳細說明。 圖23係表示離子交換膜之一實施形態之剖面模式圖。離子交換膜1具有:膜本體10,其含有具有離子交換基之烴系聚合物或含氟系聚合物;以及塗佈層11a及11b,其等形成於膜本體10之兩面。 於離子交換膜1中,膜本體10具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層3、與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層2,藉由強化芯材4強化強度及尺寸穩定性。離子交換膜1由於具備磺酸層3與羧酸層2,因此可作為陽離子交換膜而適宜地使用。 再者,離子交換膜亦可僅具有磺酸層及羧酸層之任一者。又,離子交換膜未必由強化芯材所強化,強化芯材之配置狀態亦不限定於圖23之例。 (膜本體) 首先,對構成離子交換膜1之膜本體10進行說明。 膜本體10只要為具有使陽離子選擇性地透過之功能且含有具有離子交換基之烴系聚合物或含氟系聚合物者即可,其構成或材料並無特別限定,可適當選擇適宜者。 膜本體10中之具有離子交換基之烴系聚合物或含氟系聚合物例如可由具有可藉由水解等成為離子交換基之離子交換基前驅物之烴系聚合物或含氟系聚合物獲得。具體而言,例如使用主鏈包含氟化烴、具有可藉由水解等轉換為離子交換基之基(離子交換基前驅物)作為懸垂側鏈且能夠熔融加工之聚合物(以下視情形稱為「含氟系聚合物(a)」)製作膜本體10之前驅物後,將離子交換基前驅物轉換為離子交換基,藉此可獲得膜本體10。 含氟系聚合物(a)例如可藉由使選自下述第1群之至少一種單體與選自下述第2群及/或下述第3群之至少一種單體進行共聚合而製造。又,亦可藉由選自下述第1群、下述第2群、及下述第3群之任一群之1種單體之均聚而製造。 作為第1群之單體,例如可列舉氟乙烯化合物。作為氟乙烯化合物,例如可列舉:氟乙烯、四氟乙烯、六氟丙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、全氟烷基乙烯醚等。尤其是於將離子交換膜用作鹼電解用膜之情形時,氟乙烯化合物較佳為全氟單體,較佳為選自由四氟乙烯、六氟丙烯、全氟烷基乙烯醚所組成之群中之全氟單體。 作為第2群之單體,例如可列舉具有可轉換為羧酸型離子交換基(羧酸基)之官能基之乙烯系化合物。作為具有可轉換為羧酸基之官能基之乙烯系化合物,例如可列舉以CF2 =CF(OCF2 CYF)s -O(CZF)t -COOR表示之單體等(此處,s表示0~2之整數,t表示1~12之整數,Y及Z各自獨立地表示F或CF3 ,R表示低級烷基。低級烷基例如為碳數1~3之烷基)。 該等中,較佳為以CF2 =CF(OCF2 CYF)n -O(CF2 )m -COOR表示之化合物。此處,n表示0~2之整數,m表示1~4之整數,Y表示F或CF3 ,R表示CH3 、C2 H5 、或C3 H7 。 再者,於將離子交換膜用作鹼電解用陽離子交換膜之情形時,較佳為至少使用全氟化合物作為單體,但由於酯基之烷基(參照上述R)於水解時從聚合物喪失,因此烷基(R)亦可不為全部氫原子被取代為氟原子之全氟烷基。 作為第2群之單體,於上述中,更佳為下述所表示之單體。 CF2 =CFOCF2 -CF(CF3 )OCF2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )2 COOCH3 、 CF2 =CF[OCF2 -CF(CF3 )]2 O(CF2 )2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )3 COOCH3 、 CF2 =CFO(CF2 )2 COOCH3 、 CF2 =CFO(CF2 )3 COOCH3 。 作為第3群之單體,例如可列舉具有可轉換為磺酸型離子交換基(磺酸基)之官能基之乙烯系化合物。作為具有可轉換為磺酸基之官能基之乙烯系化合物,例如較佳為以CF2 =CFO-X-CF2 -SO2 F表示之單體(此處,X表示全氟伸烷基)。作為該等之具體例,可列舉下述所表示之單體等。 CF2 =CFOCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、 CF2 =CF(CF2 )2 SO2 F、 CF2 =CFO[CF2 CF(CF3 )O]2 CF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF2 OCF3 )OCF2 CF2 SO2 F。 該等中,更佳為CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、及CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F。 由該等單體獲得之共聚物可藉由針對氟乙烯之均聚及共聚合所開發之聚合法、尤其是對四氟乙烯所使用之通常之聚合方法而製造。例如,於非水性法中,可使用全氟烴、氯氟碳等不活性溶劑,於全氟碳過氧化物或偶氮化合物等自由基聚合起始劑之存在下,於溫度0~200℃、壓力0.1~20 MPa之條件下進行聚合反應。 於上述共聚合中,上述單體之組合之種類及其比率並無特別限定,根據欲對所獲得之含氟系聚合物賦予之官能基之種類及量選擇確定。例如於製成僅含有羧酸基之含氟系聚合物之情形時,從上述第1群及第2群分別選擇至少1種單體進行共聚合即可。又,於製成僅含有磺酸基之含氟系聚合物之情形時,從上述第1群及第3群之單體中分別選擇至少1種單體進行共聚合即可。進而,於製成具有羧酸基及磺酸基之含氟系聚合物之情形時,從上述第1群、第2群及第3群之單體中分別選擇至少1種單體進行共聚合即可。於該情形時,藉由使包含上述第1群及第2群之共聚物與包含上述第1群及第3群之共聚物分開進行聚合,其後加以混合亦可獲得目標之含氟系聚合物。又,各單體之混合比率並無特別限定,於增加每單位聚合物之官能基之量之情形時,增加選自上述第2群及第3群之單體之比率即可。 含氟系共聚物之總離子交換容量並無特別限定,較佳為0.5~2.0 mg當量/g,更佳為0.6~1.5 mg當量/g。此處,所謂總離子交換容量係指相對於單位重量之乾燥樹脂之交換基之當量,可藉由中和滴定等進行測定。 於離子交換膜1之膜本體10中,積層有含有具有磺酸基之含氟系聚合物之磺酸層3與含有具有羧酸基之含氟系聚合物之羧酸層2。藉由製成此種層結構之膜本體10,能夠進一步提高鈉離子等陽離子之選擇性透過性。 於將離子交換膜1配置於電解槽之情形時,通常以磺酸層3位於電解槽之陽極側、羧酸層2位於電解槽之陰極側之方式配置。 磺酸層3較佳為由電阻較低之材料構成,就膜強度之觀點而言,較佳為其膜厚厚於羧酸層2。磺酸層3之膜厚較佳為羧酸層2之2~25倍,更佳為3~15倍。 羧酸層2較佳為即使膜厚較薄亦具有較高之陰離子排斥性者。此處所謂陰離子排斥性係指阻礙陰離子對離子交換膜1之滲入或透過之性質。為了提高陰離子排斥性,有效的是對磺酸層配置離子交換容量較小之羧酸層等。 作為磺酸層3所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F作為第3群之單體所獲得之聚合物。 作為羧酸層2所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF2 )O(CF2 )2 COOCH3 作為第2群之單體所獲得之聚合物。 (塗佈層) 離子交換膜於膜本體之至少一面上具有塗佈層。又,如圖23所示,於離子交換膜1中,於膜本體10之兩面上分別形成有塗佈層11a及11b。 塗佈層含有無機物粒子與結合劑。 無機物粒子之平均粒徑更佳為0.90 μm以上。若無機物粒子之平均粒徑為0.90 μm以上,則不僅極大地提高對氣體附著之耐久性,而且極大地提高對雜質之耐久性。即,藉由增大無機物粒子之平均粒徑,並且滿足上述比表面積之值,可獲得尤其顯著之效果。為了滿足此種平均粒徑與比表面積,較佳為不規則狀之無機物粒子。可使用藉由熔融獲得之無機物粒子、藉由原石粉碎獲得之無機物粒子。較佳可適宜地使用藉由原石粉碎獲得之無機物粒子。 又,無機物粒子之平均粒徑可設為2 μm以下。若無機物粒子之平均粒徑為2 μm以下,則能夠防止因無機物粒子而損傷膜。無機物粒子之平均粒徑更佳為0.90~1.2 μm。 此處,平均粒徑可藉由粒度分佈計(「SALD2200」島津製作所)進行測定。 無機物粒子之形狀較佳為不規則形狀。對雜質之耐性進一步提高。又,無機物粒子之粒度分佈較佳為較寬。 無機物粒子較佳為含有選自由週期表第IV族元素之氧化物、週期表第IV族元素之氮化物、及週期表第IV族元素之碳化物所組成之群中之至少一種無機物。就耐久性之觀點而言,更佳為氧化鋯之粒子。 該無機物粒子較佳為藉由將無機物粒子之原石粉碎所製造之無機物粒子,或以藉由將無機物粒子之原石熔融並加以精製而粒子之直徑一致之球狀之粒子作為無機物粒子。 作為原石粉碎方法,並無特別限定,可列舉:球磨機、珠磨機、膠體磨機、錐形磨機、盤磨機、輪輾機、磨粉機、錘磨機、造粒機、VSI磨機、威利磨機、輥磨機、噴射磨機等。又,較佳為粉碎後將其洗淨,作為此時之洗淨方法,較佳為酸處理。藉此,能夠減少附著於無機物粒子之表面之鐵等雜質。 塗佈層較佳為含有結合劑。結合劑係將無機物粒子保持於離子交換膜之表面、形成塗佈層之成分。就對電解液或電解之產物之耐性之觀點而言,結合劑較佳為含有含氟系聚合物。 作為結合劑,就對電解液或電解之產物之耐性、及對離子交換膜之表面之接著性之觀點而言,更佳為具有羧酸基或磺酸基之含氟系聚合物。於在含有具有磺酸基之含氟聚合物之層(磺酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有磺酸基之含氟系聚合物。又,於在含有具有羧酸基之含氟聚合物之層(羧酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有羧酸基之含氟系聚合物。 塗佈層中,無機物粒子之含量較佳為40~90質量%,更佳為50~90質量%。又,結合劑之含量較佳為10~60質量%,更佳為10~50質量%。 離子交換膜中之塗佈層之分佈密度較佳為每1 cm2 為0.05~2 mg。又,於離子交換膜於表面具有凹凸形狀之情形時,塗佈層之分佈密度較佳為每1 cm2 為0.5~2 mg。 作為形成塗佈層之方法,並無特別限定,可使用公知之方法。例如可列舉藉由噴射等塗佈將無機物粒子分散於含有結合劑之溶液中而成之塗佈液之方法。 (強化芯材) 離子交換膜較佳為具有配置於膜本體之內部之強化芯材。 強化芯材係強化離子交換膜之強度或尺寸穩定性之構件。藉由將強化芯材配置於膜本體之內部,尤其能夠將離子交換膜之伸縮控制為所需之範圍。該離子交換膜於電解時等不會伸縮為必要程度以上,而能夠長期維持優異之尺寸穩定性。 強化芯材之構成並無特別限定,例如可將稱為強化紗之紗進行紡紗而形成。此處所謂強化紗係構成強化芯材之構件,指能夠對離子交換膜賦予所需之尺寸穩定性及機械強度且於離子交換膜中能夠穩定地存在之紗。藉由使用將該強化紗紡紗而成之強化芯材,能夠對離子交換膜賦予更優異之尺寸穩定性及機械強度。 強化芯材及其所使用之強化紗之材料並無特別限定,較佳為對酸或鹼等具有耐性之材料,就需要長期之耐熱性、耐化學品性之方面而言,較佳為包含含氟系聚合物之纖維。 作為強化芯材所使用之含氟系聚合物,例如可列舉:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、四氟乙烯-六氟丙烯共聚物、三氟氯乙烯-乙烯共聚物及偏二氟乙烯聚合物(PVDF)等。該等中,尤其是就耐熱性及耐化學品性之觀點而言,較佳為使用包含聚四氟乙烯之纖維。 強化芯材所使用之強化紗之紗直徑並無特別限定,較佳為20~300丹尼,更佳為50~250丹尼。紡織密度(每單位長度之織入根數)較佳為5~50根/英吋。作為強化芯材之形態,並無特別限定,例如可使用織布、不織布、針織布等,較佳為織布之形態。又,使用織布之厚度較佳為30~250 μm、更佳為30~150 μm者。 織布或針織布可使用單絲、複絲或該等之紗線、切膜絲等,紡織方法可使用平織、紗羅組織、針織、凸條組織、縐條紋薄織等各種紡織方法。 膜本體中之強化芯材之紡織方法及配置並無特別限定,可考慮離子交換膜之大小或形狀、離子交換膜所需之物性及使用環境等適當設為適宜之配置。 例如,可沿膜本體之特定之一方向配置強化芯材,就尺寸穩定性之觀點而言,較佳為沿特定之第一方向配置強化芯材,且沿大致垂直於第一方向之第二方向配置其他強化芯材。藉由在膜本體之縱向膜本體之內部以大致成一列之方式配置複數個強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。例如,較佳為於膜本體之表面織入沿縱向配置之強化芯材(縱紗)與沿橫向配置之強化芯材(橫紗)之配置。就尺寸穩定性、機械強度及製造容易性之觀點而言,更佳為製成使縱紗與橫紗一上一下交替織入而紡織之平紋織物、或一邊撚轉2根經紗一邊與橫紗交織之紗羅組織物、於每2根或數根並紗配置之縱紗中織入相同數量之橫紗而紡織之斜紋織物(twill weave)等。 尤佳為沿離子交換膜之MD方向(縱向(Machine Direction)方向)及TD方向(橫向(Transverse Direction)方向)之兩方向配置強化芯材。即,較佳為沿MD方向與TD方向平織。此處,所謂MD方向係指於下文所述之離子交換膜之製造步驟中搬送膜本體或各種芯材(例如,強化芯材、強化紗、下文所述之犧牲紗等)之方向(行進方向),所謂TD方向係指大致垂直於MD方向之方向。此外,將沿MD方向紡織之紗稱為MD紗,將沿TD方向紡織之紗稱為TD紗。通常電解所使用之離子交換膜係矩形,長度方向為MD方向、寬度方向為TD方向之情況較多。藉由織入作為MD紗之強化芯材與作為TD紗之強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。 強化芯材之配置間隔並無特別限定,可考慮離子交換膜所需之物性及使用環境等適當設為適宜之配置。 強化芯材之開口率並無特別限定,較佳為30%以上,更佳為50%以上且90%以下。開口率就離子交換膜之電化學性質之觀點而言,較佳為30%以上,就離子交換膜之機械強度之觀點而言,較佳為90%以下。 所謂強化芯材之開口率係指膜本體之任一表面之面積(A)中離子等物質(電解液及其所含之陽離子(例如,鈉離子))能夠通過之表面之總面積(B)之比率(B/A)。所謂離子等物質能夠通過之表面之總面積(B)可指於離子交換膜中陽離子或電解液等不被離子交換膜所含之強化芯材等阻斷之區域之總面積。 圖24係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。圖24係將離子交換膜之一部分放大而僅圖示該區域內之強化芯材21及22之配置,其他構件省略圖示。 藉由從由沿縱向配置之強化芯材21與沿橫向配置之強化芯材22所圍成之亦包括強化芯材之面積在內之區域的面積(A)減去強化芯材之總面積(C),可求出上述區域之面積(A)中離子等物質能夠通過之區域之總面積(B)。即,開口率可藉由下述式(I)求出。 開口率=(B)/(A)=((A)-(C))/(A) …(I) 於強化芯材中,就耐化學品性及耐熱性之觀點而言,尤佳之形態係含有PTFE之帶狀紗線或高配向單絲。具體而言,更佳為如下強化芯材,其係使用將包含PTFE之高強度多孔質片材切為帶狀而成之帶狀紗線、或包含PTFE之高度配向之單絲之50~300丹尼且紡織密度為10~50根/英吋之平紋織物,其厚度為50~100 μm之範圍。含有該強化芯材之離子交換膜之開口率進而較佳為60%以上。 作為強化紗之形狀,可列舉圓紗、帶狀紗等。 (連通孔) 離子交換膜較佳為於膜本體之內部具有連通孔。 所謂連通孔係指能夠成為電解時產生之離子或電解液之流路之孔。又,所謂連通孔係形成於膜本體內部之管狀之孔,藉由下文所述之犧牲芯材(或犧牲紗)溶出而形成。連通孔之形狀或直徑等可藉由選擇犧牲芯材(犧牲紗)之形狀或直徑進行控制。 藉由在離子交換膜形成連通孔,於電解時能夠確保電解液之移動性。連通孔之形狀並無特別限定,根據下文所述之製法,可製成連通孔之形成所使用之犧牲芯材之形狀。 連通孔較佳為以交替通過強化芯材之陽極側(磺酸層側)與陰極側(羧酸層側)之方式形成。藉由設為該結構,於強化芯材之陰極側形成有連通孔之部分,通過充滿連通孔之電解液所輸送之離子(例如,鈉離子)亦能夠流至強化芯材之陰極側。其結果為,由於陽離子之流動未被遮蔽,因此能夠進一步降低離子交換膜之電阻。 連通孔可僅沿構成離子交換膜之膜本體之特定之一方向形成,就發揮出更穩定之電解性能之觀點而言,較佳為沿膜本體之縱向與橫向之兩方向形成。 [製造方法] 作為離子交換膜之適宜之製造方法,可列舉具有以下之(1)步驟~(6)步驟之方法。 (1)步驟:製造具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之含氟系聚合物之步驟。 (2)步驟:藉由視需要至少織入複數個強化芯材與具有溶於酸或鹼之性質且形成連通孔之犧牲紗而獲得於鄰接之強化芯材彼此之間配置有犧牲紗之補強材之步驟。 (3)步驟:將具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之上述含氟系聚合物進行膜化之步驟。 (4)步驟:視需要將上述補強材埋入至上述膜中而獲得內部配置有上述補強材之膜本體之步驟。 (5)步驟:將(4)步驟中獲得之膜本體進行水解之步驟(水解步驟)。 (6)步驟:於(5)步驟中獲得之膜本體設置塗佈層之步驟(塗佈步驟)。 以下,對各步驟進行詳細說明。 (1)步驟:製造含氟系聚合物之步驟 於(1)步驟中,使用上述第1群~第3群所記載之原料之單體製造含氟系聚合物。為了控制含氟系聚合物之離子交換容量,於形成各層之含氟系聚合物之製造中調整原料之單體之混合比即可。 (2)步驟:補強材之製造步驟 所謂補強材係紡織強化紗之織布等。藉由將補強材埋入至膜內而形成強化芯材。於製成具有連通孔之離子交換膜時,亦將犧牲紗一起織入至補強材中。該情形時之犧牲紗之混織量較佳為補強材整體之10~80質量%,更佳為30~70質量%。藉由織入犧牲紗,亦能夠防止強化芯材之脫線。 犧牲紗係於膜之製造步驟或電解環境下具有溶解性者,可使用嫘縈、聚對苯二甲酸乙二酯(PET)、纖維素及聚醯胺等。又,亦較佳為具有20~50丹尼之粗細程度、包含單絲或複絲之聚乙烯醇等。 再者,於(2)步驟中,可藉由調整強化芯材或犧牲紗之配置而控制開口率或連通孔之配置等。 (3)步驟:膜化步驟 於(3)步驟中,使用擠出機將上述(1)步驟中獲得之含氟系聚合物進行膜化。膜可為單層結構,亦可如上所述為磺酸層與羧酸層之2層結構,亦可為3層以上之多層結構。 作為膜化之方法,例如可列舉以下者。 分別將具有羧酸基之含氟聚合物、具有磺酸基之含氟聚合物分開進行膜化之方法。 藉由共擠出將具有羧酸基之含氟聚合物與具有磺酸基之含氟聚合物製成複合膜之方法。 再者,膜可分別為複數片。又,將異種之膜共擠出有助於提高界面之接著強度,故而較佳。 (4)步驟:獲得膜本體之步驟 於(4)步驟中,藉由將(2)步驟中獲得之補強材埋入至(3)步驟中獲得之膜之內部,而獲得內有補強材之膜本體。 作為膜本體之較佳之形成方法,可列舉:(i)藉由共擠出法將位於陰極側之具有羧酸基前驅物(例如,羧酸酯官能基)之含氟系聚合物(以下將包含其之層稱為第一層)與具有磺酸基前驅物(例如,磺醯氟官能基)之含氟系聚合物(以下將包含其之層稱為第二層)進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將補強材、第二層/第一層複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法;(ii)區別於第二層/第一層複合膜,預先將具有磺酸基前驅物之含氟系聚合物(第三層)單獨進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將第三層膜、強化芯材、包含第二層/第一層之複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法。 此處,將第一層與第二層共擠出有助於提高界面之接著強度。 又,於減壓下進行一體化之方法與加壓壓製法相比,具有補強材上之第三層之厚度變大之特徵。進而,由於將補強材固定於膜本體之內面,因此具有能夠充分保持離子交換膜之機械強度之性能。 再者,此處所說明之積層之變化係一例,可考慮所需之膜本體之層構成或物性等,適當選擇適宜之積層圖案(例如,各層之組合等)後進行共擠出。 再者,為了進一步提高離子交換膜之電性能,亦可於第一層與第二層之間進一步介置包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層,或使用包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層代替第二層。 第四層之形成方法可為分開製造具有羧酸基前驅物之含氟系聚合物與具有磺酸基前驅物之含氟系聚合物後加以混合之方法,亦可為使用將具有羧酸基前驅物之單體與具有磺酸基前驅物之單體共聚合而成者之方法。 於將第四層製成離子交換膜之構成之情形時,可將第一層與第四層之共擠出膜加以成形,第三層及第二層與其分開單獨進行膜化,藉由上文所述之方法進行積層,亦可將第一層/第四層/第二層之3層一次共擠出而進行膜化。 於該情形時,所擠出之膜行進之方向為MD方向。由此可將含有具有離子交換基之含氟系聚合物之膜本體形成於補強材上。 又,離子交換膜較佳為於包含磺酸層之表面側具有包含具有磺酸基之含氟聚合物之突出的部分、即凸部。作為形成此種凸部之方法,並無特別限定,可採用於樹脂表面形成凸部之公知之方法。具體而言,例如可列舉對膜本體之表面實施壓紋加工之方法。例如,於將上述複合膜與補強材等進行一體化時,藉由使用預先經壓紋加工之脫模紙,可形成上述凸部。於藉由壓紋加工形成凸部之情形時,凸部之高度或配置密度之控制可藉由控制所轉印之壓紋形狀(脫模紙之形狀)而進行。 (5)水解步驟 於(5)步驟中,進行將(4)步驟中獲得之膜本體水解而將離子交換基前驅物轉換為離子交換基之步驟(水解步驟)。 又,於(5)步驟中,藉由利用酸或鹼將膜本體所含之犧牲紗溶解去除,可於膜本體形成溶出孔。再者,犧牲紗亦可不完全溶解去除,而殘留於連通孔中。又,殘留於連通孔中之犧牲紗可於將離子交換膜供於電解時藉由電解液溶解去除。 犧牲紗係於離子交換膜之製造步驟或電解環境下對酸或鹼具有溶解性者,藉由使犧牲紗溶出而於該部位形成連通孔。 (5)步驟可將(4)步驟中獲得之膜本體浸漬於含有酸或鹼之水解溶液中進行。作為該水解溶液,例如可使用含有KOH與DMSO(Dimethyl sulfoxide)之混合溶液。 該混合溶液較佳為含有2.5~4.0 N之KOH,且含有25~35質量%之DMSO。 作為水解之溫度,較佳為70~100℃。溫度越高,可使視厚度更厚。更佳為75~100℃。 作為水解之時間,較佳為10~120分鐘。時間越長,可使視厚度更厚。更佳為20~120分鐘。 此處,對藉由溶出犧牲紗而形成連通孔之步驟進一步詳細地說明。圖25(a)、(b)係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 於圖25(a)、(b)中,僅圖示強化紗52、犧牲紗504a及由犧牲紗504a形成之連通孔504,膜本體等其他構件省略圖示。 首先,將於離子交換膜中構成強化芯材之強化紗52與於離子交換膜中用以形成連通孔504之犧牲紗504a製成針織織入補強材。然後,於(5)步驟中藉由使犧牲紗504a溶出而形成連通孔504。 藉由上述方法,根據於離子交換膜之膜本體內如何配置強化芯材、連通孔而調整強化紗52與犧牲紗504a之針織織入方法即可,因此較簡便。 於圖25(a)中,例示於紙面沿縱向與橫向之兩方向將強化紗52與犧牲紗504a織入之平織之補強材,可視需要變更補強材中之強化紗52與犧牲紗504a之配置。 (6)塗佈步驟 於(6)步驟中,製備含有藉由原石粉碎或原石熔融獲得之無機物粒子與結合劑之塗佈液,將塗佈液塗佈於(5)步驟中獲得之離子交換膜之表面並加以乾燥,藉此可形成塗佈層。 作為結合劑,較佳為將具有離子交換基前驅物之含氟系聚合物水解於含有二甲基亞碸(DMSO)及氫氧化鉀(KOH)之水溶液中之後,浸漬於鹽酸中將離子交換基之抗衡離子置換為H+ 而成之結合劑(例如,具有羧基或磺基之含氟系聚合物)。藉此,變得容易溶解於下文所述之水或乙醇中,故而較佳。 將該結合劑溶解於混合水與乙醇而成之溶液中。再者,水與乙醇之較佳之體積比為10:1~1:10,更佳為5:1~1:5,進而較佳為2:1~1:2。藉由球磨機使無機物粒子分散於由此獲得之溶解液中而獲得塗佈液。此時,亦可藉由調整分散時之時間、旋轉速度而調整粒子之平均粒徑等。再者,無機物粒子與結合劑之較佳之調配量如上文所述。 塗佈液中之無機物粒子及結合劑之濃度並無特別限定,較佳為製成稀薄之塗佈液。藉此,能夠均勻地塗佈於離子交換膜之表面。 又,於使無機物粒子分散時,亦可將界面活性劑添加於分散液中。作為界面活性劑,較佳為非離子系界面活性劑,例如可列舉日油股份有限公司製造之HS-210、NS-210、P-210、E-212等。 藉由利用噴射塗佈或滾筒塗敷將所獲得之塗佈液塗佈於離子交換膜表面而可獲得離子交換膜。 [微多孔膜] 作為本實施形態之微多孔膜,只要如上文所述,可與電解用電極製成積層體,則無特別限定,可應用各種微多孔膜。 本實施形態之微多孔膜之氣孔率並無特別限定,例如可設為20~90,較佳為30~85。上述氣孔率例如可藉由下述之式算出。 氣孔率=(1-(乾燥狀態之膜重量)/(由根據膜之厚度、寬度、長度算出之體積與膜素材之密度所算出之重量))×100 本實施形態之微多孔膜之平均孔徑並無特別限定,例如可設為0.01 μm~10 μ,較佳為0.05 μm~5 μm。上述平均孔徑例如係沿厚度方向將膜垂直切斷,藉由FE-SEM觀察切斷面。對所觀察之孔之直徑測定100點左右並求出平均值,藉此可求出平均孔徑。 本實施形態之微多孔膜之厚度並無特別限定,例如可設為10 μm~1000 μm,較佳為50 μm~600 μm。上述厚度例如可使用測微計(Mitutoyo股份有限公司製造)等進行測定。 作為如上所述之微多孔膜之具體例,可列舉Agfa公司製造之Zirfon Perl UTP 500(於本實施形態中亦稱為Zirfon膜)、國際公開第2013-183584號說明書、國際公開第2016-203701號說明書等所記載者。 推測本實施形態之與隔膜之積層體表現出優異之電解性能之原因如下。於作為先前技術之藉由熱壓接等方法將隔膜與電極牢固地接著之情形時,成為電極嵌入隔膜之狀態而物理性地接著。該接著部分會妨礙鈉離子之膜內之移動,電壓大幅地上升。另一方面,藉由如本實施形態般利用適度之接著力使電解用電極與隔膜或饋電體相接,而消除先前技術中作為問題之妨礙鈉離子之膜內移動之情況。藉此,於隔膜或饋電體與電解用電極藉由適度之接著力相接之情形時,為隔膜或饋電體與電解用電極之一體物,並且能夠表現出優異之電解性能。 [捲繞體] 本實施形態之捲繞體包含本實施形態之積層體。即,本實施形態之捲繞體係將本實施形態之積層體捲繞而成者。如本實施形態之捲繞體般,藉由將本實施形態之積層體進行捲繞並減小尺寸,能夠進一步提高操作性。 [電解槽] 本實施形態之電解槽包含本實施形態之積層體。以下,以使用離子交換膜作為隔膜進行食鹽電解之情形為例,對電解槽之一實施形態進行詳細說明。 [電解池] 圖26係電解池1之剖面圖。 電解池1具備陽極室10、陰極室20、設置於陽極室10及陰極室20之間之間隔壁30、設置於陽極室10之陽極11、及設置於陰極室20之陰極21。視需要亦可具備具有基材18a與形成於該基材18a上之逆向電流吸收層18b且設置於陰極室內之逆向電流吸收體18。屬於1個電解池1之陽極11及陰極21互相電性連接。換言之,電解池1具備如下陰極結構體。陰極結構體40具備陰極室20、設置於陰極室20之陰極21、及設置於陰極室20內之逆向電流吸收體18,逆向電流吸收體18如圖30所示具有基材18a與形成於該基材18a上之逆向電流吸收層18b,陰極21與逆向電流吸收層18b電性連接。陰極室20進而具有集電體23、支持該集電體之支持體24、及金屬彈性體22。金屬彈性體22係設置於集電體23及陰極21之間。支持體24係設置於集電體23及間隔壁30之間。集電體23經由金屬彈性體22而與陰極21電性連接。間隔壁30經由支持體24而與集電體23電性連接。因此,間隔壁30、支持體24、集電體23、金屬彈性體22及陰極21係電性連接。陰極21及逆向電流吸收層18b係電性連接。陰極21及逆向電流吸收層可直接連接,亦可經由集電體、支持體、金屬彈性體或間隔壁等而間接連接。陰極21之表面整體較佳為由用於還原反應之觸媒層所被覆。又,電性連接之形態可為分別直接將間隔壁30與支持體24、支持體24與集電體23、集電體23與金屬彈性體22安裝,並且於金屬彈性體22上積層陰極21之形態。作為將該等各構成構件互相直接安裝之方法,可列舉焊接等。又,亦可將逆向電流吸收體18、陰極21、及集電體23總稱為陰極結構體40。 圖27係電解槽4內鄰接之2個電解池1之剖面圖。圖28表示電解槽4。圖29表示組裝電解槽4之步驟。如圖27所示,將電解池1、陽離子交換膜2、電解池1依序串聯排列。於電解槽內鄰接之2個電解池中之一電解池1之陽極室與另一電解池1之陰極室之間配置離子交換膜2。即,電解池1之陽極室10及與其鄰接之電解池1之陰極室20係由陽離子交換膜2隔開。如圖28所示,電解槽4包含介隔離子交換膜2而串聯連接之複數個電解池1。即,電解槽4係具備串聯配置之複數個電解池1、及配置於鄰接之電解池1之間之離子交換膜2的複極式電解槽。如圖29所示,電解槽4係藉由介隔離子交換膜2將複數個電解池1串聯配置並利用壓製器5連結而組裝。 電解槽4具有連接於電源之陽極端子7與陰極端子6。於電解槽4內串聯連結之複數個電解池1中位於最靠端之電解池1之陽極11係電性連接於陽極端子7。於電解槽4內串聯連結之複數個電解池2中位於陽極端子7之相反側之端之電解池的陰極21係電性連接於陰極端子6。電解時之電流從陽極端子7側起,經過各電解池1之陽極及陰極而流向陰極端子6。再者,可於連結之電解池1之兩端配置僅具有陽極室之電解池(陽極終端池)與僅具有陰極室之電解池(陰極終端池)。於該情形時,將陽極端子7連接於配置於其一端之陽極終端池,將陰極端子6連接於配置於另一端之陰極終端池。 於進行鹽水之電解之情形時,向各陽極室10供給鹽水,向陰極室20供給純水或低濃度之氫氧化鈉水溶液。各液體係從電解液供給管(圖中省略)起,經過電解液供給軟管(圖中省略)而向各電解池1供給。又,電解液及電解之產物係由電解液回收管(圖中省略)所回收。於電解中,鹽水中之鈉離子從一電解池1之陽極室10起,通過離子交換膜2,向旁邊之電解池1之陰極室20移動。由此電解中之電流沿將電解池1串聯連結之方向流通。即,電流係經由陽離子交換膜2而從陽極室10流向陰極室20。伴隨鹽水之電解,於陽極11側產生氯氣,於陰極21側產生氫氧化鈉(溶質)與氫氣。 (陽極室) 陽極室10具有陽極11或陽極饋電體11。於將本實施形態之電解用電極插入陽極側之情形時,11作為陽極饋電體發揮功能。於不將本實施形態之電解用電極插入陽極側之情形時,11作為陽極發揮功能。又,陽極室10較佳為具有向陽極室10供給電解液之陽極側電解液供給部、配置於陽極側電解液供給部之上方且以與間隔壁30大致平行或傾斜之方式配置之擋板、及配置於擋板之上方且從混入有氣體之電解液中分離氣體之陽極側氣液分離部。 (陽極) 於不將本實施形態之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極11。作為陽極11,可使用所謂DSA(註冊商標)等金屬電極。所謂DSA係藉由以釕、銥、鈦作為成分之氧化物被覆表面之鈦基材之電極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極饋電體) 於將本實施形態之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極饋電體11。作為陽極饋電體11,可使用所謂DSA(註冊商標)等金屬電極,亦可使用未形成有觸媒塗層之鈦。又,亦可使用使觸媒塗層厚度變薄之DSA。進而,亦可使用使用過之陽極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極側電解液供給部) 陽極側電解液供給部係向陽極室10供給電解液者,其連接於電解液供給管。陽極側電解液供給部較佳為配置於陽極室10之下方。作為陽極側電解液供給部,例如可使用表面形成有開口部之管(分散管)等。該管更佳為以沿陽極11之表面平行於電解池之底部19之方式配置。該管係連接於向電解池1內供給電解液之電解液供給管(液供給噴嘴)。從液供給噴嘴供給之電解液藉由管被搬送至電解池1內,從設置於管之表面之開口部向陽極室10之內部供給。藉由將管以沿陽極11之表面平行於電解池之底部19之方式配置,能夠將電解液均勻地供給至陽極室10之內部,故而較佳。 (陽極側氣液分離部) 陽極側氣液分離部較佳為配置於擋板之上方。於電解中,陽極側氣液分離部具有將氯氣等產生氣體與電解液分離之功能。再者,只要無特別說明,則所謂上方意指圖26之電解池1中之上方向,所謂下方意指圖26之電解池1中之下方向。 電解時,若電解池1中產生之產生氣體與電解液成為混相(氣液混相)而被排出至系外,則存在因電解池1內部之壓力變動導致產生振動而引起離子交換膜之物理破損之情形。為了抑制該情形,較佳為於本實施形態之電解池1中設置用以將氣體與液體分離之陽極側氣液分離部。較佳為於陽極側氣液分離部設置用以消除氣泡之消泡板。藉由在氣液混相流通過消泡板時氣泡破裂,而可分離為電解液與氣體。其結果為,能夠防止電解時之振動。 (擋板) 擋板較佳為配置於陽極側電解液供給部之上方,且以與間隔壁30大致平行或傾斜之方式配置。擋板係控制陽極室10之電解液之流動之間隔板。藉由設置擋板,可使電解液(鹽水等)於陽極室10內部循環,使其濃度變得均勻。為了引起內部循環,擋板較佳為以將陽極11附近之空間與間隔壁30附近之空間隔開之方式配置。就該觀點而言,擋板較佳為以與陽極11及間隔壁30之各表面相對向之方式設置。於由擋板分隔之陽極附近之空間,藉由進行電解,電解液濃度(鹽水濃度)降低,又,產生氯氣等產生氣體。藉此,於由擋板分隔之陽極11附近之空間與間隔壁30附近之空間產生氣液之比重差。利用該情況,能夠促進陽極室10中之電解液之內部循環,使陽極室10之電解液之濃度分佈變得更均勻。 再者,於圖26並未圖示,但亦可於陽極室10之內部另行設置集電體。作為該集電體,亦可設為與下文所述之陰極室之集電體相同之材料或構成。又,於陽極室10中,亦可使陽極11本身作為集電體發揮功能。 (間隔壁) 間隔壁30係配置於陽極室10與陰極室20之間。間隔壁30有時亦稱為間隔件,係將陽極室10與陰極室20進行劃分者。作為間隔壁30,可使用作為電解用之間隔件所公知者,例如可列舉於陰極側焊接包含鎳之板、於陽極側焊接包含鈦之板之間隔壁等。 (陰極室) 陰極室20於將本實施形態之電解用電極插入陰極側之情形時,21作為陰極饋電體發揮功能,於不將本實施形態之電解用電極插入陰極側之情形時,21作為陰極發揮功能。於具有逆向電流吸收體之情形時,陰極或陰極饋電體21與逆向電流吸收體係電性連接。又,陰極室20較佳為與陽極室10同樣,亦具有陰極側電解液供給部、陰極側氣液分離部。再者,構成陰極室20之各部位中,關於與構成陽極室10之各部位相同者省略說明。 (陰極) 於不將本實施形態之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極21。陰極21較佳為具有鎳基材與被覆鎳基材之觸媒層。作為鎳基材上之觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可視需要對陰極21實施還原處理。再者,作為陰極21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陰極饋電體) 於將本實施形態之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極饋電體21。可對陰極饋電體21被覆觸媒成分。該觸媒成分可為原本用作陰極而殘存者。作為觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可使用未形成有觸媒塗層之鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。再者,作為陰極饋電體21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (逆向電流吸收層) 可選擇具有較上文所述之陰極之觸媒層用元素的氧化還原電位更低之氧化還原電位之材料作為逆向電流吸收層之材料。例如可列舉鎳或鐵等。 (集電體) 陰極室20較佳為具備集電體23。藉此,集電效果提高。於本實施形態中,集電體23較佳為多孔板,且以與陰極21之表面大致平行之方式配置。 作為集電體23,例如較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。集電體23可為該等金屬之混合物、合金或複合氧化物。再者,集電體23之形狀只要為作為集電體發揮功能之形狀,則可為任意形狀,可為板狀、網狀。 (金屬彈性體) 藉由在集電體23與陰極21之間設置金屬彈性體22,將串聯連接之複數個電解池1之各陰極21壓抵於離子交換膜2,各陽極11與各陰極21之間之距離變短,可降低對串聯連接之複數個電解池1整體承受之電壓。藉由電壓降低,可降低消耗電量。又,藉由設置金屬彈性體22,於將含有本實施形態之電解用電極之積層體設置於電解池時,藉由金屬彈性體22之壓抵壓,可將該電解用電極穩定地維持於起始位置。 作為金屬彈性體22,可使用螺旋彈簧、線圈等彈簧構件、緩衝性之墊等。作為金屬彈性體22,可考慮壓抵離子交換膜之應力等而適當採用適宜者。可將金屬彈性體22設置於陰極室20側之集電體23之表面上,亦可設置於陽極室10側之間隔壁之表面上。通常以陰極室20小於陽極室10之方式劃分兩室,因此就框體之強度等觀點而言,較佳為將金屬彈性體22設置於陰極室20之集電體23與陰極21之間。又,金屬彈性體23較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。 (支持體) 陰極室20較佳為具備將集電體23與間隔壁30電性連接之支持體24。藉此,能夠效率良好地流通電流。 支持體24較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。又,作為支持體24之形狀,只要為能夠支持集電體23之形狀,則可為任意形狀,可為棒狀、板狀或網狀。支持體24例如為板狀。複數個支持體24係配置於間隔壁30與集電體23之間。複數個支持體24係以各自之面互相平行之方式排列。支持體24係以大致垂直於間隔壁30及集電體23之方式配置。 (陽極側墊片、陰極側墊片) 陽極側墊片較佳為配置於構成陽極室10之框體表面。陰極側墊片較佳為配置於構成陰極室20之框體表面。1個電解池所具備之陽極側墊片及與其鄰接之電解池之陰極側墊片以夾持離子交換膜2之方式將電解池彼此連接(參照圖26、27)。藉由該等墊片,於介隔離子交換膜2將複數個電解池1串聯連接時,能夠對連接處賦予氣密性。 所謂墊片係將離子交換膜與電解池之間密封者。作為墊片之具體例,可列舉中央形成有開口部之邊框狀之橡膠製片等。對於墊片要求對腐蝕性之電解液或所產生之氣體等具有耐性而可長期使用。因此,就耐化學品性或硬度之方面而言,通常可使用乙烯-丙烯-二烯橡膠(EPDM橡膠)、乙烯-丙烯橡膠(EPM橡膠)之硫化物或過氧化物交聯物等作為墊片。又,視需要亦可使用以聚四氟乙烯(PTFE)或四氟乙烯-全氟烷基乙烯醚共聚物(PFA)等氟系樹脂被覆與液體相接之區域(接液部)之墊片。該等墊片只要以不妨礙電解液之流動之方式分別具有開口部即可,其形狀並無特別限定。例如沿構成陽極室10之陽極室框或構成陰極室20之陰極室框之各開口部之周緣,藉由接著劑等貼附邊框狀之墊片。此外,於例如介隔離子交換膜2連接2個電解池1之情形時(參照圖27),介隔離子交換膜2將貼附有墊片之各電解池1緊固即可。藉此,能夠抑制電解液、因電解而產生之鹼金屬氫氧化物、氯氣、氫氣等漏至電解池1之外部之情況。 (離子交換膜) 作為離子交換膜2,如上述離子交換膜之項所記載。 (水電解) 本實施形態之進行水電解之情形時之電解槽係具有將上述進行食鹽電解之情形時之電解槽中之離子交換膜變更為微多孔膜之構成者。又,於所供給之原料為水之方面與上述進行食鹽電解之情形時之電解槽不同。關於其他構成,進行水電解之情形時之電解槽亦可採用與進行食鹽電解之情形時之電解槽相同之構成。於食鹽電解之情形時,由於在陽極室產生氯氣,因此陽極室之材質使用鈦,於水電解之情形時,由於在陽極室僅產生氧氣,因此可使用與陰極室之材質相同者。例如可列舉鎳等。又,陽極塗層適宜為產生氧氣用之觸媒塗層。作為觸媒塗層之例,可列舉鉑族金屬及過渡金屬族之金屬、氧化物、氫氧化物等。例如可使用鉑、銥、鈀、釕、鎳、鈷、鐵等元素。 (積層體之用途) 本實施形態之積層體如上文所述,能夠提高電解槽中之電極更新時之作業效率,進而更新後亦能夠表現出優異之電解性能。換言之,本實施形態之積層體能夠適宜地用作電解槽之構件更換用之積層體。再者,應用於該用途時之積層體特別地稱為「膜電極接合體」。 (包裝體) 本實施形態之積層體較佳為於封入至包裝材中之狀態下進行搬運等。即,本實施形態之包裝體具備本實施形態之積層體、及包裝上述積層體之包裝材。由於本實施形態之包裝體以上述方式構成,因此能夠防止於搬運本實施形態之積層體等時可能產生之污垢之附著或破損。於用於電解槽之構件更換之情形時,尤佳為以本實施形態之包裝體之形式進行搬運等。作為本實施形態中之包裝材,並無特別限定,可應用各種公知之包裝材。又,本實施形態之包裝體並不限定於以下,但例如可藉由以潔淨狀態之包裝材包裝本實施形態之積層體、繼而封入等方法而製造。 <第3實施形態> 此處一邊參照圖43~62一邊對本發明之第3實施形態進行詳細地說明。 [積層體] 第3實施形態(以下於<第3實施形態>之項中簡稱為「本實施形態」)之積層體具有隔膜、及固定於上述隔膜之表面之至少一區域(以下亦簡稱為「固定區域」)之電解用電極,且上述隔膜之表面中之上述區域之比率超過0%且未達93%。由於以上述方式構成,因此本實施形態之積層體能夠提高電解槽中之電極更新時之作業效率,進而更新後亦能夠表現出優異之電解性能。即,藉由本實施形態之積層體,於更新電極時,無需伴隨剝離固定於電解池之既有電極等繁雜之作業,藉由如與隔膜之更新相同之簡單之作業即可更新電極,因此作業效率大幅提高。 進而,藉由本實施形態之積層體,能夠將既有電解池之電解性能維持為與新品時之性能相同或有所提高。因此,固定於既有之電解池且作為陽極、陰極發揮功能之電極僅作為饋電體發揮功能即可,能夠大幅地減少觸媒塗層或者甚至無觸媒塗層。作為此處所謂饋電體意指劣化之電極(即既有電極)或未形成有觸媒塗層之電極等。 [電解用電極] 本實施形態中之電解用電極只要為可用於電解之電極,則無特別限定,較佳為電解用電極與隔膜相對向之面之面積(與下文所述之通電面之面積S2相對應)為0.01 m2 以上。所謂「與隔膜相對向之面」意指電解用電極所具有之表面中隔膜所存在一側之表面。即,電解用電極中與隔膜相對向之面亦可稱為與隔膜之表面相接之面。於電解用電極中之上述與隔膜相對向之面之面積為0.01 m2 以上之情形時,能夠確保充分之生產性,尤其是於實施工業上之電解之方面有可獲得充分之生產性之傾向。由此,就確保充分之生產性,確保作為更新電解池所使用之積層體之實用性之觀點而言,電解用電極中之上述與隔膜相對向之面之面積更佳為0.1 m2 以上,進而較佳為1 m2 以上。該面積例如可藉由實施例所記載之方法進行測定。 本實施形態中之電解用電極就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、饋電體(劣化之電極及未形成有觸媒塗層之電極)等具有良好之接著力之觀點而言,每單位質量·單位面積所承受之力較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/mg・cm2 以上,進而更佳為0.14 N/(mg・cm2 )以上。就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.2 N/(mg・cm2 )以上。 上述承受力例如可藉由適當調整下文所述之開孔率、電極之厚度、算術平均表面粗糙度等而設為上述範圍。更具體而言,例如,若增大開孔率,則承受力有變小之傾向,若減小開孔率,則承受力有變大之傾向。 又,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力之觀點,進而就經濟性之觀點而言,較佳為每單位面積之質量為48 mg/cm2 以下,更佳為30 mg/cm2 以下,進而較佳為20 mg/cm2 以下,進而,就合併操作性、接著性及經濟性之綜合性之觀點而言,為15 mg/cm2 以下。下限值並無特別限定,例如為1 mg/cm2 左右。 上述每單位面積之質量例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則每單位面積之質量有變小之傾向,若減小開孔率,則每單位面積之質量有變大之傾向。 承受力可藉由以下之方法(i)或(ii)進行測定,藉由方法(i)之測定所獲得之值(亦稱為「承受力(1)」)與藉由方法(ii)之測定所獲得之值(亦稱為「承受力(2)」)可相同亦可不同,但較佳為任一值均未達1.5 N/mg・cm2 。 [方法(i)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方)、於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方)及電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。再者,噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.5~0.8 μm。算術平均表面粗糙度(Ra)之具體之算出方法如實施例所記載。 於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與離子交換膜之重疊部分之面積、及與離子交換膜重疊部分之電極樣品之質量,而算出每單位質量·單位面積所承受之力(1)(N/mg・cm2 )。 藉由方法(i)獲得之每單位質量·單位面積所承受之力(1)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。又,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 ),更佳為0.2 N/(mg・cm2 )以上。 [方法(ii)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方,與上述方法(i)相同之鎳板)與電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與鎳板之重疊部分之面積、及與鎳板重疊部分中之電極樣品之質量,而算出每單位質量•單位面積之接著力(2)(N/mg・cm2 )。 藉由方法(ii)獲得之每單位質量·單位面積所承受之力(2)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。進而,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 )以上。 本實施形態中之電解用電極較佳為包含電解用電極基材及觸媒層。該電解用電極基材之厚度(量規厚度)並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折,大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力之觀點而言,藉由以下之方法(2)所測得之比率較佳為90%以上,更佳為92%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為95%以上。上限值為100%。 [方法(2)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑280 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折之觀點而言,藉由以下之方法(3)所測得之比率較佳為75%以上,更佳為80%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為90%以上。上限值為100%。 [方法(3)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,防止電解中產生之氣體滯留之觀點而言,較佳為多孔結構,且其開孔率或空隙率為5~90%以下。開孔率更佳為10~80%以下,進而較佳為20~75%。 再者,所謂開孔率係每單位體積之開孔部之比率。開孔部亦根據考慮至次微米級抑或僅考慮目視可見之開口而有各種算出方法。於本實施形態中,藉由根據電極之量規厚度、寬度、長度之值算出體積V,進而對重量W進行實測,而利用下述之式算出開孔率A。 A=(1-(W/(V×ρ))×100 ρ係電極之材質之密度(g/cm3 )。例如於鎳之情形時為8.908 g/cm3 ,於鈦之情形時為4.506 g/cm3 。開孔率之調整係藉由如下方法進行適當調整:若為沖孔金屬,則變更每單位面積沖裁金屬之面積;若為多孔金屬,則變更SW(短徑)、LW(長徑)、進給之值;若為絲網,則變更金屬纖維之線徑、網眼數;若為電成形,則變更所使用之光阻之圖案;若為不織布,則變更金屬纖維直徑及纖維密度;若為發泡金屬,則變更用以使空隙形成之模板等。 以下,對本實施形態中之電解用電極之一形態進行說明。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。觸媒層如下所述,可包含複數層,亦可為單層結構。 如圖43所示,本實施形態之電解用電極100具備電解用電極基材10、及被覆電解用電極基材10之兩表面之一對第一層20。第一層20較佳為將電解用電極基材10整體被覆。藉此,電解用電極之觸媒活性及耐久性變得容易提高。再者,亦可僅於電解用電極基材10之一表面積層第一層20。 又,如圖43所示,第一層20之表面可由第二層30所被覆。第二層30較佳為將第一層20整體被覆。又,第二層30可僅積層於第一層20之一表面。 (電解用電極基材) 作為電解用電極基材10,並無特別限定,例如可使用鎳、鎳合金、不鏽鋼、或以鈦等為代表之閥金屬,較佳為含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 於在高濃度之鹼性水溶液中使用不鏽鋼之情形時,若考慮到鐵及鉻溶出、及不鏽鋼之導電性為鎳之1/10左右,則較佳為使用含有鎳(Ni)之基材作為電解用電極基材。 又,電解用電極基材10於在接近飽和之高濃度之食鹽水中於氯氣產生環境中使用之情形時,材質亦較佳為耐蝕性較高之鈦。 電解用電極基材10之形狀並無特別限定,可根據目的選擇合適之形狀。作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。其中,較佳為沖孔金屬或多孔金屬。再者,所謂電成形係將照相製版與電鍍法組合而製作精密之圖案之金屬薄膜的技術。其係藉由光阻於基板上形成圖案,對未受到光阻保護之部分實施電鍍而獲得金屬薄膜之方法。 關於電解用電極基材之形狀,根據電解槽中之陽極與陰極之距離而有適宜之規格。並無特別限定,於陽極與陰極具有有限之距離之情形時,可使用多孔金屬、沖孔金屬形狀,於離子交換膜與電極相接之所謂零間距電解槽之情形時,可使用編織細線而成之編織網、金屬絲網、發泡金屬、金屬不織布、多孔金屬、沖孔金屬、金屬多孔箔等。 作為電解用電極基材10,可列舉:金屬多孔箔、金屬絲網、金屬不織布、沖孔金屬、多孔金屬或發泡金屬。 作為加工為沖孔金屬、多孔金屬前之板材,較佳為經壓延成形之板材、電解箔等。電解箔較佳為進而作為後處理而藉由與母材相同之元素實施鍍覆處理,於單面或兩面形成凹凸。 又,電解用電極基材10之厚度如上文所述,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於電解用電極基材中,較佳為藉由在氧化環境中將電解用電極基材進行退火而緩和加工時之殘留應力。又,為了提高與被覆於電解用電極基材之表面之觸媒層之密接性,較佳為使用鋼砂、氧化鋁粉等於上述表面形成凹凸,其後藉由酸處理而增加表面積。或者,較佳為藉由與基材相同之元素實施鍍覆處理,增加表面積。 為了使第一層20與電解用電極基材10之表面密接,較佳為對電解用電極基材10進行增大表面積之處理。作為增大表面積之處理,可列舉使用鋼線粒、鋼砂、氧化鋁砂等之噴擊處理、使用硫酸或鹽酸之酸處理、利用與基材相同元素之鍍覆處理等。基材表面之算術平均表面粗糙度(Ra)並無特別限定,較佳為0.05 μm~50 μm,更佳為0.1~10 μm,進而較佳為0.1~8 μm。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陽極之情形進行說明。 (第一層) 於圖43中,作為觸媒層之第一層20含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物。作為釕氧化物,可列舉RuO2 等。作為銥氧化物,可列舉IrO2 等。作為鈦氧化物,可列舉TiO2 等。第一層20較佳為含有釕氧化物及鈦氧化物之兩種氧化物,或含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物。藉此,第一層20成為更穩定之層,進而,與第二層30之密接性亦進一步提高。 於第一層20含有釕氧化物及鈦氧化物之兩種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為1~9莫耳,更佳為1~4莫耳。藉由將兩種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之銥氧化物較佳為0.2~3莫耳,更佳為0.3~2.5莫耳。又,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為0.3~8莫耳,更佳為1~7莫耳。藉由將三種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有選自釕氧化物、銥氧化物及鈦氧化物中之至少兩種氧化物之情形時,該等氧化物較佳為形成固溶體。藉由形成氧化物固溶體,電解用電極100表現出優異之耐久性。 除了上述組成以外,只要含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物,則可使用各種組成者。例如,亦可使用稱為DSA(註冊商標)之含有釕、銥、鉭、鈮、鈦、錫、鈷、錳、鉑等之氧化物塗層作為第一層20。 第一層20無需為單層,亦可包含複數層。例如,第一層20可包含含有三種氧化物之層與含有兩種氧化物之層。第一層20之厚度較佳為0.05~10 μm,更佳為0.1~8 μm。 (第二層) 第二層30較佳為含有釕與鈦。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較佳為含有氧化鈀、氧化鈀與鉑之固溶體或鈀與鉑之合金。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較厚者能夠維持電解性能之時間變長,就經濟性之觀點而言,較佳為0.05~3 μm之厚度。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陰極之情形進行說明。 (第一層) 作為觸媒層之第一層20之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。 於含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少一種之情形時,較佳為鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金含有鉑、鈀、銠、釕、銥中之至少一種鉑族金屬。 作為鉑族金屬,較佳為含有鉑。 作為鉑族金屬氧化物,較佳為含有釕氧化物。 作為鉑族金屬氫氧化物,較佳為含有釕氫氧化物。 作為鉑族金屬合金,較佳為含有鉑與鎳、鐵、鈷之合金。 較佳為進而視需要含有鑭系元素之氧化物或氫氧化物作為第二成分。藉此,電解用電極100表現出優異之耐久性。 作為鑭系元素之氧化物或氫氧化物,較佳為含有選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑中之至少1種。 較佳為進而視需要含有過渡金屬之氧化物或氫氧化物作為第三成分。 藉由添加第三成分,電解用電極100能夠表現出更優異之耐久性,降低電解電壓。 作為較佳之組合之例,可列舉:僅釕、釕+鎳、釕+鈰、釕+鑭、釕+鑭+鉑、釕+鑭+鈀、釕+鐠、釕+鐠+鉑、釕+鐠+鉑+鈀、釕+釹、釕+釹+鉑、釕+釹+錳、釕+釹+鐵、釕+釹+鈷、釕+釹+鋅、釕+釹+鎵、釕+釹+硫、釕+釹+鉛、釕+釹+鎳、釕+釹+銅、釕+釤、釕+釤+錳、釕+釤+鐵、釕+釤+鈷、釕+釤+鋅、釕+釤+鎵、釕+釤+硫、釕+釤+鉛、釕+釤+鎳、鉑+鈰、鉑+鈀+鈰、鉑+鈀+鑭+鈰、鉑+銥、鉑+鈀、鉑+銥+鈀、鉑+鎳+鈀、鉑+鎳+釕、鉑與鎳之合金、鉑與鈷之合金、鉑與鐵之合金等。 於不含鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之情形時,觸媒之主成分較佳為鎳元素。 較佳為含有鎳金屬、氧化物、氫氧化物中之至少1種。 作為第二成分,可添加過渡金屬。作為所添加之第二成分,較佳為含有鈦、錫、鉬、鈷、錳、鐵、硫、鋅、銅、碳中之至少一種元素。 作為較佳之組合,可列舉:鎳+錫、鎳+鈦、鎳+鉬、鎳+鈷等。 視需要可於第一層20與電解用電極基材10之間設置中間層。藉由設置中間層,能夠提高電解用電極100之耐久性。 作為中間層,較佳為對第一層20與電解用電極基材10之兩者具有親和性者。作為中間層,較佳為鎳氧化物、鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物。作為中間層,可藉由將含有形成中間層之成分之溶液進行塗佈、燒成而形成,亦可於空氣環境中在300~600℃之溫度下對基材實施熱處理而形成表面氧化物層。除此以外,可藉由熱熔射法、離子鍍敷法等已知之方法形成。 (第二層) 作為觸媒層之第一層30之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。作為第二層所含之元素之較佳之組合例,有第一層中所列舉之組合等。第一層與第二層之組合可為組成相同而組成比不同之組合,亦可為組成不同之組合。 作為觸媒層之厚度,較佳為將所形成之觸媒層及中間層累加而成之厚度為0.01 μm~20 μm。若為0.01 μm以上,則能夠作為觸媒充分發揮功能。若為20 μm以下,則從基材脫落之情況較少,能夠形成牢固之觸媒層。更佳為0.05 μm~15 μm。更佳為0.1 μm~10 μm。進而較佳為0.2 μm~8 μm。 作為電極之厚度、即電解用電極基材與觸媒層之合計之厚度,就電極之操作性之方面而言,較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,電極之厚度可藉由利用電子數顯厚度計(Mitutoyo股份有限公司,最少顯示0.001 mm)進行測定而求出。電解用電極基材之厚度係與電極厚度同樣地進行測定。觸媒層厚度可藉由電極厚度減去電解用電極基材之厚度而求出。 於本實施形態中,就確保充分之電解性能之觀點而言,較佳為電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。 於本實施形態中,若電解用電極係彈性變形區域較廣之電極,則就可獲得更良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有更良好之接著力之觀點而言,電解用電極之厚度較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,於本實施形態中,所謂「彈性變形區域較廣」意指將電解用電極捲繞而製成捲繞體,解除捲繞狀態後不易產生由捲繞引起之翹曲。又,所謂電解用電極之厚度於包含下文所述之觸媒層之情形時,係指合併電解用電極基材與觸媒層之厚度。 (電解用電極之製造方法) 其次,對電解用電極100之製造方法之一實施形態進行詳細說明。 於本實施形態中,藉由利用氧環境下之塗膜之燒成(熱分解)、或離子鍍敷、鍍覆、熱熔射等方法於電解用電極基材上形成第一層20、較佳為第二層30,可製造電解用電極100。此種本實施形態之製造方法能夠實現電解用電極100之較高之生產性。具體而言,藉由塗佈含有觸媒之塗佈液之塗佈步驟、乾燥塗佈液之乾燥步驟、進行熱分解之熱分解步驟,而於電解用電極基材上形成觸媒層。此處所謂熱分解意指對成為前驅物之金屬鹽進行加熱而分解為金屬或金屬氧化物與氣體狀物質。根據所使用之金屬種類、鹽之種類、進行熱分解之環境等,分解產物有所不同,但於氧化性環境下多數金屬有容易形成氧化物之傾向。於電極之工業性之製造工藝中,熱分解通常於空氣中進行,多數情形時形成金屬氧化物或金屬氫氧化物。 (陽極之第一層之形成) (塗佈步驟) 第一層20係將溶解有釕、銥及鈦中之至少一種金屬之鹽的溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之釕、銥及鈦之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材100後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (第二層之形成) 第二層30係視需要而形成,例如將含有鈀化合物及鉑化合物之溶液或含有釕化合物及鈦化合物之溶液(第二塗佈液)塗佈於第一層20上後,於氧氣之存在下進行熱分解而獲得。 (利用熱分解法之陰極之第一層之形成) (塗佈步驟) 第一層20係將溶解有各種組合之金屬鹽之溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之金屬之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材10後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (中間層之形成) 中間層係視需要而形成,例如將含有鈀化合物或鉑化合物之溶液(第二塗佈液)塗佈於基材上後,於氧氣之存在下進行熱分解而獲得。或者,亦可不塗佈溶液,而僅加熱基材,藉此於基材表面形成氧化鎳中間層。 (利用離子鍍敷之陰極之第一層之形成) 第一層20亦可藉由離子鍍敷而形成。 作為一例,可列舉將基材固定於腔室內並對金屬釕靶照射電子束之方法。所蒸發之金屬釕粒子於腔室內之電漿中帶正電,而沈積於帶負電之基板上。電漿環境為氬氣、氧氣,釕係以釕氧化物之形式沈積於基材上。 (利用鍍覆之陰極之第一層之形成) 第一層20亦可藉由鍍覆法而形成。 作為一例,若使用基材作為陰極,於含有鎳及錫之電解液中實施電解鍍覆,則可形成鎳與錫之合金鍍覆。 (利用熱熔射之陰極之第一層之形成) 第一層20亦可藉由熱熔射法而形成。 作為一例,藉由將氧化鎳粒子電漿熔射於基材上,而可形成混合有金屬鎳與氧化鎳之觸媒層。 本實施形態中之電解用電極能夠與離子交換膜或微多孔膜等隔膜進行一體化而使用。因此,本實施形態之積層體可用作膜一體電極,無需更新電極時之陰極及陽極之更換貼附作業,作業效率大幅提高。 又,藉由與離子交換膜或微多孔膜等隔膜之一體電極,能夠使電解性能與新品時之性能相同或有所提高。 以下,對離子交換膜進行詳細說明。 [離子交換膜] 作為離子交換膜,只要可與電解用電極製成積層體,則無特別限定,可應用各種離子交換膜。於本實施形態中,較佳為使用具有含有具有離子交換基之烴系聚合物或含氟系聚合物之膜本體、與設置於該膜本體之至少一面上之塗佈層之離子交換膜。又,塗佈層含有無機物粒子與結合劑,塗佈層之比表面積較佳為0.1~10 m2 /g。該結構之離子交換膜於電解中所產生之氣體對電解性能之影響較少,有發揮出穩定之電解性能之傾向。 上述所謂導入有離子交換基之全氟碳聚合物之膜係具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層之任一者。就強度及尺寸穩定性之觀點而言,較佳為進而具有強化芯材。 以下於塗佈層之說明之欄對無機物粒子及結合劑進行詳細說明。 圖44係表示離子交換膜之一實施形態之剖面模式圖。離子交換膜1具有:膜本體10,其含有具有離子交換基之烴系聚合物或含氟系聚合物;以及塗佈層11a及11b,其等形成於膜本體10之兩面。 於離子交換膜1中,膜本體10具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層3、與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層2,藉由強化芯材4強化強度及尺寸穩定性。離子交換膜1由於具備磺酸層3與羧酸層2,因此可作為陽離子交換膜而適宜地使用。 再者,離子交換膜亦可僅具有磺酸層及羧酸層之任一者。又,離子交換膜未必由強化芯材所強化,強化芯材之配置狀態亦不限定於圖44之例。 (膜本體) 首先,對構成離子交換膜1之膜本體10進行說明。 膜本體10只要為具有使陽離子選擇性地透過之功能且含有具有離子交換基之烴系聚合物或含氟系聚合物者即可,其構成或材料並無特別限定,可適當選擇適宜者。 膜本體10中之具有離子交換基之烴系聚合物或含氟系聚合物例如可由具有可藉由水解等成為離子交換基之離子交換基前驅物之烴系聚合物或含氟系聚合物獲得。具體而言,例如使用主鏈包含氟化烴、具有可藉由水解等轉換為離子交換基之基(離子交換基前驅物)作為懸垂側鏈且能夠熔融加工之聚合物(以下視情形稱為「含氟系聚合物(a)」)製作膜本體10之前驅物後,將離子交換基前驅物轉換為離子交換基,藉此可獲得膜本體10。 含氟系聚合物(a)例如可藉由使選自下述第1群之至少一種單體與選自下述第2群及/或下述第3群之至少一種單體進行共聚合而製造。又,亦可藉由選自下述第1群、下述第2群、及下述第3群之任一群之1種單體之均聚而製造。 作為第1群之單體,例如可列舉氟乙烯化合物。作為氟乙烯化合物,例如可列舉:氟乙烯、四氟乙烯、六氟丙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、全氟烷基乙烯醚等。尤其是於將離子交換膜用作鹼電解用膜之情形時,氟乙烯化合物較佳為全氟單體,較佳為選自由四氟乙烯、六氟丙烯、全氟烷基乙烯醚所組成之群中之全氟單體。 作為第2群之單體,例如可列舉具有可轉換為羧酸型離子交換基(羧酸基)之官能基之乙烯系化合物。作為具有可轉換為羧酸基之官能基之乙烯系化合物,例如可列舉以CF2 =CF(OCF2 CYF)s -O(CZF)t -COOR表示之單體等(此處,s表示0~2之整數,t表示1~12之整數,Y及Z各自獨立地表示F或CF3 ,R表示低級烷基。低級烷基例如為碳數1~3之烷基)。 該等中,較佳為以CF2 =CF(OCF2 CYF)n -O(CF2 )m -COOR表示之化合物。此處,n表示0~2之整數,m表示1~4之整數,Y表示F或CF3 ,R表示CH3 、C2 H5 、或C3 H7 。 再者,於將離子交換膜用作鹼電解用陽離子交換膜之情形時,較佳為至少使用全氟化合物作為單體,但由於酯基之烷基(參照上述R)於水解時從聚合物喪失,因此烷基(R)亦可不為全部氫原子被取代為氟原子之全氟烷基。 作為第2群之單體,於上述中,更佳為下述所表示之單體。 CF2 =CFOCF2 -CF(CF3 )OCF2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )2 COOCH3 、 CF2 =CF[OCF2 -CF(CF3 )]2 O(CF2 )2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )3 COOCH3 、 CF2 =CFO(CF2 )2 COOCH3 、 CF2 =CFO(CF2 )3 COOCH3 。 作為第3群之單體,例如可列舉具有可轉換為磺酸型離子交換基(磺酸基)之官能基之乙烯系化合物。作為具有可轉換為磺酸基之官能基之乙烯系化合物,例如較佳為以CF2 =CFO-X-CF2 -SO2 F表示之單體(此處,X表示全氟伸烷基)。作為該等之具體例,可列舉下述所表示之單體等。 CF2 =CFOCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、 CF2 =CF(CF2 )2 SO2 F、 CF2 =CFO[CF2 CF(CF3 )O]2 CF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF2 OCF3 )OCF2 CF2 SO2 F。 該等中,更佳為CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、及CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F。 由該等單體獲得之共聚物可藉由針對氟乙烯之均聚及共聚合所開發之聚合法、尤其是對四氟乙烯所使用之通常之聚合方法而製造。例如,於非水性法中,可使用全氟烴、氯氟碳等不活性溶劑,於全氟碳過氧化物或偶氮化合物等自由基聚合起始劑之存在下,於溫度0~200℃、壓力0.1~20 MPa之條件下進行聚合反應。 於上述共聚合中,上述單體之組合之種類及其比率並無特別限定,根據欲對所獲得之含氟系聚合物賦予之官能基之種類及量選擇確定。例如於製成僅含有羧酸基之含氟系聚合物之情形時,從上述第1群及第2群分別選擇至少1種單體進行共聚合即可。又,於製成僅含有磺酸基之含氟系聚合物之情形時,從上述第1群及第3群之單體中分別選擇至少1種單體進行共聚合即可。進而,於製成具有羧酸基及磺酸基之含氟系聚合物之情形時,從上述第1群、第2群及第3群之單體中分別選擇至少1種單體進行共聚合即可。於該情形時,藉由使包含上述第1群及第2群之共聚物與包含上述第1群及第3群之共聚物分開進行聚合,其後加以混合亦可獲得目標之含氟系聚合物。又,各單體之混合比率並無特別限定,於增加每單位聚合物之官能基之量之情形時,增加選自上述第2群及第3群之單體之比率即可。 含氟系共聚物之總離子交換容量並無特別限定,較佳為0.5~2.0 mg當量/g,更佳為0.6~1.5 mg當量/g。此處,所謂總離子交換容量係指相對於單位重量之乾燥樹脂之交換基之當量,可藉由中和滴定等進行測定。 於離子交換膜1之膜本體10中,積層有含有具有磺酸基之含氟系聚合物之磺酸層3與含有具有羧酸基之含氟系聚合物之羧酸層2。藉由製成此種層結構之膜本體10,能夠進一步提高鈉離子等陽離子之選擇性透過性。 於將離子交換膜1配置於電解槽之情形時,通常以磺酸層3位於電解槽之陽極側、羧酸層2位於電解槽之陰極側之方式配置。 磺酸層3較佳為由電阻較低之材料構成,就膜強度之觀點而言,較佳為其膜厚厚於羧酸層2。磺酸層3之膜厚較佳為羧酸層2之2~25倍,更佳為3~15倍。 羧酸層2較佳為即使膜厚較薄亦具有較高之陰離子排斥性者。此處所謂陰離子排斥性係指阻礙陰離子對離子交換膜1之滲入或透過之性質。為了提高陰離子排斥性,有效的是對磺酸層配置離子交換容量較小之羧酸層等。 作為磺酸層3所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F作為第3群之單體所獲得之聚合物。 作為羧酸層2所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF2 )O(CF2 )2 COOCH3 作為第2群之單體所獲得之聚合物。 (塗佈層) 離子交換膜較佳為於膜本體之至少一面上具有塗佈層。又,如圖44所示,於離子交換膜1中,於膜本體10之兩面上分別形成有塗佈層11a及11b。 塗佈層含有無機物粒子與結合劑。 無機物粒子之平均粒徑更佳為0.90 μm以上。若無機物粒子之平均粒徑為0.90 μm以上,則不僅極大地提高對氣體附著之耐久性,而且極大地提高對雜質之耐久性。即,藉由增大無機物粒子之平均粒徑,並且滿足上述比表面積之值,可獲得尤其顯著之效果。為了滿足此種平均粒徑與比表面積,較佳為不規則狀之無機物粒子。可使用藉由熔融獲得之無機物粒子、藉由原石粉碎獲得之無機物粒子。較佳可適宜地使用藉由原石粉碎獲得之無機物粒子。 又,無機物粒子之平均粒徑可設為2 μm以下。若無機物粒子之平均粒徑為2 μm以下,則能夠防止因無機物粒子而損傷膜。無機物粒子之平均粒徑更佳為0.90~1.2 μm。 此處,平均粒徑可藉由粒度分佈計(「SALD2200」島津製作所)進行測定。 無機物粒子之形狀較佳為不規則形狀。對雜質之耐性進一步提高。又,無機物粒子之粒度分佈較佳為較寬。 無機物粒子較佳為含有選自由週期表第IV族元素之氧化物、週期表第IV族元素之氮化物、及週期表第IV族元素之碳化物所組成之群中之至少一種無機物。就耐久性之觀點而言,更佳為氧化鋯之粒子。 該無機物粒子較佳為藉由將無機物粒子之原石粉碎所製造之無機物粒子,或以藉由將無機物粒子之原石熔融並加以精製而粒子之直徑一致之球狀之粒子作為無機物粒子。 作為原石粉碎方法,並無特別限定,可列舉:球磨機、珠磨機、膠體磨機、錐形磨機、盤磨機、輪輾機、磨粉機、錘磨機、造粒機、VSI磨機、威利磨機、輥磨機、噴射磨機等。又,較佳為粉碎後將其洗淨,作為此時之洗淨方法,較佳為酸處理。藉此,能夠減少附著於無機物粒子之表面之鐵等雜質。 塗佈層較佳為含有結合劑。結合劑係將無機物粒子保持於離子交換膜之表面、形成塗佈層之成分。就對電解液或電解之產物之耐性之觀點而言,結合劑較佳為含有含氟系聚合物。 作為結合劑,就對電解液或電解之產物之耐性、及對離子交換膜之表面之接著性之觀點而言,更佳為具有羧酸基或磺酸基之含氟系聚合物。於在含有具有磺酸基之含氟聚合物之層(磺酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有磺酸基之含氟系聚合物。又,於在含有具有羧酸基之含氟聚合物之層(羧酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有羧酸基之含氟系聚合物。 塗佈層中,無機物粒子之含量較佳為40~90質量%,更佳為50~90質量%。又,結合劑之含量較佳為10~60質量%,更佳為10~50質量%。 離子交換膜中之塗佈層之分佈密度較佳為每1 cm2 為0.05~2 mg。又,於離子交換膜於表面具有凹凸形狀之情形時,塗佈層之分佈密度較佳為每1 cm2 為0.5~2 mg。 作為形成塗佈層之方法,並無特別限定,可使用公知之方法。例如可列舉藉由噴射等塗佈將無機物粒子分散於含有結合劑之溶液中而成之塗佈液之方法。 (強化芯材) 離子交換膜較佳為具有配置於膜本體之內部之強化芯材。 強化芯材係強化離子交換膜之強度或尺寸穩定性之構件。藉由將強化芯材配置於膜本體之內部,尤其能夠將離子交換膜之伸縮控制為所需之範圍。該離子交換膜於電解時等不會伸縮為必要程度以上,而能夠長期維持優異之尺寸穩定性。 強化芯材之構成並無特別限定,例如可將稱為強化紗之紗進行紡紗而形成。此處所謂強化紗係構成強化芯材之構件,指能夠對離子交換膜賦予所需之尺寸穩定性及機械強度且於離子交換膜中能夠穩定地存在之紗。藉由使用將該強化紗紡紗而成之強化芯材,能夠對離子交換膜賦予更優異之尺寸穩定性及機械強度。 強化芯材及其所使用之強化紗之材料並無特別限定,較佳為對酸或鹼等具有耐性之材料,就需要長期之耐熱性、耐化學品性之方面而言,較佳為包含含氟系聚合物之纖維。 作為強化芯材所使用之含氟系聚合物,例如可列舉:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、四氟乙烯-六氟丙烯共聚物、三氟氯乙烯-乙烯共聚物及偏二氟乙烯聚合物(PVDF)等。該等中,尤其是就耐熱性及耐化學品性之觀點而言,較佳為使用包含聚四氟乙烯之纖維。 強化芯材所使用之強化紗之紗直徑並無特別限定,較佳為20~300丹尼,更佳為50~250丹尼。紡織密度(每單位長度之織入根數)較佳為5~50根/英吋。作為強化芯材之形態,並無特別限定,例如可使用織布、不織布、針織布等,較佳為織布之形態。又,使用織布之厚度較佳為30~250 μm、更佳為30~150 μm者。 織布或針織布可使用單絲、複絲或該等之紗線、切膜絲等,紡織方法可使用平織、紗羅組織、針織、凸條組織、縐條紋薄織等各種紡織方法。 膜本體中之強化芯材之紡織方法及配置並無特別限定,可考慮離子交換膜之大小或形狀、離子交換膜所需之物性及使用環境等適當設為適宜之配置。 例如,可沿膜本體之特定之一方向配置強化芯材,就尺寸穩定性之觀點而言,較佳為沿特定之第一方向配置強化芯材,且沿大致垂直於第一方向之第二方向配置其他強化芯材。藉由在膜本體之縱向膜本體之內部以大致成一列之方式配置複數個強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。例如,較佳為於膜本體之表面織入沿縱向配置之強化芯材(縱紗)與沿橫向配置之強化芯材(橫紗)之配置。就尺寸穩定性、機械強度及製造容易性之觀點而言,更佳為製成使縱紗與橫紗一上一下交替織入而紡織之平紋織物、或一邊撚轉2根經紗一邊與橫紗交織之紗羅組織物、於每2根或數根並紗配置之縱紗中織入相同數量之橫紗而紡織之斜紋織物(twill weave)等。 尤佳為沿離子交換膜之MD方向(縱向(Machine Direction)方向)及TD方向(橫向(Transverse Direction)方向)之兩方向配置強化芯材。即,較佳為沿MD方向與TD方向平織。此處,所謂MD方向係指於下文所述之離子交換膜之製造步驟中搬送膜本體或各種芯材(例如,強化芯材、強化紗、下文所述之犧牲紗等)之方向(行進方向),所謂TD方向係指大致垂直於MD方向之方向。此外,將沿MD方向紡織之紗稱為MD紗,將沿TD方向紡織之紗稱為TD紗。通常電解所使用之離子交換膜係矩形,長度方向為MD方向、寬度方向為TD方向之情況較多。藉由織入作為MD紗之強化芯材與作為TD紗之強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。 強化芯材之配置間隔並無特別限定,可考慮離子交換膜所需之物性及使用環境等適當設為適宜之配置。 強化芯材之開口率並無特別限定,較佳為30%以上,更佳為50%以上且90%以下。開口率就離子交換膜之電化學性質之觀點而言,較佳為30%以上,就離子交換膜之機械強度之觀點而言,較佳為90%以下。 所謂強化芯材之開口率係指膜本體之任一表面之面積(A)中離子等物質(電解液及其所含之陽離子(例如,鈉離子))能夠通過之表面之總面積(B)之比率(B/A)。所謂離子等物質能夠通過之表面之總面積(B)可指於離子交換膜中陽離子或電解液等不被離子交換膜所含之強化芯材等阻斷之區域之總面積。 圖45係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。圖45係將離子交換膜之一部分放大而僅圖示該區域內之強化芯材21及22之配置,其他構件省略圖示。 藉由從由沿縱向配置之強化芯材21與沿橫向配置之強化芯材22所圍成之亦包括強化芯材之面積在內之區域的面積(A)減去強化芯材之總面積(C),可求出上述區域之面積(A)中離子等物質能夠通過之區域之總面積(B)。即,開口率可藉由下述式(I)求出。 開口率=(B)/(A)=((A)-(C))/(A) …(I) 於強化芯材中,就耐化學品性及耐熱性之觀點而言,尤佳之形態係含有PTFE之帶狀紗線或高配向單絲。具體而言,更佳為如下強化芯材,其係使用將包含PTFE之高強度多孔質片材切為帶狀而成之帶狀紗線、或包含PTFE之高度配向之單絲之50~300丹尼且紡織密度為10~50根/英吋之平紋織物,其厚度為50~100 μm之範圍。含有該強化芯材之離子交換膜之開口率進而較佳為60%以上。 作為強化紗之形狀,可列舉圓紗、帶狀紗等。 (連通孔) 離子交換膜較佳為於膜本體之內部具有連通孔。 所謂連通孔係指能夠成為電解時產生之離子或電解液之流路之孔。又,所謂連通孔係形成於膜本體內部之管狀之孔,藉由下文所述之犧牲芯材(或犧牲紗)溶出而形成。連通孔之形狀或直徑等可藉由選擇犧牲芯材(犧牲紗)之形狀或直徑進行控制。 藉由在離子交換膜形成連通孔,於電解時能夠確保電解液之移動性。連通孔之形狀並無特別限定,根據下文所述之製法,可製成連通孔之形成所使用之犧牲芯材之形狀。 連通孔較佳為以交替通過強化芯材之陽極側(磺酸層側)與陰極側(羧酸層側)之方式形成。藉由設為該結構,於強化芯材之陰極側形成有連通孔之部分,通過充滿連通孔之電解液所輸送之離子(例如,鈉離子)亦能夠流至強化芯材之陰極側。其結果為,由於陽離子之流動未被遮蔽,因此能夠進一步降低離子交換膜之電阻。 連通孔可僅沿構成離子交換膜之膜本體之特定之一方向形成,就發揮出更穩定之電解性能之觀點而言,較佳為沿膜本體之縱向與橫向之兩方向形成。 [製造方法] 作為離子交換膜之適宜之製造方法,可列舉具有以下之(1)步驟~(6)步驟之方法。 (1)步驟:製造具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之含氟系聚合物之步驟。 (2)步驟:藉由視需要至少織入複數個強化芯材與具有溶於酸或鹼之性質且形成連通孔之犧牲紗而獲得於鄰接之強化芯材彼此之間配置有犧牲紗之補強材之步驟。 (3)步驟:將具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之上述含氟系聚合物進行膜化之步驟。 (4)步驟:視需要將上述補強材埋入至上述膜中而獲得內部配置有上述補強材之膜本體之步驟。 (5)步驟:將(4)步驟中獲得之膜本體進行水解之步驟(水解步驟)。 (6)步驟:於(5)步驟中獲得之膜本體設置塗佈層之步驟(塗佈步驟)。 以下,對各步驟進行詳細說明。 (1)步驟:製造含氟系聚合物之步驟 於(1)步驟中,使用上述第1群~第3群所記載之原料之單體製造含氟系聚合物。為了控制含氟系聚合物之離子交換容量,於形成各層之含氟系聚合物之製造中調整原料之單體之混合比即可。 (2)步驟:補強材之製造步驟 所謂補強材係紡織強化紗之織布等。藉由將補強材埋入至膜內而形成強化芯材。於製成具有連通孔之離子交換膜時,亦將犧牲紗一起織入至補強材中。該情形時之犧牲紗之混織量較佳為補強材整體之10~80質量%,更佳為30~70質量%。藉由織入犧牲紗,亦能夠防止強化芯材之脫線。 犧牲紗係於膜之製造步驟或電解環境下具有溶解性者,可使用嫘縈、聚對苯二甲酸乙二酯(PET)、纖維素及聚醯胺等。又,亦較佳為具有20~50丹尼之粗細程度、包含單絲或複絲之聚乙烯醇等。 再者,於(2)步驟中,可藉由調整強化芯材或犧牲紗之配置而控制開口率或連通孔之配置等。 (3)步驟:膜化步驟 於(3)步驟中,使用擠出機將上述(1)步驟中獲得之含氟系聚合物進行膜化。膜可為單層結構,亦可如上所述為磺酸層與羧酸層之2層結構,亦可為3層以上之多層結構。 作為膜化之方法,例如可列舉以下者。 分別將具有羧酸基之含氟聚合物、具有磺酸基之含氟聚合物分開進行膜化之方法。 藉由共擠出將具有羧酸基之含氟聚合物與具有磺酸基之含氟聚合物製成複合膜之方法。 再者,膜可分別為複數片。又,將異種之膜共擠出有助於提高界面之接著強度,故而較佳。 (4)步驟:獲得膜本體之步驟 於(4)步驟中,藉由將(2)步驟中獲得之補強材埋入至(3)步驟中獲得之膜之內部,而獲得內有補強材之膜本體。 作為膜本體之較佳之形成方法,可列舉:(i)藉由共擠出法將位於陰極側之具有羧酸基前驅物(例如,羧酸酯官能基)之含氟系聚合物(以下將包含其之層稱為第一層)與具有磺酸基前驅物(例如,磺醯氟官能基)之含氟系聚合物(以下將包含其之層稱為第二層)進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將補強材、第二層/第一層複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法;(ii)區別於第二層/第一層複合膜,預先將具有磺酸基前驅物之含氟系聚合物(第三層)單獨進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將第三層膜、強化芯材、包含第二層/第一層之複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法。 此處,將第一層與第二層共擠出有助於提高界面之接著強度。 又,於減壓下進行一體化之方法與加壓壓製法相比,具有補強材上之第三層之厚度變大之特徵。進而,由於將補強材固定於膜本體之內面,因此具有能夠充分保持離子交換膜之機械強度之性能。 再者,此處所說明之積層之變化係一例,可考慮所需之膜本體之層構成或物性等,適當選擇適宜之積層圖案(例如,各層之組合等)後進行共擠出。 再者,為了進一步提高離子交換膜之電性能,亦可於第一層與第二層之間進一步介置包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層,或使用包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層代替第二層。 第四層之形成方法可為分開製造具有羧酸基前驅物之含氟系聚合物與具有磺酸基前驅物之含氟系聚合物後加以混合之方法,亦可為使用將具有羧酸基前驅物之單體與具有磺酸基前驅物之單體共聚合而成者之方法。 於將第四層製成離子交換膜之構成之情形時,可將第一層與第四層之共擠出膜加以成形,第三層及第二層與其分開單獨進行膜化,藉由上文所述之方法進行積層,亦可將第一層/第四層/第二層之3層一次共擠出而進行膜化。 於該情形時,所擠出之膜行進之方向為MD方向。由此可將含有具有離子交換基之含氟系聚合物之膜本體形成於補強材上。 又,離子交換膜較佳為於包含磺酸層之表面側具有包含具有磺酸基之含氟聚合物之突出的部分、即凸部。作為形成此種凸部之方法,並無特別限定,可採用於樹脂表面形成凸部之公知之方法。具體而言,例如可列舉對膜本體之表面實施壓紋加工之方法。例如,於將上述複合膜與補強材等進行一體化時,藉由使用預先經壓紋加工之脫模紙,可形成上述凸部。於藉由壓紋加工形成凸部之情形時,凸部之高度或配置密度之控制可藉由控制所轉印之壓紋形狀(脫模紙之形狀)而進行。 (5)水解步驟 於(5)步驟中,進行將(4)步驟中獲得之膜本體水解而將離子交換基前驅物轉換為離子交換基之步驟(水解步驟)。 又,於(5)步驟中,藉由利用酸或鹼將膜本體所含之犧牲紗溶解去除,可於膜本體形成溶出孔。再者,犧牲紗亦可不完全溶解去除,而殘留於連通孔中。又,殘留於連通孔中之犧牲紗可於將離子交換膜供於電解時藉由電解液溶解去除。 犧牲紗係於離子交換膜之製造步驟或電解環境下對酸或鹼具有溶解性者,藉由使犧牲紗溶出而於該部位形成連通孔。 (5)步驟可將(4)步驟中獲得之膜本體浸漬於含有酸或鹼之水解溶液中進行。作為該水解溶液,例如可使用含有KOH與DMSO(Dimethyl sulfoxide)之混合溶液。 該混合溶液較佳為含有2.5~4.0 N之KOH,且含有25~35質量%之DMSO。 作為水解之溫度,較佳為70~100℃。溫度越高,可使視厚度更厚。更佳為75~100℃。 作為水解之時間,較佳為10~120分鐘。時間越長,可使視厚度更厚。更佳為20~120分鐘。 此處,對藉由溶出犧牲紗而形成連通孔之步驟進一步詳細地說明。圖46(a)、(b)係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 於圖46(a)、(b)中,僅圖示強化紗52、犧牲紗504a及由犧牲紗504a形成之連通孔504,膜本體等其他構件省略圖示。 首先,將於離子交換膜中構成強化芯材之強化紗52與於離子交換膜中用以形成連通孔504之犧牲紗504a製成針織織入補強材。然後,於(5)步驟中藉由使犧牲紗504a溶出而形成連通孔504。 藉由上述方法,根據於離子交換膜之膜本體內如何配置強化芯材、連通孔而調整強化紗52與犧牲紗504a之針織織入方法即可,因此較簡便。 於圖46(a)中,例示於紙面沿縱向與橫向之兩方向將強化紗52與犧牲紗504a織入之平織之補強材,可視需要變更補強材中之強化紗52與犧牲紗504a之配置。 (6)塗佈步驟 於(6)步驟中,製備含有藉由原石粉碎或原石熔融獲得之無機物粒子與結合劑之塗佈液,將塗佈液塗佈於(5)步驟中獲得之離子交換膜之表面並加以乾燥,藉此可形成塗佈層。 作為結合劑,較佳為將具有離子交換基前驅物之含氟系聚合物水解於含有二甲基亞碸(DMSO)及氫氧化鉀(KOH)之水溶液中之後,浸漬於鹽酸中將離子交換基之抗衡離子置換為H+ 而成之結合劑(例如,具有羧基或磺基之含氟系聚合物)。藉此,變得容易溶解於下文所述之水或乙醇中,故而較佳。 將該結合劑溶解於混合水與乙醇而成之溶液中。再者,水與乙醇之較佳之體積比為10:1~1:10,更佳為5:1~1:5,進而較佳為2:1~1:2。藉由球磨機使無機物粒子分散於由此獲得之溶解液中而獲得塗佈液。此時,亦可藉由調整分散時之時間、旋轉速度而調整粒子之平均粒徑等。再者,無機物粒子與結合劑之較佳之調配量如上文所述。 塗佈液中之無機物粒子及結合劑之濃度並無特別限定,較佳為製成稀薄之塗佈液。藉此,能夠均勻地塗佈於離子交換膜之表面。 又,於使無機物粒子分散時,亦可將界面活性劑添加於分散液中。作為界面活性劑,較佳為非離子系界面活性劑,例如可列舉日油股份有限公司製造之HS-210、NS-210、P-210、E-212等。 藉由利用噴射塗佈或滾筒塗敷將所獲得之塗佈液塗佈於離子交換膜表面而可獲得離子交換膜。 [微多孔膜] 作為本實施形態之微多孔膜,只要如上文所述,可與電解用電極製成積層體,則無特別限定,可應用各種微多孔膜。 本實施形態之微多孔膜之氣孔率並無特別限定,例如可設為20~90,較佳為30~85。上述氣孔率例如可藉由下述之式算出。 氣孔率=(1-(乾燥狀態之膜重量)/(由根據膜之厚度、寬度、長度算出之體積與膜素材之密度所算出之重量))×100 本實施形態之微多孔膜之平均孔徑並無特別限定,例如可設為0.01 μm~10 μ,較佳為0.05 μm~5 μm。上述平均孔徑例如係沿厚度方向將膜垂直切斷,藉由FE-SEM觀察切斷面。對所觀察之孔之直徑測定100點左右並求出平均值,藉此可求出平均孔徑。 本實施形態之微多孔膜之厚度並無特別限定,例如可設為10 μm~1000 μm,較佳為50 μm~600 μm。上述厚度例如可使用測微計(Mitutoyo股份有限公司製造)等進行測定。 作為如上所述之微多孔膜之具體例,可列舉Agfa公司製造之Zirfon Perl UTP 500(於本實施形態中亦稱為Zirfon膜)、國際公開第2013-183584號說明書、國際公開第2016-203701號說明書等所記載者。 於本實施形態中,較佳為隔膜包含第1離子交換樹脂層、及具有與該第1離子交換樹脂層不同之EW(離子交換當量)之第2離子交換樹脂層。又,較佳為隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之官能基之第2離子交換樹脂層。離子交換當量可藉由所導入之官能基進行調整,關於可導入之官能基係如上文所述。 [固定區域] 於本實施形態中,電解用電極係固定於隔膜之表面之至少一區域,於<第3實施形態>之項中,亦將該1個或2個以上之區域稱為固定區域。本實施形態中之固定區域只要為具有抑制電解用電極與隔膜之分離之功能、且將電解用電極固定於隔膜之部分,則無特別限定,例如,亦存在藉由電解用電極本身成為固定機構而構成固定區域之情形,又,亦存在藉由與電解用電極不同體之固定用構件成為固定機構而構成固定區域之情形。再者,本實施形態中之固定區域可僅存在於與電解時之通電面相對應之位置,亦可延伸至與非通電面相對應之位置。再者,「通電面」與以於陽極室與陰極室之間進行電解質之移動之方式設計之部分相對應。又,所謂「非通電面」意指通電面以外之部分。 進而,於本實施形態中,隔膜之表面中之固定區域之比率(以下亦簡稱為「比率α」)超過0%且未達93%。上述比率可作為固定區域之面積(以下亦簡稱為「面積S3」)相對於隔膜之表面之面積(以下亦簡稱為「面積S1」)的比率而求出。於本實施形態中,所謂「隔膜之表面」意指隔膜所具有之表面中電解用電極所存在之側之表面。再者,於上述隔膜之表面中,未由電解用電極覆蓋之部分之面積亦算作面積S1。 就作為隔膜與電解用電極之積層體而更穩定之觀點而言,上述比率α(=100×S3/S1)超過0%,較佳為0.00000001%以上,更佳為0.0000001%以上。另一方面,如先前技術中所存在般,於藉由熱壓接等方法將隔膜與電極之接觸面之整個面牢固地接著之情形時(即,上述比率成為100%之情形時),成為電極中之接觸面之整個面嵌入隔膜之狀態而物理性地接著。此種接著部分會妨礙鈉離子之膜內之移動,電壓大幅地上升。於本實施形態中,就充分確保離子可自由移動之空間之觀點而言,上述比率未達93%,較佳為90%以下,更佳為70%以下,進而較佳為未達60%。於本實施形態中,就獲得更良好之電解性能之觀點而言,較佳為對固定區域之面積(面積S3)中僅與通電面相對應之部分之面積(以下亦簡稱為「面積S3'」)進行調整。即,較佳為對面積S3'相對於通電面之面積(以下亦簡稱為「面積S2」)之比率(以下亦簡稱為「比率β」)進行調整。再者,面積S2可作為電解用電極之表面積而特定出(下文對詳細內容進行說明)。具體而言,於本實施形態中,比率β(=100×S3'/S2)較佳為超過0%且未達100%,更佳為0.0000001%以上且未達83%,進而較佳為0.000001%以上且70%以下,進而更佳為0.00001%以上且25%以下。 上述比率α及β例如可以如下方式進行測定。 首先,算出隔膜之表面之面積S1。其次,算出電解用電極之面積S2。此處,面積S1及S2可作為從電解用電極側觀察隔膜與電解用電極之積層體時(參照圖57)之面積而特定出。 再者,電解用電極之形狀並無特別限定,可具有開孔,於形狀為網狀等具有開孔者且(i)開孔率未達90%之情形時,關於S2,其開孔部分亦算入面積S2中,另一方面,於形狀為網狀等具有開孔者且(ii)開孔率為90%以上之情形時,為了充分確保電解性能,而以去除該開孔部分之面積算出S2。此處所謂開孔率係電解用電極中之開孔部分之合計面積S'除以將該開孔部分算入面積中所獲得之電解用電極中之面積S''所獲得之數值(%,100×S'/S'')。 下文對固定區域之面積(面積S3及面積S3')進行說明。 如上所述,隔膜之表面中之上述區域之比率α(%)可藉由算出100×(S3/S1)而求出。又,作為僅與固定區域之通電面相對應之部分之面積相對於通電面之面積之比率β(%),可藉由算出100×(S3'/S2)而求出。 更具體而言,可藉由下文所述之實施例所記載之方法進行測定。以上述方式特定出之隔膜之表面之面積S1並無特別限定,較佳為通電面之面積S2之1倍以上且5倍以下,更佳為1倍以上且4倍以下,進而較佳為1倍以上且3倍以下。 於本實施形態中,並非對固定區域中之固定結構進行限定,但例如可採用以下所例示之固定結構。再者,各固定結構可僅採用1種,亦可組合2種以上而採用。 於本實施形態中,較佳為於固定區域中電解用電極之至少一部分貫通隔膜而被固定。使用圖47A對該態樣進行說明。 於圖47A中,電解用電極2之至少一部分貫通隔膜3而被固定。如圖47A所示,電解用電極2之一部分為貫通隔膜3之狀態。於圖47A中,係示出電解用電極2為金屬多孔電極之例。即,於圖47A中將複數個電解用電極2之部分獨立表示,但該等相連而表示一體之金屬多孔電極之剖面(於以下之圖48~51中亦相同)。 於此種電極結構下,例如若將特定位置(應成為固定區域之位置)之隔膜3壓抵於電解用電極2,則隔膜3之一部分進入至電解用電極2之表面之凹凸結構內或孔結構內,電極表面之凹部或孔之周圍之凸部分貫通隔膜3,較佳為如圖47A所示,穿透至隔膜3之外表面3b。 如上所述,圖47A之固定結構可藉由將隔膜3壓抵於電解用電極2而製造,於該情形時,於藉由加溫使隔膜3軟化之狀態下進行熱壓接、熱抽吸。藉此,電解用電極2將隔膜3貫通。或者,亦可於將隔膜3熔融之狀態下進行。於該情形時,較佳為於圖47B所示之狀態下從電解用電極2之外表面2b側(背面側)抽吸隔膜3。再者,將隔膜3壓抵於電解用電極2之區域構成「固定區域」。 圖47A所示之固定結構可藉由放大鏡(loupe)、光學顯微鏡或電子顯微鏡進行觀察。又,藉由電解用電極2將隔膜3貫通,利用隔膜3之外表面3b與電解用電極2之外表面2b之間的使用測試機等之導通檢查,可推測出圖47A之固定結構。 於圖47A中,較佳為由隔膜隔開之陽極室、陰極室之電解液不會透過貫通部。因此,較佳為貫通之部分之孔徑小至電解液不會透過之程度。具體而言,較佳為於實施電解試驗時發揮出與不具有貫通部之隔膜相同之性能。或者,較佳為對貫通之部分實施防止電解液之透過之加工。較佳為貫通之部分使用不會因陽極室電解液、陽極室中產生之產物、陰極室電解液、陰極室中產生之產物而溶出、分解之材料。例如較佳為EPDM、氟系之樹脂。更佳為具有離子交換基之氟樹脂。於本實施形態中,較佳為於固定區域中電解用電極之至少一部分位於隔膜之內部而被固定。使用圖48A對該態樣進行說明。 如上所述,電解用電極2之表面被設為凹凸結構或孔結構。於圖48A所示之實施形態中,電極表面之一部分插入並被固定於特定位置(應成為固定區域之位置)之隔膜3。圖48A所示之固定結構可藉由將隔膜3壓抵於電解用電極2而製造。於該情形時,較佳為於藉由加溫使隔膜3軟化之狀態下進行熱壓接、熱抽吸而形成圖48A之固定結構。或者,亦可將隔膜3熔融而形成圖48A之固定結構。於該情形時,較佳為從電解用電極2之外表面2b側(背面側)抽吸隔膜3。 圖48A所示之固定結構可藉由放大鏡(loupe)、光學顯微鏡或電子顯微鏡進行觀察。較佳為尤其是對樣品進行包埋處理後藉由切片機製作剖面並進行觀察之方法。再者,於圖48A所示之固定結構中,由於電解用電極2未貫通隔膜3,因此並不確認隔膜3之外表面3b與電解用電極2之外表面2b之間的利用導通檢查之導通。 於本實施形態中,較佳為進一步具有用以將隔膜與電解用電極加以固定之固定用構件。使用圖49A~C對該態樣進行說明。 圖49A所示之固定結構係使用與電解用電極2及隔膜3不同體之固定用構件7,且固定用構件7將電解用電極2與隔膜3貫通而加以固定之結構。電解用電極2未必一定被固定用構件7所貫通,以不與隔膜2分離之方式藉由固定用構件7進行固定即可。固定用構件7之材質並無特別限定,作為固定用構件7,例如可使用包含金屬或樹脂等者。於金屬之情形時,可列舉鎳、鎳鉻合金、鈦、不鏽鋼(SUS)等。亦可為該等之氧化物。作為樹脂,可使用氟樹脂(例如,PTFE(聚四氟乙烯)、PFA(四氟乙烯與全氟烷氧基乙烯之共聚物)、ETFE(四氟乙烯與乙烯之共聚物)或下述所記載之隔膜3之材質)或PVDF(聚偏二氟乙烯)、EPDM(乙烯-丙烯-二烯橡膠)、PP(聚乙烯)、PE(聚丙烯)、尼龍、芳香族聚醯胺等。 於本實施形態中,例如使用紗狀之固定用構件(紗狀之金屬或樹脂),如圖49B、49C所示般對電解用電極2與隔膜3之外表面2b、3b間之特定位置(應成為固定區域之位置)進行縫製,藉此亦可進行固定。作為紗狀之樹脂,並無特別限定,例如可列舉PTFE之紗等。又,亦可使用如活褶縫製器(tucker)之固定機構將電解用電極2與隔膜3加以固定。 於圖49A~C中,較佳為由隔膜隔開之陽極室、陰極室之電解液不會透過貫通部。因此,較佳為貫通之部分之孔徑小至電解液不會透過之程度。具體而言,較佳為於實施電解試驗時發揮出與不具有貫通部之隔膜相同之性能。或者,較佳為對貫通之部分實施防止電解液之透過之加工。較佳為貫通之部分使用不會因陽極室電解液、陽極室中產生之產物、陰極室電解液、陰極室中產生之產物而溶出、分解之材料。例如較佳為EPDM、氟系之樹脂。更佳為具有離子交換基之氟樹脂。 圖50所示之固定結構係於電解用電極2與隔膜3之間介置有機樹脂(接著層)進行固定之結構。即,於圖50中係將作為固定用構件7之有機樹脂配置於電解用電極2與隔膜3之間之特定位置(應成為固定區域之位置)而藉由接著進行固定之結構。例如,於電解用電極2之內表面2a、或隔膜3之內表面3a、或電解用電極2及隔膜3之內表面2a、3a之兩者或其中一者塗佈有機樹脂。然後,將電解用電極2與隔膜3貼合,藉此可形成圖50所示之固定結構。有機樹脂之材質並無特別限定,例如可使用氟樹脂(例如,PTFE、PFA、ETFE)、或與上文所述之構成隔膜3之材料相同之樹脂等。又,亦可適當地使用市售之氟系接著劑、PTFE分散液等。進而,亦可使用通用之乙酸乙烯酯系接著劑、乙烯-乙酸乙烯酯共聚合系接著劑、丙烯酸系樹脂系接著劑、α-烯烴系接著劑、苯乙烯丁二烯橡膠系乳膠接著劑、氯乙烯樹脂系接著劑、氯丁二烯系接著劑、腈橡膠系接著劑、胺基甲酸酯橡膠系接著劑、環氧系接著劑、聚矽氧樹脂系接著劑、改性聚矽氧系接著劑、環氧-改性聚矽氧樹脂系接著劑、矽烷化胺基甲酸酯樹脂系接著劑、氰基丙烯酸酯系接著劑等。 於本實施形態中,可使用溶於電解液或於電解中溶解、分解之有機樹脂。作為溶於電解液或於電解中溶解、分解之有機樹脂,並不限定於以下,例如可列舉:乙酸乙烯酯系接著劑、乙烯-乙酸乙烯酯共聚合系接著劑、丙烯酸系樹脂系接著劑、α-烯烴系接著劑、苯乙烯丁二烯橡膠系乳膠接著劑、氯乙烯樹脂系接著劑、氯丁二烯系接著劑、腈橡膠系接著劑、胺基甲酸酯橡膠系接著劑、環氧系接著劑、聚矽氧樹脂系接著劑、改性聚矽氧系接著劑、環氧-改性聚矽氧樹脂系接著劑、矽烷化胺基甲酸酯樹脂系接著劑、氰基丙烯酸酯系接著劑等。 圖50所示之固定結構可藉由光學顯微鏡或電子顯微鏡進行觀察。較佳為尤其是對樣品進行包埋處理後藉由切片機製作剖面並進行觀察之方法。 於本實施形態中,較佳為固定用構件之至少一部分從外部將隔膜與電解用電極固持。使用圖51A對該態樣進行說明。 圖51A所示之固定結構係從外部將電解用電極2與隔膜3固持並加以固定之結構。即,藉由作為固定用構件7之固持構件將電解用電極2之外表面2b與隔膜3之外表面3b之間夾持並固定。於圖51A所示之固定結構中,亦包括固持構件陷入電解用電極2或隔膜3之狀態。作為固持構件,例如可列舉膠帶、夾具等。 於本實施形態中,亦可使用溶於電解液之固持構件。作為溶於電解液之固持構件,例如可列舉PET製之膠帶、夾具、PVA(polyvinyl alcohol,聚乙烯醇)製之膠帶、夾具等。 圖51A所示之固定結構與圖47~圖50不同,並非將電解用電極2與隔膜3之界面接合者,電解用電極2與隔膜3之各內表面2a、3a僅處於接觸或相對向之狀態,藉由去除固持構件,可將電解用電極2與隔膜3之固定狀態加以解除而分離。 圖51A並未示出,但亦可使用固持構件將電解用電極2與隔膜3固定於電解池。 例如可以回折PTFE製之膠帶夾住隔膜與電極之方式進行固定。 又,於本實施形態中,較佳為固定用構件之至少一部分藉由磁力將隔膜與電解用電極進行固定。使用圖51B對該態樣進行說明。 圖51B所示之固定結構係從外部將電解用電極2與隔膜3固持並加以固定之結構。與圖51A之區別在於使用1對磁石作為用作固定用構件之固持構件之方面。於圖51B所示之固定結構之態樣中,於將積層體1安裝於電解槽後,於電解槽運轉時可將固持構件直接殘留,亦可將其從積層體1去除。 圖51B並未示出,但亦可使用固持構件將電解用電極2與隔膜3固定於電解池。又,於電解池之材質之一部分使用與磁石接著之磁性材料之情形時,亦可將1種固持材料設置於隔膜面側,將電解池、電解用電極2及隔膜3夾住而固定。 再者,亦可設置複數列固定區域。即,可從積層體1之輪廓側起朝向內側配置1、2、3、…n條固定區域。n為1以上之整數。又,第m號(m<n)固定區域與第L號(m<L≦n)固定區域可藉由不同之固定圖案形成。 形成於通電部之固定區域較佳為線對稱之形狀。藉此,有能夠抑制應力集中之傾向。例如,若將正交之2個方向設為X方向與Y方向,則可於X方向與Y方向之各方向各配置1條、或於X方向與Y方向之各方向等間隔地各配置複數條而構成固定區域。並非對X方向及Y方向之固定區域之條數進行限定,但較佳為於X方向及Y方向分別設為100條以下。又,就確保通電部之面性之觀點而言,X方向及Y方向之固定區域之條數宜分別為50條以下。 於本實施形態中之固定區域中,於具有圖47A或圖49所示之固定結構之情形時,就防止由陽極與陰極接觸引起之短路之觀點而言,較佳為於固定區域之膜面上塗佈密封材。作為密封材,例如可使用上述接著劑中所說明之素材。 於使用固定用構件之情形時,於求面積S3及面積S3'時,關於該固定用構件重複之部分,並不將重複量算入面積S3及面積S3'中。例如,於將上文所述之PTFE紗作為固定用構件進行固定時,PTFE紗彼此交叉之部分作為重複量而不算入面積中。又,於將上文所述之PTFE膠帶作為固定用構件進行固定時,PTFE膠帶彼此重疊之部分作為重複量而不算入面積中。 又,於將上文所述之PTFE紗或接著劑作為固定用構件進行固定之情形時,存在於電解用電極及/或隔膜之背面側之面積亦算入面積S3及面積S3'中。 本實施形態中之積層體可如上所述,於各種位置具有各種固定區域,但較佳為尤其是於不存在固定區域之部分(非固定區域),電解用電極滿足上述「承受力」。即,較佳為電解用電極之非固定區域中之每單位質量·單位面積所承受之力未達1.5 N/mg・cm2 。 [電解槽] 本實施形態之電解槽包含本實施形態之積層體。以下,以使用離子交換膜作為隔膜進行食鹽電解之情形為例,對電解槽之一實施形態進行詳細說明。 [電解池] 圖52係電解池1之剖面圖。 電解池1具備陽極室10、陰極室20、設置於陽極室10及陰極室20之間之間隔壁30、設置於陽極室10之陽極11、及設置於陰極室20之陰極21。視需要亦可具備具有基材18a與形成於該基材18a上之逆向電流吸收層18b且設置於陰極室內之逆向電流吸收體18。屬於1個電解池1之陽極11及陰極21互相電性連接。換言之,電解池1具備如下陰極結構體。陰極結構體40具備陰極室20、設置於陰極室20之陰極21、及設置於陰極室20內之逆向電流吸收體18,逆向電流吸收體18如圖56所示具有基材18a與形成於該基材18a上之逆向電流吸收層18b,陰極21與逆向電流吸收層18b電性連接。陰極室20進而具有集電體23、支持該集電體之支持體24、及金屬彈性體22。金屬彈性體22係設置於集電體23及陰極21之間。支持體24係設置於集電體23及間隔壁30之間。集電體23經由金屬彈性體22而與陰極21電性連接。間隔壁30經由支持體24而與集電體23電性連接。因此,間隔壁30、支持體24、集電體23、金屬彈性體22及陰極21係電性連接。陰極21及逆向電流吸收層18b係電性連接。陰極21及逆向電流吸收層可直接連接,亦可經由集電體、支持體、金屬彈性體或間隔壁等而間接連接。陰極21之表面整體較佳為由用於還原反應之觸媒層所被覆。又,電性連接之形態可為分別直接將間隔壁30與支持體24、支持體24與集電體23、集電體23與金屬彈性體22安裝,並且於金屬彈性體22上積層陰極21之形態。作為將該等各構成構件互相直接安裝之方法,可列舉焊接等。又,亦可將逆向電流吸收體18、陰極21、及集電體23總稱為陰極結構體40。 圖53係電解槽4內鄰接之2個電解池1之剖面圖。圖54表示電解槽4。圖55表示組裝電解槽4之步驟。如圖53所示,將電解池1、陽離子交換膜2、電解池1依序串聯排列。於電解槽內鄰接之2個電解池中之一電解池1之陽極室與另一電解池1之陰極室之間配置離子交換膜2。即,電解池1之陽極室10及與其鄰接之電解池1之陰極室20係由陽離子交換膜2隔開。如圖54所示,電解槽4包含介隔離子交換膜2而串聯連接之複數個電解池1。即,電解槽4係具備串聯配置之複數個電解池1、及配置於鄰接之電解池1之間之離子交換膜2的複極式電解槽。如圖55所示,電解槽4係藉由介隔離子交換膜2將複數個電解池1串聯配置並利用壓製器5連結而組裝。 電解槽4具有連接於電源之陽極端子7與陰極端子6。於電解槽4內串聯連結之複數個電解池1中位於最靠端之電解池1之陽極11係電性連接於陽極端子7。於電解槽4內串聯連結之複數個電解池2中位於陽極端子7之相反側之端之電解池的陰極21係電性連接於陰極端子6。電解時之電流從陽極端子7側起,經過各電解池1之陽極及陰極而流向陰極端子6。再者,可於連結之電解池1之兩端配置僅具有陽極室之電解池(陽極終端池)與僅具有陰極室之電解池(陰極終端池)。於該情形時,將陽極端子7連接於配置於其一端之陽極終端池,將陰極端子6連接於配置於另一端之陰極終端池。 於進行鹽水之電解之情形時,向各陽極室10供給鹽水,向陰極室20供給純水或低濃度之氫氧化鈉水溶液。各液體係從電解液供給管(圖中省略)起,經過電解液供給軟管(圖中省略)而向各電解池1供給。又,電解液及電解之產物係由電解液回收管(圖中省略)所回收。於電解中,鹽水中之鈉離子從一電解池1之陽極室10起,通過離子交換膜2,向旁邊之電解池1之陰極室20移動。由此電解中之電流沿將電解池1串聯連結之方向流通。即,電流係經由陽離子交換膜2而從陽極室10流向陰極室20。伴隨鹽水之電解,於陽極11側產生氯氣,於陰極21側產生氫氧化鈉(溶質)與氫氣。 (陽極室) 陽極室10具有陽極11或陽極饋電體11。於將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極饋電體發揮功能。於不將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極發揮功能。又,陽極室10較佳為具有向陽極室10供給電解液之陽極側電解液供給部、配置於陽極側電解液供給部之上方且以與間隔壁30大致平行或傾斜之方式配置之擋板、及配置於擋板之上方且從混入有氣體之電解液中分離氣體之陽極側氣液分離部。 (陽極) 於不將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極11。作為陽極11,可使用所謂DSA(註冊商標)等金屬電極。所謂DSA係藉由以釕、銥、鈦作為成分之氧化物被覆表面之鈦基材之電極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極饋電體) 於將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極饋電體11。作為陽極饋電體11,可使用所謂DSA(註冊商標)等金屬電極,亦可使用未形成有觸媒塗層之鈦。又,亦可使用使觸媒塗層厚度變薄之DSA。進而,亦可使用使用過之陽極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極側電解液供給部) 陽極側電解液供給部係向陽極室10供給電解液者,其連接於電解液供給管。陽極側電解液供給部較佳為配置於陽極室10之下方。作為陽極側電解液供給部,例如可使用表面形成有開口部之管(分散管)等。該管更佳為以沿陽極11之表面平行於電解池之底部19之方式配置。該管係連接於向電解池1內供給電解液之電解液供給管(液供給噴嘴)。從液供給噴嘴供給之電解液藉由管被搬送至電解池1內,從設置於管之表面之開口部向陽極室10之內部供給。藉由將管以沿陽極11之表面平行於電解池之底部19之方式配置,能夠將電解液均勻地供給至陽極室10之內部,故而較佳。 (陽極側氣液分離部) 陽極側氣液分離部較佳為配置於擋板之上方。於電解中,陽極側氣液分離部具有將氯氣等產生氣體與電解液分離之功能。再者,只要無特別說明,則所謂上方意指圖52之電解池1中之上方向,所謂下方意指圖52之電解池1中之下方向。 電解時,若電解池1中產生之產生氣體與電解液成為混相(氣液混相)而被排出至系外,則存在因電解池1內部之壓力變動導致產生振動而引起離子交換膜之物理破損之情形。為了抑制該情形,較佳為於本實施形態中之電解池1中設置用以將氣體與液體分離之陽極側氣液分離部。較佳為於陽極側氣液分離部設置用以消除氣泡之消泡板。藉由在氣液混相流通過消泡板時氣泡破裂,而可分離為電解液與氣體。其結果為,能夠防止電解時之振動。 (擋板) 擋板較佳為配置於陽極側電解液供給部之上方,且以與間隔壁30大致平行或傾斜之方式配置。擋板係控制陽極室10之電解液之流動之間隔板。藉由設置擋板,可使電解液(鹽水等)於陽極室10內部循環,使其濃度變得均勻。為了引起內部循環,擋板較佳為以將陽極11附近之空間與間隔壁30附近之空間隔開之方式配置。就該觀點而言,擋板較佳為以與陽極11及間隔壁30之各表面相對向之方式設置。於由擋板分隔之陽極附近之空間,藉由進行電解,電解液濃度(鹽水濃度)降低,又,產生氯氣等產生氣體。藉此,於由擋板分隔之陽極11附近之空間與間隔壁30附近之空間產生氣液之比重差。利用該情況,能夠促進陽極室10中之電解液之內部循環,使陽極室10之電解液之濃度分佈變得更均勻。 再者,於圖52並未圖示,但亦可於陽極室10之內部另行設置集電體。作為該集電體,亦可設為與下文所述之陰極室之集電體相同之材料或構成。又,於陽極室10中,亦可使陽極11本身作為集電體發揮功能。 (間隔壁) 間隔壁30係配置於陽極室10與陰極室20之間。間隔壁30有時亦稱為間隔件,係將陽極室10與陰極室20進行劃分者。作為間隔壁30,可使用作為電解用之間隔件所公知者,例如可列舉於陰極側焊接包含鎳之板、於陽極側焊接包含鈦之板之間隔壁等。 (陰極室) 陰極室20於將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極饋電體發揮功能,於不將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極發揮功能。於具有逆向電流吸收體之情形時,陰極或陰極饋電體21與逆向電流吸收體係電性連接。又,陰極室20較佳為與陽極室10同樣,亦具有陰極側電解液供給部、陰極側氣液分離部。再者,構成陰極室20之各部位中,關於與構成陽極室10之各部位相同者省略說明。 (陰極) 於不將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極21。陰極21較佳為具有鎳基材與被覆鎳基材之觸媒層。作為鎳基材上之觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可視需要對陰極21實施還原處理。再者,作為陰極21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陰極饋電體) 於將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極饋電體21。可對陰極饋電體21被覆觸媒成分。該觸媒成分可為原本用作陰極而殘存者。作為觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可使用未形成有觸媒塗層之鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。再者,作為陰極饋電體21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (逆向電流吸收層) 可選擇具有較上文所述之陰極之觸媒層用元素的氧化還原電位更低之氧化還原電位之材料作為逆向電流吸收層之材料。例如可列舉鎳或鐵等。 (集電體) 陰極室20較佳為具備集電體23。藉此,集電效果提高。於本實施形態中,集電體23較佳為多孔板,且以與陰極21之表面大致平行之方式配置。 作為集電體23,例如較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。集電體23可為該等金屬之混合物、合金或複合氧化物。再者,集電體23之形狀只要為作為集電體發揮功能之形狀,則可為任意形狀,可為板狀、網狀。 (金屬彈性體) 藉由在集電體23與陰極21之間設置金屬彈性體22,將串聯連接之複數個電解池1之各陰極21壓抵於離子交換膜2,各陽極11與各陰極21之間之距離變短,可降低對串聯連接之複數個電解池1整體施加之電壓。藉由電壓降低,可降低消耗電量。又,藉由設置金屬彈性體22,於將含有本實施形態之電解用電極之積層體設置於電解池時,藉由金屬彈性體22之壓抵壓,可將該電解用電極穩定地維持於起始位置。 作為金屬彈性體22,可使用螺旋彈簧、線圈等彈簧構件、緩衝性之墊等。作為金屬彈性體22,可考慮壓抵離子交換膜之應力等而適當採用適宜者。可將金屬彈性體22設置於陰極室20側之集電體23之表面上,亦可設置於陽極室10側之間隔壁之表面上。通常以陰極室20小於陽極室10之方式劃分兩室,因此就框體之強度等觀點而言,較佳為將金屬彈性體22設置於陰極室20之集電體23與陰極21之間。又,金屬彈性體23較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。 (支持體) 陰極室20較佳為具備將集電體23與間隔壁30電性連接之支持體24。藉此,能夠效率良好地流通電流。 支持體24較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。又,作為支持體24之形狀,只要為能夠支持集電體23之形狀,則可為任意形狀,可為棒狀、板狀或網狀。支持體24例如為板狀。複數個支持體24係配置於間隔壁30與集電體23之間。複數個支持體24係以各自之面互相平行之方式排列。支持體24係以大致垂直於間隔壁30及集電體23之方式配置。 (陽極側墊片、陰極側墊片) 陽極側墊片較佳為配置於構成陽極室10之框體表面。陰極側墊片較佳為配置於構成陰極室20之框體表面。1個電解池所具備之陽極側墊片及與其鄰接之電解池之陰極側墊片以夾持離子交換膜2之方式將電解池彼此連接(參照圖52、53)。藉由該等墊片,於介隔離子交換膜2將複數個電解池1串聯連接時,能夠對連接處賦予氣密性。 所謂墊片係將離子交換膜與電解池之間密封者。作為墊片之具體例,可列舉中央形成有開口部之邊框狀之橡膠製片等。對於墊片要求對腐蝕性之電解液或所產生之氣體等具有耐性而可長期使用。因此,就耐化學品性或硬度之方面而言,通常可使用乙烯-丙烯-二烯橡膠(EPDM橡膠)、乙烯-丙烯橡膠(EPM橡膠)之硫化物或過氧化物交聯物等作為墊片。又,視需要亦可使用以聚四氟乙烯(PTFE)或四氟乙烯-全氟烷基乙烯醚共聚物(PFA)等氟系樹脂被覆與液體相接之區域(接液部)之墊片。該等墊片只要以不妨礙電解液之流動之方式分別具有開口部即可,其形狀並無特別限定。例如沿構成陽極室10之陽極室框或構成陰極室20之陰極室框之各開口部之周緣,藉由接著劑等貼附邊框狀之墊片。此外,於例如介隔離子交換膜2連接2個電解池1之情形時(參照圖53),介隔離子交換膜2將貼附有墊片之各電解池1緊固即可。藉此,能夠抑制電解液、因電解而產生之鹼金屬氫氧化物、氯氣、氫氣等漏至電解池1之外部之情況。 (離子交換膜2) 作為離子交換膜2,如上述離子交換膜之項所記載。 (水電解) 本實施形態之進行水電解之情形時之電解槽係具有將上述進行食鹽電解之情形時之電解槽中之離子交換膜變更為微多孔膜之構成者。又,於所供給之原料為水之方面與上述進行食鹽電解之情形時之電解槽不同。關於其他構成,進行水電解之情形時之電解槽亦可採用與進行食鹽電解之情形時之電解槽相同之構成。於食鹽電解之情形時,由於在陽極室產生氯氣,因此陽極室之材質使用鈦,於水電解之情形時,由於在陽極室僅產生氧氣,因此可使用與陰極室之材質相同者。例如可列舉鎳等。又,陽極塗層適宜為產生氧氣用之觸媒塗層。作為觸媒塗層之例,可列舉鉑族金屬及過渡金屬族之金屬、氧化物、氫氧化物等。例如可使用鉑、銥、鈀、釕、鎳、鈷、鐵等元素。 <第4實施形態> 此處,一邊參照圖63~90一邊對本發明之第4實施形態進行詳細地說明。 [電解槽] 第4實施形態(以下於<第4實施形態>之項中簡稱為「本實施形態」)之電解槽具備陽極、支持上述陽極之陽極框、配置於上述陽極框上之陽極側墊片、與上述陽極相對向之陰極、支持上述陰極之陰極框、配置於上述陰極框上且與上述陽極側墊片相對向之陰極側墊片、配置於上述陽極側墊片與上述陰極側墊片之間之隔膜與電解用電極之積層體,且上述積層體之至少一部分由上述陽極側墊片及上述陰極側墊片所夾持,將上述電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時之通氣阻力為24 kPa・s/m以下。由於以上述方式構成,因此本實施形態之電解槽之電解性能優異並且能夠防止隔膜之損傷。 本實施形態之電解槽係包含上述構成構件者,換言之,係包含電解池者。以下,以使用離子交換膜作為隔膜進行食鹽電解之情形為例,對電解槽之一實施形態進行詳細說明。 [電解池] 首先,對可用作本實施形態之電解槽之構成單元的電解池進行說明。圖63係電解池1之剖面圖。 電解池1具備陽極室10、陰極室20、設置於陽極室10及陰極室20之間之間隔壁30、設置於陽極室10之陽極11、及設置於陰極室20之陰極21。視需要亦可具備具有基材18a與形成於該基材18a上之逆向電流吸收層18b且設置於陰極室內之逆向電流吸收體18。屬於1個電解池1之陽極11及陰極21互相電性連接。換言之,電解池1具備如下陰極結構體。陰極結構體40具備陰極室20、設置於陰極室20之陰極21、及設置於陰極室20內之逆向電流吸收體18,逆向電流吸收體18如圖67所示具有基材18a與形成於該基材18a上之逆向電流吸收層18b,陰極21與逆向電流吸收層18b電性連接。陰極室20進而具有集電體23、支持該集電體之支持體24、及金屬彈性體22。金屬彈性體22係設置於集電體23及陰極21之間。支持體24係設置於集電體23及間隔壁30之間。集電體23經由金屬彈性體22而與陰極21電性連接。間隔壁30經由支持體24而與集電體23電性連接。因此,間隔壁30、支持體24、集電體23、金屬彈性體22及陰極21係電性連接。陰極21及逆向電流吸收層18b係電性連接。陰極21及逆向電流吸收層可直接連接,亦可經由集電體、支持體、金屬彈性體或間隔壁等而間接連接。陰極21之表面整體較佳為由用於還原反應之觸媒層所被覆。又,電性連接之形態可為分別直接將間隔壁30與支持體24、支持體24與集電體23、集電體23與金屬彈性體22安裝,並且於金屬彈性體22上積層陰極21之形態。作為將該等各構成構件互相直接安裝之方法,可列舉焊接等。又,亦可將逆向電流吸收體18、陰極21、及集電體23總稱為陰極結構體40。 圖64係電解槽4內鄰接之2個電解池1之剖面圖。圖65表示電解槽4。圖66表示組裝電解槽4之步驟。 於先前之電解槽中,如圖64A所示,將電解池1、隔膜(此處為陽離子交換膜)2、電解池1依序串聯排列,於電解槽內鄰接之2個電解池中之一電解池1之陽極室與另一電解池1之陰極室之間配置離子交換膜2。即,於電解槽中,通常電解池1之陽極室10及與其鄰接之電解池1之陰極室20係由陽離子交換膜2隔開。 另一方面,於本實施形態中,如圖64B所示,將電解池1、具有隔膜(此處為陽離子交換膜)2與電解用電極(此處為更新用陰極)21a之積層體25、電解池1依序串聯排列,積層體25於其一部分(圖64B中為上端部)中係被夾持於陽極墊片12及陰極墊片13之間。 又,如圖65所示,電解槽4包含介隔離子交換膜2而串聯連接之複數個電解池1。即,電解槽4係具備串聯配置之複數個電解池1、及配置於鄰接之電解池1之間之離子交換膜2的複極式電解槽。如圖66所示,電解槽4係藉由介隔離子交換膜2將複數個電解池1串聯配置並利用壓製器5連結而組裝。 電解槽4具有連接於電源之陽極端子7與陰極端子6。於電解槽4內串聯連結之複數個電解池1中位於最靠端之電解池1之陽極11係電性連接於陽極端子7。於電解槽4內串聯連結之複數個電解池2中位於陽極端子7之相反側之端之電解池的陰極21係電性連接於陰極端子6。電解時之電流從陽極端子7側起,經過各電解池1之陽極及陰極而流向陰極端子6。再者,可於連結之電解池1之兩端配置僅具有陽極室之電解池(陽極終端池)與僅具有陰極室之電解池(陰極終端池)。於該情形時,將陽極端子7連接於配置於其一端之陽極終端池,將陰極端子6連接於配置於另一端之陰極終端池。 於進行鹽水之電解之情形時,向各陽極室10供給鹽水,向陰極室20供給純水或低濃度之氫氧化鈉水溶液。各液體係從電解液供給管(圖中省略)起,經過電解液供給軟管(圖中省略)而向各電解池1供給。又,電解液及電解之產物係由電解液回收管(圖中省略)所回收。於電解中,鹽水中之鈉離子從一電解池1之陽極室10起,通過離子交換膜2,向旁邊之電解池1之陰極室20移動。由此電解中之電流沿將電解池1串聯連結之方向流通。即,電流係經由陽離子交換膜2而從陽極室10流向陰極室20。伴隨鹽水之電解,於陽極11側產生氯氣,於陰極21側產生氫氧化鈉(溶質)與氫氣。 如上文所述,電解槽中之隔膜、陰極及陽極通常伴隨電解槽之運轉,其性能會劣化,最終必須更換為新品,於僅更換隔膜之情形時,可藉由將既有之隔膜從電解池之間抽出並插入新隔膜而簡單地更新,但於藉由焊接進行陽極或陰極之更換之情形時,必需專用之設備,因此較繁雜。 另一方面,於本實施形態中,如上所述,積層體25於其一部分(圖64B中為上端部)中係被夾持於陽極墊片12及陰極墊片13之間。尤其是於圖64B所示之例中,隔膜(此處為陽離子交換膜)2與電解用電極(此處為更新用陰極)21a至少於該等之積層體之上端部可藉由對從陽極墊片12朝向積層體25之方向之按壓、及對從陰極墊片13朝向積層體25之方向之按壓進行固定。於該情形時,無需藉由焊接將積層體25(尤其是電解用電極)固定於既有之構件(例如既有陰極),故而較佳。即,於電解用電極及隔膜之兩者被陽極側墊片及上述陰極側墊片所夾持之情形時,有提高電解槽中之電極更新時之作業效率的傾向,故而較佳。 進而,根據本實施形態之電解槽之構成,隔膜與電解用電極以積層體之形式被充分固定,因此能夠獲得優異之電解性能。 (陽極室) 陽極室10具有陽極11或陽極饋電體11。作為此處所謂饋電體意指劣化之電極(即既有電極)或未形成有觸媒塗層之電極等。於將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極饋電體發揮功能。於不將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極發揮功能。又,陽極室10較佳為具有向陽極室10供給電解液之陽極側電解液供給部、配置於陽極側電解液供給部之上方且以與間隔壁30大致平行或傾斜之方式配置之擋板、及配置於擋板之上方且從混入有氣體之電解液中分離氣體之陽極側氣液分離部。 (陽極) 於不將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框(即,陽極框)內設置有陽極11。作為陽極11,可使用所謂DSA(註冊商標)等金屬電極。所謂DSA係藉由以釕、銥、鈦作為成分之氧化物被覆表面之鈦基材之電極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極饋電體) 於將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極饋電體11。作為陽極饋電體11,可使用所謂DSA(註冊商標)等金屬電極,亦可使用未形成有觸媒塗層之鈦。又,亦可使用使觸媒塗層厚度變薄之DSA。進而,亦可使用使用過之陽極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極側電解液供給部) 陽極側電解液供給部係向陽極室10供給電解液者,其連接於電解液供給管。陽極側電解液供給部較佳為配置於陽極室10之下方。作為陽極側電解液供給部,例如可使用表面形成有開口部之管(分散管)等。該管更佳為以沿陽極11之表面平行於電解池之底部19之方式配置。該管係連接於向電解池1內供給電解液之電解液供給管(液供給噴嘴)。從液供給噴嘴供給之電解液藉由管被搬送至電解池1內,從設置於管之表面之開口部向陽極室10之內部供給。藉由將管以沿陽極11之表面平行於電解池之底部19之方式配置,能夠將電解液均勻地供給至陽極室10之內部,故而較佳。 (陽極側氣液分離部) 陽極側氣液分離部較佳為配置於擋板之上方。於電解中,陽極側氣液分離部具有將氯氣等產生氣體與電解液分離之功能。再者,只要無特別說明,則所謂上方意指圖63之電解池1中之上方向,所謂下方意指圖63之電解池1中之下方向。 電解時,若電解池1中產生之產生氣體與電解液成為混相(氣液混相)而被排出至系外,則存在因電解池1內部之壓力變動導致產生振動而引起離子交換膜之物理破損之情形。為了抑制該情形,較佳為於本實施形態中之電解池1中設置用以將氣體與液體分離之陽極側氣液分離部。較佳為於陽極側氣液分離部設置用以消除氣泡之消泡板。藉由在氣液混相流通過消泡板時氣泡破裂,而可分離為電解液與氣體。其結果為,能夠防止電解時之振動。 (擋板) 擋板較佳為配置於陽極側電解液供給部之上方,且以與間隔壁30大致平行或傾斜之方式配置。擋板係控制陽極室10之電解液之流動之間隔板。藉由設置擋板,可使電解液(鹽水等)於陽極室10內部循環,使其濃度變得均勻。為了引起內部循環,擋板較佳為以將陽極11附近之空間與間隔壁30附近之空間隔開之方式配置。就該觀點而言,擋板較佳為以與陽極11及間隔壁30之各表面相對向之方式設置。於由擋板分隔之陽極附近之空間,藉由進行電解,電解液濃度(鹽水濃度)降低,又,產生氯氣等產生氣體。藉此,於由擋板分隔之陽極11附近之空間與間隔壁30附近之空間產生氣液之比重差。利用該情況,能夠促進陽極室10中之電解液之內部循環,使陽極室10之電解液之濃度分佈變得更均勻。 再者,於圖63並未圖示,但亦可於陽極室10之內部另行設置集電體。作為該集電體,亦可設為與下文所述之陰極室之集電體相同之材料或構成。又,於陽極室10中,亦可使陽極11本身作為集電體發揮功能。 (間隔壁) 間隔壁30係配置於陽極室10與陰極室20之間。間隔壁30有時亦稱為間隔件,係將陽極室10與陰極室20進行劃分者。作為間隔壁30,可使用作為電解用之間隔件所公知者,例如可列舉於陰極側焊接包含鎳之板、於陽極側焊接包含鈦之板之間隔壁等。 (陰極室) 陰極室20於將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極饋電體發揮功能,於不將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極發揮功能。於具有逆向電流吸收體之情形時,陰極或陰極饋電體21與逆向電流吸收體係電性連接。又,陰極室20較佳為與陽極室10同樣,亦具有陰極側電解液供給部、陰極側氣液分離部。再者,構成陰極室20之各部位中,關於與構成陽極室10之各部位相同者省略說明。 (陰極) 於不將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框(即,陰極框)內設置有陰極21。陰極21較佳為具有鎳基材與被覆鎳基材之觸媒層。作為鎳基材上之觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可視需要對陰極21實施還原處理。再者,作為陰極21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陰極饋電體) 於將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極饋電體21。可對陰極饋電體21被覆觸媒成分。該觸媒成分可為原本用作陰極而殘存者。作為觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可使用未形成有觸媒塗層之鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。再者,作為陰極饋電體21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (逆向電流吸收層) 可選擇具有較上文所述之陰極之觸媒層用元素的氧化還原電位更低之氧化還原電位之材料作為逆向電流吸收層之材料。例如可列舉鎳或鐵等。 (集電體) 陰極室20較佳為具備集電體23。藉此,集電效果提高。於本實施形態中,集電體23較佳為多孔板,且以與陰極21之表面大致平行之方式配置。 作為集電體23,例如較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。集電體23可為該等金屬之混合物、合金或複合氧化物。再者,集電體23之形狀只要為作為集電體發揮功能之形狀,則可為任意形狀,可為板狀、網狀。 (金屬彈性體) 藉由在集電體23與陰極21之間設置金屬彈性體22,將串聯連接之複數個電解池1之各陰極21壓抵於離子交換膜2,各陽極11與各陰極21之間之距離變短,可降低對串聯連接之複數個電解池1整體施加之電壓。藉由電壓降低,可降低消耗電量。又,藉由設置金屬彈性體22,於將含有本實施形態中之電解用電極之積層體設置於電解池時,藉由金屬彈性體22之壓抵壓,可將該電解用電極穩定地維持於起始位置。 作為金屬彈性體22,可使用螺旋彈簧、線圈等彈簧構件、緩衝性之墊等。作為金屬彈性體22,可考慮壓抵離子交換膜之應力等而適當採用適宜者。可將金屬彈性體22設置於陰極室20側之集電體23之表面上,亦可設置於陽極室10側之間隔壁之表面上。通常以陰極室20小於陽極室10之方式劃分兩室,因此就框體之強度等觀點而言,較佳為將金屬彈性體22設置於陰極室20之集電體23與陰極21之間。又,金屬彈性體23較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。 (支持體) 陰極室20較佳為具備將集電體23與間隔壁30電性連接之支持體24。藉此,能夠效率良好地流通電流。 支持體24較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。又,作為支持體24之形狀,只要為能夠支持集電體23之形狀,則可為任意形狀,可為棒狀、板狀或網狀。支持體24例如為板狀。複數個支持體24係配置於間隔壁30與集電體23之間。複數個支持體24係以各自之面互相平行之方式排列。支持體24係以大致垂直於間隔壁30及集電體23之方式配置。 (陽極側墊片、陰極側墊片) 陽極側墊片較佳為配置於構成陽極室10之框體表面。陰極側墊片較佳為配置於構成陰極室20之框體表面。1個電解池所具備之陽極側墊片及與其鄰接之電解池之陰極側墊片以夾持積層體25之方式將電解池彼此連接(參照圖64B)。藉由該等墊片,於介隔積層體25將複數個電解池1串聯連接時,能夠對連接處賦予氣密性。 所謂墊片係將離子交換膜與電解池之間密封者。作為墊片之具體例,可列舉中央形成有開口部之邊框狀之橡膠製片等。對於墊片要求對腐蝕性之電解液或所產生之氣體等具有耐性而可長期使用。因此,就耐化學品性或硬度之方面而言,通常可使用乙烯-丙烯-二烯橡膠(EPDM橡膠)、乙烯-丙烯橡膠(EPM橡膠)之硫化物或過氧化物交聯物等作為墊片。又,視需要亦可使用以聚四氟乙烯(PTFE)或四氟乙烯-全氟烷基乙烯醚共聚物(PFA)等氟系樹脂被覆與液體相接之區域(接液部)之墊片。該等墊片只要以不妨礙電解液之流動之方式分別具有開口部即可,其形狀並無特別限定。例如沿構成陽極室10之陽極室框或構成陰極室20之陰極室框之各開口部之周緣,藉由接著劑等貼附邊框狀之墊片。藉由以陽極墊片及陰極墊片夾持積層體25,能夠抑制電解液、因電解而產生之鹼金屬氫氧化物、氯氣、氫氣等漏至電解池1之外部之情況。 [積層體] 本實施形態中之積層體具有隔膜與電解用電極。本實施形態中之積層體能夠提高電解槽中之電極更新時之作業效率,進而更新後亦能夠表現出優異之電解性能。即,藉由本實施形態中之積層體,於更新電極時,無需伴隨剝離固定於電解池之既有電極等繁雜之作業,藉由如與隔膜之更新相同之簡單之作業即可更新電極,因此作業效率大幅提高。 進而,藉由本實施形態中之積層體,能夠將既有電解池之電解性能維持為與新品時之性能相同或有所提高。因此,固定於既有之電解池且作為陽極、陰極發揮功能之電極僅作為饋電體發揮功能即可,能夠大幅地減少觸媒塗層或者甚至無觸媒塗層。 [電解用電極] 本實施形態中之電解用電極於將該電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時(以下亦稱為「測定條件1」)之通氣阻力(以下亦稱為「通氣阻力1」)為24 kPa・s/m以下。通氣阻力較大意指空氣難以流動,指密度較高之狀態。於該狀態下,電解之產物停留於電極中,反應基質難以擴散至電極內部,因此電解性能(電壓等)變差。又,膜表面之濃度提高。具體而言,於陰極面苛性濃度提高,於陽極面鹽水之供給性降低。其結果為,由於產物以高濃度滯留於隔膜與電極相接之界面,因此導致隔膜之損傷,亦導致陰極面上之電壓上升及膜損傷、陽極面上之膜損傷。於本實施形態中,為了防止該等異常,而將通氣阻力設為24 kPa・s/m以下。 再者,於本實施形態中,若通氣阻力大至一定程度以上,則於陰極之情形時有電極中產生之NaOH滯留於電極與隔膜之界面而成為高濃度之傾向,於陽極之情形時有鹽水供給性降低而鹽水濃度成為低濃度之傾向,就將可能因此種滯留產生之對隔膜之損傷防患於未然之方面而言,較佳為未達0.19 kPa・s/m,更佳為0.15 kPa・s/m以下,進而較佳為0.07 kPa・s/m以下。 另一方面,於通氣阻力較低之情形時,由於電極之面積變小,因此通電面積變小而電解性能(電壓等)變差。於通氣阻力為零之情形時,由於未設置電解用電極,因此饋電體作為電極發揮功能而電解性能(電壓等)顯著變差。就該方面而言,作為通氣阻力1而特定出之較佳之下限值並無特別限定,較佳為超過0 kPa・s/m,更佳為0.0001 kPa・s/m以上,進而較佳為0.001 kPa・s/m以上。 再者,通氣阻力1就其測定法方面而言,若為0.07 kPa・s/m以下,則存在無法獲得充分之測定精度之情形。就該觀點而言,相對於通氣阻力1為0.07 kPa・s/m以下之電解用電極,亦可實現藉由以下之測定方法(以下亦稱為「測定條件2」)獲得之通氣阻力(以下亦稱為「通氣阻力2」)之評價。即,通氣阻力2係將電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度2 cm/s及通氣量4 cc/cm2 /s之情形時之通氣阻力。 具體之通氣阻力1及2之測定方法如實施例所記載。 上述通氣阻力1及2例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則有通氣阻力1及2變小之傾向,若減小開孔率,則有通氣阻力1及2變大之傾向。 本實施形態中之電解用電極就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、饋電體(劣化之電極及未形成有觸媒塗層之電極)等具有良好之接著力之觀點而言,每單位質量·單位面積所承受之力較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/mg・cm2 以上,進而更佳為0.14 N/(mg・cm2 )以上。就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.2 N/(mg・cm2 )以上。 上述承受力例如可藉由適當調整下文所述之開孔率、電極之厚度、算術平均表面粗糙度等而設為上述範圍。更具體而言,例如,若增大開孔率,則承受力有變小之傾向,若減小開孔率,則承受力有變大之傾向。 又,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力之觀點,進而就經濟性之觀點而言,較佳為每單位面積之質量為48 mg/cm2 以下,更佳為30 mg/cm2 以下,進而較佳為20 mg/cm2 以下,進而,就合併操作性、接著性及經濟性之綜合性之觀點而言,較佳為15 mg/cm2 以下。下限值並無特別限定,例如為1 mg/cm2 左右。 上述每單位面積之質量例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則每單位面積之質量有變小之傾向,若減小開孔率,則每單位面積之質量有變大之傾向。 承受力可藉由以下之方法(i)或(ii)進行測定,詳細而言,如實施例所記載。關於承受力,藉由方法(i)之測定所獲得之值(亦稱為「承受力(1)」)與藉由方法(ii)之測定所獲得之值(亦稱為「承受力(2)」)可相同亦可不同,但較佳為任一值均未達1.5 N/mg・cm2 。 [方法(i)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方)、於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方,關於此處所謂離子交換膜之詳細如實施例所記載)及電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。再者,噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.5~0.8 μm。算術平均表面粗糙度(Ra)之具體之算出方法如實施例所記載。 於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與離子交換膜之重疊部分之面積、及與離子交換膜重疊部分之電極樣品之質量,而算出每單位質量·單位面積所承受之力(1)(N/mg・cm2 )。 藉由方法(i)獲得之每單位質量·單位面積所承受之力(1)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。又,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 ),更佳為0.2 N/(mg・cm2 )以上。 [方法(ii)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方,與上述方法(i)相同之鎳板)與電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與鎳板之重疊部分之面積、及與鎳板重疊部分中之電極樣品之質量,而算出每單位質量•單位面積之接著力(2)(N/mg・cm2 )。 藉由方法(ii)獲得之每單位質量·單位面積所承受之力(2)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。進而,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 )以上。 本實施形態中之電解用電極較佳為包含電解用電極基材及觸媒層。該電解用電極基材之厚度(量規厚度)並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折,大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力之觀點而言,藉由以下之方法(2)所測得之比率較佳為90%以上,更佳為92%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為95%以上。上限值為100%。 [方法(2)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑280 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折之觀點而言,藉由以下之方法(3)所測得之比率較佳為75%以上,更佳為80%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為90%以上。上限值為100%。 [方法(3)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極就操作性之觀點而言,藉由以下之方法(A)所測得之值較佳為40 mm以下,更佳為29 mm以下,進而較佳為19 mm以下。 [方法(A)] 於溫度23±2℃、相對濕度30±5%之條件下,將積層於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方,關於此處所謂離子交換膜之詳細如實施例所記載)與上述電解用電極而成之樣品捲繞並固定於外徑f32 mm之氯乙烯製芯材之曲面上,靜置6小時後將該電解用電極分離並載置於水平之板,測定此時該電解用電極之兩端部之垂直方向之高度L1 及L2 ,以該等之平均值作為測定值。本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,防止電解中產生之氣體滯留之觀點而言,較佳為多孔結構,且其開孔率或空隙率為5~90%以下。開孔率更佳為10~80%以下,進而較佳為20~75%。 再者,所謂開孔率係每單位體積之開孔部之比率。開孔部亦根據考慮至次微米級抑或僅考慮目視可見之開口而有各種算出方法。於本實施形態中,藉由根據電極之量規厚度、寬度、長度之值算出體積V,進而對重量W進行實測,而利用下述之式算出開孔率A。 A=(1-(W/(V×ρ))×100 ρ係電極之材質之密度(g/cm3 )。例如於鎳之情形時為8.908 g/cm3 ,於鈦之情形時為4.506 g/cm3 。開孔率之調整可藉由如下方法進行適當調整:若為沖孔金屬,則變更每單位面積沖裁金屬之面積;若為多孔金屬,則變更SW(短徑)、LW(長徑)、進給之值;若為絲網,則變更金屬纖維之線徑、網眼數;若為電成形,則變更所使用之光阻之圖案;若為不織布,則變更金屬纖維直徑及纖維密度;若為發泡金屬,則變更用以使空隙形成之模板等。 以下,對本實施形態中之電解用電極之一形態進行說明。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。觸媒層如下所述,可包含複數層,亦可為單層結構。 如圖68所示,本實施形態之電解用電極100具備電解用電極基材10、及被覆電解用電極基材10之兩表面之一對第一層20。第一層20較佳為將電解用電極基材10整體被覆。藉此,電解用電極之觸媒活性及耐久性變得容易提高。再者,亦可僅於電解用電極基材10之一表面積層第一層20。 又,如圖68所示,第一層20之表面可由第二層30所被覆。第二層30較佳為將第一層20整體被覆。又,第二層30可僅積層於第一層20之一表面。 (電解用電極基材) 作為電解用電極基材10,並無特別限定,例如可使用鎳、鎳合金、不鏽鋼、或以鈦等為代表之閥金屬,較佳為含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 於在高濃度之鹼性水溶液中使用不鏽鋼之情形時,若考慮到鐵及鉻溶出、及不鏽鋼之導電性為鎳之1/10左右,則較佳為使用含有鎳(Ni)之基材作為電解用電極基材。 又,電解用電極基材10於在接近飽和之高濃度之食鹽水中於氯氣產生環境中使用之情形時,材質亦較佳為耐蝕性較高之鈦。 電解用電極基材10之形狀並無特別限定,可根據目的選擇合適之形狀。作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。其中,較佳為沖孔金屬或多孔金屬。再者,所謂電成形係將照相製版與電鍍法組合而製作精密之圖案之金屬薄膜的技術。其係藉由光阻於基板上形成圖案,對未受到光阻保護之部分實施電鍍而獲得金屬薄膜之方法。 關於電解用電極基材之形狀,根據電解槽中之陽極與陰極之距離而有適宜之規格。並無特別限定,於陽極與陰極具有有限之距離之情形時,可使用多孔金屬、沖孔金屬形狀,於離子交換膜與電極相接之所謂零間距電解槽之情形時,可使用編織細線而成之編織網、金屬絲網、發泡金屬、金屬不織布、多孔金屬、沖孔金屬、金屬多孔箔等。 作為電解用電極基材10,可列舉:金屬多孔箔、金屬絲網、金屬不織布、沖孔金屬、多孔金屬或發泡金屬。 作為加工為沖孔金屬、多孔金屬前之板材,較佳為經壓延成形之板材、電解箔等。電解箔較佳為進而作為後處理而藉由與母材相同之元素實施鍍覆處理,於單面或兩面形成凹凸。 又,電解用電極基材10之厚度如上文所述,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於電解用電極基材中,較佳為藉由在氧化環境中將電解用電極基材進行退火而緩和加工時之殘留應力。又,為了提高與被覆於電解用電極基材之表面之觸媒層之密接性,較佳為使用鋼砂、氧化鋁粉等於上述表面形成凹凸,其後藉由酸處理而增加表面積。或者,較佳為藉由與基材相同之元素實施鍍覆處理,增加表面積。 為了使第一層20與電解用電極基材10之表面密接,較佳為對電解用電極基材10進行增大表面積之處理。作為增大表面積之處理,可列舉使用鋼線粒、鋼砂、氧化鋁砂等之噴擊處理、使用硫酸或鹽酸之酸處理、利用與基材相同元素之鍍覆處理等。基材表面之算術平均表面粗糙度(Ra)並無特別限定,較佳為0.05 μm~50 μm,更佳為0.1~10 μm,進而較佳為0.1~8 μm。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陽極之情形進行說明。 (第一層) 於圖68中,作為觸媒層之第一層20含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物。作為釕氧化物,可列舉RuO2 等。作為銥氧化物,可列舉IrO2 等。作為鈦氧化物,可列舉TiO2 等。第一層20較佳為含有釕氧化物及鈦氧化物之兩種氧化物,或含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物。藉此,第一層20成為更穩定之層,進而,與第二層30之密接性亦進一步提高。 於第一層20含有釕氧化物及鈦氧化物之兩種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為1~9莫耳,更佳為1~4莫耳。藉由將兩種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之銥氧化物較佳為0.2~3莫耳,更佳為0.3~2.5莫耳。又,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為0.3~8莫耳,更佳為1~7莫耳。藉由將三種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有選自釕氧化物、銥氧化物及鈦氧化物中之至少兩種氧化物之情形時,該等氧化物較佳為形成固溶體。藉由形成氧化物固溶體,電解用電極100表現出優異之耐久性。 除了上述組成以外,只要含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物,則可使用各種組成者。例如,亦可使用稱為DSA(註冊商標)之含有釕、銥、鉭、鈮、鈦、錫、鈷、錳、鉑等之氧化物塗層作為第一層20。 第一層20無需為單層,亦可包含複數層。例如,第一層20可包含含有三種氧化物之層與含有兩種氧化物之層。第一層20之厚度較佳為0.05~10 μm,更佳為0.1~8 μm。 (第二層) 第二層30較佳為含有釕與鈦。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較佳為含有氧化鈀、氧化鈀與鉑之固溶體或鈀與鉑之合金。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較厚者能夠維持電解性能之時間變長,就經濟性之觀點而言,較佳為0.05~3 μm之厚度。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陰極之情形進行說明。 (第一層) 作為觸媒層之第一層20之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。 於含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少一種之情形時,較佳為鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金含有鉑、鈀、銠、釕、銥中之至少一種鉑族金屬。 作為鉑族金屬,較佳為含有鉑。 作為鉑族金屬氧化物,較佳為含有釕氧化物。 作為鉑族金屬氫氧化物,較佳為含有釕氫氧化物。 作為鉑族金屬合金,較佳為含有鉑與鎳、鐵、鈷之合金。 較佳為進而視需要含有鑭系元素之氧化物或氫氧化物作為第二成分。藉此,電解用電極100表現出優異之耐久性。 作為鑭系元素之氧化物或氫氧化物,較佳為含有選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑中之至少1種。 較佳為進而視需要含有過渡金屬之氧化物或氫氧化物作為第三成分。 藉由添加第三成分,電解用電極100能夠表現出更優異之耐久性,降低電解電壓。 作為較佳之組合之例,可列舉:僅釕、釕+鎳、釕+鈰、釕+鑭、釕+鑭+鉑、釕+鑭+鈀、釕+鐠、釕+鐠+鉑、釕+鐠+鉑+鈀、釕+釹、釕+釹+鉑、釕+釹+錳、釕+釹+鐵、釕+釹+鈷、釕+釹+鋅、釕+釹+鎵、釕+釹+硫、釕+釹+鉛、釕+釹+鎳、釕+釹+銅、釕+釤、釕+釤+錳、釕+釤+鐵、釕+釤+鈷、釕+釤+鋅、釕+釤+鎵、釕+釤+硫、釕+釤+鉛、釕+釤+鎳、鉑+鈰、鉑+鈀+鈰、鉑+鈀+鑭+鈰、鉑+銥、鉑+鈀、鉑+銥+鈀、鉑+鎳+鈀、鉑+鎳+釕、鉑與鎳之合金、鉑與鈷之合金、鉑與鐵之合金等。 於不含鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之情形時,觸媒之主成分較佳為鎳元素。 較佳為含有鎳金屬、氧化物、氫氧化物中之至少1種。 作為第二成分,可添加過渡金屬。作為所添加之第二成分,較佳為含有鈦、錫、鉬、鈷、錳、鐵、硫、鋅、銅、碳中之至少一種元素。 作為較佳之組合,可列舉:鎳+錫、鎳+鈦、鎳+鉬、鎳+鈷等。 視需要可於第一層20與電解用電極基材10之間設置中間層。藉由設置中間層,能夠提高電解用電極100之耐久性。 作為中間層,較佳為對第一層20與電解用電極基材10之兩者具有親和性者。作為中間層,較佳為鎳氧化物、鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物。作為中間層,可藉由將含有形成中間層之成分之溶液進行塗佈、燒成而形成,亦可於空氣環境中在300~600℃之溫度下對基材實施熱處理而形成表面氧化物層。除此以外,可藉由熱熔射法、離子鍍敷法等已知之方法形成。 (第二層) 作為觸媒層之第一層30之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。作為第二層所含之元素之較佳之組合例,有第一層中所列舉之組合等。第一層與第二層之組合可為組成相同而組成比不同之組合,亦可為組成不同之組合。 作為觸媒層之厚度,較佳為將所形成之觸媒層及中間層累加而成之厚度為0.01 μm~20 μm。若為0.01 μm以上,則能夠作為觸媒充分發揮功能。若為20 μm以下,則從基材脫落之情況較少,能夠形成牢固之觸媒層。更佳為0.05 μm~15 μm。更佳為0.1 μm~10 μm。進而較佳為0.2 μm~8 μm。 作為電極之厚度、即電解用電極基材與觸媒層之合計之厚度,就電極之操作性之方面而言,較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,電極之厚度可藉由利用電子數顯厚度計(Mitutoyo股份有限公司,最少顯示0.001 mm)進行測定而求出。電解用電極基材之厚度係與電極厚度同樣地進行測定。觸媒層厚度可藉由電極厚度減去電解用電極基材之厚度而求出。 於本實施形態中,就確保充分之電解性能之觀點而言,較佳為電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。 於本實施形態中,若電解用電極係彈性變形區域較廣之電極,則就可獲得更良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有更良好之接著力之觀點而言,電解用電極之厚度較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,於本實施形態中,所謂「彈性變形區域較廣」意指將電解用電極捲繞而製成捲繞體,解除捲繞狀態後不易產生由捲繞引起之翹曲。又,所謂電解用電極之厚度於包含下文所述之觸媒層之情形時,係指合併電解用電極基材與觸媒層之厚度。 (電解用電極之製造方法) 其次,對電解用電極100之製造方法之一實施形態進行詳細說明。 於本實施形態中,藉由利用氧環境下之塗膜之燒成(熱分解)、或離子鍍敷、鍍覆、熱熔射等方法於電解用電極基材上形成第一層20、較佳為第二層30,可製造電解用電極100。此種本實施形態之製造方法能夠實現電解用電極100之較高之生產性。具體而言,藉由塗佈含有觸媒之塗佈液之塗佈步驟、乾燥塗佈液之乾燥步驟、進行熱分解之熱分解步驟,而於電解用電極基材上形成觸媒層。此處所謂熱分解意指對成為前驅物之金屬鹽進行加熱而分解為金屬或金屬氧化物與氣體狀物質。根據所使用之金屬種類、鹽之種類、進行熱分解之環境等,分解產物有所不同,但於氧化性環境下多數金屬有容易形成氧化物之傾向。於電極之工業性之製造工藝中,熱分解通常於空氣中進行,多數情形時形成金屬氧化物或金屬氫氧化物。 (陽極之第一層之形成) (塗佈步驟) 第一層20係將溶解有釕、銥及鈦中之至少一種金屬之鹽的溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之釕、銥及鈦之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材100後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (第二層之形成) 第二層30係視需要而形成,例如將含有鈀化合物及鉑化合物之溶液或含有釕化合物及鈦化合物之溶液(第二塗佈液)塗佈於第一層20上後,於氧氣之存在下進行熱分解而獲得。 (利用熱分解法之陰極之第一層之形成) (塗佈步驟) 第一層20係將溶解有各種組合之金屬鹽之溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之金屬之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材10後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (中間層之形成) 中間層係視需要而形成,例如將含有鈀化合物或鉑化合物之溶液(第二塗佈液)塗佈於基材上後,於氧氣之存在下進行熱分解而獲得。或者,亦可不塗佈溶液,而僅加熱基材,藉此於基材表面形成氧化鎳中間層。 (利用離子鍍敷之陰極之第一層之形成) 第一層20亦可藉由離子鍍敷而形成。 作為一例,可列舉將基材固定於腔室內並對金屬釕靶照射電子束之方法。所蒸發之金屬釕粒子於腔室內之電漿中帶正電,而沈積於帶負電之基板上。電漿環境為氬氣、氧氣,釕係以釕氧化物之形式沈積於基材上。 (利用鍍覆之陰極之第一層之形成) 第一層20亦可藉由鍍覆法而形成。 作為一例,若使用基材作為陰極,於含有鎳及錫之電解液中實施電解鍍覆,則可形成鎳與錫之合金鍍覆。 (利用熱熔射之陰極之第一層之形成) 第一層20亦可藉由熱熔射法而形成。 作為一例,藉由將氧化鎳粒子電漿熔射於基材上,而可形成混合有金屬鎳與氧化鎳之觸媒層。 本實施形態中之電解用電極能夠與離子交換膜或微多孔膜等隔膜進行一體化而使用。因此,本實施形態中之積層體可用作膜一體電極,無需更新電極時之陰極及陽極之更換貼附作業,作業效率大幅提高。 又,藉由與離子交換膜或微多孔膜等隔膜之一體電極,能夠使電解性能與新品時之性能相同或有所提高。 以下,對離子交換膜進行詳細說明。 [離子交換膜] 作為離子交換膜,只要可與電解用電極製成積層體,則無特別限定,可應用各種離子交換膜。於本實施形態中,較佳為使用具有含有具有離子交換基之烴系聚合物或含氟系聚合物之膜本體、與設置於該膜本體之至少一面上之塗佈層之離子交換膜。又,塗佈層含有無機物粒子與結合劑,塗佈層之比表面積較佳為0.1~10 m2 /g。該結構之離子交換膜於電解中所產生之氣體對電解性能之影響較少,有發揮出穩定之電解性能之傾向。 上述所謂導入有離子交換基之全氟碳聚合物之膜係具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層之任一者。就強度及尺寸穩定性之觀點而言,較佳為進而具有強化芯材。 以下於塗佈層之說明之欄對無機物粒子及結合劑進行詳細說明。 圖69係表示離子交換膜之一實施形態之剖面模式圖。離子交換膜1具有:膜本體10,其含有具有離子交換基之烴系聚合物或含氟系聚合物;以及塗佈層11a及11b,其等形成於膜本體10之兩面。 於離子交換膜1中,膜本體10具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層3、與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層2,藉由強化芯材4強化強度及尺寸穩定性。離子交換膜1由於具備磺酸層3與羧酸層2,因此可作為陽離子交換膜而適宜地使用。 再者,離子交換膜亦可僅具有磺酸層及羧酸層之任一者。又,離子交換膜未必由強化芯材所強化,強化芯材之配置狀態亦不限定於圖69之例。 (膜本體) 首先,對構成離子交換膜1之膜本體10進行說明。 膜本體10只要為具有使陽離子選擇性地透過之功能且含有具有離子交換基之烴系聚合物或含氟系聚合物者即可,其構成或材料並無特別限定,可適當選擇適宜者。 膜本體10中之具有離子交換基之烴系聚合物或含氟系聚合物例如可由具有可藉由水解等成為離子交換基之離子交換基前驅物之烴系聚合物或含氟系聚合物獲得。具體而言,例如使用主鏈包含氟化烴、具有可藉由水解等轉換為離子交換基之基(離子交換基前驅物)作為懸垂側鏈且能夠熔融加工之聚合物(以下視情形稱為「含氟系聚合物(a)」)製作膜本體10之前驅物後,將離子交換基前驅物轉換為離子交換基,藉此可獲得膜本體10。 含氟系聚合物(a)例如可藉由使選自下述第1群之至少一種單體與選自下述第2群及/或下述第3群之至少一種單體進行共聚合而製造。又,亦可藉由選自下述第1群、下述第2群、及下述第3群之任一群之1種單體之均聚而製造。 作為第1群之單體,例如可列舉氟乙烯化合物。作為氟乙烯化合物,例如可列舉:氟乙烯、四氟乙烯、六氟丙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、全氟烷基乙烯醚等。尤其是於將離子交換膜用作鹼電解用膜之情形時,氟乙烯化合物較佳為全氟單體,較佳為選自由四氟乙烯、六氟丙烯、全氟烷基乙烯醚所組成之群中之全氟單體。 作為第2群之單體,例如可列舉具有可轉換為羧酸型離子交換基(羧酸基)之官能基之乙烯系化合物。作為具有可轉換為羧酸基之官能基之乙烯系化合物,例如可列舉以CF2 =CF(OCF2 CYF)s -O(CZF)t -COOR表示之單體等(此處,s表示0~2之整數,t表示1~12之整數,Y及Z各自獨立地表示F或CF3 ,R表示低級烷基。低級烷基例如為碳數1~3之烷基)。 該等中,較佳為以CF2 =CF(OCF2 CYF)n -O(CF2 )m -COOR表示之化合物。此處,n表示0~2之整數,m表示1~4之整數,Y表示F或CF3 ,R表示CH3 、C2 H5 、或C3 H7 。 再者,於將離子交換膜用作鹼電解用陽離子交換膜之情形時,較佳為至少使用全氟化合物作為單體,但由於酯基之烷基(參照上述R)於水解時從聚合物喪失,因此烷基(R)亦可不為全部氫原子被取代為氟原子之全氟烷基。 作為第2群之單體,於上述中,更佳為下述所表示之單體。 CF2 =CFOCF2 -CF(CF3 )OCF2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )2 COOCH3 、 CF2 =CF[OCF2 -CF(CF3 )]2 O(CF2 )2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )3 COOCH3 、 CF2 =CFO(CF2 )2 COOCH3 、 CF2 =CFO(CF2 )3 COOCH3 。 作為第3群之單體,例如可列舉具有可轉換為磺酸型離子交換基(磺酸基)之官能基之乙烯系化合物。作為具有可轉換為磺酸基之官能基之乙烯系化合物,例如較佳為以CF2 =CFO-X-CF2 -SO2 F表示之單體(此處,X表示全氟伸烷基)。作為該等之具體例,可列舉下述所表示之單體等。 CF2 =CFOCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、 CF2 =CF(CF2 )2 SO2 F、 CF2 =CFO[CF2 CF(CF3 )O]2 CF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF2 OCF3 )OCF2 CF2 SO2 F。 該等中,更佳為CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、及CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F。 由該等單體獲得之共聚物可藉由針對氟乙烯之均聚及共聚合所開發之聚合法、尤其是對四氟乙烯所使用之通常之聚合方法而製造。例如,於非水性法中,可使用全氟烴、氯氟碳等不活性溶劑,於全氟碳過氧化物或偶氮化合物等自由基聚合起始劑之存在下,於溫度0~200℃、壓力0.1~20 MPa之條件下進行聚合反應。 於上述共聚合中,上述單體之組合之種類及其比率並無特別限定,根據欲對所獲得之含氟系聚合物賦予之官能基之種類及量選擇確定。例如於製成僅含有羧酸基之含氟系聚合物之情形時,從上述第1群及第2群分別選擇至少1種單體進行共聚合即可。又,於製成僅含有磺酸基之含氟系聚合物之情形時,從上述第1群及第3群之單體中分別選擇至少1種單體進行共聚合即可。進而,於製成具有羧酸基及磺酸基之含氟系聚合物之情形時,從上述第1群、第2群及第3群之單體中分別選擇至少1種單體進行共聚合即可。於該情形時,藉由使包含上述第1群及第2群之共聚物與包含上述第1群及第3群之共聚物分開進行聚合,其後加以混合亦可獲得目標之含氟系聚合物。又,各單體之混合比率並無特別限定,於增加每單位聚合物之官能基之量之情形時,增加選自上述第2群及第3群之單體之比率即可。 含氟系共聚物之總離子交換容量並無特別限定,較佳為0.5~2.0 mg當量/g,更佳為0.6~1.5 mg當量/g。此處,所謂總離子交換容量係指相對於單位重量之乾燥樹脂之交換基之當量,可藉由中和滴定等進行測定。 於離子交換膜1之膜本體10中,積層有含有具有磺酸基之含氟系聚合物之磺酸層3與含有具有羧酸基之含氟系聚合物之羧酸層2。藉由製成此種層結構之膜本體10,能夠進一步提高鈉離子等陽離子之選擇性透過性。 於將離子交換膜1配置於電解槽之情形時,通常以磺酸層3位於電解槽之陽極側、羧酸層2位於電解槽之陰極側之方式配置。 磺酸層3較佳為由電阻較低之材料構成,就膜強度之觀點而言,較佳為其膜厚厚於羧酸層2。磺酸層3之膜厚較佳為羧酸層2之2~25倍,更佳為3~15倍。 羧酸層2較佳為即使膜厚較薄亦具有較高之陰離子排斥性者。此處所謂陰離子排斥性係指阻礙陰離子對離子交換膜1之滲入或透過之性質。為了提高陰離子排斥性,有效的是對磺酸層配置離子交換容量較小之羧酸層等。 作為磺酸層3所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F作為第3群之單體所獲得之聚合物。 作為羧酸層2所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF2 )O(CF2 )2 COOCH3 作為第2群之單體所獲得之聚合物。 (塗佈層) 離子交換膜較佳為於膜本體之至少一面上具有塗佈層。又,如圖69所示,於離子交換膜1中,於膜本體10之兩面上分別形成有塗佈層11a及11b。 塗佈層含有無機物粒子與結合劑。 無機物粒子之平均粒徑更佳為0.90 μm以上。若無機物粒子之平均粒徑為0.90 μm以上,則不僅極大地提高對氣體附著之耐久性,而且極大地提高對雜質之耐久性。即,藉由增大無機物粒子之平均粒徑,並且滿足上述比表面積之值,可獲得尤其顯著之效果。為了滿足此種平均粒徑與比表面積,較佳為不規則狀之無機物粒子。可使用藉由熔融獲得之無機物粒子、藉由原石粉碎獲得之無機物粒子。較佳可適宜地使用藉由原石粉碎獲得之無機物粒子。 又,無機物粒子之平均粒徑可設為2 μm以下。若無機物粒子之平均粒徑為2 μm以下,則能夠防止因無機物粒子而損傷膜。無機物粒子之平均粒徑更佳為0.90~1.2 μm。 此處,平均粒徑可藉由粒度分佈計(「SALD2200」島津製作所)進行測定。 無機物粒子之形狀較佳為不規則形狀。對雜質之耐性進一步提高。又,無機物粒子之粒度分佈較佳為較寬。 無機物粒子較佳為含有選自由週期表第IV族元素之氧化物、週期表第IV族元素之氮化物、及週期表第IV族元素之碳化物所組成之群中之至少一種無機物。就耐久性之觀點而言,更佳為氧化鋯之粒子。 該無機物粒子較佳為藉由將無機物粒子之原石粉碎所製造之無機物粒子,或以藉由將無機物粒子之原石熔融並加以精製而粒子之直徑一致之球狀之粒子作為無機物粒子。 作為原石粉碎方法,並無特別限定,可列舉:球磨機、珠磨機、膠體磨機、錐形磨機、盤磨機、輪輾機、磨粉機、錘磨機、造粒機、VSI磨機、威利磨機、輥磨機、噴射磨機等。又,較佳為粉碎後將其洗淨,作為此時之洗淨方法,較佳為酸處理。藉此,能夠減少附著於無機物粒子之表面之鐵等雜質。 塗佈層較佳為含有結合劑。結合劑係將無機物粒子保持於離子交換膜之表面、形成塗佈層之成分。就對電解液或電解之產物之耐性之觀點而言,結合劑較佳為含有含氟系聚合物。 作為結合劑,就對電解液或電解之產物之耐性、及對離子交換膜之表面之接著性之觀點而言,更佳為具有羧酸基或磺酸基之含氟系聚合物。於在含有具有磺酸基之含氟聚合物之層(磺酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有磺酸基之含氟系聚合物。又,於在含有具有羧酸基之含氟聚合物之層(羧酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有羧酸基之含氟系聚合物。 塗佈層中,無機物粒子之含量較佳為40~90質量%,更佳為50~90質量%。又,結合劑之含量較佳為10~60質量%,更佳為10~50質量%。 離子交換膜中之塗佈層之分佈密度較佳為每1 cm2 為0.05~2 mg。又,於離子交換膜於表面具有凹凸形狀之情形時,塗佈層之分佈密度較佳為每1 cm2 為0.5~2 mg。 作為形成塗佈層之方法,並無特別限定,可使用公知之方法。例如可列舉藉由噴射等塗佈將無機物粒子分散於含有結合劑之溶液中而成之塗佈液之方法。 (強化芯材) 離子交換膜較佳為具有配置於膜本體之內部之強化芯材。 強化芯材係強化離子交換膜之強度或尺寸穩定性之構件。藉由將強化芯材配置於膜本體之內部,尤其能夠將離子交換膜之伸縮控制為所需之範圍。該離子交換膜於電解時等不會伸縮為必要程度以上,而能夠長期維持優異之尺寸穩定性。 強化芯材之構成並無特別限定,例如可將稱為強化紗之紗進行紡紗而形成。此處所謂強化紗係構成強化芯材之構件,指能夠對離子交換膜賦予所需之尺寸穩定性及機械強度且於離子交換膜中能夠穩定地存在之紗。藉由使用將該強化紗紡紗而成之強化芯材,能夠對離子交換膜賦予更優異之尺寸穩定性及機械強度。 強化芯材及其所使用之強化紗之材料並無特別限定,較佳為對酸或鹼等具有耐性之材料,就需要長期之耐熱性、耐化學品性之方面而言,較佳為包含含氟系聚合物之纖維。 作為強化芯材所使用之含氟系聚合物,例如可列舉:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、四氟乙烯-六氟丙烯共聚物、三氟氯乙烯-乙烯共聚物及偏二氟乙烯聚合物(PVDF)等。該等中,尤其是就耐熱性及耐化學品性之觀點而言,較佳為使用包含聚四氟乙烯之纖維。 強化芯材所使用之強化紗之紗直徑並無特別限定,較佳為20~300丹尼,更佳為50~250丹尼。紡織密度(每單位長度之織入根數)較佳為5~50根/英吋。作為強化芯材之形態,並無特別限定,例如可使用織布、不織布、針織布等,較佳為織布之形態。又,使用織布之厚度較佳為30~250 μm、更佳為30~150 μm者。 織布或針織布可使用單絲、複絲或該等之紗線、切膜絲等,紡織方法可使用平織、紗羅組織、針織、凸條組織、縐條紋薄織等各種紡織方法。 膜本體中之強化芯材之紡織方法及配置並無特別限定,可考慮離子交換膜之大小或形狀、離子交換膜所需之物性及使用環境等適當設為適宜之配置。 例如,可沿膜本體之特定之一方向配置強化芯材,就尺寸穩定性之觀點而言,較佳為沿特定之第一方向配置強化芯材,且沿大致垂直於第一方向之第二方向配置其他強化芯材。藉由在膜本體之縱向膜本體之內部以大致成一列之方式配置複數個強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。例如,較佳為於膜本體之表面織入沿縱向配置之強化芯材(縱紗)與沿橫向配置之強化芯材(橫紗)之配置。就尺寸穩定性、機械強度及製造容易性之觀點而言,更佳為製成使縱紗與橫紗一上一下交替織入而紡織之平紋織物、或一邊撚轉2根經紗一邊與橫紗交織之紗羅組織物、於每2根或數根並紗配置之縱紗中織入相同數量之橫紗而紡織之斜紋織物(twill weave)等。 尤佳為沿離子交換膜之MD方向(縱向(Machine Direction)方向)及TD方向(橫向(Transverse Direction)方向)之兩方向配置強化芯材。即,較佳為沿MD方向與TD方向平織。此處,所謂MD方向係指於下文所述之離子交換膜之製造步驟中搬送膜本體或各種芯材(例如,強化芯材、強化紗、下文所述之犧牲紗等)之方向(行進方向),所謂TD方向係指大致垂直於MD方向之方向。此外,將沿MD方向紡織之紗稱為MD紗,將沿TD方向紡織之紗稱為TD紗。通常電解所使用之離子交換膜係矩形,長度方向為MD方向、寬度方向為TD方向之情況較多。藉由織入作為MD紗之強化芯材與作為TD紗之強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。 強化芯材之配置間隔並無特別限定,可考慮離子交換膜所需之物性及使用環境等適當設為適宜之配置。 強化芯材之開口率並無特別限定,較佳為30%以上,更佳為50%以上且90%以下。開口率就離子交換膜之電化學性質之觀點而言,較佳為30%以上,就離子交換膜之機械強度之觀點而言,較佳為90%以下。 所謂強化芯材之開口率係指膜本體之任一表面之面積(A)中離子等物質(電解液及其所含之陽離子(例如,鈉離子))能夠通過之表面之總面積(B)之比率(B/A)。所謂離子等物質能夠通過之表面之總面積(B)可指於離子交換膜中陽離子或電解液等不被離子交換膜所含之強化芯材等阻斷之區域之總面積。 圖70係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。圖70係將離子交換膜之一部分放大而僅圖示該區域內之強化芯材21及22之配置,其他構件省略圖示。 藉由從由沿縱向配置之強化芯材21與沿橫向配置之強化芯材22所圍成之亦包括強化芯材之面積在內之區域的面積(A)減去強化芯材之總面積(C),可求出上述區域之面積(A)中離子等物質能夠通過之區域之總面積(B)。即,開口率可藉由下述式(I)求出。 開口率=(B)/(A)=((A)-(C))/(A) …(I) 於強化芯材中,就耐化學品性及耐熱性之觀點而言,尤佳之形態係含有PTFE之帶狀紗線或高配向單絲。具體而言,更佳為如下強化芯材,其係使用將包含PTFE之高強度多孔質片材切為帶狀而成之帶狀紗線、或包含PTFE之高度配向之單絲之50~300丹尼且紡織密度為10~50根/英吋之平紋織物,其厚度為50~100 μm之範圍。含有該強化芯材之離子交換膜之開口率進而較佳為60%以上。 作為強化紗之形狀,可列舉圓紗、帶狀紗等。 (連通孔) 離子交換膜較佳為於膜本體之內部具有連通孔。 所謂連通孔係指能夠成為電解時產生之離子或電解液之流路之孔。又,所謂連通孔係形成於膜本體內部之管狀之孔,藉由下文所述之犧牲芯材(或犧牲紗)溶出而形成。連通孔之形狀或直徑等可藉由選擇犧牲芯材(犧牲紗)之形狀或直徑進行控制。 藉由在離子交換膜形成連通孔,於電解時能夠確保電解液之移動性。連通孔之形狀並無特別限定,根據下文所述之製法,可製成連通孔之形成所使用之犧牲芯材之形狀。 連通孔較佳為以交替通過強化芯材之陽極側(磺酸層側)與陰極側(羧酸層側)之方式形成。藉由設為該結構,於強化芯材之陰極側形成有連通孔之部分,通過充滿連通孔之電解液所輸送之離子(例如,鈉離子)亦能夠流至強化芯材之陰極側。其結果為,由於陽離子之流動未被遮蔽,因此能夠進一步降低離子交換膜之電阻。 連通孔可僅沿構成離子交換膜之膜本體之特定之一方向形成,就發揮出更穩定之電解性能之觀點而言,較佳為沿膜本體之縱向與橫向之兩方向形成。 [製造方法] 作為離子交換膜之適宜之製造方法,可列舉具有以下之(1)步驟~(6)步驟之方法。 (1)步驟:製造具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之含氟系聚合物之步驟。 (2)步驟:藉由視需要至少織入複數個強化芯材與具有溶於酸或鹼之性質且形成連通孔之犧牲紗而獲得於鄰接之強化芯材彼此之間配置有犧牲紗之補強材之步驟。 (3)步驟:將具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之上述含氟系聚合物進行膜化之步驟。 (4)步驟:視需要將上述補強材埋入至上述膜中而獲得內部配置有上述補強材之膜本體之步驟。 (5)步驟:將(4)步驟中獲得之膜本體進行水解之步驟(水解步驟)。 (6)步驟:於(5)步驟中獲得之膜本體設置塗佈層之步驟(塗佈步驟)。 以下,對各步驟進行詳細說明。 (1)步驟:製造含氟系聚合物之步驟 於(1)步驟中,使用上述第1群~第3群所記載之原料之單體製造含氟系聚合物。為了控制含氟系聚合物之離子交換容量,於形成各層之含氟系聚合物之製造中調整原料之單體之混合比即可。 (2)步驟:補強材之製造步驟 所謂補強材係紡織強化紗之織布等。藉由將補強材埋入至膜內而形成強化芯材。於製成具有連通孔之離子交換膜時,亦將犧牲紗一起織入至補強材中。該情形時之犧牲紗之混織量較佳為補強材整體之10~80質量%,更佳為30~70質量%。藉由織入犧牲紗,亦能夠防止強化芯材之脫線。 犧牲紗係於膜之製造步驟或電解環境下具有溶解性者,可使用嫘縈、聚對苯二甲酸乙二酯(PET)、纖維素及聚醯胺等。又,亦較佳為具有20~50丹尼之粗細程度、包含單絲或複絲之聚乙烯醇等。 再者,於(2)步驟中,可藉由調整強化芯材或犧牲紗之配置而控制開口率或連通孔之配置等。 (3)步驟:膜化步驟 於(3)步驟中,使用擠出機將上述(1)步驟中獲得之含氟系聚合物進行膜化。膜可為單層結構,亦可如上所述為磺酸層與羧酸層之2層結構,亦可為3層以上之多層結構。 作為膜化之方法,例如可列舉以下者。 分別將具有羧酸基之含氟聚合物、具有磺酸基之含氟聚合物分開進行膜化之方法。 藉由共擠出將具有羧酸基之含氟聚合物與具有磺酸基之含氟聚合物製成複合膜之方法。 再者,膜可分別為複數片。又,將異種之膜共擠出有助於提高界面之接著強度,故而較佳。 (4)步驟:獲得膜本體之步驟 於(4)步驟中,藉由將(2)步驟中獲得之補強材埋入至(3)步驟中獲得之膜之內部,而獲得內有補強材之膜本體。 作為膜本體之較佳之形成方法,可列舉:(i)藉由共擠出法將位於陰極側之具有羧酸基前驅物(例如,羧酸酯官能基)之含氟系聚合物(以下將包含其之層稱為第一層)與具有磺酸基前驅物(例如,磺醯氟官能基)之含氟系聚合物(以下將包含其之層稱為第二層)進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將補強材、第二層/第一層複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法;(ii)區別於第二層/第一層複合膜,預先將具有磺酸基前驅物之含氟系聚合物(第三層)單獨進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將第三層膜、強化芯材、包含第二層/第一層之複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法。 此處,將第一層與第二層共擠出有助於提高界面之接著強度。 又,於減壓下進行一體化之方法與加壓壓製法相比,具有補強材上之第三層之厚度變大之特徵。進而,由於將補強材固定於膜本體之內面,因此具有能夠充分保持離子交換膜之機械強度之性能。 再者,此處所說明之積層之變化係一例,可考慮所需之膜本體之層構成或物性等,適當選擇適宜之積層圖案(例如,各層之組合等)後進行共擠出。 再者,為了進一步提高離子交換膜之電性能,亦可於第一層與第二層之間進一步介置包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層,或使用包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層代替第二層。 第四層之形成方法可為分開製造具有羧酸基前驅物之含氟系聚合物與具有磺酸基前驅物之含氟系聚合物後加以混合之方法,亦可為使用將具有羧酸基前驅物之單體與具有磺酸基前驅物之單體共聚合而成者之方法。 於將第四層製成離子交換膜之構成之情形時,可將第一層與第四層之共擠出膜加以成形,第三層及第二層與其分開單獨進行膜化,藉由上文所述之方法進行積層,亦可將第一層/第四層/第二層之3層一次共擠出而進行膜化。 於該情形時,所擠出之膜行進之方向為MD方向。由此可將含有具有離子交換基之含氟系聚合物之膜本體形成於補強材上。 又,離子交換膜較佳為於包含磺酸層之表面側具有包含具有磺酸基之含氟聚合物之突出的部分、即凸部。作為形成此種凸部之方法,並無特別限定,可採用於樹脂表面形成凸部之公知之方法。具體而言,例如可列舉對膜本體之表面實施壓紋加工之方法。例如,於將上述複合膜與補強材等進行一體化時,藉由使用預先經壓紋加工之脫模紙,可形成上述凸部。於藉由壓紋加工形成凸部之情形時,凸部之高度或配置密度之控制可藉由控制所轉印之壓紋形狀(脫模紙之形狀)而進行。 (5)水解步驟 於(5)步驟中,進行將(4)步驟中獲得之膜本體水解而將離子交換基前驅物轉換為離子交換基之步驟(水解步驟)。 又,於(5)步驟中,藉由利用酸或鹼將膜本體所含之犧牲紗溶解去除,可於膜本體形成溶出孔。再者,犧牲紗亦可不完全溶解去除,而殘留於連通孔中。又,殘留於連通孔中之犧牲紗可於將離子交換膜供於電解時藉由電解液溶解去除。 犧牲紗係於離子交換膜之製造步驟或電解環境下對酸或鹼具有溶解性者,藉由使犧牲紗溶出而於該部位形成連通孔。 (5)步驟可將(4)步驟中獲得之膜本體浸漬於含有酸或鹼之水解溶液中進行。作為該水解溶液,例如可使用含有KOH與DMSO(Dimethyl sulfoxide)之混合溶液。 該混合溶液較佳為含有2.5~4.0 N之KOH,且含有25~35質量%之DMSO。 作為水解之溫度,較佳為70~100℃。溫度越高,可使視厚度更厚。更佳為75~100℃。 作為水解之時間,較佳為10~120分鐘。時間越長,可使視厚度更厚。更佳為20~120分鐘。 此處,對藉由溶出犧牲紗而形成連通孔之步驟進一步詳細地說明。圖71(a)、(b)係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 於圖71(a)、(b)中,僅圖示強化紗52、犧牲紗504a及由犧牲紗504a形成之連通孔504,膜本體等其他構件省略圖示。 首先,將於離子交換膜中構成強化芯材之強化紗52與於離子交換膜中用以形成連通孔504之犧牲紗504a製成針織織入補強材。然後,於(5)步驟中藉由使犧牲紗504a溶出而形成連通孔504。 藉由上述方法,根據於離子交換膜之膜本體內如何配置強化芯材、連通孔而調整強化紗52與犧牲紗504a之針織織入方法即可,因此較簡便。 於圖71(a)中,例示於紙面沿縱向與橫向之兩方向將強化紗52與犧牲紗504a織入之平織之補強材,可視需要變更補強材中之強化紗52與犧牲紗504a之配置。 (6)塗佈步驟 於(6)步驟中,製備含有藉由原石粉碎或原石熔融獲得之無機物粒子與結合劑之塗佈液,將塗佈液塗佈於(5)步驟中獲得之離子交換膜之表面並加以乾燥,藉此可形成塗佈層。 作為結合劑,較佳為將具有離子交換基前驅物之含氟系聚合物水解於含有二甲基亞碸(DMSO)及氫氧化鉀(KOH)之水溶液中之後,浸漬於鹽酸中將離子交換基之抗衡離子置換為H+ 而成之結合劑(例如,具有羧基或磺基之含氟系聚合物)。藉此,變得容易溶解於下文所述之水或乙醇中,故而較佳。 將該結合劑溶解於混合水與乙醇而成之溶液中。再者,水與乙醇之較佳之體積比為10:1~1:10,更佳為5:1~1:5,進而較佳為2:1~1:2。藉由球磨機使無機物粒子分散於由此獲得之溶解液中而獲得塗佈液。此時,亦可藉由調整分散時之時間、旋轉速度而調整粒子之平均粒徑等。再者,無機物粒子與結合劑之較佳之調配量如上文所述。 塗佈液中之無機物粒子及結合劑之濃度並無特別限定,較佳為製成稀薄之塗佈液。藉此,能夠均勻地塗佈於離子交換膜之表面。 又,於使無機物粒子分散時,亦可將界面活性劑添加於分散液中。作為界面活性劑,較佳為非離子系界面活性劑,例如可列舉日油股份有限公司製造之HS-210、NS-210、P-210、E-212等。 藉由利用噴射塗佈或滾筒塗敷將所獲得之塗佈液塗佈於離子交換膜表面而可獲得離子交換膜。 [微多孔膜] 作為本實施形態之微多孔膜,只要如上文所述,可與電解用電極製成積層體,則無特別限定,可應用各種微多孔膜。 本實施形態之微多孔膜之氣孔率並無特別限定,例如可設為20~90,較佳為30~85。上述氣孔率例如可藉由下述之式算出。 氣孔率=(1-(乾燥狀態之膜重量)/(由根據膜之厚度、寬度、長度算出之體積與膜素材之密度所算出之重量))×100 本實施形態之微多孔膜之平均孔徑並無特別限定,例如可設為0.01 μm~10 μ,較佳為0.05 μm~5 μm。上述平均孔徑例如係沿厚度方向將膜垂直切斷,藉由FE-SEM觀察切斷面。對所觀察之孔之直徑測定100點左右並求出平均值,藉此可求出平均孔徑。 本實施形態之微多孔膜之厚度並無特別限定,例如可設為10 μm~1000 μm,較佳為50 μm~600 μm。上述厚度例如可使用測微計(Mitutoyo股份有限公司製造)等進行測定。 作為如上所述之微多孔膜之具體例,可列舉Agfa公司製造之Zirfon Perl UTP 500(於本實施形態中亦稱為Zirfon膜)、國際公開第2013-183584號說明書、國際公開第2016-203701號說明書等所記載者。 於本實施形態中,較佳為隔膜包含第1離子交換樹脂層、及具有與該第1離子交換樹脂層不同之EW(離子交換當量)之第2離子交換樹脂層。又,較佳為隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之官能基之第2離子交換樹脂層。離子交換當量可藉由所導入之官能基進行調整,關於可導入之官能基係如上文所述。 於本實施形態中,夾持於陽極墊片12及陰極墊片13之間之積層體25之部分較佳為非通電面。再者,「通電面」與以於陽極室與陰極室之間進行電解質之移動之方式設計之部分相對應,「非通電面」係不屬於通電面之部分。 又,於本實施形態中,積層體之最外周緣與陽極側墊片及陰極側墊片之最外周緣相比,可位於通電面方向內側,亦可位於外側,較佳為位於外側。於以此種方式構成之情形時,可抓持位於外側之最外周緣,因此有組裝電解槽時之作業性提高之傾向。此處,積層體之最外周緣係將隔膜與電解用電極組合之狀態下之最外周緣。即,若與隔膜之最外周緣相比,電解用電極之最外周緣處於互相之接觸面外側,則意指電解用電極之最外周緣,又,若與隔膜之最外周緣相比,電解用電極之最外周緣處於互相之接觸面內側,則意指隔膜之最外周緣。 使用圖72、73對該位置關係進行說明。圖72、73係表示於例如從圖64B所示之α方向觀察2個電解池之情形時尤其是墊片及積層體之位置關係。於圖72、73中,中央具有開口部之長方形狀之墊片A位於最靠近前之位置。長方形狀之隔膜B位於其背側,進而長方形狀之電解用電極C位於其背側。即,墊片A之開口部係與積層體之通電面相對應之部分。 於圖72中,墊片A之最外周緣A1與隔膜B之最外周緣B1及電解用電極C之最外周緣C1相比,位於通電面方向內側。 又,於圖73中,墊片A之最外周緣A1與電解用電極C之最外周緣C1相比,位於通電面方向外側,但隔膜B之最外周緣B1與墊片A之最外周緣A1相比,位於通電面方向外側。 再者,於本實施形態中,作為積層體,被陽極側墊片及陰極側墊片夾持即可,電解用電極本身亦可不被陽極側墊片及陰極側墊片直接夾持。即,只要將電解用電極本身固定於隔膜,則亦可僅隔膜被陽極側墊片及陰極側墊片直接夾持。於本實施形態中,就於電解槽中將電解用電極更穩定地固定之觀點而言,較佳為電解用電極及隔膜之兩者被陽極側墊片及陰極側墊片夾持。 於本實施形態中,隔膜與電解用電極至少由陽極墊片及陰極墊片所固定,以積層體之形式存在,但亦可具有其他固定結構,例如可採用以下所例示之固定結構。再者,各固定結構可僅採用1種,亦可組合2種以上而採用。 於本實施形態中,較佳為電解用電極之至少一部分貫通隔膜而被固定。使用圖74A對該態樣進行說明。 於圖74A中,電解用電極2之至少一部分貫通隔膜3而被固定。於圖74A中係示出電解用電極2為金屬多孔電極之例。即,於圖74A中將複數個電解用電極2之部分獨立表示,但該等相連而表示一體之金屬多孔電極之剖面(於以下之圖75~78中亦相同)。 於此種電極結構下,例如若將特定位置(應成為固定部之位置)之隔膜3壓抵於電解用電極2,則隔膜3之一部分進入至電解用電極2之表面之凹凸結構內或孔結構內,電極表面之凹部或孔之周圍之凸部分貫通隔膜3,較佳為如圖74A所示,穿透至隔膜3之外表面3b。 如上所述,圖74A之固定結構可藉由將隔膜3壓抵於電解用電極2而製造,於該情形時,於藉由加溫使隔膜3軟化之狀態下進行熱壓接、熱抽吸。藉此,電解用電極2將隔膜3貫通。或者,亦可於將隔膜3熔融之狀態下進行。於該情形時,較佳為於圖74B所示之狀態下從電解用電極2之外表面2b側(背面側)抽吸隔膜3。再者,將隔膜3壓抵於電解用電極2之區域構成「固定部」。 圖74A所示之固定結構可藉由放大鏡(loupe)、光學顯微鏡或電子顯微鏡進行觀察。又,藉由電解用電極2將隔膜3貫通,利用隔膜3之外表面3b與電解用電極2之外表面2b之間的使用測試機等之導通檢查,可推測出圖74A之固定結構。 於本實施形態中,較佳為於固定部中電解用電極之至少一部分位於隔膜之內部而被固定。使用圖75A對該態樣進行說明。 如上所述,電解用電極2之表面被設為凹凸結構或孔結構。於圖75A所示之實施形態中,電極表面之一部分插入並被固定於特定位置(應成為固定部之位置)之隔膜3。圖75A所示之固定結構可藉由將隔膜3壓抵於電解用電極2而製造。於該情形時,較佳為於藉由加溫使隔膜3軟化之狀態下進行熱壓接、熱抽吸而形成圖75A之固定結構。或者,亦可將隔膜3熔融而形成圖75A之固定結構。於該情形時,較佳為從電解用電極2之外表面2b側(背面側)抽吸隔膜3。 圖75A所示之固定結構可藉由放大鏡(loupe)、光學顯微鏡或電子顯微鏡進行觀察。較佳為尤其是對樣品進行包埋處理後藉由切片機製作剖面並進行觀察之方法。再者,於圖75A所示之固定結構中,由於電解用電極2未貫通隔膜3,因此並不確認隔膜3之外表面3b與電解用電極2之外表面2b之間的利用導通檢查之導通。 於本實施形態中,較佳為於積層體中進一步具有用以將隔膜與電解用電極加以固定之固定用構件。使用圖76A~C對該態樣進行說明。 圖76A所示之固定結構係使用與電解用電極2及隔膜3不同體之固定用構件7,且固定用構件7將電解用電極2與隔膜3貫通而加以固定之結構。電解用電極2未必一定被固定用構件7所貫通,以不與隔膜2分離之方式藉由固定用構件7進行固定即可。固定用構件7之材質並無特別限定,作為固定用構件7,例如可使用包含金屬或樹脂等者。於金屬之情形時,可列舉鎳、鎳鉻合金、鈦、不鏽鋼(SUS)等。亦可為該等之氧化物。作為樹脂,可使用氟樹脂(例如,PTFE(聚四氟乙烯)、PFA(四氟乙烯與全氟烷氧基乙烯之共聚物)、ETFE(四氟乙烯與乙烯之共聚物)或下述所記載之隔膜3之材質)或PVDF(聚偏二氟乙烯)、EPDM(乙烯-丙烯-二烯橡膠)、PP(聚乙烯)、PE(聚丙烯)、尼龍、芳香族聚醯胺等。 於本實施形態中,例如使用紗狀之金屬或樹脂,如圖76B、76C所示般,對電解用電極2與隔膜3之外表面2b、3b間之特定位置(應成為固定部之位置)進行縫製,藉此亦可進行固定。又,亦可使用如活褶縫製器之固定機構將電解用電極2與隔膜3加以固定。 圖77所示之固定結構係於電解用電極2與隔膜3之間介置有機樹脂(接著層)進行固定之結構。即,於圖77中係將作為固定用構件7之有機樹脂配置於電解用電極2與隔膜3之間之特定位置(應成為固定部之位置)而藉由接著進行固定之結構。例如,於電解用電極2之內表面2a、或隔膜3之內表面3a、或電解用電極2及隔膜3之內表面2a、3a之兩者或其中一者塗佈有機樹脂。然後,將電解用電極2與隔膜3貼合,藉此可形成圖77所示之固定結構。有機樹脂之材質並無特別限定,例如可使用氟樹脂(例如,PTFE、PFE(Polyfluoroethylene,聚氟乙烯)、PFPE(perfluoropolyether,全氟聚醚))、或與上文所述之構成隔膜3之材料相同之樹脂等。又,亦可適當地使用市售之氟系接著劑、PTFE分散液等。進而,亦可使用通用之乙酸乙烯酯系接著劑、乙烯-乙酸乙烯酯共聚合系接著劑、丙烯酸系樹脂系接著劑、α-烯烴系接著劑、苯乙烯丁二烯橡膠系乳膠接著劑、氯乙烯樹脂系接著劑、氯丁二烯系接著劑、腈橡膠系接著劑、胺基甲酸酯橡膠系接著劑、環氧系接著劑、聚矽氧樹脂系接著劑、改性聚矽氧系接著劑、環氧-改性聚矽氧樹脂系接著劑、矽烷化胺基甲酸酯樹脂系接著劑、氰基丙烯酸酯系接著劑等。 於本實施形態中,可使用溶於電解液或於電解中溶解、分解之有機樹脂。作為溶於電解液或於電解中溶解、分解之有機樹脂,並不限定於以下,例如可列舉:乙酸乙烯酯系接著劑、乙烯-乙酸乙烯酯共聚合系接著劑、丙烯酸系樹脂系接著劑、α-烯烴系接著劑、苯乙烯丁二烯橡膠系乳膠接著劑、氯乙烯樹脂系接著劑、氯丁二烯系接著劑、腈橡膠系接著劑、胺基甲酸酯橡膠系接著劑、環氧系接著劑、聚矽氧樹脂系接著劑、改性聚矽氧系接著劑、環氧-改性聚矽氧樹脂系接著劑、矽烷化胺基甲酸酯樹脂系接著劑、氰基丙烯酸酯系接著劑等。 圖77所示之固定結構可藉由光學顯微鏡或電子顯微鏡進行觀察。較佳為尤其是對樣品進行包埋處理後藉由切片機製作剖面並進行觀察之方法。 於本實施形態中,較佳為固定用構件之至少一部分從外部將隔膜與電解用電極固持。使用圖78A對該態樣進行說明。 圖78A所示之固定結構係從外部將電解用電極2與隔膜3固持並加以固定之結構。即,藉由作為固定用構件7之固持構件將電解用電極2之外表面2b與隔膜3之外表面3b之間夾持並固定。於圖78A所示之固定結構中,亦包括固持構件陷入電解用電極2或隔膜3之狀態。作為固持構件,例如可列舉膠帶、夾具等。 於本實施形態中,亦可使用溶於電解液之固持構件。作為溶於電解液之固持構件,例如可列舉PET製之膠帶、夾具、PVA製之膠帶、夾具等。 圖78A所示之固定結構與圖74~圖77不同,並非將電解用電極2與隔膜3之界面接合者,電解用電極2與隔膜3之各內表面2a、3a僅處於接觸或相對向之狀態,藉由去除固持構件,可將電解用電極2與隔膜3之固定狀態加以解除而分離。 圖78A並未示出,但亦可使用固持構件將電解用電極2與隔膜3固定於電解池。 又,於本實施形態中,較佳為固定用構件之至少一部分藉由磁力將隔膜與電解用電極進行固定。使用圖78B對該態樣進行說明。 圖78B所示之固定結構係從外部將電解用電極2與隔膜3固持並加以固定之結構。與圖78A之區別在於使用1對磁石作為用作固定用構件之固持構件之方面。於圖78B所示之固定結構之態樣中,於將積層體1安裝於電解槽後,於電解槽運轉時可將固持構件直接殘留,亦可將其從積層體1去除。 圖78B並未示出,但亦可使用固持構件將電解用電極2與隔膜3固定於電解池。又,於電解池之材質之一部分使用與磁石接著之磁性材料之情形時,亦可將1種固持材料設置於隔膜面側,將電解池、電解用電極2及隔膜3夾住而固定。 再者,亦可設置複數列固定部。即,可從積層體1之輪廓側起朝向內側配置1、2、3、…n條固定部。n為1以上之整數。又,第m號(m<n)固定部與第L號(m<L≦n)固定部可藉由不同之固定圖案形成。 形成於通電面之固定部較佳為線對稱之形狀。藉此,有能夠抑制應力集中之傾向。例如,若將正交之2個方向設為X方向與Y方向,則可於X方向與Y方向之各方向各配置1條、或於X方向與Y方向之各方向等間隔地各配置複數條而構成固定部。並非對X方向及Y方向之固定部之條數進行限定,但較佳為於X方向及Y方向分別設為100條以下。又,就確保通電面之面性之觀點而言,X方向及Y方向之固定部之條數宜分別為50條以下。 於本實施形態中之固定部中,於具有圖74A或圖76所示之固定結構之情形時,就防止由陽極與陰極接觸引起之短路之觀點而言,較佳為於固定部之膜面上塗佈密封材。作為密封材,例如可使用上述接著劑中所說明之素材。 本實施形態中之積層體可如上所述,於各種位置具有各種固定部,就充分確保電解性能之觀點而言,該等固定部較佳為存在於非通電面。 本實施形態中之積層體可如上所述,於各種位置具有各種固定部,但較佳為尤其是於不存在固定部之部分(非固定部),電解用電極滿足上述「承受力」。即,較佳為電解用電極之非固定部中之每單位質量·單位面積所承受之力未達1.5 N/mg・cm2 。 又,於本實施形態中,較佳為隔膜包含於表面層含有有機樹脂之離子交換膜,且於該有機樹脂中電解用電極被固定。該有機樹脂如上所述,可藉由各種公知之方法作為離子交換膜之表面層而形成。 (水電解) 本實施形態之進行水電解之情形時之電解槽係具有將上述進行食鹽電解之情形時之電解槽中之離子交換膜變更為微多孔膜之構成者。又,於所供給之原料為水之方面與上述進行食鹽電解之情形時之電解槽不同。關於其他構成,進行水電解之情形時之電解槽亦可採用與進行食鹽電解之情形時之電解槽相同之構成。於食鹽電解之情形時,由於在陽極室產生氯氣,因此陽極室之材質使用鈦,於水電解之情形時,由於在陽極室僅產生氧氣,因此可使用與陰極室之材質相同者。例如可列舉鎳等。又,陽極塗層適宜為產生氧氣用之觸媒塗層。作為觸媒塗層之例,可列舉鉑族金屬及過渡金屬族之金屬、氧化物、氫氧化物等。例如可使用鉑、銥、鈀、釕、鎳、鈷、鐵等元素。 (電解槽之製造方法及積層體之更新方法) 本實施形態之電解槽中之積層體之更新方法具有:藉由將本實施形態中之積層體從陽極側墊片及陰極側墊片分離而將該積層體從電解槽取出之驟;及於陽極側墊片與陰極側墊片之間夾持新的積層體之步驟。再者,所謂新積層體意指本實施形態中之積層體,電解用電極及隔膜之至少一者為新品即可。 於上述夾持積層體之步驟中,就於電解槽中將電解用電極更穩定地固定之觀點而言,較佳為電解用電極及隔膜之兩者被陽極側墊片及陰極側墊片夾持。 又,本實施形態之電解槽之製造方法具有於陽極側墊片與陰極側墊片之間夾持本實施形態中之積層體之步驟。 本實施形態之電解槽之製造方法及積層體之更新方法由於以上述方式構成,因此能夠提高電解槽中之電極更新時之作業效率,進而更新後亦可獲得優異之電解性能。 於上述夾持積層體之步驟中,就於電解槽中將電解用電極更穩定地固定之觀點而言,亦較佳為電解用電極及隔膜之兩者被陽極側墊片及陰極側墊片夾持。 <第5實施形態> 此處,一邊參照圖91~102一邊對本發明之第5實施形態進行詳細地說明。 [電解槽之製造方法] 第5實施形態(以下於<第5實施形態>之項中簡稱為「本實施形態」)之電解槽之製造方法係用以藉由對具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽配置電解用電極或該電解用電極與新隔膜之積層體而製造新電解槽之方法,並且使用上述電解用電極或上述積層體之捲繞體。如上所述,根據本實施形態之電解槽之製造方法,由於使用電解用電極或該電解用電極與新隔膜之積層體之捲繞體,因此能夠減小用作電解槽之構件時之電解用電極或積層體之尺寸後進行搬運等,能夠提高電解槽中之電極更新時之作業效率。 於本實施形態中,既有電解槽包含陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜作為構成構件,換言之,其包含電解池。既有電解槽只要包含上述構成構件,則無特別限定,可應用各種公知之構成。 於本實施形態中,新電解槽係除了於既有電解槽中已作為陽極或陰極而發揮功能之構件以外,進而具備電解用電極或積層體者。即,於製造新電解槽時所配置之「電解用電極」係作為陽極或陰極而發揮功能者,與既有電解槽中之陰極及陽極不同體。於本實施形態中,即使於伴隨既有電解槽之運轉陽極及/或陰極之電解性能劣化之情形時,藉由配置與該等不同體之電解用電極,亦可更新陽極及/或陰極之性能。又,於本實施形態中使用積層體之情形時,由於一併配置新離子交換膜,因此伴隨運轉性能劣化之離子交換膜之性能亦可同時更新。此處所謂「更新性能」意指設為與將既有電解槽供於運轉前所具有之初始性能相同之性能、或高於該初始性能之性能。 於本實施形態中,假定既有電解槽係「已供於運轉之電解槽」,又,假定新電解槽係「尚未供於運轉之電解槽」。即,若將作為新電解槽所製造之電解槽供於運轉一次,則成為「本實施形態中之既有電解槽」,對該既有電解槽配置電解用電極或積層體而成者成為「本實施形態中之新電解槽」。 以下,以使用離子交換膜作為隔膜進行食鹽電解之情形為例,對電解槽之一實施形態進行詳細說明。再者,於<第5實施形態>之項中,只要無特別說明,則「本實施形態中之電解槽」包含「本實施形態中之既有電解槽」及「本實施形態中之新電解槽」之兩者。 [電解池] 首先,對可用作本實施形態中之電解槽之構成單元的電解池進行說明。圖91係電解池1之剖面圖。 電解池1具備陽極室10、陰極室20、設置於陽極室10及陰極室20之間之間隔壁30、設置於陽極室10之陽極11、及設置於陰極室20之陰極21。視需要亦可具備具有基材18a與形成於該基材18a上之逆向電流吸收層18b且設置於陰極室內之逆向電流吸收體18。屬於1個電解池1之陽極11及陰極21互相電性連接。換言之,電解池1具備如下陰極結構體。陰極結構體40具備陰極室20、設置於陰極室20之陰極21、及設置於陰極室20內之逆向電流吸收體18,逆向電流吸收體18如圖95所示具有基材18a與形成於該基材18a上之逆向電流吸收層18b,陰極21與逆向電流吸收層18b電性連接。陰極室20進而具有集電體23、支持該集電體之支持體24、及金屬彈性體22。金屬彈性體22係設置於集電體23及陰極21之間。支持體24係設置於集電體23及間隔壁30之間。集電體23經由金屬彈性體22而與陰極21電性連接。間隔壁30經由支持體24而與集電體23電性連接。因此,間隔壁30、支持體24、集電體23、金屬彈性體22及陰極21係電性連接。陰極21及逆向電流吸收層18b係電性連接。陰極21及逆向電流吸收層可直接連接,亦可經由集電體、支持體、金屬彈性體或間隔壁等而間接連接。陰極21之表面整體較佳為由用於還原反應之觸媒層所被覆。又,電性連接之形態可為分別直接將間隔壁30與支持體24、支持體24與集電體23、集電體23與金屬彈性體22安裝,並且於金屬彈性體22上積層陰極21之形態。作為將該等各構成構件互相直接安裝之方法,可列舉焊接等。又,亦可將逆向電流吸收體18、陰極21、及集電體23總稱為陰極結構體40。 圖92係電解槽4內鄰接之2個電解池1之剖面圖。圖93表示電解槽4。圖94表示組裝電解槽4之步驟。 如圖92所示,將電解池1、陽離子交換膜2、電解池1依序串聯排列。於電解槽內鄰接之2個電解池中之一電解池1之陽極室與另一電解池1之陰極室之間配置離子交換膜2。即,電解池1之陽極室10及與其鄰接之電解池1之陰極室20係由陽離子交換膜2隔開。如圖93所示,電解槽4包含介隔離子交換膜2而串聯連接之複數個電解池1。即,電解槽4係具備串聯配置之複數個電解池1、及配置於鄰接之電解池1之間之離子交換膜2的複極式電解槽。如圖94所示,電解槽4係藉由介隔離子交換膜2將複數個電解池1串聯配置並利用壓製器5連結而組裝。 電解槽4具有連接於電源之陽極端子7與陰極端子6。於電解槽4內串聯連結之複數個電解池1中位於最靠端之電解池1之陽極11係電性連接於陽極端子7。於電解槽4內串聯連結之複數個電解池2中位於陽極端子7之相反側之端之電解池的陰極21係電性連接於陰極端子6。電解時之電流從陽極端子7側起,經過各電解池1之陽極及陰極而流向陰極端子6。再者,可於連結之電解池1之兩端配置僅具有陽極室之電解池(陽極終端池)與僅具有陰極室之電解池(陰極終端池)。於該情形時,將陽極端子7連接於配置於其一端之陽極終端池,將陰極端子6連接於配置於另一端之陰極終端池。 於進行鹽水之電解之情形時,向各陽極室10供給鹽水,向陰極室20供給純水或低濃度之氫氧化鈉水溶液。各液體係從電解液供給管(圖中省略)起,經過電解液供給軟管(圖中省略)而向各電解池1供給。又,電解液及電解之產物係由電解液回收管(圖中省略)所回收。於電解中,鹽水中之鈉離子從一電解池1之陽極室10起,通過離子交換膜2,向旁邊之電解池1之陰極室20移動。由此電解中之電流沿將電解池1串聯連結之方向流通。即,電流係經由陽離子交換膜2而從陽極室10流向陰極室20。伴隨鹽水之電解,於陽極11側產生氯氣,於陰極21側產生氫氧化鈉(溶質)與氫氣。 (陽極室) 陽極室10具有陽極11或陽極饋電體11。作為此處所謂饋電體意指劣化之電極(即既有電極)或未形成有觸媒塗層之電極等。於將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極饋電體發揮功能。於不將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極發揮功能。又,陽極室10較佳為具有向陽極室10供給電解液之陽極側電解液供給部、配置於陽極側電解液供給部之上方且以與間隔壁30大致平行或傾斜之方式配置之擋板、及配置於擋板之上方且從混入有氣體之電解液中分離氣體之陽極側氣液分離部。 (陽極) 於不將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框(即,陽極框)內設置有陽極11。作為陽極11,可使用所謂DSA(註冊商標)等金屬電極。所謂DSA係藉由以釕、銥、鈦作為成分之氧化物被覆表面之鈦基材之電極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極饋電體) 於將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極饋電體11。作為陽極饋電體11,可使用所謂DSA(註冊商標)等金屬電極,亦可使用未形成有觸媒塗層之鈦。又,亦可使用使觸媒塗層厚度變薄之DSA。進而,亦可使用使用過之陽極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極側電解液供給部) 陽極側電解液供給部係向陽極室10供給電解液者,其連接於電解液供給管。陽極側電解液供給部較佳為配置於陽極室10之下方。作為陽極側電解液供給部,例如可使用表面形成有開口部之管(分散管)等。該管更佳為以沿陽極11之表面平行於電解池之底部19之方式配置。該管係連接於向電解池1內供給電解液之電解液供給管(液供給噴嘴)。從液供給噴嘴供給之電解液藉由管被搬送至電解池1內,從設置於管之表面之開口部向陽極室10之內部供給。藉由將管以沿陽極11之表面平行於電解池之底部19之方式配置,能夠將電解液均勻地供給至陽極室10之內部,故而較佳。 (陽極側氣液分離部) 陽極側氣液分離部較佳為配置於擋板之上方。於電解中,陽極側氣液分離部具有將氯氣等產生氣體與電解液分離之功能。再者,只要無特別說明,則所謂上方意指圖91之電解池1中之上方向,所謂下方意指圖91之電解池1中之下方向。 電解時,若電解池1中產生之產生氣體與電解液成為混相(氣液混相)而被排出至系外,則存在因電解池1內部之壓力變動導致產生振動而引起離子交換膜之物理破損之情形。為了抑制該情形,較佳為於本實施形態中之電解池1中設置用以將氣體與液體分離之陽極側氣液分離部。較佳為於陽極側氣液分離部設置用以消除氣泡之消泡板。藉由在氣液混相流通過消泡板時氣泡破裂,而可分離為電解液與氣體。其結果為,能夠防止電解時之振動。 (擋板) 擋板較佳為配置於陽極側電解液供給部之上方,且以與間隔壁30大致平行或傾斜之方式配置。擋板係控制陽極室10之電解液之流動之間隔板。藉由設置擋板,可使電解液(鹽水等)於陽極室10內部循環,使其濃度變得均勻。為了引起內部循環,擋板較佳為以將陽極11附近之空間與間隔壁30附近之空間隔開之方式配置。就該觀點而言,擋板較佳為以與陽極11及間隔壁30之各表面相對向之方式設置。於由擋板分隔之陽極附近之空間,藉由進行電解,電解液濃度(鹽水濃度)降低,又,產生氯氣等產生氣體。藉此,於由擋板分隔之陽極11附近之空間與間隔壁30附近之空間產生氣液之比重差。利用該情況,能夠促進陽極室10中之電解液之內部循環,使陽極室10之電解液之濃度分佈變得更均勻。 再者,於圖91並未圖示,但亦可於陽極室10之內部另行設置集電體。作為該集電體,亦可設為與下文所述之陰極室之集電體相同之材料或構成。又,於陽極室10中,亦可使陽極11本身作為集電體發揮功能。 (間隔壁) 間隔壁30係配置於陽極室10與陰極室20之間。間隔壁30有時亦稱為間隔件,係將陽極室10與陰極室20進行劃分者。作為間隔壁30,可使用作為電解用之間隔件所公知者,例如可列舉於陰極側焊接包含鎳之板、於陽極側焊接包含鈦之板之間隔壁等。 (陰極室) 陰極室20於將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極饋電體發揮功能,於不將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極發揮功能。於具有逆向電流吸收體之情形時,陰極或陰極饋電體21與逆向電流吸收體係電性連接。又,陰極室20較佳為與陽極室10同樣,亦具有陰極側電解液供給部、陰極側氣液分離部。再者,構成陰極室20之各部位中,關於與構成陽極室10之各部位相同者省略說明。 (陰極) 於不將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框(即,陰極框)內設置有陰極21。陰極21較佳為具有鎳基材與被覆鎳基材之觸媒層。作為鎳基材上之觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可視需要對陰極21實施還原處理。再者,作為陰極21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陰極饋電體) 於將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極饋電體21。可對陰極饋電體21被覆觸媒成分。該觸媒成分可為原本用作陰極而殘存者。作為觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可使用未形成有觸媒塗層之鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。再者,作為陰極饋電體21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (逆向電流吸收層) 可選擇具有較上文所述之陰極之觸媒層用元素的氧化還原電位更低之氧化還原電位之材料作為逆向電流吸收層之材料。例如可列舉鎳或鐵等。 (集電體) 陰極室20較佳為具備集電體23。藉此,集電效果提高。於本實施形態中,集電體23較佳為多孔板,且以與陰極21之表面大致平行之方式配置。 作為集電體23,例如較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。集電體23可為該等金屬之混合物、合金或複合氧化物。再者,集電體23之形狀只要為作為集電體發揮功能之形狀,則可為任意形狀,可為板狀、網狀。 (金屬彈性體) 藉由在集電體23與陰極21之間設置金屬彈性體22,將串聯連接之複數個電解池1之各陰極21壓抵於離子交換膜2,各陽極11與各陰極21之間之距離變短,可降低對串聯連接之複數個電解池1整體施加之電壓。藉由電壓降低,可降低消耗電量。又,藉由設置金屬彈性體22,於將含有本實施形態中之電解用電極之積層體設置於電解池時,藉由金屬彈性體22之壓抵壓,可將該電解用電極穩定地維持於起始位置。 作為金屬彈性體22,可使用螺旋彈簧、線圈等彈簧構件、緩衝性之墊等。作為金屬彈性體22,可考慮壓抵離子交換膜之應力等而適當採用適宜者。可將金屬彈性體22設置於陰極室20側之集電體23之表面上,亦可設置於陽極室10側之間隔壁之表面上。通常以陰極室20小於陽極室10之方式劃分兩室,因此就框體之強度等觀點而言,較佳為將金屬彈性體22設置於陰極室20之集電體23與陰極21之間。又,金屬彈性體23較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。 (支持體) 陰極室20較佳為具備將集電體23與間隔壁30電性連接之支持體24。藉此,能夠效率良好地流通電流。 支持體24較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。又,作為支持體24之形狀,只要為能夠支持集電體23之形狀,則可為任意形狀,可為棒狀、板狀或網狀。支持體24例如為板狀。複數個支持體24係配置於間隔壁30與集電體23之間。複數個支持體24係以各自之面互相平行之方式排列。支持體24係以大致垂直於間隔壁30及集電體23之方式配置。 (陽極側墊片、陰極側墊片) 陽極側墊片較佳為配置於構成陽極室10之框體表面。陰極側墊片較佳為配置於構成陰極室20之框體表面。1個電解池所具備之陽極側墊片及與其鄰接之電解池之陰極側墊片以夾持離子交換膜2之方式將電解池彼此連接(參照圖92)。藉由該等墊片,於介隔離子交換膜2將複數個電解池1串聯連接時,能夠對連接處賦予氣密性。 所謂墊片係將離子交換膜與電解池之間密封者。作為墊片之具體例,可列舉中央形成有開口部之邊框狀之橡膠製片等。對於墊片要求對腐蝕性之電解液或所產生之氣體等具有耐性而可長期使用。因此,就耐化學品性或硬度之方面而言,通常可使用乙烯-丙烯-二烯橡膠(EPDM橡膠)、乙烯-丙烯橡膠(EPM橡膠)之硫化物或過氧化物交聯物等作為墊片。又,視需要亦可使用以聚四氟乙烯(PTFE)或四氟乙烯-全氟烷基乙烯醚共聚物(PFA)等氟系樹脂被覆與液體相接之區域(接液部)之墊片。該等墊片只要以不妨礙電解液之流動之方式分別具有開口部即可,其形狀並無特別限定。例如沿構成陽極室10之陽極室框或構成陰極室20之陰極室框之各開口部之周緣,藉由接著劑等貼附邊框狀之墊片。此外,於例如介隔離子交換膜2連接2個電解池1之情形時(參照圖92),介隔離子交換膜2將貼附有墊片之各電解池1緊固即可。藉此,能夠抑制電解液、因電解而產生之鹼金屬氫氧化物、氯氣、氫氣等漏至電解池1之外部之情況。 [使用捲繞體之步驟] 本實施形態中之捲繞體可為電解用電極之捲繞體,亦可為電解用電極與新隔膜之積層體之捲繞體。於本實施形態之電解槽之製造方法中,使用該捲繞體。作為使用捲繞體之步驟之具體例,並不限定於以下,可列舉如下方法等:首先,於既有電解槽中將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,於該電解池及離子交換膜之間形成空隙,其次,將解除電解用電極之捲繞體之捲繞狀態而成者插入至該空隙,再次藉由壓製器將各構件連結。再者,於使用積層體之捲繞體之情形時,例如可列舉如下方法等:以上述方式於電解池及離子交換膜之間形成空隙後,去除成為更新對象之既有之離子交換膜,其次,將解除積層體之捲繞體之捲繞狀態而成者插入至該空隙,再次藉由壓製器將各構件連結。藉由此種方法,能夠將電解用電極或積層體配置於既有電解槽中之陽極或陰極之表面上,而能夠更新離子交換膜、陽極及/或陰極之性能。 如上所述,於本實施形態中,較佳為使用捲繞體之步驟具有將捲繞體之捲繞狀態加以解除之步驟(B),又,更佳為具有於步驟(B)之後將電解用電極或積層體配置於陽極及陰極之至少一者之表面上之步驟(C)。 又,於本實施形態中,較佳為使用捲繞體之步驟具有將電解用電極或積層體保持為捲繞狀態而獲得捲繞體之步驟(A)。於步驟(A)中,可將電解用電極或積層體本身進行捲繞而製成捲繞體,亦可將電解用電極或積層體纏繞至芯而製成捲繞體。作為此處可使用之芯,並無特別限定,例如可使用具有大致圓柱形狀且與電解用電極或積層體相適應之尺寸之構件。 [電解用電極] 於本實施形態中,電解用電極只要如上所述可用作捲繞體、即為能夠捲繞者,則無特別限定。電解用電極可為於電解槽中作為陰極而發揮功能者,亦可為作為陽極而發揮功能者。又,關於電解用電極之材質或形狀等,可考慮本實施形態中之使用捲繞體之步驟或電解槽之構成等,適當選擇於製成捲繞體之方面合適者。以下,對本實施形態中之電解用電極之較佳之態樣進行說明,但該等終歸僅為於製成捲繞體之方面較佳之態樣之例示,亦可適當採用下文所述之態樣以外之電解用電極。 本實施形態中之電解用電極就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、饋電體(劣化之電極及未形成有觸媒塗層之電極)等具有良好之接著力之觀點而言,每單位質量·單位面積所承受之力較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/mg・cm2 以上,進而更佳為0.14 N/(mg・cm2 )以上。就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.2 N/(mg・cm2 )以上。 上述承受力例如可藉由適當調整下文所述之開孔率、電極之厚度、算術平均表面粗糙度等而設為上述範圍。更具體而言,例如,若增大開孔率,則承受力有變小之傾向,若減小開孔率,則承受力有變大之傾向。 又,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力之觀點,進而就經濟性之觀點而言,較佳為每單位面積之質量為48 mg/cm2 以下,更佳為30 mg/cm2 以下,進而較佳為20 mg/cm2 以下,進而,就合併操作性、接著性及經濟性之綜合性之觀點而言,較佳為15 mg/cm2 以下。下限值並無特別限定,例如為1 mg/cm2 左右。 上述每單位面積之質量例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則每單位面積之質量有變小之傾向,若減小開孔率,則每單位面積之質量有變大之傾向。 承受力可藉由以下之方法(i)或(ii)進行測定,詳細而言,如實施例所記載。關於承受力,藉由方法(i)之測定所獲得之值(亦稱為「承受力(1)」)與藉由方法(ii)之測定所獲得之值(亦稱為「承受力(2)」)可相同亦可不同,但較佳為任一值均未達1.5 N/mg・cm2 。 [方法(i)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方)、於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方,關於此處所謂離子交換膜之詳細如實施例所記載)及電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。再者,噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.5~0.8 μm。算術平均表面粗糙度(Ra)之具體之算出方法如實施例所記載。 於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與離子交換膜之重疊部分之面積、及與離子交換膜重疊部分之電極樣品之質量,而算出每單位質量·單位面積所承受之力(1)(N/mg・cm2 )。 藉由方法(i)獲得之每單位質量·單位面積所承受之力(1)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。又,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 ),更佳為0.2 N/(mg・cm2 )以上。 [方法(ii)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方,與上述方法(i)相同之鎳板)與電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與鎳板之重疊部分之面積、及與鎳板重疊部分中之電極樣品之質量,而算出每單位質量•單位面積之接著力(2)(N/mg・cm2 )。 藉由方法(ii)獲得之每單位質量·單位面積所承受之力(2)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。進而,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 )以上。 本實施形態中之電解用電極較佳為包含電解用電極基材及觸媒層。該電解用電極基材之厚度(量規厚度)並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折,大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力之觀點而言,藉由以下之方法(2)所測得之比率較佳為90%以上,更佳為92%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為95%以上。上限值為100%。 [方法(2)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑280 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折之觀點而言,藉由以下之方法(3)所測得之比率較佳為75%以上,更佳為80%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為90%以上。上限值為100%。 [方法(3)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,防止電解中產生之氣體滯留之觀點而言,較佳為多孔結構,且其開孔率或空隙率為5~90%以下。開孔率更佳為10~80%以下,進而較佳為20~75%。 再者,所謂開孔率係每單位體積之開孔部之比率。開孔部亦根據考慮至次微米級抑或僅考慮目視可見之開口而有各種算出方法。於本實施形態中,可藉由根據電極之量規厚度、寬度、長度之值算出體積V,進而實測重量W,而利用下述之式算出開孔率A。 A=(1-(W/(V×ρ))×100 ρ係電極之材質之密度(g/cm3 )。例如於鎳之情形時為8.908 g/cm3 ,於鈦之情形時為4.506 g/cm3 。開孔率之調整可藉由如下方法進行適當調整:若為沖孔金屬,則變更每單位面積沖裁金屬之面積;若為多孔金屬,則變更SW(短徑)、LW(長徑)、進給之值;若為絲網,則變更金屬纖維之線徑、網眼數;若為電成形,則變更所使用之光阻之圖案;若為不織布,則變更金屬纖維直徑及纖維密度;若為發泡金屬,則變更用以使空隙形成之模板等。 以下,對本實施形態中之電解用電極之更具體之實施形態進行說明。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。觸媒層如下所述,可包含複數層,亦可為單層結構。 如圖96所示,本實施形態之電解用電極100具備電解用電極基材10、及被覆電解用電極基材10之兩表面之一對第一層20。第一層20較佳為將電解用電極基材10整體被覆。藉此,電解用電極之觸媒活性及耐久性變得容易提高。再者,亦可僅於電解用電極基材10之一表面積層第一層20。 又,如圖96所示,第一層20之表面可由第二層30所被覆。第二層30較佳為將第一層20整體被覆。又,第二層30可僅積層於第一層20之一表面。 (電解用電極基材) 作為電解用電極基材10,並無特別限定,例如可使用鎳、鎳合金、不鏽鋼、或以鈦等為代表之閥金屬,較佳為含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 於在高濃度之鹼性水溶液中使用不鏽鋼之情形時,若考慮到鐵及鉻溶出、及不鏽鋼之導電性為鎳之1/10左右,則較佳為使用含有鎳(Ni)之基材作為電解用電極基材。 又,電解用電極基材10於在接近飽和之高濃度之食鹽水中於氯氣產生環境中使用之情形時,材質亦較佳為耐蝕性較高之鈦。 電解用電極基材10之形狀並無特別限定,可根據目的選擇合適之形狀。作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。其中,較佳為沖孔金屬或多孔金屬。再者,所謂電成形係將照相製版與電鍍法組合而製作精密之圖案之金屬薄膜的技術。其係藉由光阻於基板上形成圖案,對未受到光阻保護之部分實施電鍍而獲得金屬薄膜之方法。 關於電解用電極基材之形狀,根據電解槽中之陽極與陰極之距離而有適宜之規格。並無特別限定,於陽極與陰極具有有限之距離之情形時,可使用多孔金屬、沖孔金屬形狀,於離子交換膜與電極相接之所謂零間距電解槽之情形時,可使用編織細線而成之編織網、金屬絲網、發泡金屬、金屬不織布、多孔金屬、沖孔金屬、金屬多孔箔等。 作為電解用電極基材10,可列舉:金屬多孔箔、金屬絲網、金屬不織布、沖孔金屬、多孔金屬或發泡金屬。 作為加工為沖孔金屬、多孔金屬前之板材,較佳為經壓延成形之板材、電解箔等。電解箔較佳為進而作為後處理而藉由與母材相同之元素實施鍍覆處理,於單面或兩面形成凹凸。 又,電解用電極基材10之厚度如上文所述,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於電解用電極基材中,較佳為藉由在氧化環境中將電解用電極基材進行退火而緩和加工時之殘留應力。又,為了提高與被覆於電解用電極基材之表面之觸媒層之密接性,較佳為使用鋼砂、氧化鋁粉等於上述表面形成凹凸,其後藉由酸處理而增加表面積。或者,較佳為藉由與基材相同之元素實施鍍覆處理,增加表面積。 為了使第一層20與電解用電極基材10之表面密接,較佳為對電解用電極基材10進行增大表面積之處理。作為增大表面積之處理,可列舉使用鋼線粒、鋼砂、氧化鋁砂等之噴擊處理、使用硫酸或鹽酸之酸處理、利用與基材相同元素之鍍覆處理等。基材表面之算術平均表面粗糙度(Ra)並無特別限定,較佳為0.05 μm~50 μm,更佳為0.1~10 μm,進而較佳為0.1~8 μm。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陽極之情形進行說明。 (第一層) 於圖96中,作為觸媒層之第一層20含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物。作為釕氧化物,可列舉RuO2 等。作為銥氧化物,可列舉IrO2 等。作為鈦氧化物,可列舉TiO2 等。第一層20較佳為含有釕氧化物及鈦氧化物之兩種氧化物,或含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物。藉此,第一層20成為更穩定之層,進而,與第二層30之密接性亦進一步提高。 於第一層20含有釕氧化物及鈦氧化物之兩種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為1~9莫耳,更佳為1~4莫耳。藉由將兩種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之銥氧化物較佳為0.2~3莫耳,更佳為0.3~2.5莫耳。又,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為0.3~8莫耳,更佳為1~7莫耳。藉由將三種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有選自釕氧化物、銥氧化物及鈦氧化物中之至少兩種氧化物之情形時,該等氧化物較佳為形成固溶體。藉由形成氧化物固溶體,電解用電極100表現出優異之耐久性。 除了上述組成以外,只要含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物,則可使用各種組成者。例如,亦可使用稱為DSA(註冊商標)之含有釕、銥、鉭、鈮、鈦、錫、鈷、錳、鉑等之氧化物塗層作為第一層20。 第一層20無需為單層,亦可包含複數層。例如,第一層20可包含含有三種氧化物之層與含有兩種氧化物之層。第一層20之厚度較佳為0.05~10 μm,更佳為0.1~8 μm。 (第二層) 第二層30較佳為含有釕與鈦。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較佳為含有氧化鈀、氧化鈀與鉑之固溶體或鈀與鉑之合金。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較厚者能夠維持電解性能之時間變長,就經濟性之觀點而言,較佳為0.05~3 μm之厚度。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陰極之情形進行說明。 (第一層) 作為觸媒層之第一層20之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。 於含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少一種之情形時,較佳為鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金含有鉑、鈀、銠、釕、銥中之至少一種鉑族金屬。 作為鉑族金屬,較佳為含有鉑。 作為鉑族金屬氧化物,較佳為含有釕氧化物。 作為鉑族金屬氫氧化物,較佳為含有釕氫氧化物。 作為鉑族金屬合金,較佳為含有鉑與鎳、鐵、鈷之合金。 較佳為進而視需要含有鑭系元素之氧化物或氫氧化物作為第二成分。藉此,電解用電極100表現出優異之耐久性。 作為鑭系元素之氧化物或氫氧化物,較佳為含有選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑中之至少1種。 較佳為進而視需要含有過渡金屬之氧化物或氫氧化物作為第三成分。 藉由添加第三成分,電解用電極100能夠表現出更優異之耐久性,降低電解電壓。 作為較佳之組合之例,可列舉:僅釕、釕+鎳、釕+鈰、釕+鑭、釕+鑭+鉑、釕+鑭+鈀、釕+鐠、釕+鐠+鉑、釕+鐠+鉑+鈀、釕+釹、釕+釹+鉑、釕+釹+錳、釕+釹+鐵、釕+釹+鈷、釕+釹+鋅、釕+釹+鎵、釕+釹+硫、釕+釹+鉛、釕+釹+鎳、釕+釹+銅、釕+釤、釕+釤+錳、釕+釤+鐵、釕+釤+鈷、釕+釤+鋅、釕+釤+鎵、釕+釤+硫、釕+釤+鉛、釕+釤+鎳、鉑+鈰、鉑+鈀+鈰、鉑+鈀+鑭+鈰、鉑+銥、鉑+鈀、鉑+銥+鈀、鉑+鎳+鈀、鉑+鎳+釕、鉑與鎳之合金、鉑與鈷之合金、鉑與鐵之合金等。 於不含鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之情形時,觸媒之主成分較佳為鎳元素。 較佳為含有鎳金屬、氧化物、氫氧化物中之至少1種。 作為第二成分,可添加過渡金屬。作為所添加之第二成分,較佳為含有鈦、錫、鉬、鈷、錳、鐵、硫、鋅、銅、碳中之至少一種元素。 作為較佳之組合,可列舉:鎳+錫、鎳+鈦、鎳+鉬、鎳+鈷等。 視需要可於第一層20與電解用電極基材10之間設置中間層。藉由設置中間層,能夠提高電解用電極100之耐久性。 作為中間層,較佳為對第一層20與電解用電極基材10之兩者具有親和性者。作為中間層,較佳為鎳氧化物、鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物。作為中間層,可藉由將含有形成中間層之成分之溶液進行塗佈、燒成而形成,亦可於空氣環境中在300~600℃之溫度下對基材實施熱處理而形成表面氧化物層。除此以外,可藉由熱熔射法、離子鍍敷法等已知之方法形成。 (第二層) 作為觸媒層之第一層30之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。作為第二層所含之元素之較佳之組合例,有第一層中所列舉之組合等。第一層與第二層之組合可為組成相同而組成比不同之組合,亦可為組成不同之組合。 作為觸媒層之厚度,較佳為將所形成之觸媒層及中間層累加而成之厚度為0.01 μm~20 μm。若為0.01 μm以上,則能夠作為觸媒充分發揮功能。若為20 μm以下,則從基材脫落之情況較少,能夠形成牢固之觸媒層。更佳為0.05 μm~15 μm。更佳為0.1 μm~10 μm。進而較佳為0.2 μm~8 μm。 作為電極之厚度、即電解用電極基材與觸媒層之合計之厚度,就電極之操作性之方面而言,較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,電極之厚度可藉由利用電子數顯厚度計(Mitutoyo股份有限公司,最少顯示0.001 mm)進行測定而求出。電解用電極基材之厚度係與電極厚度同樣地進行測定。觸媒層厚度可藉由電極厚度減去電解用電極基材之厚度而求出。 於本實施形態中,就確保充分之電解性能之觀點而言,較佳為電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。 於本實施形態中,若電解用電極係彈性變形區域較廣之電極,則就可獲得更良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有更良好之接著力之觀點而言,電解用電極之厚度較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,於本實施形態中,所謂「彈性變形區域較廣」意指將電解用電極捲繞而製成捲繞體,解除捲繞狀態後不易產生由捲繞引起之翹曲。又,所謂電解用電極之厚度於包含下文所述之觸媒層之情形時,係指合併電解用電極基材與觸媒層之厚度。 (電解用電極之製造方法) 其次,對電解用電極100之製造方法之一實施形態進行詳細說明。 於本實施形態中,藉由利用氧環境下之塗膜之燒成(熱分解)、或離子鍍敷、鍍覆、熱熔射等方法於電解用電極基材上形成第一層20、較佳為第二層30,可製造電解用電極100。此種本實施形態之製造方法能夠實現電解用電極100之較高之生產性。具體而言,藉由塗佈含有觸媒之塗佈液之塗佈步驟、乾燥塗佈液之乾燥步驟、進行熱分解之熱分解步驟,而於電解用電極基材上形成觸媒層。此處所謂熱分解意指對成為前驅物之金屬鹽進行加熱而分解為金屬或金屬氧化物與氣體狀物質。根據所使用之金屬種類、鹽之種類、進行熱分解之環境等,分解產物有所不同,但於氧化性環境下多數金屬有容易形成氧化物之傾向。於電極之工業性之製造工藝中,熱分解通常於空氣中進行,多數情形時形成金屬氧化物或金屬氫氧化物。 (陽極之第一層之形成) (塗佈步驟) 第一層20係將溶解有釕、銥及鈦中之至少一種金屬之鹽的溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之釕、銥及鈦之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材100後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (第二層之形成) 第二層30係視需要而形成,例如將含有鈀化合物及鉑化合物之溶液或含有釕化合物及鈦化合物之溶液(第二塗佈液)塗佈於第一層20上後,於氧氣之存在下進行熱分解而獲得。 (利用熱分解法之陰極之第一層之形成) (塗佈步驟) 第一層20係將溶解有各種組合之金屬鹽之溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之金屬之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材10後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (中間層之形成) 中間層係視需要而形成,例如將含有鈀化合物或鉑化合物之溶液(第二塗佈液)塗佈於基材上後,於氧氣之存在下進行熱分解而獲得。或者,亦可不塗佈溶液,而僅加熱基材,藉此於基材表面形成氧化鎳中間層。 (利用離子鍍敷之陰極之第一層之形成) 第一層20亦可藉由離子鍍敷而形成。 作為一例,可列舉將基材固定於腔室內並對金屬釕靶照射電子束之方法。所蒸發之金屬釕粒子於腔室內之電漿中帶正電,而沈積於帶負電之基板上。電漿環境為氬氣、氧氣,釕係以釕氧化物之形式沈積於基材上。 (利用鍍覆之陰極之第一層之形成) 第一層20亦可藉由鍍覆法而形成。 作為一例,若使用基材作為陰極,於含有鎳及錫之電解液中實施電解鍍覆,則可形成鎳與錫之合金鍍覆。 (利用熱熔射之陰極之第一層之形成) 第一層20亦可藉由熱熔射法而形成。 作為一例,藉由將氧化鎳粒子電漿熔射於基材上,而可形成混合有金屬鎳與氧化鎳之觸媒層。 [積層體] 本實施形態中之電解用電極可作為與離子交換膜或微多孔膜等隔膜之積層體而使用。即,本實施形態中之積層體係包含電解用電極與新隔膜者。所謂新隔膜,只要與既有電解槽中之隔膜不同體,則無特別限定,可應用各種公知之隔膜。又,新隔膜可為材質、形狀、物性等與既有電解槽中之隔膜相同者。 以下,對隔膜之一態樣之離子交換膜進行詳細說明。 [離子交換膜] 作為離子交換膜,只要可與電解用電極製成積層體,則無特別限定,可應用各種離子交換膜。於本實施形態中,較佳為使用具有含有具有離子交換基之烴系聚合物或含氟系聚合物之膜本體、與設置於該膜本體之至少一面上之塗佈層之離子交換膜。又,塗佈層含有無機物粒子與結合劑,塗佈層之比表面積較佳為0.1~10 m2 /g。該結構之離子交換膜於電解中所產生之氣體對電解性能之影響較少,有發揮出穩定之電解性能之傾向。 上述所謂導入有離子交換基之全氟碳聚合物之膜係具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層之任一者。就強度及尺寸穩定性之觀點而言,較佳為進而具有強化芯材。 以下於塗佈層之說明之欄對無機物粒子及結合劑進行詳細說明。 圖97係表示離子交換膜之一實施形態之剖面模式圖。離子交換膜1具有:膜本體10,其含有具有離子交換基之烴系聚合物或含氟系聚合物;以及塗佈層11a及11b,其等形成於膜本體10之兩面。 於離子交換膜1中,膜本體10具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層3、與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層2,藉由強化芯材4強化強度及尺寸穩定性。離子交換膜1由於具備磺酸層3與羧酸層2,因此可作為陽離子交換膜而適宜地使用。 再者,離子交換膜亦可僅具有磺酸層及羧酸層之任一者。又,離子交換膜未必由強化芯材所強化,強化芯材之配置狀態亦不限定於圖97之例。 (膜本體) 首先,對構成離子交換膜1之膜本體10進行說明。 膜本體10只要為具有使陽離子選擇性地透過之功能且含有具有離子交換基之烴系聚合物或含氟系聚合物者即可,其構成或材料並無特別限定,可適當選擇適宜者。 膜本體10中之具有離子交換基之烴系聚合物或含氟系聚合物例如可由具有可藉由水解等成為離子交換基之離子交換基前驅物之烴系聚合物或含氟系聚合物獲得。具體而言,例如使用主鏈包含氟化烴、具有可藉由水解等轉換為離子交換基之基(離子交換基前驅物)作為懸垂側鏈且能夠熔融加工之聚合物(以下視情形稱為「含氟系聚合物(a)」)製作膜本體10之前驅物後,將離子交換基前驅物轉換為離子交換基,藉此可獲得膜本體10。 含氟系聚合物(a)例如可藉由使選自下述第1群之至少一種單體與選自下述第2群及/或下述第3群之至少一種單體進行共聚合而製造。又,亦可藉由選自下述第1群、下述第2群、及下述第3群之任一群之1種單體之均聚而製造。 作為第1群之單體,例如可列舉氟乙烯化合物。作為氟乙烯化合物,例如可列舉:氟乙烯、四氟乙烯、六氟丙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、全氟烷基乙烯醚等。尤其是於將離子交換膜用作鹼電解用膜之情形時,氟乙烯化合物較佳為全氟單體,較佳為選自由四氟乙烯、六氟丙烯、全氟烷基乙烯醚所組成之群中之全氟單體。 作為第2群之單體,例如可列舉具有可轉換為羧酸型離子交換基(羧酸基)之官能基之乙烯系化合物。作為具有可轉換為羧酸基之官能基之乙烯系化合物,例如可列舉以CF2 =CF(OCF2 CYF)s -O(CZF)t -COOR表示之單體等(此處,s表示0~2之整數,t表示1~12之整數,Y及Z各自獨立地表示F或CF3 ,R表示低級烷基。低級烷基例如為碳數1~3之烷基)。 該等中,較佳為以CF2 =CF(OCF2 CYF)n -O(CF2 )m -COOR表示之化合物。此處,n表示0~2之整數,m表示1~4之整數,Y表示F或CF3 ,R表示CH3 、C2 H5 、或C3 H7 。 再者,於將離子交換膜用作鹼電解用陽離子交換膜之情形時,較佳為至少使用全氟化合物作為單體,但由於酯基之烷基(參照上述R)於水解時從聚合物喪失,因此烷基(R)亦可不為全部氫原子被取代為氟原子之全氟烷基。 作為第2群之單體,於上述中,更佳為下述所表示之單體。 CF2 =CFOCF2 -CF(CF3 )OCF2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )2 COOCH3 、 CF2 =CF[OCF2 -CF(CF3 )]2 O(CF2 )2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )3 COOCH3 、 CF2 =CFO(CF2 )2 COOCH3 、 CF2 =CFO(CF2 )3 COOCH3 。 作為第3群之單體,例如可列舉具有可轉換為磺酸型離子交換基(磺酸基)之官能基之乙烯系化合物。作為具有可轉換為磺酸基之官能基之乙烯系化合物,例如較佳為以CF2 =CFO-X-CF2 -SO2 F表示之單體(此處,X表示全氟伸烷基)。作為該等之具體例,可列舉下述所表示之單體等。 CF2 =CFOCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、 CF2 =CF(CF2 )2 SO2 F、 CF2 =CFO[CF2 CF(CF3 )O]2 CF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF2 OCF3 )OCF2 CF2 SO2 F。 該等中,更佳為CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、及CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F。 由該等單體獲得之共聚物可藉由針對氟乙烯之均聚及共聚合所開發之聚合法、尤其是對四氟乙烯所使用之通常之聚合方法而製造。例如,於非水性法中,可使用全氟烴、氯氟碳等不活性溶劑,於全氟碳過氧化物或偶氮化合物等自由基聚合起始劑之存在下,於溫度0~200℃、壓力0.1~20 MPa之條件下進行聚合反應。 於上述共聚合中,上述單體之組合之種類及其比率並無特別限定,根據欲對所獲得之含氟系聚合物賦予之官能基之種類及量選擇確定。例如於製成僅含有羧酸基之含氟系聚合物之情形時,從上述第1群及第2群分別選擇至少1種單體進行共聚合即可。又,於製成僅含有磺酸基之含氟系聚合物之情形時,從上述第1群及第3群之單體中分別選擇至少1種單體進行共聚合即可。進而,於製成具有羧酸基及磺酸基之含氟系聚合物之情形時,從上述第1群、第2群及第3群之單體中分別選擇至少1種單體進行共聚合即可。於該情形時,藉由使包含上述第1群及第2群之共聚物與包含上述第1群及第3群之共聚物分開進行聚合,其後加以混合亦可獲得目標之含氟系聚合物。又,各單體之混合比率並無特別限定,於增加每單位聚合物之官能基之量之情形時,增加選自上述第2群及第3群之單體之比率即可。 含氟系共聚物之總離子交換容量並無特別限定,較佳為0.5~2.0 mg當量/g,更佳為0.6~1.5 mg當量/g。此處,所謂總離子交換容量係指相對於單位重量之乾燥樹脂之交換基之當量,可藉由中和滴定等進行測定。 於離子交換膜1之膜本體10中,積層有含有具有磺酸基之含氟系聚合物之磺酸層3與含有具有羧酸基之含氟系聚合物之羧酸層2。藉由製成此種層結構之膜本體10,能夠進一步提高鈉離子等陽離子之選擇性透過性。 於將離子交換膜1配置於電解槽之情形時,通常以磺酸層3位於電解槽之陽極側、羧酸層2位於電解槽之陰極側之方式配置。 磺酸層3較佳為由電阻較低之材料構成,就膜強度之觀點而言,較佳為其膜厚厚於羧酸層2。磺酸層3之膜厚較佳為羧酸層2之2~25倍,更佳為3~15倍。 羧酸層2較佳為即使膜厚較薄亦具有較高之陰離子排斥性者。此處所謂陰離子排斥性係指阻礙陰離子對離子交換膜1之滲入或透過之性質。為了提高陰離子排斥性,有效的是對磺酸層配置離子交換容量較小之羧酸層等。 作為磺酸層3所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F作為第3群之單體所獲得之聚合物。 作為羧酸層2所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF2 )O(CF2 )2 COOCH3 作為第2群之單體所獲得之聚合物。 (塗佈層) 離子交換膜較佳為於膜本體之至少一面上具有塗佈層。又,如圖97所示,於離子交換膜1中,於膜本體10之兩面上分別形成有塗佈層11a及11b。 塗佈層含有無機物粒子與結合劑。 無機物粒子之平均粒徑更佳為0.90 μm以上。若無機物粒子之平均粒徑為0.90 μm以上,則不僅極大地提高對氣體附著之耐久性,而且極大地提高對雜質之耐久性。即,藉由增大無機物粒子之平均粒徑,並且滿足上述比表面積之值,可獲得尤其顯著之效果。為了滿足此種平均粒徑與比表面積,較佳為不規則狀之無機物粒子。可使用藉由熔融獲得之無機物粒子、藉由原石粉碎獲得之無機物粒子。較佳可適宜地使用藉由原石粉碎獲得之無機物粒子。 又,無機物粒子之平均粒徑可設為2 μm以下。若無機物粒子之平均粒徑為2 μm以下,則能夠防止因無機物粒子而損傷膜。無機物粒子之平均粒徑更佳為0.90~1.2 μm。 此處,平均粒徑可藉由粒度分佈計(「SALD2200」島津製作所)進行測定。 無機物粒子之形狀較佳為不規則形狀。對雜質之耐性進一步提高。又,無機物粒子之粒度分佈較佳為較寬。 無機物粒子較佳為含有選自由週期表第IV族元素之氧化物、週期表第IV族元素之氮化物、及週期表第IV族元素之碳化物所組成之群中之至少一種無機物。就耐久性之觀點而言,更佳為氧化鋯之粒子。 該無機物粒子較佳為藉由將無機物粒子之原石粉碎所製造之無機物粒子,或以藉由將無機物粒子之原石熔融並加以精製而粒子之直徑一致之球狀之粒子作為無機物粒子。 作為原石粉碎方法,並無特別限定,可列舉:球磨機、珠磨機、膠體磨機、錐形磨機、盤磨機、輪輾機、磨粉機、錘磨機、造粒機、VSI磨機、威利磨機、輥磨機、噴射磨機等。又,較佳為粉碎後將其洗淨,作為此時之洗淨方法,較佳為酸處理。藉此,能夠減少附著於無機物粒子之表面之鐵等雜質。 塗佈層較佳為含有結合劑。結合劑係將無機物粒子保持於離子交換膜之表面、形成塗佈層之成分。就對電解液或電解之產物之耐性之觀點而言,結合劑較佳為含有含氟系聚合物。 作為結合劑,就對電解液或電解之產物之耐性、及對離子交換膜之表面之接著性之觀點而言,更佳為具有羧酸基或磺酸基之含氟系聚合物。於在含有具有磺酸基之含氟聚合物之層(磺酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有磺酸基之含氟系聚合物。又,於在含有具有羧酸基之含氟聚合物之層(羧酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有羧酸基之含氟系聚合物。 塗佈層中,無機物粒子之含量較佳為40~90質量%,更佳為50~90質量%。又,結合劑之含量較佳為10~60質量%,更佳為10~50質量%。 離子交換膜中之塗佈層之分佈密度較佳為每1 cm2 為0.05~2 mg。又,於離子交換膜於表面具有凹凸形狀之情形時,塗佈層之分佈密度較佳為每1 cm2 為0.5~2 mg。 作為形成塗佈層之方法,並無特別限定,可使用公知之方法。例如可列舉藉由噴射等塗佈將無機物粒子分散於含有結合劑之溶液中而成之塗佈液之方法。 (強化芯材) 離子交換膜較佳為具有配置於膜本體之內部之強化芯材。 強化芯材係強化離子交換膜之強度或尺寸穩定性之構件。藉由將強化芯材配置於膜本體之內部,尤其能夠將離子交換膜之伸縮控制為所需之範圍。該離子交換膜於電解時等不會伸縮為必要程度以上,而能夠長期維持優異之尺寸穩定性。 強化芯材之構成並無特別限定,例如可將稱為強化紗之紗進行紡紗而形成。此處所謂強化紗係構成強化芯材之構件,指能夠對離子交換膜賦予所需之尺寸穩定性及機械強度且於離子交換膜中能夠穩定地存在之紗。藉由使用將該強化紗紡紗而成之強化芯材,能夠對離子交換膜賦予更優異之尺寸穩定性及機械強度。 強化芯材及其所使用之強化紗之材料並無特別限定,較佳為對酸或鹼等具有耐性之材料,就需要長期之耐熱性、耐化學品性之方面而言,較佳為包含含氟系聚合物之纖維。 作為強化芯材所使用之含氟系聚合物,例如可列舉:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、四氟乙烯-六氟丙烯共聚物、三氟氯乙烯-乙烯共聚物及偏二氟乙烯聚合物(PVDF)等。該等中,尤其是就耐熱性及耐化學品性之觀點而言,較佳為使用包含聚四氟乙烯之纖維。 強化芯材所使用之強化紗之紗直徑並無特別限定,較佳為20~300丹尼,更佳為50~250丹尼。紡織密度(每單位長度之織入根數)較佳為5~50根/英吋。作為強化芯材之形態,並無特別限定,例如可使用織布、不織布、針織布等,較佳為織布之形態。又,使用織布之厚度較佳為30~250 μm、更佳為30~150 μm者。 織布或針織布可使用單絲、複絲或該等之紗線、切膜絲等,紡織方法可使用平織、紗羅組織、針織、凸條組織、縐條紋薄織等各種紡織方法。 膜本體中之強化芯材之紡織方法及配置並無特別限定,可考慮離子交換膜之大小或形狀、離子交換膜所需之物性及使用環境等適當設為適宜之配置。 例如,可沿膜本體之特定之一方向配置強化芯材,就尺寸穩定性之觀點而言,較佳為沿特定之第一方向配置強化芯材,且沿大致垂直於第一方向之第二方向配置其他強化芯材。藉由在膜本體之縱向膜本體之內部以大致成一列之方式配置複數個強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。例如,較佳為於膜本體之表面織入沿縱向配置之強化芯材(縱紗)與沿橫向配置之強化芯材(橫紗)之配置。就尺寸穩定性、機械強度及製造容易性之觀點而言,更佳為製成使縱紗與橫紗一上一下交替織入而紡織之平紋織物、或一邊撚轉2根經紗一邊與橫紗交織之紗羅組織物、於每2根或數根並紗配置之縱紗中織入相同數量之橫紗而紡織之斜紋織物(twill weave)等。 尤佳為沿離子交換膜之MD方向(縱向(Machine Direction)方向)及TD方向(橫向(Transverse Direction)方向)之兩方向配置強化芯材。即,較佳為沿MD方向與TD方向平織。此處,所謂MD方向係指於下文所述之離子交換膜之製造步驟中搬送膜本體或各種芯材(例如,強化芯材、強化紗、下文所述之犧牲紗等)之方向(行進方向),所謂TD方向係指大致垂直於MD方向之方向。此外,將沿MD方向紡織之紗稱為MD紗,將沿TD方向紡織之紗稱為TD紗。通常電解所使用之離子交換膜係矩形,長度方向為MD方向、寬度方向為TD方向之情況較多。藉由織入作為MD紗之強化芯材與作為TD紗之強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。 強化芯材之配置間隔並無特別限定,可考慮離子交換膜所需之物性及使用環境等適當設為適宜之配置。 強化芯材之開口率並無特別限定,較佳為30%以上,更佳為50%以上且90%以下。開口率就離子交換膜之電化學性質之觀點而言,較佳為30%以上,就離子交換膜之機械強度之觀點而言,較佳為90%以下。 所謂強化芯材之開口率係指膜本體之任一表面之面積(A)中離子等物質(電解液及其所含之陽離子(例如,鈉離子))能夠通過之表面之總面積(B)之比率(B/A)。所謂離子等物質能夠通過之表面之總面積(B)可指於離子交換膜中陽離子或電解液等不被離子交換膜所含之強化芯材等阻斷之區域之總面積。 圖98係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。圖98係將離子交換膜之一部分放大而僅圖示該區域內之強化芯材21及22之配置,其他構件省略圖示。 藉由從由沿縱向配置之強化芯材21與沿橫向配置之強化芯材22所圍成之亦包括強化芯材之面積在內之區域的面積(A)減去強化芯材之總面積(C),可求出上述區域之面積(A)中離子等物質能夠通過之區域之總面積(B)。即,開口率可藉由下述式(I)求出。 開口率=(B)/(A)=((A)-(C))/(A) …(I) 於強化芯材中,就耐化學品性及耐熱性之觀點而言,尤佳之形態係含有PTFE之帶狀紗線或高配向單絲。具體而言,更佳為如下強化芯材,其係使用將包含PTFE之高強度多孔質片材切為帶狀而成之帶狀紗線、或包含PTFE之高度配向之單絲之50~300丹尼且紡織密度為10~50根/英吋之平紋織物,其厚度為50~100 μm之範圍。含有該強化芯材之離子交換膜之開口率進而較佳為60%以上。 作為強化紗之形狀,可列舉圓紗、帶狀紗等。 (連通孔) 離子交換膜較佳為於膜本體之內部具有連通孔。 所謂連通孔係指能夠成為電解時產生之離子或電解液之流路之孔。又,所謂連通孔係形成於膜本體內部之管狀之孔,藉由下文所述之犧牲芯材(或犧牲紗)溶出而形成。連通孔之形狀或直徑等可藉由選擇犧牲芯材(犧牲紗)之形狀或直徑進行控制。 藉由在離子交換膜形成連通孔,於電解時能夠確保電解液之移動性。連通孔之形狀並無特別限定,根據下文所述之製法,可製成連通孔之形成所使用之犧牲芯材之形狀。 連通孔較佳為以交替通過強化芯材之陽極側(磺酸層側)與陰極側(羧酸層側)之方式形成。藉由設為該結構,於強化芯材之陰極側形成有連通孔之部分,通過充滿連通孔之電解液所輸送之離子(例如,鈉離子)亦能夠流至強化芯材之陰極側。其結果為,由於陽離子之流動未被遮蔽,因此能夠進一步降低離子交換膜之電阻。 連通孔可僅沿構成離子交換膜之膜本體之特定之一方向形成,就發揮出更穩定之電解性能之觀點而言,較佳為沿膜本體之縱向與橫向之兩方向形成。 [製造方法] 作為離子交換膜之適宜之製造方法,可列舉具有以下之(1)步驟~(6)步驟之方法。 (1)步驟:製造具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之含氟系聚合物之步驟。 (2)步驟:藉由視需要至少織入複數個強化芯材與具有溶於酸或鹼之性質且形成連通孔之犧牲紗而獲得於鄰接之強化芯材彼此之間配置有犧牲紗之補強材之步驟。 (3)步驟:將具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之上述含氟系聚合物進行膜化之步驟。 (4)步驟:視需要將上述補強材埋入至上述膜中而獲得內部配置有上述補強材之膜本體之步驟。 (5)步驟:將(4)步驟中獲得之膜本體進行水解之步驟(水解步驟)。 (6)步驟:於(5)步驟中獲得之膜本體設置塗佈層之步驟(塗佈步驟)。 以下,對各步驟進行詳細說明。 (1)步驟:製造含氟系聚合物之步驟 於(1)步驟中,使用上述第1群~第3群所記載之原料之單體製造含氟系聚合物。為了控制含氟系聚合物之離子交換容量,於形成各層之含氟系聚合物之製造中調整原料之單體之混合比即可。 (2)步驟:補強材之製造步驟 所謂補強材係紡織強化紗之織布等。藉由將補強材埋入至膜內而形成強化芯材。於製成具有連通孔之離子交換膜時,亦將犧牲紗一起織入至補強材中。該情形時之犧牲紗之混織量較佳為補強材整體之10~80質量%,更佳為30~70質量%。藉由織入犧牲紗,亦能夠防止強化芯材之脫線。 犧牲紗係於膜之製造步驟或電解環境下具有溶解性者,可使用嫘縈、聚對苯二甲酸乙二酯(PET)、纖維素及聚醯胺等。又,亦較佳為具有20~50丹尼之粗細程度、包含單絲或複絲之聚乙烯醇等。 再者,於(2)步驟中,可藉由調整強化芯材或犧牲紗之配置而控制開口率或連通孔之配置等。 (3)步驟:膜化步驟 於(3)步驟中,使用擠出機將上述(1)步驟中獲得之含氟系聚合物進行膜化。膜可為單層結構,亦可如上所述為磺酸層與羧酸層之2層結構,亦可為3層以上之多層結構。 作為膜化之方法,例如可列舉以下者。 分別將具有羧酸基之含氟聚合物、具有磺酸基之含氟聚合物分開進行膜化之方法。 藉由共擠出將具有羧酸基之含氟聚合物與具有磺酸基之含氟聚合物製成複合膜之方法。 再者,膜可分別為複數片。又,將異種之膜共擠出有助於提高界面之接著強度,故而較佳。 (4)步驟:獲得膜本體之步驟 於(4)步驟中,藉由將(2)步驟中獲得之補強材埋入至(3)步驟中獲得之膜之內部,而獲得內有補強材之膜本體。 作為膜本體之較佳之形成方法,可列舉:(i)藉由共擠出法將位於陰極側之具有羧酸基前驅物(例如,羧酸酯官能基)之含氟系聚合物(以下將包含其之層稱為第一層)與具有磺酸基前驅物(例如,磺醯氟官能基)之含氟系聚合物(以下將包含其之層稱為第二層)進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將補強材、第二層/第一層複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法;(ii)區別於第二層/第一層複合膜,預先將具有磺酸基前驅物之含氟系聚合物(第三層)單獨進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將第三層膜、強化芯材、包含第二層/第一層之複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法。 此處,將第一層與第二層共擠出有助於提高界面之接著強度。 又,於減壓下進行一體化之方法與加壓壓製法相比,具有補強材上之第三層之厚度變大之特徵。進而,由於將補強材固定於膜本體之內面,因此具有能夠充分保持離子交換膜之機械強度之性能。 再者,此處所說明之積層之變化係一例,可考慮所需之膜本體之層構成或物性等,適當選擇適宜之積層圖案(例如,各層之組合等)後進行共擠出。 再者,為了進一步提高離子交換膜之電性能,亦可於第一層與第二層之間進一步介置包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層,或使用包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層代替第二層。 第四層之形成方法可為分開製造具有羧酸基前驅物之含氟系聚合物與具有磺酸基前驅物之含氟系聚合物後加以混合之方法,亦可為使用將具有羧酸基前驅物之單體與具有磺酸基前驅物之單體共聚合而成者之方法。 於將第四層製成離子交換膜之構成之情形時,可將第一層與第四層之共擠出膜加以成形,第三層及第二層與其分開單獨進行膜化,藉由上文所述之方法進行積層,亦可將第一層/第四層/第二層之3層一次共擠出而進行膜化。 於該情形時,所擠出之膜行進之方向為MD方向。由此可將含有具有離子交換基之含氟系聚合物之膜本體形成於補強材上。 又,離子交換膜較佳為於包含磺酸層之表面側具有包含具有磺酸基之含氟聚合物之突出的部分、即凸部。作為形成此種凸部之方法,並無特別限定,可採用於樹脂表面形成凸部之公知之方法。具體而言,例如可列舉對膜本體之表面實施壓紋加工之方法。例如,於將上述複合膜與補強材等進行一體化時,藉由使用預先經壓紋加工之脫模紙,可形成上述凸部。於藉由壓紋加工形成凸部之情形時,凸部之高度或配置密度之控制可藉由控制所轉印之壓紋形狀(脫模紙之形狀)而進行。 (5)水解步驟 於(5)步驟中,進行將(4)步驟中獲得之膜本體水解而將離子交換基前驅物轉換為離子交換基之步驟(水解步驟)。 又,於(5)步驟中,藉由利用酸或鹼將膜本體所含之犧牲紗溶解去除,可於膜本體形成溶出孔。再者,犧牲紗亦可不完全溶解去除,而殘留於連通孔中。又,殘留於連通孔中之犧牲紗可於將離子交換膜供於電解時藉由電解液溶解去除。 犧牲紗係於離子交換膜之製造步驟或電解環境下對酸或鹼具有溶解性者,藉由使犧牲紗溶出而於該部位形成連通孔。 (5)步驟可將(4)步驟中獲得之膜本體浸漬於含有酸或鹼之水解溶液中進行。作為該水解溶液,例如可使用含有KOH與DMSO(Dimethyl sulfoxide)之混合溶液。 該混合溶液較佳為含有2.5~4.0 N之KOH,且含有25~35質量%之DMSO。 作為水解之溫度,較佳為70~100℃。溫度越高,可使視厚度更厚。更佳為75~100℃。 作為水解之時間,較佳為10~120分鐘。時間越長,可使視厚度更厚。更佳為20~120分鐘。 此處,對藉由溶出犧牲紗而形成連通孔之步驟進一步詳細地說明。圖99(a)、(b)係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 於圖99(a)、(b)中,僅圖示強化紗52、犧牲紗504a及由犧牲紗504a形成之連通孔504,膜本體等其他構件省略圖示。 首先,將於離子交換膜中構成強化芯材之強化紗52與於離子交換膜中用以形成連通孔504之犧牲紗504a製成針織織入補強材。然後,於(5)步驟中藉由使犧牲紗504a溶出而形成連通孔504。 藉由上述方法,根據於離子交換膜之膜本體內如何配置強化芯材、連通孔而調整強化紗52與犧牲紗504a之針織織入方法即可,因此較簡便。 於圖99(a)中,例示於紙面沿縱向與橫向之兩方向將強化紗52與犧牲紗504a織入之平織之補強材,可視需要變更補強材中之強化紗52與犧牲紗504a之配置。 (6)塗佈步驟 於(6)步驟中,製備含有藉由原石粉碎或原石熔融獲得之無機物粒子與結合劑之塗佈液,將塗佈液塗佈於(5)步驟中獲得之離子交換膜之表面並加以乾燥,藉此可形成塗佈層。 作為結合劑,較佳為將具有離子交換基前驅物之含氟系聚合物水解於含有二甲基亞碸(DMSO)及氫氧化鉀(KOH)之水溶液中之後,浸漬於鹽酸中將離子交換基之抗衡離子置換為H+ 而成之結合劑(例如,具有羧基或磺基之含氟系聚合物)。藉此,變得容易溶解於下文所述之水或乙醇中,故而較佳。 將該結合劑溶解於混合水與乙醇而成之溶液中。再者,水與乙醇之較佳之體積比為10:1~1:10,更佳為5:1~1:5,進而較佳為2:1~1:2。藉由球磨機使無機物粒子分散於由此獲得之溶解液中而獲得塗佈液。此時,亦可藉由調整分散時之時間、旋轉速度而調整粒子之平均粒徑等。再者,無機物粒子與結合劑之較佳之調配量如上文所述。 塗佈液中之無機物粒子及結合劑之濃度並無特別限定,較佳為製成稀薄之塗佈液。藉此,能夠均勻地塗佈於離子交換膜之表面。 又,於使無機物粒子分散時,亦可將界面活性劑添加於分散液中。作為界面活性劑,較佳為非離子系界面活性劑,例如可列舉日油股份有限公司製造之HS-210、NS-210、P-210、E-212等。 藉由利用噴射塗佈或滾筒塗敷將所獲得之塗佈液塗佈於離子交換膜表面而可獲得離子交換膜。 [微多孔膜] 作為本實施形態之微多孔膜,只要如上文所述,可與電解用電極製成積層體,則無特別限定,可應用各種微多孔膜。 本實施形態之微多孔膜之氣孔率並無特別限定,例如可設為20~90,較佳為30~85。上述氣孔率例如可藉由下述之式算出。 氣孔率=(1-(乾燥狀態之膜重量)/(由根據膜之厚度、寬度、長度算出之體積與膜素材之密度所算出之重量))×100 本實施形態之微多孔膜之平均孔徑並無特別限定,例如可設為0.01 μm~10 μ,較佳為0.05 μm~5 μm。上述平均孔徑例如係沿厚度方向將膜垂直切斷,藉由FE-SEM觀察切斷面。對所觀察之孔之直徑測定100點左右並求出平均值,藉此可求出平均孔徑。 本實施形態之微多孔膜之厚度並無特別限定,例如可設為10 μm~1000 μm,較佳為50 μm~600 μm。上述厚度例如可使用測微計(Mitutoyo股份有限公司製造)等進行測定。 作為如上所述之微多孔膜之具體例,可列舉Agfa公司製造之Zirfon Perl UTP 500(於本實施形態中亦稱為Zirfon膜)、國際公開第2013-183584號說明書、國際公開第2016-203701號說明書等所記載者。 於本實施形態中,較佳為隔膜包含第1離子交換樹脂層、及具有與該第1離子交換樹脂層不同之EW(離子交換當量)之第2離子交換樹脂層。又,較佳為隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之官能基之第2離子交換樹脂層。離子交換當量可藉由所導入之官能基進行調整,關於可導入之官能基係如上文所述。 (水電解) 本實施形態中之進行水電解之情形時之電解槽係具有將上述進行食鹽電解之情形時之電解槽中之離子交換膜變更為微多孔膜之構成者。又,於所供給之原料為水之方面與上述進行食鹽電解之情形時之電解槽不同。關於其他構成,進行水電解之情形時之電解槽亦可採用與進行食鹽電解之情形時之電解槽相同之構成。於食鹽電解之情形時,由於在陽極室產生氯氣,因此陽極室之材質使用鈦,於水電解之情形時,由於在陽極室僅產生氧氣,因此可使用與陰極室之材質相同者。例如可列舉鎳等。又,陽極塗層適宜為產生氧氣用之觸媒塗層。作為觸媒塗層之例,可列舉鉑族金屬及過渡金屬族之金屬、氧化物、氫氧化物等。例如可使用鉑、銥、鈀、釕、鎳、鈷、鐵等元素。 [電極之更新方法] 本實施形態之電解槽之製造方法亦可作為電極(陽極及/或陰極)之更新方法而實施。即,本實施形態之電極之更新方法係用以藉由使用電解用電極而更新既有之電極之方法,並且使用上述電解用電極之捲繞體。 作為使用捲繞體之步驟之具體例,並不限定於以下,可列舉將解除電解用電極之捲繞體之捲繞狀態而成者配置於既有之電極之表面上的方法等。藉由此種方法,能夠將電解用電極配置於既有之陽極或陰極之表面上,而能夠更新陽極及/或陰極之性能。 如上所述,於本實施形態中,較佳為使用捲繞體之步驟具有將捲繞體之捲繞狀態加以解除之步驟(B'),又,更佳為具有於步驟(B')之後將電解用電極配置於既有之電極之表面上的步驟(C')。 又,於本實施形態之電極之更新方法中,較佳為使用捲繞體之步驟具有將電解用電極保持為捲繞狀態而獲得捲繞體之步驟(A')。於步驟(A')中,可將電解用電極本身進行捲繞而製成捲繞體,亦可將電解用電極纏繞至芯而製成捲繞體。作為此處可使用之芯,並無特別限定,例如可使用具有大致圓柱形狀且與電解用電極相適應之尺寸之構件。 [捲繞體之製造方法] 於本實施形態之電解槽之製造方法及本實施形態之電極之更新方法中,可實施之步驟(A)或(A')亦可作為捲繞體之製造方法而實施。即,本實施形態之捲繞體之製造方法係用以更新具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽的捲繞體之製造方法,並且具有將電解用電極或該電解用電極與新隔膜之積層體捲繞而獲得上述捲繞體之步驟。於獲得捲繞體之步驟中,可將電解用電極本身進行捲繞而製成捲繞體,亦可將電解用電極纏繞至芯而製成捲繞體。作為此處可使用之芯,並無特別限定,例如可使用具有大致圓柱形狀且與電解用電極相適應之尺寸之構件。 <第6實施形態> 此處,一邊參照圖103~111一邊對本發明之第6實施形態進行詳細地說明。 [電解槽之製造方法] 第6實施形態(以下於<第6實施形態>之項中簡稱為「本實施形態」)之電解槽之製造方法係用以藉由對具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽配置積層體而製造新電解槽之方法,並且具有:藉由將電解用電極與新隔膜於該隔膜不熔融之溫度下進行一體化,而獲得上述積層體之步驟(A);及於上述步驟(A)後將既有電解槽中之上述隔膜更換為上述積層體之步驟(B)。 如上所述,根據本實施形態之電解槽之製造方法,不藉由熱壓接之類之不實用之方法而能夠將電解用電極與隔膜進行一體化使用,因此能夠提高電解槽中之電極更新時之作業效率。 於本實施形態中,既有電解槽包含陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜作為構成構件,換言之,其包含電解池。既有電解槽只要包含上述構成構件,則無特別限定,可應用各種公知之構成。 於本實施形態中,新電解槽係除了於既有電解槽中已作為陽極或陰極而發揮功能之構件以外,進而具備電解用電極或積層體者。即,於製造新電解槽時所配置之「電解用電極」係作為陽極或陰極而發揮功能者,與既有電解槽中之陰極及陽極不同體。於本實施形態中,即使於伴隨既有電解槽之運轉陽極及/或陰極之電解性能劣化之情形時,藉由配置與該等不同體之電解用電極,亦可更新陽極及/或陰極之性能。進而,由於亦一併配置構成積層體之新離子交換膜,因此伴隨運轉性能劣化之離子交換膜之性能亦可同時更新。此處所謂「更新性能」意指設為與將既有電解槽供於運轉前所具有之初始性能相同之性能、或高於該初始性能之性能。 於本實施形態中,假定既有電解槽係「已供於運轉之電解槽」,又,假定新電解槽係「尚未供於運轉之電解槽」。即,若將作為新電解槽所製造之電解槽供於運轉一次,則成為「本實施形態中之既有電解槽」,對該既有電解槽配置電解用電極或積層體而成者成為「本實施形態中之新電解槽」。 以下,以使用離子交換膜作為隔膜進行食鹽電解之情形為例,對電解槽之一實施形態進行詳細說明。再者,於<第6實施形態>之項中,只要無特別說明,則「本實施形態中之電解槽」包含「本實施形態中之既有電解槽」及「本實施形態中之新電解槽」之兩者。 [電解池] 首先,對可用作本實施形態中之電解槽之構成單元的電解池進行說明。圖103係電解池1之剖面圖。 電解池1具備陽極室10、陰極室20、設置於陽極室10及陰極室20之間之間隔壁30、設置於陽極室10之陽極11、及設置於陰極室20之陰極21。視需要亦可具備具有基材18a與形成於該基材18a上之逆向電流吸收層18b且設置於陰極室內之逆向電流吸收體18。屬於1個電解池1之陽極11及陰極21互相電性連接。換言之,電解池1具備如下陰極結構體。陰極結構體40具備陰極室20、設置於陰極室20之陰極21、及設置於陰極室20內之逆向電流吸收體18,逆向電流吸收體18如圖107所示具有基材18a與形成於該基材18a上之逆向電流吸收層18b,陰極21與逆向電流吸收層18b電性連接。陰極室20進而具有集電體23、支持該集電體之支持體24、及金屬彈性體22。金屬彈性體22係設置於集電體23及陰極21之間。支持體24係設置於集電體23及間隔壁30之間。集電體23經由金屬彈性體22而與陰極21電性連接。間隔壁30經由支持體24而與集電體23電性連接。因此,間隔壁30、支持體24、集電體23、金屬彈性體22及陰極21係電性連接。陰極21及逆向電流吸收層18b係電性連接。陰極21及逆向電流吸收層可直接連接,亦可經由集電體、支持體、金屬彈性體或間隔壁等而間接連接。陰極21之表面整體較佳為由用於還原反應之觸媒層所被覆。又,電性連接之形態可為分別直接將間隔壁30與支持體24、支持體24與集電體23、集電體23與金屬彈性體22安裝,並且於金屬彈性體22上積層陰極21之形態。作為將該等各構成構件互相直接安裝之方法,可列舉焊接等。又,亦可將逆向電流吸收體18、陰極21、及集電體23總稱為陰極結構體40。 圖104係電解槽4內鄰接之2個電解池1之剖面圖。圖105表示電解槽4。圖106表示組裝電解槽4之步驟。 如圖104所示,將電解池1、陽離子交換膜2、電解池1依序串聯排列。於電解槽內鄰接之2個電解池中之一電解池1之陽極室與另一電解池1之陰極室之間配置離子交換膜2。即,電解池1之陽極室10及與其鄰接之電解池1之陰極室20係由陽離子交換膜2隔開。如圖105所示,電解槽4包含介隔離子交換膜2而串聯連接之複數個電解池1。即,電解槽4係具備串聯配置之複數個電解池1、及配置於鄰接之電解池1之間之離子交換膜2的複極式電解槽。如圖106所示,電解槽4係藉由介隔離子交換膜2將複數個電解池1串聯配置並利用壓製器5連結而組裝。 電解槽4具有連接於電源之陽極端子7與陰極端子6。於電解槽4內串聯連結之複數個電解池1中位於最靠端之電解池1之陽極11係電性連接於陽極端子7。於電解槽4內串聯連結之複數個電解池2中位於陽極端子7之相反側之端之電解池的陰極21係電性連接於陰極端子6。電解時之電流從陽極端子7側起,經過各電解池1之陽極及陰極而流向陰極端子6。再者,可於連結之電解池1之兩端配置僅具有陽極室之電解池(陽極終端池)與僅具有陰極室之電解池(陰極終端池)。於該情形時,將陽極端子7連接於配置於其一端之陽極終端池,將陰極端子6連接於配置於另一端之陰極終端池。 於進行鹽水之電解之情形時,向各陽極室10供給鹽水,向陰極室20供給純水或低濃度之氫氧化鈉水溶液。各液體係從電解液供給管(圖中省略)起,經過電解液供給軟管(圖中省略)而向各電解池1供給。又,電解液及電解之產物係由電解液回收管(圖中省略)所回收。於電解中,鹽水中之鈉離子從一電解池1之陽極室10起,通過離子交換膜2,向旁邊之電解池1之陰極室20移動。由此電解中之電流沿將電解池1串聯連結之方向流通。即,電流係經由陽離子交換膜2而從陽極室10流向陰極室20。伴隨鹽水之電解,於陽極11側產生氯氣,於陰極21側產生氫氧化鈉(溶質)與氫氣。 (陽極室) 陽極室10具有陽極11或陽極饋電體11。作為此處所謂饋電體意指劣化之電極(即既有電極)或未形成有觸媒塗層之電極等。於將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極饋電體發揮功能。於不將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極發揮功能。又,陽極室10較佳為具有向陽極室10供給電解液之陽極側電解液供給部、配置於陽極側電解液供給部之上方且以與間隔壁30大致平行或傾斜之方式配置之擋板、及配置於擋板之上方且從混入有氣體之電解液中分離氣體之陽極側氣液分離部。 (陽極) 於不將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框(即,陽極框)內設置有陽極11。作為陽極11,可使用所謂DSA(註冊商標)等金屬電極。所謂DSA係藉由以釕、銥、鈦作為成分之氧化物被覆表面之鈦基材之電極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極饋電體) 於將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極饋電體11。作為陽極饋電體11,可使用所謂DSA(註冊商標)等金屬電極,亦可使用未形成有觸媒塗層之鈦。又,亦可使用使觸媒塗層厚度變薄之DSA。進而,亦可使用使用過之陽極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極側電解液供給部) 陽極側電解液供給部係向陽極室10供給電解液者,其連接於電解液供給管。陽極側電解液供給部較佳為配置於陽極室10之下方。作為陽極側電解液供給部,例如可使用表面形成有開口部之管(分散管)等。該管更佳為以沿陽極11之表面平行於電解池之底部19之方式配置。該管係連接於向電解池1內供給電解液之電解液供給管(液供給噴嘴)。從液供給噴嘴供給之電解液藉由管被搬送至電解池1內,從設置於管之表面之開口部向陽極室10之內部供給。藉由將管以沿陽極11之表面平行於電解池之底部19之方式配置,能夠將電解液均勻地供給至陽極室10之內部,故而較佳。 (陽極側氣液分離部) 陽極側氣液分離部較佳為配置於擋板之上方。於電解中,陽極側氣液分離部具有將氯氣等產生氣體與電解液分離之功能。再者,只要無特別說明,則所謂上方意指圖103之電解池1中之上方向,所謂下方意指圖103之電解池1中之下方向。 電解時,若電解池1中產生之產生氣體與電解液成為混相(氣液混相)而被排出至系外,則存在因電解池1內部之壓力變動導致產生振動而引起離子交換膜之物理破損之情形。為了抑制該情形,較佳為於本實施形態中之電解池1中設置用以將氣體與液體分離之陽極側氣液分離部。較佳為於陽極側氣液分離部設置用以消除氣泡之消泡板。藉由在氣液混相流通過消泡板時氣泡破裂,而可分離為電解液與氣體。其結果為,能夠防止電解時之振動。 (擋板) 擋板較佳為配置於陽極側電解液供給部之上方,且以與間隔壁30大致平行或傾斜之方式配置。擋板係控制陽極室10之電解液之流動之間隔板。藉由設置擋板,可使電解液(鹽水等)於陽極室10內部循環,使其濃度變得均勻。為了引起內部循環,擋板較佳為以將陽極11附近之空間與間隔壁30附近之空間隔開之方式配置。就該觀點而言,擋板較佳為以與陽極11及間隔壁30之各表面相對向之方式設置。於由擋板分隔之陽極附近之空間,藉由進行電解,電解液濃度(鹽水濃度)降低,又,產生氯氣等產生氣體。藉此,於由擋板分隔之陽極11附近之空間與間隔壁30附近之空間產生氣液之比重差。利用該情況,能夠促進陽極室10中之電解液之內部循環,使陽極室10之電解液之濃度分佈變得更均勻。 再者,於圖103並未圖示,但亦可於陽極室10之內部另行設置集電體。作為該集電體,亦可設為與下文所述之陰極室之集電體相同之材料或構成。又,於陽極室10中,亦可使陽極11本身作為集電體發揮功能。 (間隔壁) 間隔壁30係配置於陽極室10與陰極室20之間。間隔壁30有時亦稱為間隔件,係將陽極室10與陰極室20進行劃分者。作為間隔壁30,可使用作為電解用之間隔件所公知者,例如可列舉於陰極側焊接包含鎳之板、於陽極側焊接包含鈦之板之間隔壁等。 (陰極室) 陰極室20於將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極饋電體發揮功能,於不將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極發揮功能。於具有逆向電流吸收體之情形時,陰極或陰極饋電體21與逆向電流吸收體係電性連接。又,陰極室20較佳為與陽極室10同樣,亦具有陰極側電解液供給部、陰極側氣液分離部。再者,構成陰極室20之各部位中,關於與構成陽極室10之各部位相同者省略說明。 (陰極) 於不將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框(即,陰極框)內設置有陰極21。陰極21較佳為具有鎳基材與被覆鎳基材之觸媒層。作為鎳基材上之觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可視需要對陰極21實施還原處理。再者,作為陰極21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陰極饋電體) 於將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極饋電體21。可對陰極饋電體21被覆觸媒成分。該觸媒成分可為原本用作陰極而殘存者。作為觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可使用未形成有觸媒塗層之鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。再者,作為陰極饋電體21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (逆向電流吸收層) 可選擇具有較上文所述之陰極之觸媒層用元素的氧化還原電位更低之氧化還原電位之材料作為逆向電流吸收層之材料。例如可列舉鎳或鐵等。 (集電體) 陰極室20較佳為具備集電體23。藉此,集電效果提高。於本實施形態中,集電體23較佳為多孔板,且以與陰極21之表面大致平行之方式配置。 作為集電體23,例如較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。集電體23可為該等金屬之混合物、合金或複合氧化物。再者,集電體23之形狀只要為作為集電體發揮功能之形狀,則可為任意形狀,可為板狀、網狀。 (金屬彈性體) 藉由在集電體23與陰極21之間設置金屬彈性體22,將串聯連接之複數個電解池1之各陰極21壓抵於離子交換膜2,各陽極11與各陰極21之間之距離變短,可降低對串聯連接之複數個電解池1整體施加之電壓。藉由電壓降低,可降低消耗電量。又,藉由設置金屬彈性體22,於將含有本實施形態中之電解用電極之積層體設置於電解池時,藉由金屬彈性體22之壓抵壓,可將該電解用電極穩定地維持於起始位置。 作為金屬彈性體22,可使用螺旋彈簧、線圈等彈簧構件、緩衝性之墊等。作為金屬彈性體22,可考慮壓抵離子交換膜之應力等而適當採用適宜者。可將金屬彈性體22設置於陰極室20側之集電體23之表面上,亦可設置於陽極室10側之間隔壁之表面上。通常以陰極室20小於陽極室10之方式劃分兩室,因此就框體之強度等觀點而言,較佳為將金屬彈性體22設置於陰極室20之集電體23與陰極21之間。又,金屬彈性體23較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。 (支持體) 陰極室20較佳為具備將集電體23與間隔壁30電性連接之支持體24。藉此,能夠效率良好地流通電流。 支持體24較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。又,作為支持體24之形狀,只要為能夠支持集電體23之形狀,則可為任意形狀,可為棒狀、板狀或網狀。支持體24例如為板狀。複數個支持體24係配置於間隔壁30與集電體23之間。複數個支持體24係以各自之面互相平行之方式排列。支持體24係以大致垂直於間隔壁30及集電體23之方式配置。 (陽極側墊片、陰極側墊片) 陽極側墊片較佳為配置於構成陽極室10之框體表面。陰極側墊片較佳為配置於構成陰極室20之框體表面。1個電解池所具備之陽極側墊片及與其鄰接之電解池之陰極側墊片以夾持離子交換膜2之方式將電解池彼此連接(參照圖104)。藉由該等墊片,於介隔離子交換膜2將複數個電解池1串聯連接時,能夠對連接處賦予氣密性。 所謂墊片係將離子交換膜與電解池之間密封者。作為墊片之具體例,可列舉中央形成有開口部之邊框狀之橡膠製片等。對於墊片要求對腐蝕性之電解液或所產生之氣體等具有耐性而可長期使用。因此,就耐化學品性或硬度之方面而言,通常可使用乙烯-丙烯-二烯橡膠(EPDM橡膠)、乙烯-丙烯橡膠(EPM橡膠)之硫化物或過氧化物交聯物等作為墊片。又,視需要亦可使用以聚四氟乙烯(PTFE)或四氟乙烯-全氟烷基乙烯醚共聚物(PFA)等氟系樹脂被覆與液體相接之區域(接液部)之墊片。該等墊片只要以不妨礙電解液之流動之方式分別具有開口部即可,其形狀並無特別限定。例如沿構成陽極室10之陽極室框或構成陰極室20之陰極室框之各開口部之周緣,藉由接著劑等貼附邊框狀之墊片。此外,於例如介隔離子交換膜2連接2個電解池1之情形時(參照圖104),介隔離子交換膜2將貼附有墊片之各電解池1緊固即可。藉此,能夠抑制電解液、因電解而產生之鹼金屬氫氧化物、氯氣、氫氣等漏至電解池1之外部之情況。 [積層體] 本實施形態中之電解用電極係作為與離子交換膜或微多孔膜等隔膜之積層體而使用。即,本實施形態中之積層體係包含電解用電極與新隔膜者。所謂新隔膜,只要與既有電解槽中之隔膜不同體,則無特別限定,可應用各種公知之隔膜。又,新隔膜可為材質、形狀、物性等與既有電解槽中之隔膜相同者。對電解用電極及隔膜之具體例追加詳細說明。 (步驟(A)) 於本實施形態中之步驟(A)中,藉由將電解用電極與新隔膜於該隔膜不熔融之溫度下進行一體化,而獲得積層體。 「隔膜不熔融之溫度」可作為新隔膜之軟化點而特定出。該溫度可根據構成隔膜之材料而變動,較佳為0~100℃,更佳為5~80℃,進而較佳為10~50℃。 又,上述一體化較佳為於常壓下進行。 作為上述一體化之具體之方法,可使用除了熱壓接等將隔膜熔融之典型之方法以外之所有方法,並無特別限定。作為較佳之一例,可列舉下文所述之將液體介置於電解用電極與隔膜之間而藉由該液體之表面張力進行一體化之方法等。 [步驟(B)] 於本實施形態中之步驟(B)中,於步驟(A)之後,將既有電解槽中之隔膜與積層體交換。作為交換之方法,並無特別限定,例如可列舉如下方法等:首先,於既有電解槽中將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,於該電解池及離子交換膜之間形成空隙,其次將成為更新對象之既有之離子交換膜去除,繼而,將積層體插入至該空隙,再次藉由壓製器將各構件連結。藉由此種方法,能夠將積層體配置於既有電解槽中之陽極或陰極之表面上,而能夠更新離子交換膜、陽極及/或陰極之性能。 [電解用電極] 於本實施形態中,電解用電極只要如上所述可與新隔膜進行一體化、即為能夠一體化者,則無特別限定。電解用電極可為於電解槽中作為陰極而發揮功能者,亦可為作為陽極而發揮功能者。又,關於電解用電極之材質或形狀等,可考慮本實施形態中之步驟(A)、(B)或電解槽之構成等而適當選擇合適者。以下,對本實施形態中之電解用電極之較佳之態樣進行說明,但該等終歸僅為於與新隔膜進行一體化之方面較佳之態樣之例示,亦可適當採用下文所述之態樣以外之電解用電極。 本實施形態中之電解用電極就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、饋電體(劣化之電極及未形成有觸媒塗層之電極)等具有良好之接著力之觀點而言,每單位質量·單位面積所承受之力較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/mg・cm2 以上,進而更佳為0.14 N/(mg・cm2 )以上。就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.2 N/(mg・cm2 )以上。 上述承受力例如可藉由適當調整下文所述之開孔率、電極之厚度、算術平均表面粗糙度等而設為上述範圍。更具體而言,例如,若增大開孔率,則承受力有變小之傾向,若減小開孔率,則承受力有變大之傾向。 又,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力之觀點,進而就經濟性之觀點而言,較佳為每單位面積之質量為48 mg/cm2 以下,更佳為30 mg/cm2 以下,進而較佳為20 mg/cm2 以下,進而,就合併操作性、接著性及經濟性之綜合性之觀點而言,較佳為15 mg/cm2 以下。下限值並無特別限定,例如為1 mg/cm2 左右。 上述每單位面積之質量例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則每單位面積之質量有變小之傾向,若減小開孔率,則每單位面積之質量有變大之傾向。 承受力可藉由以下之方法(i)或(ii)進行測定,詳細而言,如實施例所記載。關於承受力,藉由方法(i)之測定所獲得之值(亦稱為「承受力(1)」)與藉由方法(ii)之測定所獲得之值(亦稱為「承受力(2)」)可相同亦可不同,但較佳為任一值均未達1.5 N/mg・cm2 。 [方法(i)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方)、於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方,關於此處所謂離子交換膜之詳細如實施例所記載)及電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。再者,噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.5~0.8 μm。算術平均表面粗糙度(Ra)之具體之算出方法如實施例所記載。 於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與離子交換膜之重疊部分之面積、及與離子交換膜重疊部分之電極樣品之質量,而算出每單位質量·單位面積所承受之力(1)(N/mg・cm2 )。 藉由方法(i)獲得之每單位質量·單位面積所承受之力(1)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。又,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 ),更佳為0.2 N/(mg・cm2 )以上。 [方法(ii)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方,與上述方法(i)相同之鎳板)與電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與鎳板之重疊部分之面積、及與鎳板重疊部分中之電極樣品之質量,而算出每單位質量•單位面積之接著力(2)(N/mg・cm2 )。 藉由方法(ii)獲得之每單位質量·單位面積所承受之力(2)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。進而,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 )以上。 本實施形態中之電解用電極較佳為包含電解用電極基材及觸媒層。該電解用電極基材之厚度(量規厚度)並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折,大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於本實施形態中,較佳為將新隔膜與電解用電極進行一體化後,於該等之間介置液體。該液體只要為水、有機溶劑等產生表面張力者,則可使用任意液體。液體之表面張力越大,對新隔膜與電解用電極之間承受之力越大,因此較佳為表面張力較大之液體。作為液體,可列舉如下者(括號內之數值係該液體於20℃下之表面張力)。 己烷(20.44 mN/m)、丙酮(23.30 mN/m)、甲醇(24.00 mN/m)、乙醇(24.05 mN/m)、乙二醇(50.21 mN/m)水(72.76 mN/m) 若為表面張力較大之液體,則新隔膜與電解用電極成為一體(成為積層體),有電極更新變得更容易之傾向。新隔膜與電解用電極之間之液體為藉由表面張力而互相貼附之程度之量即可,其結果為液體量較少,因此即使於將該積層體設置於電解池後混入至電解液中,亦不會對電解本身造成影響。 就實用上之觀點而言,作為液體,較佳為使用乙醇、乙二醇、水等表面張力為24 mN/m至80 mN/m之液體。尤佳為水或將苛性鈉、氫氧化鉀、氫氧化鋰、碳酸氫鈉、碳酸氫鉀、碳酸鈉、碳酸鉀等溶解於水中製成鹼性之水溶液。又,亦可使該等液體含有界面活性劑而調整表面張力。藉由含有界面活性劑,新隔膜與電解用電極之接著性發生變化,而可調整操作性。作為界面活性劑,並無特別限定,可使用離子性界面活性劑、非離子性界面活性劑之任一種。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力之觀點而言,藉由以下之方法(2)所測得之比率較佳為90%以上,更佳為92%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為95%以上。上限值為100%。 [方法(2)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑280 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折之觀點而言,藉由以下之方法(3)所測得之比率較佳為75%以上,更佳為80%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為90%以上。上限值為100%。 [方法(3)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,防止電解中產生之氣體滯留之觀點而言,較佳為多孔結構,且其開孔率或空隙率為5~90%以下。開孔率更佳為10~80%以下,進而較佳為20~75%。 再者,所謂開孔率係每單位體積之開孔部之比率。開孔部亦根據考慮至次微米級抑或僅考慮目視可見之開口而有各種算出方法。於本實施形態中,可藉由根據電極之量規厚度、寬度、長度之值算出體積V,進而實測重量W,而利用下述之式算出開孔率A。 A=(1-(W/(V×ρ))×100 ρ係電極之材質之密度(g/cm3 )。例如於鎳之情形時為8.908 g/cm3 ,於鈦之情形時為4.506 g/cm3 。開孔率之調整可藉由如下方法進行適當調整:若為沖孔金屬,則變更每單位面積沖裁金屬之面積;若為多孔金屬,則變更SW(短徑)、LW(長徑)、進給之值;若為絲網,則變更金屬纖維之線徑、網眼數;若為電成形,則變更所使用之光阻之圖案;若為不織布,則變更金屬纖維直徑及纖維密度;若為發泡金屬,則變更用以使空隙形成之模板等。 以下,對本實施形態中之電解用電極之更具體之實施形態進行說明。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。觸媒層如下所述,可包含複數層,亦可為單層結構。 如圖108所示,本實施形態之電解用電極100具備電解用電極基材10、及被覆電解用電極基材10之兩表面之一對第一層20。第一層20較佳為將電解用電極基材10整體被覆。藉此,電解用電極之觸媒活性及耐久性變得容易提高。再者,亦可僅於電解用電極基材10之一表面積層第一層20。 又,如圖108所示,第一層20之表面可由第二層30所被覆。第二層30較佳為將第一層20整體被覆。又,第二層30可僅積層於第一層20之一表面。 (電解用電極基材) 作為電解用電極基材10,並無特別限定,例如可使用鎳、鎳合金、不鏽鋼、或以鈦等為代表之閥金屬,較佳為含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 於在高濃度之鹼性水溶液中使用不鏽鋼之情形時,若考慮到鐵及鉻溶出、及不鏽鋼之導電性為鎳之1/10左右,則較佳為使用含有鎳(Ni)之基材作為電解用電極基材。 又,電解用電極基材10於在接近飽和之高濃度之食鹽水中於氯氣產生環境中使用之情形時,材質亦較佳為耐蝕性較高之鈦。 電解用電極基材10之形狀並無特別限定,可根據目的選擇合適之形狀。作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。其中,較佳為沖孔金屬或多孔金屬。再者,所謂電成形係將照相製版與電鍍法組合而製作精密之圖案之金屬薄膜的技術。其係藉由光阻於基板上形成圖案,對未受到光阻保護之部分實施電鍍而獲得金屬薄膜之方法。 關於電解用電極基材之形狀,根據電解槽中之陽極與陰極之距離而有適宜之規格。並無特別限定,於陽極與陰極具有有限之距離之情形時,可使用多孔金屬、沖孔金屬形狀,於離子交換膜與電極相接之所謂零間距電解槽之情形時,可使用編織細線而成之編織網、金屬絲網、發泡金屬、金屬不織布、多孔金屬、沖孔金屬、金屬多孔箔等。 作為電解用電極基材10,可列舉:金屬多孔箔、金屬絲網、金屬不織布、沖孔金屬、多孔金屬或發泡金屬。 作為加工為沖孔金屬、多孔金屬前之板材,較佳為經壓延成形之板材、電解箔等。電解箔較佳為進而作為後處理而藉由與母材相同之元素實施鍍覆處理,於單面或兩面形成凹凸。 又,電解用電極基材10之厚度如上文所述,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於電解用電極基材中,較佳為藉由在氧化環境中將電解用電極基材進行退火而緩和加工時之殘留應力。又,為了提高與被覆於電解用電極基材之表面之觸媒層之密接性,較佳為使用鋼砂、氧化鋁粉等於上述表面形成凹凸,其後藉由酸處理而增加表面積。或者,較佳為藉由與基材相同之元素實施鍍覆處理,增加表面積。 為了使第一層20與電解用電極基材10之表面密接,較佳為對電解用電極基材10進行增大表面積之處理。作為增大表面積之處理,可列舉使用鋼線粒、鋼砂、氧化鋁砂等之噴擊處理、使用硫酸或鹽酸之酸處理、利用與基材相同元素之鍍覆處理等。基材表面之算術平均表面粗糙度(Ra)並無特別限定,較佳為0.05 μm~50 μm,更佳為0.1~10 μm,進而較佳為0.1~8 μm。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陽極之情形進行說明。 (第一層) 於圖108中,作為觸媒層之第一層20含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物。作為釕氧化物,可列舉RuO2 等。作為銥氧化物,可列舉IrO2 等。作為鈦氧化物,可列舉TiO2 等。第一層20較佳為含有釕氧化物及鈦氧化物之兩種氧化物,或含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物。藉此,第一層20成為更穩定之層,進而,與第二層30之密接性亦進一步提高。 於第一層20含有釕氧化物及鈦氧化物之兩種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為1~9莫耳,更佳為1~4莫耳。藉由將兩種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之銥氧化物較佳為0.2~3莫耳,更佳為0.3~2.5莫耳。又,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為0.3~8莫耳,更佳為1~7莫耳。藉由將三種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有選自釕氧化物、銥氧化物及鈦氧化物中之至少兩種氧化物之情形時,該等氧化物較佳為形成固溶體。藉由形成氧化物固溶體,電解用電極100表現出優異之耐久性。 除了上述組成以外,只要含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物,則可使用各種組成者。例如,亦可使用稱為DSA(註冊商標)之含有釕、銥、鉭、鈮、鈦、錫、鈷、錳、鉑等之氧化物塗層作為第一層20。 第一層20無需為單層,亦可包含複數層。例如,第一層20可包含含有三種氧化物之層與含有兩種氧化物之層。第一層20之厚度較佳為0.05~10 μm,更佳為0.1~8 μm。 (第二層) 第二層30較佳為含有釕與鈦。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較佳為含有氧化鈀、氧化鈀與鉑之固溶體或鈀與鉑之合金。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較厚者能夠維持電解性能之時間變長,就經濟性之觀點而言,較佳為0.05~3 μm之厚度。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陰極之情形進行說明。 (第一層) 作為觸媒層之第一層20之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。 於含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少一種之情形時,較佳為鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金含有鉑、鈀、銠、釕、銥中之至少一種鉑族金屬。 作為鉑族金屬,較佳為含有鉑。 作為鉑族金屬氧化物,較佳為含有釕氧化物。 作為鉑族金屬氫氧化物,較佳為含有釕氫氧化物。 作為鉑族金屬合金,較佳為含有鉑與鎳、鐵、鈷之合金。 較佳為進而視需要含有鑭系元素之氧化物或氫氧化物作為第二成分。藉此,電解用電極100表現出優異之耐久性。 作為鑭系元素之氧化物或氫氧化物,較佳為含有選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑中之至少1種。 較佳為進而視需要含有過渡金屬之氧化物或氫氧化物作為第三成分。 藉由添加第三成分,電解用電極100能夠表現出更優異之耐久性,降低電解電壓。 作為較佳之組合之例,可列舉:僅釕、釕+鎳、釕+鈰、釕+鑭、釕+鑭+鉑、釕+鑭+鈀、釕+鐠、釕+鐠+鉑、釕+鐠+鉑+鈀、釕+釹、釕+釹+鉑、釕+釹+錳、釕+釹+鐵、釕+釹+鈷、釕+釹+鋅、釕+釹+鎵、釕+釹+硫、釕+釹+鉛、釕+釹+鎳、釕+釹+銅、釕+釤、釕+釤+錳、釕+釤+鐵、釕+釤+鈷、釕+釤+鋅、釕+釤+鎵、釕+釤+硫、釕+釤+鉛、釕+釤+鎳、鉑+鈰、鉑+鈀+鈰、鉑+鈀+鑭+鈰、鉑+銥、鉑+鈀、鉑+銥+鈀、鉑+鎳+鈀、鉑+鎳+釕、鉑與鎳之合金、鉑與鈷之合金、鉑與鐵之合金等。 於不含鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之情形時,觸媒之主成分較佳為鎳元素。 較佳為含有鎳金屬、氧化物、氫氧化物中之至少1種。 作為第二成分,可添加過渡金屬。作為所添加之第二成分,較佳為含有鈦、錫、鉬、鈷、錳、鐵、硫、鋅、銅、碳中之至少一種元素。 作為較佳之組合,可列舉:鎳+錫、鎳+鈦、鎳+鉬、鎳+鈷等。 視需要可於第一層20與電解用電極基材10之間設置中間層。藉由設置中間層,能夠提高電解用電極100之耐久性。 作為中間層,較佳為對第一層20與電解用電極基材10之兩者具有親和性者。作為中間層,較佳為鎳氧化物、鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物。作為中間層,可藉由將含有形成中間層之成分之溶液進行塗佈、燒成而形成,亦可於空氣環境中在300~600℃之溫度下對基材實施熱處理而形成表面氧化物層。除此以外,可藉由熱熔射法、離子鍍敷法等已知之方法形成。 (第二層) 作為觸媒層之第一層30之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。作為第二層所含之元素之較佳之組合例,有第一層中所列舉之組合等。第一層與第二層之組合可為組成相同而組成比不同之組合,亦可為組成不同之組合。 作為觸媒層之厚度,較佳為將所形成之觸媒層及中間層累加而成之厚度為0.01 μm~20 μm。若為0.01 μm以上,則能夠作為觸媒充分發揮功能。若為20 μm以下,則從基材脫落之情況較少,能夠形成牢固之觸媒層。更佳為0.05 μm~15 μm。更佳為0.1 μm~10 μm。進而較佳為0.2 μm~8 μm。 作為電極之厚度、即電解用電極基材與觸媒層之合計之厚度,就電極之操作性之方面而言,較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,電極之厚度可藉由利用電子數顯厚度計(Mitutoyo股份有限公司,最少顯示0.001 mm)進行測定而求出。電解用電極基材之厚度係與電極厚度同樣地進行測定。觸媒層厚度可藉由電極厚度減去電解用電極基材之厚度而求出。 於本實施形態中,就確保充分之電解性能之觀點而言,較佳為電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。 於本實施形態中,若電解用電極係彈性變形區域較廣之電極,則就可獲得更良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有更良好之接著力之觀點而言,電解用電極之厚度較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,於本實施形態中,所謂「彈性變形區域較廣」意指將電解用電極捲繞而製成捲繞體,解除捲繞狀態後不易產生由捲繞引起之翹曲。又,所謂電解用電極之厚度於包含下文所述之觸媒層之情形時,係指合併電解用電極基材與觸媒層之厚度。 (電解用電極之製造方法) 其次,對電解用電極100之製造方法之一實施形態進行詳細說明。 於本實施形態中,藉由利用氧環境下之塗膜之燒成(熱分解)、或離子鍍敷、鍍覆、熱熔射等方法於電解用電極基材上形成第一層20、較佳為第二層30,可製造電解用電極100。此種本實施形態之製造方法能夠實現電解用電極100之較高之生產性。具體而言,藉由塗佈含有觸媒之塗佈液之塗佈步驟、乾燥塗佈液之乾燥步驟、進行熱分解之熱分解步驟,而於電解用電極基材上形成觸媒層。此處所謂熱分解意指對成為前驅物之金屬鹽進行加熱而分解為金屬或金屬氧化物與氣體狀物質。根據所使用之金屬種類、鹽之種類、進行熱分解之環境等,分解產物有所不同,但於氧化性環境下多數金屬有容易形成氧化物之傾向。於電極之工業性之製造工藝中,熱分解通常於空氣中進行,多數情形時形成金屬氧化物或金屬氫氧化物。 (陽極之第一層之形成) (塗佈步驟) 第一層20係將溶解有釕、銥及鈦中之至少一種金屬之鹽的溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之釕、銥及鈦之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材100後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (第二層之形成) 第二層30係視需要而形成,例如將含有鈀化合物及鉑化合物之溶液或含有釕化合物及鈦化合物之溶液(第二塗佈液)塗佈於第一層20上後,於氧氣之存在下進行熱分解而獲得。 (利用熱分解法之陰極之第一層之形成) (塗佈步驟) 第一層20係將溶解有各種組合之金屬鹽之溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之金屬之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材10後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (中間層之形成) 中間層係視需要而形成,例如將含有鈀化合物或鉑化合物之溶液(第二塗佈液)塗佈於基材上後,於氧氣之存在下進行熱分解而獲得。或者,亦可不塗佈溶液,而僅加熱基材,藉此於基材表面形成氧化鎳中間層。 (利用離子鍍敷之陰極之第一層之形成) 第一層20亦可藉由離子鍍敷而形成。 作為一例,可列舉將基材固定於腔室內並對金屬釕靶照射電子束之方法。所蒸發之金屬釕粒子於腔室內之電漿中帶正電,而沈積於帶負電之基板上。電漿環境為氬氣、氧氣,釕係以釕氧化物之形式沈積於基材上。 (利用鍍覆之陰極之第一層之形成) 第一層20亦可藉由鍍覆法而形成。 作為一例,若使用基材作為陰極,於含有鎳及錫之電解液中實施電解鍍覆,則可形成鎳與錫之合金鍍覆。 (利用熱熔射之陰極之第一層之形成) 第一層20亦可藉由熱熔射法而形成。 作為一例,藉由將氧化鎳粒子電漿熔射於基材上,而可形成混合有金屬鎳與氧化鎳之觸媒層。 以下,對隔膜之一態樣之離子交換膜進行詳細說明。 [離子交換膜] 作為離子交換膜,只要可與電解用電極製成積層體,則無特別限定,可應用各種離子交換膜。於本實施形態中,較佳為使用具有含有具有離子交換基之烴系聚合物或含氟系聚合物之膜本體、與設置於該膜本體之至少一面上之塗佈層之離子交換膜。又,塗佈層含有無機物粒子與結合劑,塗佈層之比表面積較佳為0.1~10 m2 /g。該結構之離子交換膜於電解中所產生之氣體對電解性能之影響較少,有發揮出穩定之電解性能之傾向。 上述所謂導入有離子交換基之全氟碳聚合物之膜係具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層之任一者。就強度及尺寸穩定性之觀點而言,較佳為進而具有強化芯材。 以下於塗佈層之說明之欄對無機物粒子及結合劑進行詳細說明。 圖109係表示離子交換膜之一實施形態之剖面模式圖。離子交換膜1具有:膜本體10,其含有具有離子交換基之烴系聚合物或含氟系聚合物;以及塗佈層11a及11b,其等形成於膜本體10之兩面。 於離子交換膜1中,膜本體10具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層3、與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層2,藉由強化芯材4強化強度及尺寸穩定性。離子交換膜1由於具備磺酸層3與羧酸層2,因此可作為陽離子交換膜而適宜地使用。 再者,離子交換膜亦可僅具有磺酸層及羧酸層之任一者。又,離子交換膜未必由強化芯材所強化,強化芯材之配置狀態亦不限定於圖109之例。 (膜本體) 首先,對構成離子交換膜1之膜本體10進行說明。 膜本體10只要為具有使陽離子選擇性地透過之功能且含有具有離子交換基之烴系聚合物或含氟系聚合物者即可,其構成或材料並無特別限定,可適當選擇適宜者。 膜本體10中之具有離子交換基之烴系聚合物或含氟系聚合物例如可由具有可藉由水解等成為離子交換基之離子交換基前驅物之烴系聚合物或含氟系聚合物獲得。具體而言,例如使用主鏈包含氟化烴、具有可藉由水解等轉換為離子交換基之基(離子交換基前驅物)作為懸垂側鏈且能夠熔融加工之聚合物(以下視情形稱為「含氟系聚合物(a)」)製作膜本體10之前驅物後,將離子交換基前驅物轉換為離子交換基,藉此可獲得膜本體10。 含氟系聚合物(a)例如可藉由使選自下述第1群之至少一種單體與選自下述第2群及/或下述第3群之至少一種單體進行共聚合而製造。又,亦可藉由選自下述第1群、下述第2群、及下述第3群之任一群之1種單體之均聚而製造。 作為第1群之單體,例如可列舉氟乙烯化合物。作為氟乙烯化合物,例如可列舉:氟乙烯、四氟乙烯、六氟丙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、全氟烷基乙烯醚等。尤其是於將離子交換膜用作鹼電解用膜之情形時,氟乙烯化合物較佳為全氟單體,較佳為選自由四氟乙烯、六氟丙烯、全氟烷基乙烯醚所組成之群中之全氟單體。 作為第2群之單體,例如可列舉具有可轉換為羧酸型離子交換基(羧酸基)之官能基之乙烯系化合物。作為具有可轉換為羧酸基之官能基之乙烯系化合物,例如可列舉以CF2 =CF(OCF2 CYF)s -O(CZF)t -COOR表示之單體等(此處,s表示0~2之整數,t表示1~12之整數,Y及Z各自獨立地表示F或CF3 ,R表示低級烷基。低級烷基例如為碳數1~3之烷基)。 該等中,較佳為以CF2 =CF(OCF2 CYF)n -O(CF2 )m -COOR表示之化合物。此處,n表示0~2之整數,m表示1~4之整數,Y表示F或CF3 ,R表示CH3 、C2 H5 、或C3 H7 。 再者,於將離子交換膜用作鹼電解用陽離子交換膜之情形時,較佳為至少使用全氟化合物作為單體,但由於酯基之烷基(參照上述R)於水解時從聚合物喪失,因此烷基(R)亦可不為全部氫原子被取代為氟原子之全氟烷基。 作為第2群之單體,於上述中,更佳為下述所表示之單體。 CF2 =CFOCF2 -CF(CF3 )OCF2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )2 COOCH3 、 CF2 =CF[OCF2 -CF(CF3 )]2 O(CF2 )2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )3 COOCH3 、 CF2 =CFO(CF2 )2 COOCH3 、 CF2 =CFO(CF2 )3 COOCH3 。 作為第3群之單體,例如可列舉具有可轉換為磺酸型離子交換基(磺酸基)之官能基之乙烯系化合物。作為具有可轉換為磺酸基之官能基之乙烯系化合物,例如較佳為以CF2 =CFO-X-CF2 -SO2 F表示之單體(此處,X表示全氟伸烷基)。作為該等之具體例,可列舉下述所表示之單體等。 CF2 =CFOCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、 CF2 =CF(CF2 )2 SO2 F、 CF2 =CFO[CF2 CF(CF3 )O]2 CF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF2 OCF3 )OCF2 CF2 SO2 F。 該等中,更佳為CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、及CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F。 由該等單體獲得之共聚物可藉由針對氟乙烯之均聚及共聚合所開發之聚合法、尤其是對四氟乙烯所使用之通常之聚合方法而製造。例如,於非水性法中,可使用全氟烴、氯氟碳等不活性溶劑,於全氟碳過氧化物或偶氮化合物等自由基聚合起始劑之存在下,於溫度0~200℃、壓力0.1~20 MPa之條件下進行聚合反應。 於上述共聚合中,上述單體之組合之種類及其比率並無特別限定,根據欲對所獲得之含氟系聚合物賦予之官能基之種類及量選擇確定。例如於製成僅含有羧酸基之含氟系聚合物之情形時,從上述第1群及第2群分別選擇至少1種單體進行共聚合即可。又,於製成僅含有磺酸基之含氟系聚合物之情形時,從上述第1群及第3群之單體中分別選擇至少1種單體進行共聚合即可。進而,於製成具有羧酸基及磺酸基之含氟系聚合物之情形時,從上述第1群、第2群及第3群之單體中分別選擇至少1種單體進行共聚合即可。於該情形時,藉由使包含上述第1群及第2群之共聚物與包含上述第1群及第3群之共聚物分開進行聚合,其後加以混合亦可獲得目標之含氟系聚合物。又,各單體之混合比率並無特別限定,於增加每單位聚合物之官能基之量之情形時,增加選自上述第2群及第3群之單體之比率即可。 含氟系共聚物之總離子交換容量並無特別限定,較佳為0.5~2.0 mg當量/g,更佳為0.6~1.5 mg當量/g。此處,所謂總離子交換容量係指相對於單位重量之乾燥樹脂之交換基之當量,可藉由中和滴定等進行測定。 於離子交換膜1之膜本體10中,積層有含有具有磺酸基之含氟系聚合物之磺酸層3與含有具有羧酸基之含氟系聚合物之羧酸層2。藉由製成此種層結構之膜本體10,能夠進一步提高鈉離子等陽離子之選擇性透過性。 於將離子交換膜1配置於電解槽之情形時,通常以磺酸層3位於電解槽之陽極側、羧酸層2位於電解槽之陰極側之方式配置。 磺酸層3較佳為由電阻較低之材料構成,就膜強度之觀點而言,較佳為其膜厚厚於羧酸層2。磺酸層3之膜厚較佳為羧酸層2之2~25倍,更佳為3~15倍。 羧酸層2較佳為即使膜厚較薄亦具有較高之陰離子排斥性者。此處所謂陰離子排斥性係指阻礙陰離子對離子交換膜1之滲入或透過之性質。為了提高陰離子排斥性,有效的是對磺酸層配置離子交換容量較小之羧酸層等。 作為磺酸層3所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F作為第3群之單體所獲得之聚合物。 作為羧酸層2所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF2 )O(CF2 )2 COOCH3 作為第2群之單體所獲得之聚合物。 (塗佈層) 離子交換膜較佳為於膜本體之至少一面上具有塗佈層。又,如圖109所示,於離子交換膜1中,於膜本體10之兩面上分別形成有塗佈層11a及11b。 塗佈層含有無機物粒子與結合劑。 無機物粒子之平均粒徑更佳為0.90 μm以上。若無機物粒子之平均粒徑為0.90 μm以上,則不僅極大地提高對氣體附著之耐久性,而且極大地提高對雜質之耐久性。即,藉由增大無機物粒子之平均粒徑,並且滿足上述比表面積之值,可獲得尤其顯著之效果。為了滿足此種平均粒徑與比表面積,較佳為不規則狀之無機物粒子。可使用藉由熔融獲得之無機物粒子、藉由原石粉碎獲得之無機物粒子。較佳可適宜地使用藉由原石粉碎獲得之無機物粒子。 又,無機物粒子之平均粒徑可設為2 μm以下。若無機物粒子之平均粒徑為2 μm以下,則能夠防止因無機物粒子而損傷膜。無機物粒子之平均粒徑更佳為0.90~1.2 μm。 此處,平均粒徑可藉由粒度分佈計(「SALD2200」島津製作所)進行測定。 無機物粒子之形狀較佳為不規則形狀。對雜質之耐性進一步提高。又,無機物粒子之粒度分佈較佳為較寬。 無機物粒子較佳為含有選自由週期表第IV族元素之氧化物、週期表第IV族元素之氮化物、及週期表第IV族元素之碳化物所組成之群中之至少一種無機物。就耐久性之觀點而言,更佳為氧化鋯之粒子。 該無機物粒子較佳為藉由將無機物粒子之原石粉碎所製造之無機物粒子,或以藉由將無機物粒子之原石熔融並加以精製而粒子之直徑一致之球狀之粒子作為無機物粒子。 作為原石粉碎方法,並無特別限定,可列舉:球磨機、珠磨機、膠體磨機、錐形磨機、盤磨機、輪輾機、磨粉機、錘磨機、造粒機、VSI磨機、威利磨機、輥磨機、噴射磨機等。又,較佳為粉碎後將其洗淨,作為此時之洗淨方法,較佳為酸處理。藉此,能夠減少附著於無機物粒子之表面之鐵等雜質。 塗佈層較佳為含有結合劑。結合劑係將無機物粒子保持於離子交換膜之表面、形成塗佈層之成分。就對電解液或電解之產物之耐性之觀點而言,結合劑較佳為含有含氟系聚合物。 作為結合劑,就對電解液或電解之產物之耐性、及對離子交換膜之表面之接著性之觀點而言,更佳為具有羧酸基或磺酸基之含氟系聚合物。於在含有具有磺酸基之含氟聚合物之層(磺酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有磺酸基之含氟系聚合物。又,於在含有具有羧酸基之含氟聚合物之層(羧酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有羧酸基之含氟系聚合物。 塗佈層中,無機物粒子之含量較佳為40~90質量%,更佳為50~90質量%。又,結合劑之含量較佳為10~60質量%,更佳為10~50質量%。 離子交換膜中之塗佈層之分佈密度較佳為每1 cm2 為0.05~2 mg。又,於離子交換膜於表面具有凹凸形狀之情形時,塗佈層之分佈密度較佳為每1 cm2 為0.5~2 mg。 作為形成塗佈層之方法,並無特別限定,可使用公知之方法。例如可列舉藉由噴射等塗佈將無機物粒子分散於含有結合劑之溶液中而成之塗佈液之方法。 (強化芯材) 離子交換膜較佳為具有配置於膜本體之內部之強化芯材。 強化芯材係強化離子交換膜之強度或尺寸穩定性之構件。藉由將強化芯材配置於膜本體之內部,尤其能夠將離子交換膜之伸縮控制為所需之範圍。該離子交換膜於電解時等不會伸縮為必要程度以上,而能夠長期維持優異之尺寸穩定性。 強化芯材之構成並無特別限定,例如可將稱為強化紗之紗進行紡紗而形成。此處所謂強化紗係構成強化芯材之構件,指能夠對離子交換膜賦予所需之尺寸穩定性及機械強度且於離子交換膜中能夠穩定地存在之紗。藉由使用將該強化紗紡紗而成之強化芯材,能夠對離子交換膜賦予更優異之尺寸穩定性及機械強度。 強化芯材及其所使用之強化紗之材料並無特別限定,較佳為對酸或鹼等具有耐性之材料,就需要長期之耐熱性、耐化學品性之方面而言,較佳為包含含氟系聚合物之纖維。 作為強化芯材所使用之含氟系聚合物,例如可列舉:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、四氟乙烯-六氟丙烯共聚物、三氟氯乙烯-乙烯共聚物及偏二氟乙烯聚合物(PVDF)等。該等中,尤其是就耐熱性及耐化學品性之觀點而言,較佳為使用包含聚四氟乙烯之纖維。 強化芯材所使用之強化紗之紗直徑並無特別限定,較佳為20~300丹尼,更佳為50~250丹尼。紡織密度(每單位長度之織入根數)較佳為5~50根/英吋。作為強化芯材之形態,並無特別限定,例如可使用織布、不織布、針織布等,較佳為織布之形態。又,使用織布之厚度較佳為30~250 μm、更佳為30~150 μm者。 織布或針織布可使用單絲、複絲或該等之紗線、切膜絲等,紡織方法可使用平織、紗羅組織、針織、凸條組織、縐條紋薄織等各種紡織方法。 膜本體中之強化芯材之紡織方法及配置並無特別限定,可考慮離子交換膜之大小或形狀、離子交換膜所需之物性及使用環境等適當設為適宜之配置。 例如,可沿膜本體之特定之一方向配置強化芯材,就尺寸穩定性之觀點而言,較佳為沿特定之第一方向配置強化芯材,且沿大致垂直於第一方向之第二方向配置其他強化芯材。藉由在膜本體之縱向膜本體之內部以大致成一列之方式配置複數個強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。例如,較佳為於膜本體之表面織入沿縱向配置之強化芯材(縱紗)與沿橫向配置之強化芯材(橫紗)之配置。就尺寸穩定性、機械強度及製造容易性之觀點而言,更佳為製成使縱紗與橫紗一上一下交替織入而紡織之平紋織物、或一邊撚轉2根經紗一邊與橫紗交織之紗羅組織物、於每2根或數根並紗配置之縱紗中織入相同數量之橫紗而紡織之斜紋織物(twill weave)等。 尤佳為沿離子交換膜之MD方向(縱向(Machine Direction)方向)及TD方向(橫向(Transverse Direction)方向)之兩方向配置強化芯材。即,較佳為沿MD方向與TD方向平織。此處,所謂MD方向係指於下文所述之離子交換膜之製造步驟中搬送膜本體或各種芯材(例如,強化芯材、強化紗、下文所述之犧牲紗等)之方向(行進方向),所謂TD方向係指大致垂直於MD方向之方向。此外,將沿MD方向紡織之紗稱為MD紗,將沿TD方向紡織之紗稱為TD紗。通常電解所使用之離子交換膜係矩形,長度方向為MD方向、寬度方向為TD方向之情況較多。藉由織入作為MD紗之強化芯材與作為TD紗之強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。 強化芯材之配置間隔並無特別限定,可考慮離子交換膜所需之物性及使用環境等適當設為適宜之配置。 強化芯材之開口率並無特別限定,較佳為30%以上,更佳為50%以上且90%以下。開口率就離子交換膜之電化學性質之觀點而言,較佳為30%以上,就離子交換膜之機械強度之觀點而言,較佳為90%以下。 所謂強化芯材之開口率係指膜本體之任一表面之面積(A)中離子等物質(電解液及其所含之陽離子(例如,鈉離子))能夠通過之表面之總面積(B)之比率(B/A)。所謂離子等物質能夠通過之表面之總面積(B)可指於離子交換膜中陽離子或電解液等不被離子交換膜所含之強化芯材等阻斷之區域之總面積。 圖110係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。圖110係將離子交換膜之一部分放大而僅圖示該區域內之強化芯材21及22之配置,其他構件省略圖示。 藉由從由沿縱向配置之強化芯材21與沿橫向配置之強化芯材22所圍成之亦包括強化芯材之面積在內之區域的面積(A)減去強化芯材之總面積(C),可求出上述區域之面積(A)中離子等物質能夠通過之區域之總面積(B)。即,開口率可藉由下述式(I)求出。 開口率=(B)/(A)=((A)-(C))/(A) …(I) 於強化芯材中,就耐化學品性及耐熱性之觀點而言,尤佳之形態係含有PTFE之帶狀紗線或高配向單絲。具體而言,更佳為如下強化芯材,其係使用將包含PTFE之高強度多孔質片材切為帶狀而成之帶狀紗線、或包含PTFE之高度配向之單絲之50~300丹尼且紡織密度為10~50根/英吋之平紋織物,其厚度為50~100 μm之範圍。含有該強化芯材之離子交換膜之開口率進而較佳為60%以上。 作為強化紗之形狀,可列舉圓紗、帶狀紗等。 (連通孔) 離子交換膜較佳為於膜本體之內部具有連通孔。 所謂連通孔係指能夠成為電解時產生之離子或電解液之流路之孔。又,所謂連通孔係形成於膜本體內部之管狀之孔,藉由下文所述之犧牲芯材(或犧牲紗)溶出而形成。連通孔之形狀或直徑等可藉由選擇犧牲芯材(犧牲紗)之形狀或直徑進行控制。 藉由在離子交換膜形成連通孔,於電解時能夠確保電解液之移動性。連通孔之形狀並無特別限定,根據下文所述之製法,可製成連通孔之形成所使用之犧牲芯材之形狀。 連通孔較佳為以交替通過強化芯材之陽極側(磺酸層側)與陰極側(羧酸層側)之方式形成。藉由設為該結構,於強化芯材之陰極側形成有連通孔之部分,通過充滿連通孔之電解液所輸送之離子(例如,鈉離子)亦能夠流至強化芯材之陰極側。其結果為,由於陽離子之流動未被遮蔽,因此能夠進一步降低離子交換膜之電阻。 連通孔可僅沿構成離子交換膜之膜本體之特定之一方向形成,就發揮出更穩定之電解性能之觀點而言,較佳為沿膜本體之縱向與橫向之兩方向形成。 [製造方法] 作為離子交換膜之適宜之製造方法,可列舉具有以下之(1)步驟~(6)步驟之方法。 (1)步驟:製造具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之含氟系聚合物之步驟。 (2)步驟:藉由視需要至少織入複數個強化芯材與具有溶於酸或鹼之性質且形成連通孔之犧牲紗而獲得於鄰接之強化芯材彼此之間配置有犧牲紗之補強材之步驟。 (3)步驟:將具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之上述含氟系聚合物進行膜化之步驟。 (4)步驟:視需要將上述補強材埋入至上述膜中而獲得內部配置有上述補強材之膜本體之步驟。 (5)步驟:將(4)步驟中獲得之膜本體進行水解之步驟(水解步驟)。 (6)步驟:於(5)步驟中獲得之膜本體設置塗佈層之步驟(塗佈步驟)。 以下,對各步驟進行詳細說明。 (1)步驟:製造含氟系聚合物之步驟 於(1)步驟中,使用上述第1群~第3群所記載之原料之單體製造含氟系聚合物。為了控制含氟系聚合物之離子交換容量,於形成各層之含氟系聚合物之製造中調整原料之單體之混合比即可。 (2)步驟:補強材之製造步驟 所謂補強材係紡織強化紗之織布等。藉由將補強材埋入至膜內而形成強化芯材。於製成具有連通孔之離子交換膜時,亦將犧牲紗一起織入至補強材中。該情形時之犧牲紗之混織量較佳為補強材整體之10~80質量%,更佳為30~70質量%。藉由織入犧牲紗,亦能夠防止強化芯材之脫線。 犧牲紗係於膜之製造步驟或電解環境下具有溶解性者,可使用嫘縈、聚對苯二甲酸乙二酯(PET)、纖維素及聚醯胺等。又,亦較佳為具有20~50丹尼之粗細程度、包含單絲或複絲之聚乙烯醇等。 再者,於(2)步驟中,可藉由調整強化芯材或犧牲紗之配置而控制開口率或連通孔之配置等。 (3)步驟:膜化步驟 於(3)步驟中,使用擠出機將上述(1)步驟中獲得之含氟系聚合物進行膜化。膜可為單層結構,亦可如上所述為磺酸層與羧酸層之2層結構,亦可為3層以上之多層結構。 作為膜化之方法,例如可列舉以下者。 分別將具有羧酸基之含氟聚合物、具有磺酸基之含氟聚合物分開進行膜化之方法。 藉由共擠出將具有羧酸基之含氟聚合物與具有磺酸基之含氟聚合物製成複合膜之方法。 再者,膜可分別為複數片。又,將異種之膜共擠出有助於提高界面之接著強度,故而較佳。 (4)步驟:獲得膜本體之步驟 於(4)步驟中,藉由將(2)步驟中獲得之補強材埋入至(3)步驟中獲得之膜之內部,而獲得內有補強材之膜本體。 作為膜本體之較佳之形成方法,可列舉:(i)藉由共擠出法將位於陰極側之具有羧酸基前驅物(例如,羧酸酯官能基)之含氟系聚合物(以下將包含其之層稱為第一層)與具有磺酸基前驅物(例如,磺醯氟官能基)之含氟系聚合物(以下將包含其之層稱為第二層)進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將補強材、第二層/第一層複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法;(ii)區別於第二層/第一層複合膜,預先將具有磺酸基前驅物之含氟系聚合物(第三層)單獨進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將第三層膜、強化芯材、包含第二層/第一層之複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法。 此處,將第一層與第二層共擠出有助於提高界面之接著強度。 又,於減壓下進行一體化之方法與加壓壓製法相比,具有補強材上之第三層之厚度變大之特徵。進而,由於將補強材固定於膜本體之內面,因此具有能夠充分保持離子交換膜之機械強度之性能。 再者,此處所說明之積層之變化係一例,可考慮所需之膜本體之層構成或物性等,適當選擇適宜之積層圖案(例如,各層之組合等)後進行共擠出。 再者,為了進一步提高離子交換膜之電性能,亦可於第一層與第二層之間進一步介置包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層,或使用包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層代替第二層。 第四層之形成方法可為分開製造具有羧酸基前驅物之含氟系聚合物與具有磺酸基前驅物之含氟系聚合物後加以混合之方法,亦可為使用將具有羧酸基前驅物之單體與具有磺酸基前驅物之單體共聚合而成者之方法。 於將第四層製成離子交換膜之構成之情形時,可將第一層與第四層之共擠出膜加以成形,第三層及第二層與其分開單獨進行膜化,藉由上文所述之方法進行積層,亦可將第一層/第四層/第二層之3層一次共擠出而進行膜化。 於該情形時,所擠出之膜行進之方向為MD方向。由此可將含有具有離子交換基之含氟系聚合物之膜本體形成於補強材上。 又,離子交換膜較佳為於包含磺酸層之表面側具有包含具有磺酸基之含氟聚合物之突出的部分、即凸部。作為形成此種凸部之方法,並無特別限定,可採用於樹脂表面形成凸部之公知之方法。具體而言,例如可列舉對膜本體之表面實施壓紋加工之方法。例如,於將上述複合膜與補強材等進行一體化時,藉由使用預先經壓紋加工之脫模紙,可形成上述凸部。於藉由壓紋加工形成凸部之情形時,凸部之高度或配置密度之控制可藉由控制所轉印之壓紋形狀(脫模紙之形狀)而進行。 (5)水解步驟 於(5)步驟中,進行將(4)步驟中獲得之膜本體水解而將離子交換基前驅物轉換為離子交換基之步驟(水解步驟)。 又,於(5)步驟中,藉由利用酸或鹼將膜本體所含之犧牲紗溶解去除,可於膜本體形成溶出孔。再者,犧牲紗亦可不完全溶解去除,而殘留於連通孔中。又,殘留於連通孔中之犧牲紗可於將離子交換膜供於電解時藉由電解液溶解去除。 犧牲紗係於離子交換膜之製造步驟或電解環境下對酸或鹼具有溶解性者,藉由使犧牲紗溶出而於該部位形成連通孔。 (5)步驟可將(4)步驟中獲得之膜本體浸漬於含有酸或鹼之水解溶液中進行。作為該水解溶液,例如可使用含有KOH與DMSO(Dimethyl sulfoxide)之混合溶液。 該混合溶液較佳為含有2.5~4.0 N之KOH,且含有25~35質量%之DMSO。 作為水解之溫度,較佳為70~100℃。溫度越高,可使視厚度更厚。更佳為75~100℃。 作為水解之時間,較佳為10~120分鐘。時間越長,可使視厚度更厚。更佳為20~120分鐘。 此處,對藉由溶出犧牲紗而形成連通孔之步驟進一步詳細地說明。圖111(a)、(b)係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 於圖111(a)、(b)中,僅圖示強化紗52、犧牲紗504a及由犧牲紗504a形成之連通孔504,膜本體等其他構件省略圖示。 首先,將於離子交換膜中構成強化芯材之強化紗52與於離子交換膜中用以形成連通孔504之犧牲紗504a製成針織織入補強材。然後,於(5)步驟中藉由使犧牲紗504a溶出而形成連通孔504。 藉由上述方法,根據於離子交換膜之膜本體內如何配置強化芯材、連通孔而調整強化紗52與犧牲紗504a之針織織入方法即可,因此較簡便。 於圖111(a)中,例示於紙面沿縱向與橫向之兩方向將強化紗52與犧牲紗504a織入之平織之補強材,可視需要變更補強材中之強化紗52與犧牲紗504a之配置。 (6)塗佈步驟 於(6)步驟中,製備含有藉由原石粉碎或原石熔融獲得之無機物粒子與結合劑之塗佈液,將塗佈液塗佈於(5)步驟中獲得之離子交換膜之表面並加以乾燥,藉此可形成塗佈層。 作為結合劑,較佳為將具有離子交換基前驅物之含氟系聚合物水解於含有二甲基亞碸(DMSO)及氫氧化鉀(KOH)之水溶液中之後,浸漬於鹽酸中將離子交換基之抗衡離子置換為H+ 而成之結合劑(例如,具有羧基或磺基之含氟系聚合物)。藉此,變得容易溶解於下文所述之水或乙醇中,故而較佳。 將該結合劑溶解於混合水與乙醇而成之溶液中。再者,水與乙醇之較佳之體積比為10:1~1:10,更佳為5:1~1:5,進而較佳為2:1~1:2。藉由球磨機使無機物粒子分散於由此獲得之溶解液中而獲得塗佈液。此時,亦可藉由調整分散時之時間、旋轉速度而調整粒子之平均粒徑等。再者,無機物粒子與結合劑之較佳之調配量如上文所述。 塗佈液中之無機物粒子及結合劑之濃度並無特別限定,較佳為製成稀薄之塗佈液。藉此,能夠均勻地塗佈於離子交換膜之表面。 又,於使無機物粒子分散時,亦可將界面活性劑添加於分散液中。作為界面活性劑,較佳為非離子系界面活性劑,例如可列舉日油股份有限公司製造之HS-210、NS-210、P-210、E-212等。 藉由利用噴射塗佈或滾筒塗敷將所獲得之塗佈液塗佈於離子交換膜表面而可獲得離子交換膜。 [微多孔膜] 作為本實施形態之微多孔膜,只要如上文所述,可與電解用電極製成積層體,則無特別限定,可應用各種微多孔膜。 本實施形態之微多孔膜之氣孔率並無特別限定,例如可設為20~90,較佳為30~85。上述氣孔率例如可藉由下述之式算出。 氣孔率=(1-(乾燥狀態之膜重量)/(由根據膜之厚度、寬度、長度算出之體積與膜素材之密度所算出之重量))×100 本實施形態之微多孔膜之平均孔徑並無特別限定,例如可設為0.01 μm~10 μ,較佳為0.05 μm~5 μm。上述平均孔徑例如係沿厚度方向將膜垂直切斷,藉由FE-SEM觀察切斷面。對所觀察之孔之直徑測定100點左右並求出平均值,藉此可求出平均孔徑。 本實施形態之微多孔膜之厚度並無特別限定,例如可設為10 μm~1000 μm,較佳為50 μm~600 μm。上述厚度例如可使用測微計(Mitutoyo股份有限公司製造)等進行測定。 作為如上所述之微多孔膜之具體例,可列舉Agfa公司製造之Zirfon Perl UTP 500(於本實施形態中亦稱為Zirfon膜)、國際公開第2013-183584號說明書、國際公開第2016-203701號說明書等所記載者。 於本實施形態中,較佳為隔膜包含第1離子交換樹脂層、及具有與該第1離子交換樹脂層不同之EW(離子交換當量)之第2離子交換樹脂層。又,較佳為隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之官能基之第2離子交換樹脂層。離子交換當量可藉由所導入之官能基進行調整,關於可導入之官能基係如上文所述。 (水電解) 本實施形態中之進行水電解之情形時之電解槽係具有將上述進行食鹽電解之情形時之電解槽中之離子交換膜變更為微多孔膜之構成者。又,於所供給之原料為水之方面與上述進行食鹽電解之情形時之電解槽不同。關於其他構成,進行水電解之情形時之電解槽亦可採用與進行食鹽電解之情形時之電解槽相同之構成。於食鹽電解之情形時,由於在陽極室產生氯氣,因此陽極室之材質使用鈦,於水電解之情形時,由於在陽極室僅產生氧氣,因此可使用與陰極室之材質相同者。例如可列舉鎳等。又,陽極塗層適宜為產生氧氣用之觸媒塗層。作為觸媒塗層之例,可列舉鉑族金屬及過渡金屬族之金屬、氧化物、氫氧化物等。例如可使用鉑、銥、鈀、釕、鎳、鈷、鐵等元素。 <第7實施形態> 此處,一邊參照圖112~122一邊對本發明之第7實施形態進行詳細地說明。 [電解槽之製造方法] 第7實施形態(以下於<第7實施形態>之項中簡稱為「本實施形態」)之第1態樣(以下亦簡稱為「第1態樣」)之電解槽之製造方法係用以藉由對具備陽極、與上述陽極相對向之陰極、固定於上述陽極與上述陰極之間之隔膜、以及支持上述陽極、上述陰極及上述隔膜之電解槽架的既有電解槽配置包含電解用電極及新隔膜之積層體而製造新電解槽之方法,並且具有於上述電解槽架內解除上述隔膜之固定之步驟(A)、及於上述步驟(A)後將上述隔膜與上述積層體交換之步驟(B)。如上所述,根據第1態樣之電解槽之製造方法,能夠於不將各構件取出至電解槽架之外側之情況下更新電極,而能夠提高電解槽中之電極更新時之作業效率。 又,本實施形態之第2態樣(以下亦簡稱為「第2態樣」)之電解槽之製造方法係用以藉由對具備陽極、與上述陽極相對向之陰極、固定於上述陽極與上述陰極之間之隔膜、以及支持上述陽極、上述陰極及上述隔膜之電解槽架的既有電解槽配置電解用電極而製造新電解槽之方法,並且具有於上述電解槽架內解除上述隔膜之固定之步驟(A)、及於上述步驟(A)後於上述隔膜與上述陽極或上述陰極之間配置上述電解用電極之步驟(B')。 如上所述,根據第2態樣之電解槽之製造方法,亦能夠於不將各構件取出至電解槽架之外側之情況下更新電極,而能夠提高電解槽中之電極更新時之作業效率。 以下,於稱為「本實施形態之電解槽之製造方法」時,包括第1態樣之電解槽之製造方法及第2態樣之電解槽之製造方法。 於本實施形態之電解槽之製造方法中,既有電解槽包含陽極、與上述陽極相對向之陰極、配置於上述陽極與上述陰極之間之隔膜、以及支持上述陽極、上述陰極及上述隔膜之電解槽架作為構成構件。換言之,既有電解槽包含隔膜、電解池、及支持該等之電解槽架。既有電解槽只要包含上述構成構件,則無特別限定,可應用各種公知之構成。 於本實施形態之電解槽之製造方法中,新電解槽係除了於既有電解槽中已作為陽極或陰極而發揮功能之構件以外,進而具備電解用電極或積層體者。即,於第1態樣及第2態樣中,於製造新電解槽時所配置之「電解用電極」係作為陽極或陰極而發揮功能者,與既有電解槽中之陰極及陽極不同體。於本實施形態之電解槽之製造方法中,即使於伴隨既有電解槽之運轉陽極及/或陰極之電解性能劣化之情形時,藉由配置與該等不同體之電解用電極,亦可更新陽極及/或陰極之性能。又,於使用積層體之第1態樣中,由於一併配置新離子交換膜,因此伴隨運轉性能劣化之離子交換膜之性能亦可同時更新。此處所謂「更新性能」意指設為與將既有電解槽供於運轉前所具有之初始性能相同之性能、或高於該初始性能之性能。 於本實施形態之電解槽之製造方法中,假定既有電解槽係「已供於運轉之電解槽」,又,假定新電解槽係「尚未供於運轉之電解槽」。即,若將作為新電解槽所製造之電解槽供於運轉一次,則成為「本實施形態中之既有電解槽」,對該既有電解槽配置電解用電極或積層體而成者成為「本實施形態中之新電解槽」。 以下,以使用離子交換膜作為隔膜進行食鹽電解之情形為例,對電解槽之一實施形態進行詳細說明。再者,於<第7實施形態>之項中,只要無特別說明,則「本實施形態中之電解槽」包含「本實施形態中之既有電解槽」及「本實施形態中之新電解槽」之兩者。 [電解池] 首先,對可用作本實施形態中之電解槽之構成單元的電解池進行說明。圖112係電解池1之剖面圖。 電解池1具備陽極室10、陰極室20、設置於陽極室10及陰極室20之間之間隔壁30、設置於陽極室10之陽極11、及設置於陰極室20之陰極21。視需要亦可具備具有基材18a與形成於該基材18a上之逆向電流吸收層18b且設置於陰極室內之逆向電流吸收體18。屬於1個電解池1之陽極11及陰極21互相電性連接。換言之,電解池1具備如下陰極結構體。陰極結構體40具備陰極室20、設置於陰極室20之陰極21、及設置於陰極室20內之逆向電流吸收體18,逆向電流吸收體18如圖116所示具有基材18a與形成於該基材18a上之逆向電流吸收層18b,陰極21與逆向電流吸收層18b電性連接。陰極室20進而具有集電體23、支持該集電體之支持體24、及金屬彈性體22。金屬彈性體22係設置於集電體23及陰極21之間。支持體24係設置於集電體23及間隔壁30之間。集電體23經由金屬彈性體22而與陰極21電性連接。間隔壁30經由支持體24而與集電體23電性連接。因此,間隔壁30、支持體24、集電體23、金屬彈性體22及陰極21係電性連接。陰極21及逆向電流吸收層18b係電性連接。陰極21及逆向電流吸收層可直接連接,亦可經由集電體、支持體、金屬彈性體或間隔壁等而間接連接。陰極21之表面整體較佳為由用於還原反應之觸媒層所被覆。又,電性連接之形態可為分別直接將間隔壁30與支持體24、支持體24與集電體23、集電體23與金屬彈性體22安裝,並且於金屬彈性體22上積層陰極21之形態。作為將該等各構成構件互相直接安裝之方法,可列舉焊接等。又,亦可將逆向電流吸收體18、陰極21、及集電體23總稱為陰極結構體40。 圖113係電解槽4內鄰接之2個電解池1之剖面圖。圖114表示作為既有電解槽之電解槽4。圖115表示組裝電解槽4之步驟(與步驟(A)~(B)及步驟(A')~(B')不同)。 如圖113所示,將電解池1、陽離子交換膜2、電解池1依序串聯排列。於電解槽內鄰接之2個電解池中之一電解池1之陽極室與另一電解池1之陰極室之間配置離子交換膜2。即,電解池1之陽極室10及與其鄰接之電解池1之陰極室20係由陽離子交換膜2隔開。如圖114所示,電解槽4係以藉由電解槽架8支持介隔離子交換膜2而串聯連接之複數個電解池1之形式構成。即,電解槽4係具備串聯配置之複數個電解池1、配置於鄰接之電解池1之間之離子交換膜2、及支持該等之電解槽架8之複極式電解槽。如圖115所示,電解槽4係藉由介隔離子交換膜2串聯配置複數個電解池1並利用電解槽架8中之壓製器5連結而組裝。再者,作為電解槽架,只要可支持各構件並且可連結,則無特別限定,可應用各種公知之形態。作為電解槽架所具備之連結各構件之機構,亦無特別限定,例如,可列舉利用油壓之壓製機構、或具備連接桿作為機構者。 電解槽4具有連接於電源之陽極端子7與陰極端子6。於電解槽4內串聯連結之複數個電解池1中位於最靠端之電解池1之陽極11係電性連接於陽極端子7。於電解槽4內串聯連結之複數個電解池2中位於陽極端子7之相反側之端之電解池的陰極21係電性連接於陰極端子6。電解時之電流從陽極端子7側起,經過各電解池1之陽極及陰極而流向陰極端子6。再者,可於連結之電解池1之兩端配置僅具有陽極室之電解池(陽極終端池)與僅具有陰極室之電解池(陰極終端池)。於該情形時,將陽極端子7連接於配置於其一端之陽極終端池,將陰極端子6連接於配置於另一端之陰極終端池。 於進行鹽水之電解之情形時,向各陽極室10供給鹽水,向陰極室20供給純水或低濃度之氫氧化鈉水溶液。各液體係從電解液供給管(圖中省略)起,經過電解液供給軟管(圖中省略)而向各電解池1供給。又,電解液及電解之產物係由電解液回收管(圖中省略)所回收。於電解中,鹽水中之鈉離子從一電解池1之陽極室10起,通過離子交換膜2,向旁邊之電解池1之陰極室20移動。由此電解中之電流沿將電解池1串聯連結之方向流通。即,電流係經由陽離子交換膜2而從陽極室10流向陰極室20。伴隨鹽水之電解,於陽極11側產生氯氣,於陰極21側產生氫氧化鈉(溶質)與氫氣。 (陽極室) 陽極室10具有陽極11或陽極饋電體11。作為此處所謂饋電體意指劣化之電極(即既有電極)或未形成有觸媒塗層之電極等。於將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極饋電體發揮功能。於不將本實施形態中之電解用電極插入陽極側之情形時,11作為陽極發揮功能。又,陽極室10較佳為具有向陽極室10供給電解液之陽極側電解液供給部、配置於陽極側電解液供給部之上方且以與間隔壁30大致平行或傾斜之方式配置之擋板、及配置於擋板之上方且從混入有氣體之電解液中分離氣體之陽極側氣液分離部。 (陽極) 於不將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框(即,陽極框)內設置有陽極11。作為陽極11,可使用所謂DSA(註冊商標)等金屬電極。所謂DSA係藉由以釕、銥、鈦作為成分之氧化物被覆表面之鈦基材之電極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極饋電體) 於將本實施形態中之電解用電極插入陽極側之情形時,於陽極室10之框內設置有陽極饋電體11。作為陽極饋電體11,可使用所謂DSA(註冊商標)等金屬電極,亦可使用未形成有觸媒塗層之鈦。又,亦可使用使觸媒塗層厚度變薄之DSA。進而,亦可使用使用過之陽極。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陽極側電解液供給部) 陽極側電解液供給部係向陽極室10供給電解液者,其連接於電解液供給管。陽極側電解液供給部較佳為配置於陽極室10之下方。作為陽極側電解液供給部,例如可使用表面形成有開口部之管(分散管)等。該管更佳為以沿陽極11之表面平行於電解池之底部19之方式配置。該管係連接於向電解池1內供給電解液之電解液供給管(液供給噴嘴)。從液供給噴嘴供給之電解液藉由管被搬送至電解池1內,從設置於管之表面之開口部向陽極室10之內部供給。藉由將管以沿陽極11之表面平行於電解池之底部19之方式配置,能夠將電解液均勻地供給至陽極室10之內部,故而較佳。 (陽極側氣液分離部) 陽極側氣液分離部較佳為配置於擋板之上方。於電解中,陽極側氣液分離部具有將氯氣等產生氣體與電解液分離之功能。再者,只要無特別說明,則所謂上方意指圖112之電解池1中之上方向,所謂下方意指圖112之電解池1中之下方向。 電解時,若電解池1中產生之產生氣體與電解液成為混相(氣液混相)而被排出至系外,則存在因電解池1內部之壓力變動導致產生振動而引起離子交換膜之物理破損之情形。為了抑制該情形,較佳為於本實施形態中之電解池1中設置用以將氣體與液體分離之陽極側氣液分離部。較佳為於陽極側氣液分離部設置用以消除氣泡之消泡板。藉由在氣液混相流通過消泡板時氣泡破裂,而可分離為電解液與氣體。其結果為,能夠防止電解時之振動。 (擋板) 擋板較佳為配置於陽極側電解液供給部之上方,且以與間隔壁30大致平行或傾斜之方式配置。擋板係控制陽極室10之電解液之流動之間隔板。藉由設置擋板,可使電解液(鹽水等)於陽極室10內部循環,使其濃度變得均勻。為了引起內部循環,擋板較佳為以將陽極11附近之空間與間隔壁30附近之空間隔開之方式配置。就該觀點而言,擋板較佳為以與陽極11及間隔壁30之各表面相對向之方式設置。於由擋板分隔之陽極附近之空間,藉由進行電解,電解液濃度(鹽水濃度)降低,又,產生氯氣等產生氣體。藉此,於由擋板分隔之陽極11附近之空間與間隔壁30附近之空間產生氣液之比重差。利用該情況,能夠促進陽極室10中之電解液之內部循環,使陽極室10之電解液之濃度分佈變得更均勻。 再者,於圖112並未圖示,但亦可於陽極室10之內部另行設置集電體。作為該集電體,亦可設為與下文所述之陰極室之集電體相同之材料或構成。又,於陽極室10中,亦可使陽極11本身作為集電體發揮功能。 (間隔壁) 間隔壁30係配置於陽極室10與陰極室20之間。間隔壁30有時亦稱為間隔件,係將陽極室10與陰極室20進行劃分者。作為間隔壁30,可使用作為電解用之間隔件所公知者,例如可列舉於陰極側焊接包含鎳之板、於陽極側焊接包含鈦之板之間隔壁等。 (陰極室) 陰極室20於將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極饋電體發揮功能,於不將本實施形態中之電解用電極插入陰極側之情形時,21作為陰極發揮功能。於具有逆向電流吸收體之情形時,陰極或陰極饋電體21與逆向電流吸收體係電性連接。又,陰極室20較佳為與陽極室10同樣,亦具有陰極側電解液供給部、陰極側氣液分離部。再者,構成陰極室20之各部位中,關於與構成陽極室10之各部位相同者省略說明。 (陰極) 於不將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框(即,陰極框)內設置有陰極21。陰極21較佳為具有鎳基材與被覆鎳基材之觸媒層。作為鎳基材上之觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可視需要對陰極21實施還原處理。再者,作為陰極21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (陰極饋電體) 於將本實施形態中之電解用電極插入陰極側之情形時,於陰極室20之框內設置有陰極饋電體21。可對陰極饋電體21被覆觸媒成分。該觸媒成分可為原本用作陰極而殘存者。作為觸媒層之成分,可列舉:Ru、C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。作為觸媒層之形成方法,可列舉:鍍覆、合金鍍覆、分散/複合鍍覆、CVD、PVD、熱分解及熔射。亦可將該等方法加以組合。觸媒層可視需要具有複數層、複數種元素。又,可使用未形成有觸媒塗層之鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。再者,作為陰極饋電體21之基材,可使用鎳、鎳合金、對鐵或不鏽鋼鍍覆鎳而成者。 作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。 (逆向電流吸收層) 可選擇具有較上文所述之陰極之觸媒層用元素的氧化還原電位更低之氧化還原電位之材料作為逆向電流吸收層之材料。例如可列舉鎳或鐵等。 (集電體) 陰極室20較佳為具備集電體23。藉此,集電效果提高。於本實施形態中,集電體23較佳為多孔板,且以與陰極21之表面大致平行之方式配置。 作為集電體23,例如較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。集電體23可為該等金屬之混合物、合金或複合氧化物。再者,集電體23之形狀只要為作為集電體發揮功能之形狀,則可為任意形狀,可為板狀、網狀。 (金屬彈性體) 藉由在集電體23與陰極21之間設置金屬彈性體22,將串聯連接之複數個電解池1之各陰極21壓抵於離子交換膜2,各陽極11與各陰極21之間之距離變短,可降低對串聯連接之複數個電解池1整體施加之電壓。藉由電壓降低,可降低消耗電量。又,藉由設置金屬彈性體22,於將含有本實施形態中之電解用電極之積層體設置於電解池時,藉由金屬彈性體22之壓抵壓,可將該電解用電極穩定地維持於起始位置。 作為金屬彈性體22,可使用螺旋彈簧、線圈等彈簧構件、緩衝性之墊等。作為金屬彈性體22,可考慮壓抵離子交換膜之應力等而適當採用適宜者。可將金屬彈性體22設置於陰極室20側之集電體23之表面上,亦可設置於陽極室10側之間隔壁之表面上。通常以陰極室20小於陽極室10之方式劃分兩室,因此就框體之強度等觀點而言,較佳為將金屬彈性體22設置於陰極室20之集電體23與陰極21之間。又,金屬彈性體23較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。 (支持體) 陰極室20較佳為具備將集電體23與間隔壁30電性連接之支持體24。藉此,能夠效率良好地流通電流。 支持體24較佳為包含鎳、鐵、銅、銀、鈦等具有導電性之金屬。又,作為支持體24之形狀,只要為能夠支持集電體23之形狀,則可為任意形狀,可為棒狀、板狀或網狀。支持體24例如為板狀。複數個支持體24係配置於間隔壁30與集電體23之間。複數個支持體24係以各自之面互相平行之方式排列。支持體24係以大致垂直於間隔壁30及集電體23之方式配置。 (陽極側墊片、陰極側墊片) 陽極側墊片較佳為配置於構成陽極室10之框體表面。陰極側墊片較佳為配置於構成陰極室20之框體表面。1個電解池所具備之陽極側墊片及與其鄰接之電解池之陰極側墊片以夾持離子交換膜2之方式將電解池彼此連接(參照圖113)。藉由該等墊片,於介隔離子交換膜2將複數個電解池1串聯連接時,能夠對連接處賦予氣密性。 所謂墊片係將離子交換膜與電解池之間密封者。作為墊片之具體例,可列舉中央形成有開口部之邊框狀之橡膠製片等。對於墊片要求對腐蝕性之電解液或所產生之氣體等具有耐性而可長期使用。因此,就耐化學品性或硬度之方面而言,通常可使用乙烯-丙烯-二烯橡膠(EPDM橡膠)、乙烯-丙烯橡膠(EPM橡膠)之硫化物或過氧化物交聯物等作為墊片。又,視需要亦可使用以聚四氟乙烯(PTFE)或四氟乙烯-全氟烷基乙烯醚共聚物(PFA)等氟系樹脂被覆與液體相接之區域(接液部)之墊片。該等墊片只要以不妨礙電解液之流動之方式分別具有開口部即可,其形狀並無特別限定。例如沿構成陽極室10之陽極室框或構成陰極室20之陰極室框之各開口部之周緣,藉由接著劑等貼附邊框狀之墊片。此外,於例如介隔離子交換膜2連接2個電解池1之情形時(參照圖113),介隔離子交換膜2將貼附有墊片之各電解池1緊固即可。藉此,能夠抑制電解液、因電解而產生之鹼金屬氫氧化物、氯氣、氫氣等漏至電解池1之外部之情況。 [積層體] 於本實施形態之電解槽之製造方法中,電解用電極可作為與離子交換膜或微多孔膜等隔膜之積層體而使用。即,本實施形態中之積層體係包含電解用電極與新隔膜者。新隔膜只要與既有電解槽中之隔膜不同體,則無特別限定,可應用各種公知之隔膜。又,新隔膜可為材質、形狀、物性等與既有電解槽中之隔膜相同者。對電解用電極及隔膜之具體例追加詳細說明。 (步驟(A)) 於第1態樣中之步驟(A)中,於電解槽架內解除隔膜之固定。所謂「於電解槽架內」意指一邊保持電解池(即,包含陽極及陰極之構件)及隔膜由電解槽架所支持之狀態一邊進行步驟(A),將電解池從電解槽架去除之態樣除外。作為解除隔膜之固定之方法,並無特別限定,例如可列舉解除利用電解槽架中之壓製器之按壓,於電解池與隔膜之間形成空隙,設為將隔膜取出至電解槽架之外之狀態之方法等。於步驟(A)中,較佳為藉由使陽極及陰極分別沿該等之排列方向滑動,而於電解槽架內解除隔膜之固定。藉由此種操作,可設為能夠於不將電解池取出至電解槽架之外之情況下將隔膜取出至電解槽架之外之狀態。 [步驟(B)] 於第1態樣中之步驟(B)中,於步驟(A)之後,將既有電解槽中之隔膜與積層體交換。作為交換之方法,並無特別限定,例如可列舉於該電解池及離子交換膜之間形成空隙後,將成為更新對象之既有之隔膜去除,繼而將積層體插入至該空隙之方法等。藉由此種方法,能夠將積層體配置於既有電解槽中之陽極或陰極之表面上,而能夠更新離子交換膜、陽極及/或陰極之性能。 於實施步驟(B)後,較佳為藉由從陽極及陰極進行按壓,而將上述積層體固定於上述電解槽架內。具體而言,可將既有電解槽中之隔膜與積層體交換後,再次藉由壓製器對積層體與電解池等既有電解槽中之各構件進行按壓而加以連結。藉由此種方法,能夠將積層體固定於既有電解槽中之陽極或陰極之表面上。 基於圖117(A)及(B),對第1態樣中之步驟(A)~(B)之具體例進行說明。首先,解除利用壓製器5之按壓,使複數個電解池1及離子交換膜2沿該等之排列方向α滑動。藉此,能夠在不將電解池1取出至電解槽架8之外之情況下於電解池1及離子交換膜2之間形成空隙S,離子交換膜2成為可取出至電解槽架8之外之狀態。繼而,將成為交換對象之既有電解槽之離子交換膜2從電解槽架8取出,取而代之,將新離子交換膜2a與電解用電極100之積層體9插入至鄰接之電解池1之間(即,空隙S)。由此,於鄰接之電解池1之間配置積層體9,該等成為由電解槽架8所支持之狀態。繼而,利用壓製器5沿排列方向α進行按壓,藉此將複數個電解池1與積層體9連結。 (步驟(A')) 於第2態樣中之步驟(A')中,亦與第1態樣同樣地於電解槽架內解除隔膜之固定。於步驟(A')中,亦較佳為藉由使陽極及陰極分別沿該等之排列方向滑動,而於電解槽架內解除隔膜之固定。藉由此種操作,可設為能夠於不將電解池取出至電解槽架之外之情況下將隔膜取出至電解槽架之外之狀態。 [步驟(B')] 於第2態樣中之步驟(B')中,於步驟(A')之後,於隔膜與陽極或陰極之間配置電解用電極。作為配置電解用電極之方法,並無特別限定,例如可列舉於電解池及離子交換膜之間形成空隙後,將電解用電極插入至該空隙之方法等。藉由此種方法,能夠將電解用電極配置於既有電解槽中之陽極或陰極之表面上,而能夠更新陽極或陰極之性能。 於實施步驟(B')後,較佳為藉由從陽極及陰極進行按壓,而將電解用電極固定於電解槽架內。具體而言,可將電解用電極配置於既有電解槽中之陽極或陰極之表面上後,再次藉由壓製器對電解用電極與電解池等既有電解槽中之各構件進行按壓而加以連結。藉由此種方法,能夠將積層體固定於既有電解槽中之陽極或陰極之表面上。 基於圖118(A)及(B),對第2態樣中之步驟(A')~(B')之具體例進行說明。首先,解除利用壓製器5之按壓,使複數個電解池1及離子交換膜2沿該等之排列方向α滑動。藉此,能夠於不將電解池1取出至電解槽架8之外之情況下於電解池1與離子交換膜2之間形成空隙S。繼而,將電解用電極100插入至鄰接之電解池1之間(即,空隙S)。由此,於鄰接之電解池1之間配置電解用電極100,該等成為由電解槽架8所支持之狀態。繼而,利用壓製器5沿排列方向α進行按壓,藉此將複數個電解池1與電解用電極100連結。 再者,於第1態樣中之步驟(B)中,較佳為於積層體不熔融之溫度下,將該積層體固定於陽極及陰極之至少一者之表面上。 「積層體不熔融之溫度」可作為新隔膜之軟化點而特定出。該溫度可根據構成隔膜之材料而變動,較佳為0~100℃,更佳為5~80℃,進而較佳為10~50℃。 又,上述之固定較佳為於常壓下進行。 較佳為進而藉由將電解用電極與新隔膜於該隔膜不熔融之溫度下進行一體化,獲得積層體後用於步驟(B)。 作為上述一體化之具體之方法,可使用除了熱壓接等將隔膜熔融之典型之方法以外之所有方法,並無特別限定。作為較佳之一例,可列舉下文所述之將液體介置於電解用電極與隔膜之間而藉由該液體之表面張力進行一體化之方法等。 [電解用電極] 於本實施形態之電解槽之製造方法中,電解用電極只要為可用於電解者,則無特別限定。電解用電極可為於電解槽中作為陰極而發揮功能者,亦可為作為陽極而發揮功能者。又,關於電解用電極之材質或形狀等,可考慮電解槽之構成等而適當選擇合適者。以下,對本實施形態中之電解用電極之較佳之態樣進行說明,但該等僅為對於第1態樣中與新隔膜進行一體化而製成積層體之情形而言較佳之態樣之例示,亦可適當採用下文所述之態樣以外之電解用電極。 本實施形態中之電解用電極就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、饋電體(劣化之電極及未形成有觸媒塗層之電極)等具有良好之接著力之觀點而言,每單位質量·單位面積所承受之力較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。 就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/mg・cm2 以上,進而更佳為0.14 N/(mg・cm2 )以上。就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.2 N/(mg・cm2 )以上。 上述承受力例如可藉由適當調整下文所述之開孔率、電極之厚度、算術平均表面粗糙度等而設為上述範圍。更具體而言,例如,若增大開孔率,則承受力有變小之傾向,若減小開孔率,則承受力有變大之傾向。 又,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有良好之接著力之觀點,進而就經濟性之觀點而言,較佳為每單位面積之質量為48 mg/cm2 以下,更佳為30 mg/cm2 以下,進而較佳為20 mg/cm2 以下,進而,就合併操作性、接著性及經濟性之綜合性之觀點而言,較佳為15 mg/cm2 以下。下限值並無特別限定,例如為1 mg/cm2 左右。 上述每單位面積之質量例如可藉由適當調整下文所述之開孔率、電極之厚度等而設為上述範圍。更具體而言,例如,若為相同之厚度,則若增大開孔率,則每單位面積之質量有變小之傾向,若減小開孔率,則每單位面積之質量有變大之傾向。 承受力可藉由以下之方法(i)或(ii)進行測定,詳細而言,如實施例所記載。關於承受力,藉由方法(i)之測定所獲得之值(亦稱為「承受力(1)」)與藉由方法(ii)之測定所獲得之值(亦稱為「承受力(2)」)可相同亦可不同,但較佳為任一值均未達1.5 N/mg・cm2 。 [方法(i)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方)、於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方,關於此處所謂離子交換膜之詳細如實施例所記載)及電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。再者,噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.5~0.8 μm。算術平均表面粗糙度(Ra)之具體之算出方法如實施例所記載。 於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與離子交換膜之重疊部分之面積、及與離子交換膜重疊部分之電極樣品之質量,而算出每單位質量·單位面積所承受之力(1)(N/mg・cm2 )。 藉由方法(i)獲得之每單位質量·單位面積所承受之力(1)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。又,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 ),更佳為0.2 N/(mg・cm2 )以上。 [方法(ii)] 依序積層以粒編號320之氧化鋁實施噴擊加工所獲得之鎳板(厚度1.2 mm,200 mm見方,與上述方法(i)相同之鎳板)與電極樣品(130 mm見方),將該積層體於純水中充分浸漬後,去除附著於積層體表面之多餘之水分,藉此獲得測定用樣品。於溫度23±2℃、相對濕度30±5%之條件下,使用拉伸壓縮試驗機,僅使該測定用樣品中之電極樣品以10 mm/分鐘沿垂直方向上升,測定電極樣品沿垂直方向上升10 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極樣品與鎳板之重疊部分之面積、及與鎳板重疊部分中之電極樣品之質量,而算出每單位質量•單位面積之接著力(2)(N/mg・cm2 )。 藉由方法(ii)獲得之每單位質量·單位面積所承受之力(2)就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體具有良好之接著力之觀點而言,較佳為1.6 N/(mg・cm2 )以下,更佳為未達1.6 N/(mg・cm2 ),進而較佳為未達1.5 N/(mg・cm2 ),進而更佳為1.2 N/mg・cm2 以下,更佳為1.20 N/mg・cm2 以下。進而更佳為1.1 N/mg・cm2 以下,進而更佳為1.10 N/mg・cm2 以下,尤佳為1.0 N/mg・cm2 以下,特佳為1.00 N/mg・cm2 以下。進而,就進一步提高電解性能之觀點而言,較佳為超過0.005 N/(mg・cm2 ),更佳為0.08 N/(mg・cm2 )以上,進而較佳為0.1 N/(mg・cm2 )以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而更佳為0.14 N/(mg・cm2 )以上。 本實施形態中之電解用電極較佳為包含電解用電極基材及觸媒層。該電解用電極基材之厚度(量規厚度)並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折,大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於本實施形態之電解槽之製造方法中,較佳為將新隔膜與電解用電極進行一體化後,於該等之間介置液體。該液體只要為水、有機溶劑等產生表面張力者,則可使用任意液體。液體之表面張力越大,對新隔膜與電解用電極之間承受之力越大,因此較佳為表面張力較大之液體。作為液體,可列舉如下者(括號內之數值係該液體於20℃下之表面張力)。 己烷(20.44 mN/m)、丙酮(23.30 mN/m)、甲醇(24.00 mN/m)、乙醇(24.05 mN/m)、乙二醇(50.21 mN/m)水(72.76 mN/m) 若為表面張力較大之液體,則新隔膜與電解用電極成為一體(成為積層體),有電極更新變得更容易之傾向。新隔膜與電解用電極之間之液體為藉由表面張力而互相貼附之程度之量即可,其結果為液體量較少,因此即使於將該積層體設置於電解池後混入至電解液中,亦不會對電解本身造成影響。 就實用上之觀點而言,作為液體,較佳為使用乙醇、乙二醇、水等表面張力為24 mN/m至80 mN/m之液體。尤佳為水或將苛性鈉、氫氧化鉀、氫氧化鋰、碳酸氫鈉、碳酸氫鉀、碳酸鈉、碳酸鉀等溶解於水中製成鹼性之水溶液。又,亦可使該等液體含有界面活性劑而調整表面張力。藉由含有界面活性劑,新隔膜與電解用電極之接著性發生變化,而可調整操作性。作為界面活性劑,並無特別限定,可使用離子性界面活性劑、非離子性界面活性劑之任一種。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力之觀點而言,藉由以下之方法(2)所測得之比率較佳為90%以上,更佳為92%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為95%以上。上限值為100%。 [方法(2)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑280 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,可適宜地捲繞為滾筒狀而良好地彎折之觀點而言,藉由以下之方法(3)所測得之比率較佳為75%以上,更佳為80%以上,進而,就大型尺寸(例如,尺寸1.5 m×2.5 m)下之處理變得容易之觀點而言,進而較佳為90%以上。上限值為100%。 [方法(3)] 依序積層離子交換膜(170 mm見方)與電極樣品(130 mm見方)。於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,於其1分鐘後,對離子交換膜(170 mm見方)與電極樣品密接之部分之面積的比率(%)進行測定。 本實施形態中之電解用電極並無特別限定,就可獲得良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極(饋電體)及未形成有觸媒塗層之電極(饋電體)具有良好之接著力,防止電解中產生之氣體滯留之觀點而言,較佳為多孔結構,且其開孔率或空隙率為5~90%以下。開孔率更佳為10~80%以下,進而較佳為20~75%。 再者,所謂開孔率係每單位體積之開孔部之比率。開孔部亦根據考慮至次微米級抑或僅考慮目視可見之開口而有各種算出方法。於本實施形態中,可藉由根據電極之量規厚度、寬度、長度之值算出體積V,進而實測重量W,而利用下述之式算出開孔率A。 A=(1-(W/(V×ρ))×100 ρ係電極之材質之密度(g/cm3 )。例如於鎳之情形時為8.908 g/cm3 ,於鈦之情形時為4.506 g/cm3 。開孔率之調整可藉由如下方法進行適當調整:若為沖孔金屬,則變更每單位面積沖裁金屬之面積;若為多孔金屬,則變更SW(短徑)、LW(長徑)、進給之值;若為絲網,則變更金屬纖維之線徑、網眼數;若為電成形,則變更所使用之光阻之圖案;若為不織布,則變更金屬纖維直徑及纖維密度;若為發泡金屬,則變更用以使空隙形成之模板等。 以下,對本實施形態中之電解用電極之更具體之實施形態進行說明。 本實施形態之電解用電極較佳為包含電解用電極基材及觸媒層。觸媒層如下所述,可包含複數層,亦可為單層結構。 如圖119所示,本實施形態之電解用電極100具備電解用電極基材10、及被覆電解用電極基材10之兩表面之一對第一層20。第一層20較佳為將電解用電極基材10整體被覆。藉此,電解用電極之觸媒活性及耐久性變得容易提高。再者,亦可僅於電解用電極基材10之一表面積層第一層20。 又,如圖119所示,第一層20之表面可由第二層30所被覆。第二層30較佳為將第一層20整體被覆。又,第二層30可僅積層於第一層20之一表面。 (電解用電極基材) 作為電解用電極基材10,並無特別限定,例如可使用鎳、鎳合金、不鏽鋼、或以鈦等為代表之閥金屬,較佳為含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。 於在高濃度之鹼性水溶液中使用不鏽鋼之情形時,若考慮到鐵及鉻溶出、及不鏽鋼之導電性為鎳之1/10左右,則較佳為使用含有鎳(Ni)之基材作為電解用電極基材。 又,電解用電極基材10於在接近飽和之高濃度之食鹽水中於氯氣產生環境中使用之情形時,材質亦較佳為耐蝕性較高之鈦。 電解用電極基材10之形狀並無特別限定,可根據目的選擇合適之形狀。作為形狀,可使用沖孔金屬、不織布、發泡金屬、多孔金屬、藉由電成形所形成之金屬多孔箔、編織金屬線所製作之所謂編織網等任一者。其中,較佳為沖孔金屬或多孔金屬。再者,所謂電成形係將照相製版與電鍍法組合而製作精密之圖案之金屬薄膜的技術。其係藉由光阻於基板上形成圖案,對未受到光阻保護之部分實施電鍍而獲得金屬薄膜之方法。 關於電解用電極基材之形狀,根據電解槽中之陽極與陰極之距離而有適宜之規格。並無特別限定,於陽極與陰極具有有限之距離之情形時,可使用多孔金屬、沖孔金屬形狀,於離子交換膜與電極相接之所謂零間距電解槽之情形時,可使用編織細線而成之編織網、金屬絲網、發泡金屬、金屬不織布、多孔金屬、沖孔金屬、金屬多孔箔等。 作為電解用電極基材10,可列舉:金屬多孔箔、金屬絲網、金屬不織布、沖孔金屬、多孔金屬或發泡金屬。 作為加工為沖孔金屬、多孔金屬前之板材,較佳為經壓延成形之板材、電解箔等。電解箔較佳為進而作為後處理而藉由與母材相同之元素實施鍍覆處理,於單面或兩面形成凹凸。 又,電解用電極基材10之厚度如上文所述,較佳為300 μm以下,更佳為205 μm以下,進而較佳為155 μm以下,進而更佳為135 μm以下,進而更佳為125 μm以下,更佳為120 μm以下,進而更佳為100 μm以下,就操作性與經濟性之觀點而言,進而更佳為50 μm以下。下限值並無特別限定,例如為1 μm,較佳為5 μm,更佳為15 μm。 於電解用電極基材中,較佳為藉由在氧化環境中將電解用電極基材進行退火而緩和加工時之殘留應力。又,為了提高與被覆於電解用電極基材之表面之觸媒層之密接性,較佳為使用鋼砂、氧化鋁粉等於上述表面形成凹凸,其後藉由酸處理而增加表面積。或者,較佳為藉由與基材相同之元素實施鍍覆處理,增加表面積。 為了使第一層20與電解用電極基材10之表面密接,較佳為對電解用電極基材10進行增大表面積之處理。作為增大表面積之處理,可列舉使用鋼線粒、鋼砂、氧化鋁砂等之噴擊處理、使用硫酸或鹽酸之酸處理、利用與基材相同元素之鍍覆處理等。基材表面之算術平均表面粗糙度(Ra)並無特別限定,較佳為0.05 μm~50 μm,更佳為0.1~10 μm,進而較佳為0.1~8 μm。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陽極之情形進行說明。 (第一層) 於圖119中,作為觸媒層之第一層20含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物。作為釕氧化物,可列舉RuO2 等。作為銥氧化物,可列舉IrO2 等。作為鈦氧化物,可列舉TiO2 等。第一層20較佳為含有釕氧化物及鈦氧化物之兩種氧化物,或含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物。藉此,第一層20成為更穩定之層,進而,與第二層30之密接性亦進一步提高。 於第一層20含有釕氧化物及鈦氧化物之兩種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為1~9莫耳,更佳為1~4莫耳。藉由將兩種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有釕氧化物、銥氧化物及鈦氧化物之三種氧化物之情形時,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之銥氧化物較佳為0.2~3莫耳,更佳為0.3~2.5莫耳。又,相對於第一層20所含之釕氧化物1莫耳,第一層20所含之鈦氧化物較佳為0.3~8莫耳,更佳為1~7莫耳。藉由將三種氧化物之組成比設為該範圍,電解用電極100表現出優異之耐久性。 於第一層20含有選自釕氧化物、銥氧化物及鈦氧化物中之至少兩種氧化物之情形時,該等氧化物較佳為形成固溶體。藉由形成氧化物固溶體,電解用電極100表現出優異之耐久性。 除了上述組成以外,只要含有釕氧化物、銥氧化物及鈦氧化物中之至少一種氧化物,則可使用各種組成者。例如,亦可使用稱為DSA(註冊商標)之含有釕、銥、鉭、鈮、鈦、錫、鈷、錳、鉑等之氧化物塗層作為第一層20。 第一層20無需為單層,亦可包含複數層。例如,第一層20可包含含有三種氧化物之層與含有兩種氧化物之層。第一層20之厚度較佳為0.05~10 μm,更佳為0.1~8 μm。 (第二層) 第二層30較佳為含有釕與鈦。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較佳為含有氧化鈀、氧化鈀與鉑之固溶體或鈀與鉑之合金。藉此,能夠進一步降低剛電解後之氯過電壓。 第二層30較厚者能夠維持電解性能之時間變長,就經濟性之觀點而言,較佳為0.05~3 μm之厚度。 繼而,對將本實施形態中之電解用電極用作食鹽電解用陰極之情形進行說明。 (第一層) 作為觸媒層之第一層20之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。 於含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少一種之情形時,較佳為鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金含有鉑、鈀、銠、釕、銥中之至少一種鉑族金屬。 作為鉑族金屬,較佳為含有鉑。 作為鉑族金屬氧化物,較佳為含有釕氧化物。 作為鉑族金屬氫氧化物,較佳為含有釕氫氧化物。 作為鉑族金屬合金,較佳為含有鉑與鎳、鐵、鈷之合金。 較佳為進而視需要含有鑭系元素之氧化物或氫氧化物作為第二成分。藉此,電解用電極100表現出優異之耐久性。 作為鑭系元素之氧化物或氫氧化物,較佳為含有選自鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑中之至少1種。 較佳為進而視需要含有過渡金屬之氧化物或氫氧化物作為第三成分。 藉由添加第三成分,電解用電極100能夠表現出更優異之耐久性,降低電解電壓。 作為較佳之組合之例,可列舉:僅釕、釕+鎳、釕+鈰、釕+鑭、釕+鑭+鉑、釕+鑭+鈀、釕+鐠、釕+鐠+鉑、釕+鐠+鉑+鈀、釕+釹、釕+釹+鉑、釕+釹+錳、釕+釹+鐵、釕+釹+鈷、釕+釹+鋅、釕+釹+鎵、釕+釹+硫、釕+釹+鉛、釕+釹+鎳、釕+釹+銅、釕+釤、釕+釤+錳、釕+釤+鐵、釕+釤+鈷、釕+釤+鋅、釕+釤+鎵、釕+釤+硫、釕+釤+鉛、釕+釤+鎳、鉑+鈰、鉑+鈀+鈰、鉑+鈀+鑭+鈰、鉑+銥、鉑+鈀、鉑+銥+鈀、鉑+鎳+鈀、鉑+鎳+釕、鉑與鎳之合金、鉑與鈷之合金、鉑與鐵之合金等。 於不含鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之情形時,觸媒之主成分較佳為鎳元素。 較佳為含有鎳金屬、氧化物、氫氧化物中之至少1種。 作為第二成分,可添加過渡金屬。作為所添加之第二成分,較佳為含有鈦、錫、鉬、鈷、錳、鐵、硫、鋅、銅、碳中之至少一種元素。 作為較佳之組合,可列舉:鎳+錫、鎳+鈦、鎳+鉬、鎳+鈷等。 視需要可於第一層20與電解用電極基材10之間設置中間層。藉由設置中間層,能夠提高電解用電極100之耐久性。 作為中間層,較佳為對第一層20與電解用電極基材10之兩者具有親和性者。作為中間層,較佳為鎳氧化物、鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物。作為中間層,可藉由將含有形成中間層之成分之溶液進行塗佈、燒成而形成,亦可於空氣環境中在300~600℃之溫度下對基材實施熱處理而形成表面氧化物層。除此以外,可藉由熱熔射法、離子鍍敷法等已知之方法形成。 (第二層) 作為觸媒層之第一層30之成分可列舉:C、Si、P、S、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、In、Sn、Ta、W、Re、Os、Ir、Pt、Au、Hg、Pb、Bi、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等金屬及該等金屬之氧化物或氫氧化物。 可含有鉑族金屬、鉑族金屬氧化物、鉑族金屬氫氧化物、含有鉑族金屬之合金之至少1種,亦可不含。作為第二層所含之元素之較佳之組合例,有第一層中所列舉之組合等。第一層與第二層之組合可為組成相同而組成比不同之組合,亦可為組成不同之組合。 作為觸媒層之厚度,較佳為將所形成之觸媒層及中間層累加而成之厚度為0.01 μm~20 μm。若為0.01 μm以上,則能夠作為觸媒充分發揮功能。若為20 μm以下,則從基材脫落之情況較少,能夠形成牢固之觸媒層。更佳為0.05 μm~15 μm。更佳為0.1 μm~10 μm。進而較佳為0.2 μm~8 μm。 作為電極之厚度、即電解用電極基材與觸媒層之合計之厚度,就電極之操作性之方面而言,較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,電極之厚度可藉由利用電子數顯厚度計(Mitutoyo股份有限公司,最少顯示0.001 mm)進行測定而求出。電解用電極基材之厚度係與電極厚度同樣地進行測定。觸媒層厚度可藉由電極厚度減去電解用電極基材之厚度而求出。 於本實施形態之電解槽之製造方法中,就確保充分之電解性能之觀點而言,較佳為電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。 於本實施形態中,若電解用電極係彈性變形區域較廣之電極,則就可獲得更良好之操作性,與離子交換膜或微多孔膜等隔膜、劣化之電極及未形成有觸媒塗層之饋電體等具有更良好之接著力之觀點而言,電解用電極之厚度較佳為315 μm以下,更佳為220 μm以下,進而較佳為170 μm以下,進而更佳為150 μm以下,尤佳為145 μm以下,更佳為140 μm以下,進而更佳為138 μm以下,進而更佳為135 μm以下。若為135 μm以下,則可獲得良好之操作性。進而,就與上述同樣之觀點而言,較佳為130 μm以下,更佳為未達130 μm,進而較佳為115 μm以下,進而更佳為65 μm以下。下限值並無特別限定,較佳為1 μm以上,就實用上而言更佳為5 μm以上,更佳為20 μm以上。再者,於本實施形態中,所謂「彈性變形區域較廣」意指將電解用電極捲繞而製成捲繞體,解除捲繞狀態後不易產生由捲繞引起之翹曲。又,所謂電解用電極之厚度於包含下文所述之觸媒層之情形時,係指合併電解用電極基材與觸媒層之厚度。 (電解用電極之製造方法) 其次,對電解用電極100之製造方法之一實施形態進行詳細說明。 於本實施形態中,藉由利用氧環境下之塗膜之燒成(熱分解)、或離子鍍敷、鍍覆、熱熔射等方法於電解用電極基材上形成第一層20、較佳為第二層30,可製造電解用電極100。此種本實施形態之製造方法能夠實現電解用電極100之較高之生產性。具體而言,藉由塗佈含有觸媒之塗佈液之塗佈步驟、乾燥塗佈液之乾燥步驟、進行熱分解之熱分解步驟,而於電解用電極基材上形成觸媒層。此處所謂熱分解意指對成為前驅物之金屬鹽進行加熱而分解為金屬或金屬氧化物與氣體狀物質。根據所使用之金屬種類、鹽之種類、進行熱分解之環境等,分解產物有所不同,但於氧化性環境下多數金屬有容易形成氧化物之傾向。於電極之工業性之製造工藝中,熱分解通常於空氣中進行,多數情形時形成金屬氧化物或金屬氫氧化物。 (陽極之第一層之形成) (塗佈步驟) 第一層20係將溶解有釕、銥及鈦中之至少一種金屬之鹽的溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之釕、銥及鈦之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材100後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (第二層之形成) 第二層30係視需要而形成,例如將含有鈀化合物及鉑化合物之溶液或含有釕化合物及鈦化合物之溶液(第二塗佈液)塗佈於第一層20上後,於氧氣之存在下進行熱分解而獲得。 (利用熱分解法之陰極之第一層之形成) (塗佈步驟) 第一層20係將溶解有各種組合之金屬鹽之溶液(第一塗佈液)塗佈於電解用電極基材後,於氧氣之存在下進行熱分解(燒成)而獲得。第一塗佈液中之金屬之含有率與第一層20大致相等。 作為金屬鹽,可為氯化物鹽、硝酸鹽、硫酸鹽、金屬烷氧化物、其他任一形態。第一塗佈液之溶劑可根據金屬鹽之種類進行選擇,可使用水及丁醇等醇類等。作為溶劑,較佳為水或水與醇類之混合溶劑。溶解有金屬鹽之第一塗佈液中之總金屬濃度並無特別限定,就兼顧藉由1次塗佈所形成之塗膜之厚度之方面而言,較佳為10~150 g/L之範圍。 作為將第一塗佈液塗佈於電解用電極基材10上之方法,可使用將電解用電極基材10浸漬於第一塗佈液中之浸漬法、以毛刷塗佈第一塗佈液之方法、使用含浸有第一塗佈液之海綿狀滾筒之滾筒法、使電解用電極基材10與第一塗佈液帶有相反電荷而進行噴射噴霧之靜電塗佈法等。其中,較佳為工業上之生產性優異之滾筒法或靜電塗佈法。 (乾燥步驟、熱分解步驟) 將第一塗佈液塗佈於電解用電極基材10後,於10~90℃之溫度下加以乾燥,於加熱至350~650℃之燒成爐中進行熱分解。亦可視需要於乾燥與熱分解之間在100~350℃下實施預燒成。乾燥、預燒成及熱分解溫度可根據第一塗佈液之組成或溶劑種類而適當選擇。每次之熱分解之時間較佳為較長,就電極之生產性之觀點而言,較佳為3~60分鐘,更佳為5~20分鐘。 重複上述塗佈、乾燥及熱分解之循環,將被覆(第一層20)形成為特定之厚度。形成第一層20後,若視需要進一步進行長時間燒成之後期加熱,則能夠進一步提高第一層20之穩定性。 (中間層之形成) 中間層係視需要而形成,例如將含有鈀化合物或鉑化合物之溶液(第二塗佈液)塗佈於基材上後,於氧氣之存在下進行熱分解而獲得。或者,亦可不塗佈溶液,而僅加熱基材,藉此於基材表面形成氧化鎳中間層。 (利用離子鍍敷之陰極之第一層之形成) 第一層20亦可藉由離子鍍敷而形成。 作為一例,可列舉將基材固定於腔室內並對金屬釕靶照射電子束之方法。所蒸發之金屬釕粒子於腔室內之電漿中帶正電,而沈積於帶負電之基板上。電漿環境為氬氣、氧氣,釕係以釕氧化物之形式沈積於基材上。 (利用鍍覆之陰極之第一層之形成) 第一層20亦可藉由鍍覆法而形成。 作為一例,若使用基材作為陰極,於含有鎳及錫之電解液中實施電解鍍覆,則可形成鎳與錫之合金鍍覆。 (利用熱熔射之陰極之第一層之形成) 第一層20亦可藉由熱熔射法而形成。 作為一例,藉由將氧化鎳粒子電漿熔射於基材上,而可形成混合有金屬鎳與氧化鎳之觸媒層。 以下,對隔膜之一態樣之離子交換膜進行詳細說明。 [離子交換膜] 作為離子交換膜,只要可與電解用電極製成積層體,則無特別限定,可應用各種離子交換膜。於本實施形態之電解槽之製造方法中,較佳為使用具有含有具有離子交換基之烴系聚合物或含氟系聚合物之膜本體、與設置於該膜本體之至少一面上之塗佈層之離子交換膜。又,塗佈層含有無機物粒子與結合劑,塗佈層之比表面積較佳為0.1~10 m2 /g。該結構之離子交換膜於電解中所產生之氣體對電解性能之影響較少,有發揮出穩定之電解性能之傾向。 上述所謂導入有離子交換基之全氟碳聚合物之膜係具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層之任一者。就強度及尺寸穩定性之觀點而言,較佳為進而具有強化芯材。 以下於塗佈層之說明之欄對無機物粒子及結合劑進行詳細說明。 圖120係表示離子交換膜之一實施形態之剖面模式圖。離子交換膜1具有:膜本體10,其含有具有離子交換基之烴系聚合物或含氟系聚合物;以及塗佈層11a及11b,其等形成於膜本體10之兩面。 於離子交換膜1中,膜本體10具備具有源自磺基之離子交換基(以-SO3 - 表示之基,以下亦稱為「磺酸基」)之磺酸層3、與具有源自羧基之離子交換基(以-CO2 - 表示之基,以下亦稱為「羧酸基」)之羧酸層2,藉由強化芯材4強化強度及尺寸穩定性。離子交換膜1由於具備磺酸層3與羧酸層2,因此可作為陽離子交換膜而適宜地使用。 再者,離子交換膜亦可僅具有磺酸層及羧酸層之任一者。又,離子交換膜未必由強化芯材所強化,強化芯材之配置狀態亦不限定於圖120之例。 (膜本體) 首先,對構成離子交換膜1之膜本體10進行說明。 膜本體10只要為具有使陽離子選擇性地透過之功能且含有具有離子交換基之烴系聚合物或含氟系聚合物者即可,其構成或材料並無特別限定,可適當選擇適宜者。 膜本體10中之具有離子交換基之烴系聚合物或含氟系聚合物例如可由具有可藉由水解等成為離子交換基之離子交換基前驅物之烴系聚合物或含氟系聚合物獲得。具體而言,例如使用主鏈包含氟化烴、具有可藉由水解等轉換為離子交換基之基(離子交換基前驅物)作為懸垂側鏈且能夠熔融加工之聚合物(以下視情形稱為「含氟系聚合物(a)」)製作膜本體10之前驅物後,將離子交換基前驅物轉換為離子交換基,藉此可獲得膜本體10。 含氟系聚合物(a)例如可藉由使選自下述第1群之至少一種單體與選自下述第2群及/或下述第3群之至少一種單體進行共聚合而製造。又,亦可藉由選自下述第1群、下述第2群、及下述第3群之任一群之1種單體之均聚而製造。 作為第1群之單體,例如可列舉氟乙烯化合物。作為氟乙烯化合物,例如可列舉:氟乙烯、四氟乙烯、六氟丙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、全氟烷基乙烯醚等。尤其是於將離子交換膜用作鹼電解用膜之情形時,氟乙烯化合物較佳為全氟單體,較佳為選自由四氟乙烯、六氟丙烯、全氟烷基乙烯醚所組成之群中之全氟單體。 作為第2群之單體,例如可列舉具有可轉換為羧酸型離子交換基(羧酸基)之官能基之乙烯系化合物。作為具有可轉換為羧酸基之官能基之乙烯系化合物,例如可列舉以CF2 =CF(OCF2 CYF)s -O(CZF)t -COOR表示之單體等(此處,s表示0~2之整數,t表示1~12之整數,Y及Z各自獨立地表示F或CF3 ,R表示低級烷基。低級烷基例如為碳數1~3之烷基)。 該等中,較佳為以CF2 =CF(OCF2 CYF)n -O(CF2 )m -COOR表示之化合物。此處,n表示0~2之整數,m表示1~4之整數,Y表示F或CF3 ,R表示CH3 、C2 H5 、或C3 H7 。 再者,於將離子交換膜用作鹼電解用陽離子交換膜之情形時,較佳為至少使用全氟化合物作為單體,但由於酯基之烷基(參照上述R)於水解時從聚合物喪失,因此烷基(R)亦可不為全部氫原子被取代為氟原子之全氟烷基。 作為第2群之單體,於上述中,更佳為下述所表示之單體。 CF2 =CFOCF2 -CF(CF3 )OCF2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )2 COOCH3 、 CF2 =CF[OCF2 -CF(CF3 )]2 O(CF2 )2 COOCH3 、 CF2 =CFOCF2 CF(CF3 )O(CF2 )3 COOCH3 、 CF2 =CFO(CF2 )2 COOCH3 、 CF2 =CFO(CF2 )3 COOCH3 。 作為第3群之單體,例如可列舉具有可轉換為磺酸型離子交換基(磺酸基)之官能基之乙烯系化合物。作為具有可轉換為磺酸基之官能基之乙烯系化合物,例如較佳為以CF2 =CFO-X-CF2 -SO2 F表示之單體(此處,X表示全氟伸烷基)。作為該等之具體例,可列舉下述所表示之單體等。 CF2 =CFOCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、 CF2 =CF(CF2 )2 SO2 F、 CF2 =CFO[CF2 CF(CF3 )O]2 CF2 CF2 SO2 F、 CF2 =CFOCF2 CF(CF2 OCF3 )OCF2 CF2 SO2 F。 該等中,更佳為CF2 =CFOCF2 CF(CF3 )OCF2 CF2 CF2 SO2 F、及CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F。 由該等單體獲得之共聚物可藉由針對氟乙烯之均聚及共聚合所開發之聚合法、尤其是對四氟乙烯所使用之通常之聚合方法而製造。例如,於非水性法中,可使用全氟烴、氯氟碳等不活性溶劑,於全氟碳過氧化物或偶氮化合物等自由基聚合起始劑之存在下,於溫度0~200℃、壓力0.1~20 MPa之條件下進行聚合反應。 於上述共聚合中,上述單體之組合之種類及其比率並無特別限定,根據欲對所獲得之含氟系聚合物賦予之官能基之種類及量選擇確定。例如於製成僅含有羧酸基之含氟系聚合物之情形時,從上述第1群及第2群分別選擇至少1種單體進行共聚合即可。又,於製成僅含有磺酸基之含氟系聚合物之情形時,從上述第1群及第3群之單體中分別選擇至少1種單體進行共聚合即可。進而,於製成具有羧酸基及磺酸基之含氟系聚合物之情形時,從上述第1群、第2群及第3群之單體中分別選擇至少1種單體進行共聚合即可。於該情形時,藉由使包含上述第1群及第2群之共聚物與包含上述第1群及第3群之共聚物分開進行聚合,其後加以混合亦可獲得目標之含氟系聚合物。又,各單體之混合比率並無特別限定,於增加每單位聚合物之官能基之量之情形時,增加選自上述第2群及第3群之單體之比率即可。 含氟系共聚物之總離子交換容量並無特別限定,較佳為0.5~2.0 mg當量/g,更佳為0.6~1.5 mg當量/g。此處,所謂總離子交換容量係指相對於單位重量之乾燥樹脂之交換基之當量,可藉由中和滴定等進行測定。 於離子交換膜1之膜本體10中,積層有含有具有磺酸基之含氟系聚合物之磺酸層3與含有具有羧酸基之含氟系聚合物之羧酸層2。藉由製成此種層結構之膜本體10,能夠進一步提高鈉離子等陽離子之選擇性透過性。 於將離子交換膜1配置於電解槽之情形時,通常以磺酸層3位於電解槽之陽極側、羧酸層2位於電解槽之陰極側之方式配置。 磺酸層3較佳為由電阻較低之材料構成,就膜強度之觀點而言,較佳為其膜厚厚於羧酸層2。磺酸層3之膜厚較佳為羧酸層2之2~25倍,更佳為3~15倍。 羧酸層2較佳為即使膜厚較薄亦具有較高之陰離子排斥性者。此處所謂陰離子排斥性係指阻礙陰離子對離子交換膜1之滲入或透過之性質。為了提高陰離子排斥性,有效的是對磺酸層配置離子交換容量較小之羧酸層等。 作為磺酸層3所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F作為第3群之單體所獲得之聚合物。 作為羧酸層2所使用之含氟系聚合物,例如適宜為使用CF2 =CFOCF2 CF(CF2 )O(CF2 )2 COOCH3 作為第2群之單體所獲得之聚合物。 (塗佈層) 離子交換膜較佳為於膜本體之至少一面上具有塗佈層。又,如圖120所示,於離子交換膜1中,於膜本體10之兩面上分別形成有塗佈層11a及11b。 塗佈層含有無機物粒子與結合劑。 無機物粒子之平均粒徑更佳為0.90 μm以上。若無機物粒子之平均粒徑為0.90 μm以上,則不僅極大地提高對氣體附著之耐久性,而且極大地提高對雜質之耐久性。即,藉由增大無機物粒子之平均粒徑,並且滿足上述比表面積之值,可獲得尤其顯著之效果。為了滿足此種平均粒徑與比表面積,較佳為不規則狀之無機物粒子。可使用藉由熔融獲得之無機物粒子、藉由原石粉碎獲得之無機物粒子。較佳可適宜地使用藉由原石粉碎獲得之無機物粒子。 又,無機物粒子之平均粒徑可設為2 μm以下。若無機物粒子之平均粒徑為2 μm以下,則能夠防止因無機物粒子而損傷膜。無機物粒子之平均粒徑更佳為0.90~1.2 μm。 此處,平均粒徑可藉由粒度分佈計(「SALD2200」島津製作所)進行測定。 無機物粒子之形狀較佳為不規則形狀。對雜質之耐性進一步提高。又,無機物粒子之粒度分佈較佳為較寬。 無機物粒子較佳為含有選自由週期表第IV族元素之氧化物、週期表第IV族元素之氮化物、及週期表第IV族元素之碳化物所組成之群中之至少一種無機物。就耐久性之觀點而言,更佳為氧化鋯之粒子。 該無機物粒子較佳為藉由將無機物粒子之原石粉碎所製造之無機物粒子,或以藉由將無機物粒子之原石熔融並加以精製而粒子之直徑一致之球狀之粒子作為無機物粒子。 作為原石粉碎方法,並無特別限定,可列舉:球磨機、珠磨機、膠體磨機、錐形磨機、盤磨機、輪輾機、磨粉機、錘磨機、造粒機、VSI磨機、威利磨機、輥磨機、噴射磨機等。又,較佳為粉碎後將其洗淨,作為此時之洗淨方法,較佳為酸處理。藉此,能夠減少附著於無機物粒子之表面之鐵等雜質。 塗佈層較佳為含有結合劑。結合劑係將無機物粒子保持於離子交換膜之表面、形成塗佈層之成分。就對電解液或電解之產物之耐性之觀點而言,結合劑較佳為含有含氟系聚合物。 作為結合劑,就對電解液或電解之產物之耐性、及對離子交換膜之表面之接著性之觀點而言,更佳為具有羧酸基或磺酸基之含氟系聚合物。於在含有具有磺酸基之含氟聚合物之層(磺酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有磺酸基之含氟系聚合物。又,於在含有具有羧酸基之含氟聚合物之層(羧酸層)上設置塗佈層之情形時,作為該塗佈層之結合劑,進而較佳為使用具有羧酸基之含氟系聚合物。 塗佈層中,無機物粒子之含量較佳為40~90質量%,更佳為50~90質量%。又,結合劑之含量較佳為10~60質量%,更佳為10~50質量%。 離子交換膜中之塗佈層之分佈密度較佳為每1 cm2 為0.05~2 mg。又,於離子交換膜於表面具有凹凸形狀之情形時,塗佈層之分佈密度較佳為每1 cm2 為0.5~2 mg。 作為形成塗佈層之方法,並無特別限定,可使用公知之方法。例如可列舉藉由噴射等塗佈將無機物粒子分散於含有結合劑之溶液中而成之塗佈液之方法。 (強化芯材) 離子交換膜較佳為具有配置於膜本體之內部之強化芯材。 強化芯材係強化離子交換膜之強度或尺寸穩定性之構件。藉由將強化芯材配置於膜本體之內部,尤其能夠將離子交換膜之伸縮控制為所需之範圍。該離子交換膜於電解時等不會伸縮為必要程度以上,而能夠長期維持優異之尺寸穩定性。 強化芯材之構成並無特別限定,例如可將稱為強化紗之紗進行紡紗而形成。此處所謂強化紗係構成強化芯材之構件,指能夠對離子交換膜賦予所需之尺寸穩定性及機械強度且於離子交換膜中能夠穩定地存在之紗。藉由使用將該強化紗紡紗而成之強化芯材,能夠對離子交換膜賦予更優異之尺寸穩定性及機械強度。 強化芯材及其所使用之強化紗之材料並無特別限定,較佳為對酸或鹼等具有耐性之材料,就需要長期之耐熱性、耐化學品性之方面而言,較佳為包含含氟系聚合物之纖維。 作為強化芯材所使用之含氟系聚合物,例如可列舉:聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-乙烯共聚物(ETFE)、四氟乙烯-六氟丙烯共聚物、三氟氯乙烯-乙烯共聚物及偏二氟乙烯聚合物(PVDF)等。該等中,尤其是就耐熱性及耐化學品性之觀點而言,較佳為使用包含聚四氟乙烯之纖維。 強化芯材所使用之強化紗之紗直徑並無特別限定,較佳為20~300丹尼,更佳為50~250丹尼。紡織密度(每單位長度之織入根數)較佳為5~50根/英吋。作為強化芯材之形態,並無特別限定,例如可使用織布、不織布、針織布等,較佳為織布之形態。又,使用織布之厚度較佳為30~250 μm、更佳為30~150 μm者。 織布或針織布可使用單絲、複絲或該等之紗線、切膜絲等,紡織方法可使用平織、紗羅組織、針織、凸條組織、縐條紋薄織等各種紡織方法。 膜本體中之強化芯材之紡織方法及配置並無特別限定,可考慮離子交換膜之大小或形狀、離子交換膜所需之物性及使用環境等適當設為適宜之配置。 例如,可沿膜本體之特定之一方向配置強化芯材,就尺寸穩定性之觀點而言,較佳為沿特定之第一方向配置強化芯材,且沿大致垂直於第一方向之第二方向配置其他強化芯材。藉由在膜本體之縱向膜本體之內部以大致成一列之方式配置複數個強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。例如,較佳為於膜本體之表面織入沿縱向配置之強化芯材(縱紗)與沿橫向配置之強化芯材(橫紗)之配置。就尺寸穩定性、機械強度及製造容易性之觀點而言,更佳為製成使縱紗與橫紗一上一下交替織入而紡織之平紋織物、或一邊撚轉2根經紗一邊與橫紗交織之紗羅組織物、於每2根或數根並紗配置之縱紗中織入相同數量之橫紗而紡織之斜紋織物(twill weave)等。 尤佳為沿離子交換膜之MD方向(縱向(Machine Direction)方向)及TD方向(橫向(Transverse Direction)方向)之兩方向配置強化芯材。即,較佳為沿MD方向與TD方向平織。此處,所謂MD方向係指於下文所述之離子交換膜之製造步驟中搬送膜本體或各種芯材(例如,強化芯材、強化紗、下文所述之犧牲紗等)之方向(行進方向),所謂TD方向係指大致垂直於MD方向之方向。此外,將沿MD方向紡織之紗稱為MD紗,將沿TD方向紡織之紗稱為TD紗。通常電解所使用之離子交換膜係矩形,長度方向為MD方向、寬度方向為TD方向之情況較多。藉由織入作為MD紗之強化芯材與作為TD紗之強化芯材,可於多方向賦予更優異之尺寸穩定性及機械強度。 強化芯材之配置間隔並無特別限定,可考慮離子交換膜所需之物性及使用環境等適當設為適宜之配置。 強化芯材之開口率並無特別限定,較佳為30%以上,更佳為50%以上且90%以下。開口率就離子交換膜之電化學性質之觀點而言,較佳為30%以上,就離子交換膜之機械強度之觀點而言,較佳為90%以下。 所謂強化芯材之開口率係指膜本體之任一表面之面積(A)中離子等物質(電解液及其所含之陽離子(例如,鈉離子))能夠通過之表面之總面積(B)之比率(B/A)。所謂離子等物質能夠通過之表面之總面積(B)可指於離子交換膜中陽離子或電解液等不被離子交換膜所含之強化芯材等阻斷之區域之總面積。 圖121係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。圖121係將離子交換膜之一部分放大而僅圖示該區域內之強化芯材21及22之配置,其他構件省略圖示。 藉由從由沿縱向配置之強化芯材21與沿橫向配置之強化芯材22所圍成之亦包括強化芯材之面積在內之區域的面積(A)減去強化芯材之總面積(C),可求出上述區域之面積(A)中離子等物質能夠通過之區域之總面積(B)。即,開口率可藉由下述式(I)求出。 開口率=(B)/(A)=((A)-(C))/(A) …(I) 於強化芯材中,就耐化學品性及耐熱性之觀點而言,尤佳之形態係含有PTFE之帶狀紗線或高配向單絲。具體而言,更佳為如下強化芯材,其係使用將包含PTFE之高強度多孔質片材切為帶狀而成之帶狀紗線、或包含PTFE之高度配向之單絲之50~300丹尼且紡織密度為10~50根/英吋之平紋織物,其厚度為50~100 μm之範圍。含有該強化芯材之離子交換膜之開口率進而較佳為60%以上。 作為強化紗之形狀,可列舉圓紗、帶狀紗等。 (連通孔) 離子交換膜較佳為於膜本體之內部具有連通孔。 所謂連通孔係指能夠成為電解時產生之離子或電解液之流路之孔。又,所謂連通孔係形成於膜本體內部之管狀之孔,藉由下文所述之犧牲芯材(或犧牲紗)溶出而形成。連通孔之形狀或直徑等可藉由選擇犧牲芯材(犧牲紗)之形狀或直徑進行控制。 藉由在離子交換膜形成連通孔,於電解時能夠確保電解液之移動性。連通孔之形狀並無特別限定,根據下文所述之製法,可製成連通孔之形成所使用之犧牲芯材之形狀。 連通孔較佳為以交替通過強化芯材之陽極側(磺酸層側)與陰極側(羧酸層側)之方式形成。藉由設為該結構,於強化芯材之陰極側形成有連通孔之部分,通過充滿連通孔之電解液所輸送之離子(例如,鈉離子)亦能夠流至強化芯材之陰極側。其結果為,由於陽離子之流動未被遮蔽,因此能夠進一步降低離子交換膜之電阻。 連通孔可僅沿構成離子交換膜之膜本體之特定之一方向形成,就發揮出更穩定之電解性能之觀點而言,較佳為沿膜本體之縱向與橫向之兩方向形成。 [製造方法] 作為離子交換膜之適宜之製造方法,可列舉具有以下之(1)步驟~(6)步驟之方法。 (1)步驟:製造具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之含氟系聚合物之步驟。 (2)步驟:藉由視需要至少織入複數個強化芯材與具有溶於酸或鹼之性質且形成連通孔之犧牲紗而獲得於鄰接之強化芯材彼此之間配置有犧牲紗之補強材之步驟。 (3)步驟:將具有離子交換基、或能夠藉由水解成為離子交換基之離子交換基前驅物之上述含氟系聚合物進行膜化之步驟。 (4)步驟:視需要將上述補強材埋入至上述膜中而獲得內部配置有上述補強材之膜本體之步驟。 (5)步驟:將(4)步驟中獲得之膜本體進行水解之步驟(水解步驟)。 (6)步驟:於(5)步驟中獲得之膜本體設置塗佈層之步驟(塗佈步驟)。 以下,對各步驟進行詳細說明。 (1)步驟:製造含氟系聚合物之步驟 於(1)步驟中,使用上述第1群~第3群所記載之原料之單體製造含氟系聚合物。為了控制含氟系聚合物之離子交換容量,於形成各層之含氟系聚合物之製造中調整原料之單體之混合比即可。 (2)步驟:補強材之製造步驟 所謂補強材係紡織強化紗之織布等。藉由將補強材埋入至膜內而形成強化芯材。於製成具有連通孔之離子交換膜時,亦將犧牲紗一起織入至補強材中。該情形時之犧牲紗之混織量較佳為補強材整體之10~80質量%,更佳為30~70質量%。藉由織入犧牲紗,亦能夠防止強化芯材之脫線。 犧牲紗係於膜之製造步驟或電解環境下具有溶解性者,可使用嫘縈、聚對苯二甲酸乙二酯(PET)、纖維素及聚醯胺等。又,亦較佳為具有20~50丹尼之粗細程度、包含單絲或複絲之聚乙烯醇等。 再者,於(2)步驟中,可藉由調整強化芯材或犧牲紗之配置而控制開口率或連通孔之配置等。 (3)步驟:膜化步驟 於(3)步驟中,使用擠出機將上述(1)步驟中獲得之含氟系聚合物進行膜化。膜可為單層結構,亦可如上所述為磺酸層與羧酸層之2層結構,亦可為3層以上之多層結構。 作為膜化之方法,例如可列舉以下者。 分別將具有羧酸基之含氟聚合物、具有磺酸基之含氟聚合物分開進行膜化之方法。 藉由共擠出將具有羧酸基之含氟聚合物與具有磺酸基之含氟聚合物製成複合膜之方法。 再者,膜可分別為複數片。又,將異種之膜共擠出有助於提高界面之接著強度,故而較佳。 (4)步驟:獲得膜本體之步驟 於(4)步驟中,藉由將(2)步驟中獲得之補強材埋入至(3)步驟中獲得之膜之內部,而獲得內有補強材之膜本體。 作為膜本體之較佳之形成方法,可列舉:(i)藉由共擠出法將位於陰極側之具有羧酸基前驅物(例如,羧酸酯官能基)之含氟系聚合物(以下將包含其之層稱為第一層)與具有磺酸基前驅物(例如,磺醯氟官能基)之含氟系聚合物(以下將包含其之層稱為第二層)進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將補強材、第二層/第一層複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法;(ii)區別於第二層/第一層複合膜,預先將具有磺酸基前驅物之含氟系聚合物(第三層)單獨進行膜化,視需要使用加熱源及真空源,介隔具有透氣性之耐熱性之脫模紙,將第三層膜、強化芯材、包含第二層/第一層之複合膜依序積層於表面具有大量細孔之平板或轉筒上,於各聚合物熔融之溫度下,一邊藉由減壓去除各層間之空氣一邊進行一體化之方法。 此處,將第一層與第二層共擠出有助於提高界面之接著強度。 又,於減壓下進行一體化之方法與加壓壓製法相比,具有補強材上之第三層之厚度變大之特徵。進而,由於將補強材固定於膜本體之內面,因此具有能夠充分保持離子交換膜之機械強度之性能。 再者,此處所說明之積層之變化係一例,可考慮所需之膜本體之層構成或物性等,適當選擇適宜之積層圖案(例如,各層之組合等)後進行共擠出。 再者,為了進一步提高離子交換膜之電性能,亦可於第一層與第二層之間進一步介置包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層,或使用包含具有羧酸基前驅物與磺酸基前驅物之兩者之含氟系聚合物的第四層代替第二層。 第四層之形成方法可為分開製造具有羧酸基前驅物之含氟系聚合物與具有磺酸基前驅物之含氟系聚合物後加以混合之方法,亦可為使用將具有羧酸基前驅物之單體與具有磺酸基前驅物之單體共聚合而成者之方法。 於將第四層製成離子交換膜之構成之情形時,可將第一層與第四層之共擠出膜加以成形,第三層及第二層與其分開單獨進行膜化,藉由上文所述之方法進行積層,亦可將第一層/第四層/第二層之3層一次共擠出而進行膜化。 於該情形時,所擠出之膜行進之方向為MD方向。由此可將含有具有離子交換基之含氟系聚合物之膜本體形成於補強材上。 又,離子交換膜較佳為於包含磺酸層之表面側具有包含具有磺酸基之含氟聚合物之突出的部分、即凸部。作為形成此種凸部之方法,並無特別限定,可採用於樹脂表面形成凸部之公知之方法。具體而言,例如可列舉對膜本體之表面實施壓紋加工之方法。例如,於將上述複合膜與補強材等進行一體化時,藉由使用預先經壓紋加工之脫模紙,可形成上述凸部。於藉由壓紋加工形成凸部之情形時,凸部之高度或配置密度之控制可藉由控制所轉印之壓紋形狀(脫模紙之形狀)而進行。 (5)水解步驟 於(5)步驟中,進行將(4)步驟中獲得之膜本體水解而將離子交換基前驅物轉換為離子交換基之步驟(水解步驟)。 又,於(5)步驟中,藉由利用酸或鹼將膜本體所含之犧牲紗溶解去除,可於膜本體形成溶出孔。再者,犧牲紗亦可不完全溶解去除,而殘留於連通孔中。又,殘留於連通孔中之犧牲紗可於將離子交換膜供於電解時藉由電解液溶解去除。 犧牲紗係於離子交換膜之製造步驟或電解環境下對酸或鹼具有溶解性者,藉由使犧牲紗溶出而於該部位形成連通孔。 (5)步驟可將(4)步驟中獲得之膜本體浸漬於含有酸或鹼之水解溶液中進行。作為該水解溶液,例如可使用含有KOH與DMSO(Dimethyl sulfoxide)之混合溶液。 該混合溶液較佳為含有2.5~4.0 N之KOH,且含有25~35質量%之DMSO。 作為水解之溫度,較佳為70~100℃。溫度越高,可使視厚度更厚。更佳為75~100℃。 作為水解之時間,較佳為10~120分鐘。時間越長,可使視厚度更厚。更佳為20~120分鐘。 此處,對藉由溶出犧牲紗而形成連通孔之步驟進一步詳細地說明。圖122(a)、(b)係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 於圖122(a)、(b)中,僅圖示強化紗52、犧牲紗504a及由犧牲紗504a形成之連通孔504,膜本體等其他構件省略圖示。 首先,將於離子交換膜中構成強化芯材之強化紗52與於離子交換膜中用以形成連通孔504之犧牲紗504a製成針織織入補強材。然後,於(5)步驟中藉由使犧牲紗504a溶出而形成連通孔504。 藉由上述方法,根據於離子交換膜之膜本體內如何配置強化芯材、連通孔而調整強化紗52與犧牲紗504a之針織織入方法即可,因此較簡便。 於圖122(a)中,例示於紙面沿縱向與橫向之兩方向將強化紗52與犧牲紗504a織入之平織之補強材,可視需要變更補強材中之強化紗52與犧牲紗504a之配置。 (6)塗佈步驟 於(6)步驟中,製備含有藉由原石粉碎或原石熔融獲得之無機物粒子與結合劑之塗佈液,將塗佈液塗佈於(5)步驟中獲得之離子交換膜之表面並加以乾燥,藉此可形成塗佈層。 作為結合劑,較佳為將具有離子交換基前驅物之含氟系聚合物水解於含有二甲基亞碸(DMSO)及氫氧化鉀(KOH)之水溶液中之後,浸漬於鹽酸中將離子交換基之抗衡離子置換為H+ 而成之結合劑(例如,具有羧基或磺基之含氟系聚合物)。藉此,變得容易溶解於下文所述之水或乙醇中,故而較佳。 將該結合劑溶解於混合水與乙醇而成之溶液中。再者,水與乙醇之較佳之體積比為10:1~1:10,更佳為5:1~1:5,進而較佳為2:1~1:2。藉由球磨機使無機物粒子分散於由此獲得之溶解液中而獲得塗佈液。此時,亦可藉由調整分散時之時間、旋轉速度而調整粒子之平均粒徑等。再者,無機物粒子與結合劑之較佳之調配量如上文所述。 塗佈液中之無機物粒子及結合劑之濃度並無特別限定,較佳為製成稀薄之塗佈液。藉此,能夠均勻地塗佈於離子交換膜之表面。 又,於使無機物粒子分散時,亦可將界面活性劑添加於分散液中。作為界面活性劑,較佳為非離子系界面活性劑,例如可列舉日油股份有限公司製造之HS-210、NS-210、P-210、E-212等。 藉由利用噴射塗佈或滾筒塗敷將所獲得之塗佈液塗佈於離子交換膜表面而可獲得離子交換膜。 [微多孔膜] 作為本實施形態之微多孔膜,只要如上文所述,可與電解用電極製成積層體,則無特別限定,可應用各種微多孔膜。 本實施形態之微多孔膜之氣孔率並無特別限定,例如可設為20~90,較佳為30~85。上述氣孔率例如可藉由下述之式算出。 氣孔率=(1-(乾燥狀態之膜重量)/(由根據膜之厚度、寬度、長度算出之體積與膜素材之密度所算出之重量))×100 本實施形態之微多孔膜之平均孔徑並無特別限定,例如可設為0.01 μm~10 μ,較佳為0.05 μm~5 μm。上述平均孔徑例如係沿厚度方向將膜垂直切斷,藉由FE-SEM觀察切斷面。對所觀察之孔之直徑測定100點左右並求出平均值,藉此可求出平均孔徑。 本實施形態之微多孔膜之厚度並無特別限定,例如可設為10 μm~1000 μm,較佳為50 μm~600 μm。上述厚度例如可使用測微計(Mitutoyo股份有限公司製造)等進行測定。 作為如上所述之微多孔膜之具體例,可列舉Agfa公司製造之Zirfon Perl UTP 500、國際公開第2013-183584號說明書、國際公開第2016-203701號說明書等所記載者。 於本實施形態之電解槽之製造方法中,較佳為隔膜包含第1離子交換樹脂層、及具有與該第1離子交換樹脂層不同之EW(離子交換當量)之第2離子交換樹脂層。又,較佳為隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之官能基之第2離子交換樹脂層。離子交換當量可藉由所導入之官能基進行調整,關於可導入之官能基係如上文所述。 (水電解) 本實施形態中之進行水電解之情形時之電解槽係具有將上述進行食鹽電解之情形時之電解槽中之離子交換膜變更為微多孔膜之構成者。又,於所供給之原料為水之方面與上述進行食鹽電解之情形時之電解槽不同。關於其他構成,進行水電解之情形時之電解槽亦可採用與進行食鹽電解之情形時之電解槽相同之構成。於食鹽電解之情形時,由於在陽極室產生氯氣,因此陽極室之材質使用鈦,於水電解之情形時,由於在陽極室僅產生氧氣,因此可使用與陰極室之材質相同者。例如可列舉鎳等。又,陽極塗層適宜為產生氧氣用之觸媒塗層。作為觸媒塗層之例,可列舉鉑族金屬及過渡金屬族之金屬、氧化物、氫氧化物等。例如可使用鉑、銥、鈀、釕、鎳、鈷、鐵等元素。 [實施例] 藉由以下之實施例及比較例進一步詳細地說明本發明,但本發明並不受以下之實施例任何限定。 <第1實施形態之驗證> 如下所述準備與第1實施形態相對應之實驗例(於以下之<第1實施形態之驗證>之項中簡稱為「實施例」)、及不與第1實施形態相對應之實驗例(於以下之<第1實施形態之驗證>之項中簡稱為「比較例」),藉由以下方法對該等進行評價。一邊適當參照圖10~21一邊對其詳細內容進行說明。 [評價方法] (1)開孔率 將電極切成130 mm×100 mm之尺寸。使用電子數顯厚度計(Mitutoyo股份有限公司製造,最少顯示0.001 mm)於面內均勻地測定10點,並算出平均值。以其作為電極之厚度(量規厚度)而算出體積。其後,利用電子天平測定質量,根據金屬之比重(鎳之比重=8.908 g/cm3 、鈦之比重=4.506 g/cm3 )算出開孔率或空隙率。 開孔率(空隙率)(%)=(1-(電極質量)/(電極體積×金屬之比重))×100 (2)每單位面積之質量(mg/cm2 ) 將電極切成130 mm×100 mm之尺寸,利用電子天平測定質量。用該值除以面積(130 mm×100 mm)而算出每單位面積之質量。 (3)每單位質量·單位面積所承受之力(1)(接著力)(N/mg・cm2 )) [方法(i)] 測定係使用拉伸壓縮試驗機(今田製作所股份有限公司,試驗機本體:SDT-52NA型 拉伸壓縮試驗機,負荷計:SL-6001型負荷計)。 藉由粒編號320之氧化鋁對厚度1.2 mm、200 mm見方之鎳板實施噴擊加工。噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.7 μm。此處,表面粗糙度測定係使用觸針式之表面粗糙度測定機SJ-310(Mitutoyo股份有限公司)。將測定樣品設置於與地面平行之平台上,於下述之測定條件下測定算術平均粗糙度Ra。將測定實施6次時,記載其平均值。 <觸針之形狀>圓錐,錐角度=60°,前端半徑=2 μm,靜態測定力=0.75 mN <粗糙度標準>JIS2001 <評價曲線>R <濾波>GAUSS <臨界值 λc>0.8 mm <臨界值 λs>2.5 μm <區間數>5 <前掃、後掃>有 將該鎳板以成為鉛直之方式固定於拉伸壓縮試驗機之下側之夾頭。 使用下述之離子交換膜A作為隔膜。 作為強化芯材,使用聚四氟乙烯(PTFE)製且90丹尼之單絲(以下稱為PTFE紗)。作為犧牲紗,使用35丹尼、6根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。首先,以沿TD及MD之兩方向之各方向以24根/英吋配置PTFE紗、且於鄰接之PTFE紗間配置2根犧牲紗之方式進行平織而獲得織布。藉由滾筒將所獲得之織布進行壓接而獲得厚度70 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.85 mg當量/g之乾燥樹脂之樹脂A、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之乾燥樹脂之樹脂B。 使用該等樹脂A及B,藉由共擠出T模法獲得樹脂A層之厚度為15 μm、樹脂B層之厚度為104 μm之2層膜X。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙(高度50 μm之圓錐形狀之壓紋加工)、補強材及膜X,於加熱板表面溫度223℃、減壓度0.067 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。 藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)30質量%、氫氧化鉀(KOH)15質量%之80℃之水溶液中浸漬20分鐘而進行皂化。其後,於含有氫氧化鈉(NaOH)0.5 N之50℃之水溶液中浸漬1小時,將離子交換基之抗衡離子置換為Na,繼而進行水洗。進而於60℃下加以乾燥。 進而,於樹脂B之酸型樹脂之5質量%乙醇溶液中添加1次粒徑1 μm之氧化鋯20質量%並使其分散而調製懸浮液,藉由懸浮液噴射法對上述複合膜之兩面進行噴霧,於複合膜之表面形成氧化鋯之塗層,而獲得離子交換膜A。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.5 mg/cm2 。再者,平均粒徑係利用粒度分佈計(島津製作所製造之「SALD(註冊商標)2200」)進行測定。 將上述所獲得之離子交換膜(隔膜)於純水中浸漬12小時以上後用於試驗。使其與以純水充分濡濕之上述鎳板接觸,藉由水之張力進行接著。此時,以鎳板與離子交換膜之上端之位置對齊之方式設置。 測定所使用之電解用電極樣品(電極)係切成130 mm見方。離子交換膜A係切成170 mm見方。以2塊不鏽鋼板(厚度1 mm、縱9 mm、橫170 mm)夾著電極之一邊,以不鏽鋼板、電極之中心對齊之方式對位後,藉由4個夾具均勻地固定。將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。此時,將對試驗機承受之荷重設為0 N。暫時從拉伸壓縮試驗機卸下不鏽鋼板、電極、夾具一體物,為了利用純水將電極充分濡濕,而浸漬於裝有純水之槽中。其後,再次將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。 使拉伸壓縮試驗機之上側夾頭下降,利用純水之表面張力使電解用電極樣品接著於離子交換膜表面。此時之接著面係橫130 mm、縱110 mm。將裝入至洗瓶中之純水吹送至電極及離子交換膜整體,製成隔膜、電極再次充分濡濕之狀態。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從上向下滾動,從而將多餘之純水去除。輥僅施加1次。 以10 mm/分鐘之速度使電極上升,開始負荷測定,記錄電極與隔膜之重疊部分成為橫130 mm、縱100 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極與離子交換膜之重疊部分之面積、及與離子交換膜重疊之部分之電極質量,而算出每單位質量·單位面積所承受之力(1)。與離子交換膜重疊之部分之電極質量係根據上述(2)之每單位面積之質量(mg/cm2 )中所獲得之值,藉由比例計算而求出。 測定室之環境係溫度23±2℃、相對濕度30±5%。 再者,實施例、比較例中所使用之電極於接著於藉由表面張力接著於鉛直地固定之鎳板之離子交換膜時,可不下垂或剝離而獨立地接著。 再者,將承受力(1)之評價方法之模式圖示於圖10。 再者,拉伸試驗機之測定下限為0.01(N)。 (4)每單位質量·單位面積所承受之力(2)(接著力)(N/mg・cm2 )) [方法(ii)] 測定係使用拉伸壓縮試驗機(今田製作所股份有限公司,試驗機本體:SDT-52NA型 拉伸壓縮試驗機,負荷計:SL-6001型負荷計)。 將與方法(i)相同之鎳板以成為鉛直之方式固定於拉伸壓縮試驗機之下側之夾頭。 測定所使用之電解用電極樣品(電極)係切成130 mm見方。離子交換膜A係切成170 mm見方。以2塊不鏽鋼板(厚度1 mm、縱9 mm、橫170 mm)夾著電極之一邊,以不鏽鋼板、電極之中心對齊之方式對位後,藉由4個夾具均勻地固定。將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。此時,將對試驗機承受之荷重設為0 N。暫時從拉伸壓縮試驗機卸下不鏽鋼板、電極、夾具一體物,為了利用純水將電極充分濡濕,而浸漬於裝有純水之槽中。其後,再次將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。 使拉伸壓縮試驗機之上側夾頭下降,藉由溶液之表面張力使電解用電極樣品接著於鎳板表面。此時之接著面係橫130 mm、縱110 mm。將裝入至洗瓶中之純水吹送至電極及鎳板整體,製成鎳板、電極再次充分濡濕之狀態。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從上向下滾動,從而將多餘之溶液去除。輥僅施加1次。 以10 mm/分鐘之速度使電極上升,開始負荷測定,記錄電極與鎳板之縱向之重疊部分成為100 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極與鎳板之重疊部分之面積、及與鎳板重疊之部分之電極質量,而算出每單位質量·單位面積所承受之力(2)。與隔膜重疊之部分之電極質量係根據上述(2)之每單位面積之質量(mg/cm2 )中所獲得之值,藉由比例計算而求出。 又,測定室之環境係溫度23±2℃、相對濕度30±5%。 再者,實施例、比較例中所使用之電極於藉由表面張力接著於鉛直地固定之鎳板時,可不下垂或剝離而獨立地接著。 再者,拉伸試驗機之測定下限為0.01(N)。 (5)直徑280 mm圓柱捲繞評價方法(1)(%) (膜與圓柱) 按照以下之順序實施評價方法(1)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸。將離子交換膜於純水中浸漬12小時以上後用於試驗。比較例10及11中電極藉由熱壓製而與離子交換膜成為一體,因此準備離子交換膜與電極之一體物(電極係130 mm見方)。將離子交換膜於純水中充分浸漬後,置於外徑280 mm之塑膠(聚乙烯)製之管之曲面上。其後,藉由將厚度5 mm之獨立發泡型之EPDM海綿橡膠捲繞於氯乙烯管(外徑38 mm)而成之輥將多餘之溶液去除。輥係從圖11所示之模式圖之左側向右側於離子交換膜上滾動。輥僅施加1次。1分鐘後,測定離子交換膜與外徑280 mm之塑膠製之管電極密接之部分之比率。 (6)直徑280 mm圓柱捲繞評價方法(2)(%) (膜與電極) 按照以下之順序實施評價方法(2)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成130 mm見方。將離子交換膜於純水中浸漬12小時以上後用於試驗。將離子交換膜與電極於純水中充分浸漬後進行積層。將該積層體以電極成為外側之方式置於外徑280 mm之塑膠(聚乙烯)製之管之曲面上。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從圖12所示之模式圖之左側向右側滾動,從而將多餘之溶液去除。輥僅施加1次。1分鐘後,測定離子交換膜與電極密接之部分之比率。 (7)直徑145 mm圓柱捲繞評價方法(3)(%) (膜與電極) 按照以下之順序實施評價方法(3)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成130 mm見方。將離子交換膜於純水中浸漬12小時以上後用於試驗。將離子交換膜與電極於純水中充分浸漬後進行積層。將該積層體以電極成為外側之方式置於外徑145 mm之塑膠(聚乙烯)製之管之曲面上。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從圖13所示之模式圖之左側向右側滾動,從而將多餘之溶液去除。輥僅施加1次。1分鐘後,測定離子交換膜與電極密接之部分之比率。 (8)操作性(感應評價) (A)將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成95×110 mm。將離子交換膜於純水中浸漬12小時以上後用於試驗。於各實施例中將離子交換膜與電極於碳酸氫鈉水溶液、0.1 N之NaOH水溶液、純水之三種溶液中充分浸漬後進行積層,靜置於鐵氟龍板上。將電解評價所使用之陽極池與陰極池之間隔設為約3 cm,提起靜置之積層體而實施插入並夾於其間之操作。於實施該操作時一邊操作一邊確認電極是否偏離、掉落。 (B)將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成95×110 mm。將離子交換膜於純水中浸漬12小時以上後用於試驗。於各實施例中將離子交換膜與電極於碳酸氫鈉水溶液、0.1 N之NaOH水溶液、純水之三種溶液中充分浸漬後進行積層,靜置於鐵氟龍板上。手持積層體之膜部分之相鄰的兩處之角,以積層體成為鉛直之方式提起。從該狀態起,以將手持之兩處之角靠近之方式移動,使膜成為凸狀、凹狀。將該操作再重複1次,確認電極對膜之追隨性。基於以下之指標,按照1~4之4個等級對該結果進行評價。 1:操作良好 2:能夠操作 3:操作困難 4:大體無法操作 此處,對於比較例5之樣品,以與電極為1.3 m×2.5 m、離子交換膜為1.5 m×2.8 m之尺寸之大型電解池相同之尺寸實施操作。比較例5之評價結果(如下文所述為「3」)係作為對上述(A)、(B)之評價與製成大型尺寸時之不同進行評價之指標。即,於對小型之積層體進行評價所獲得之結果為「1」、「2」之情形時,評價為即使於製成大型尺寸之情形時操作性亦無問題。 (9)電解評價(電壓(V)、電流效率(%)、苛性鈉中食鹽濃度(ppm,50%換算)) 藉由下述電解實驗評價電解性能。 使具有設置有陽極之陽極室之鈦製的陽極池(陽極終端池)與具有設置有陰極之鎳製的陰極室(陰極終端池)之陰極池相對。於池間配置一對墊片,將積層體(離子交換膜A與電解用電極之積層體)夾於一對墊片間。然後,使陽極池、墊片、積層體、墊片及陰極密接而獲得電解池,準備包含該電解池之電解槽。 作為陽極,係藉由將氯化釕、氯化銥及四氯化鈦之混合溶液塗佈於已實施噴擊及酸蝕刻處理作為預處理之鈦基材上並進行乾燥、燒成而製作。陽極係藉由焊接而固定於陽極室。作為陰極,使用各實施例、比較例所記載者。作為陰極室之集電體,使用鎳製多孔金屬。集電體之尺寸為縱95 mm×橫110 mm。作為金屬彈性體,使用以鎳細線編織而成之墊。將作為金屬彈性體之墊置於集電體上。於其上覆蓋以40目之網眼將直徑150 μm之鎳線平織而成之鎳網,藉由利用鐵氟龍(註冊商標)製作之繩將Ni網之四角固定於集電體。以該Ni網作為饋電體。於該電解池中,利用作為金屬彈性體之墊之反彈力而成為零間距結構。作為墊片,使用EPDM(乙烯丙烯二烯)製之橡膠墊片。作為隔膜,使用[方法(i)]中製作之離子交換膜A(160 mm見方)。 使用上述電解池進行食鹽之電解。陽極室之鹽水濃度(氯化鈉濃度)係調整為205 g/L。陰極室之氫氧化鈉濃度係調整為32質量%。以各電解池內之溫度成為90℃之方式調節陽極室及陰極室之各溫度。於電流密度6 kA/m2 下實施食鹽電解,測定電壓、電流效率、苛性鈉中食鹽濃度。此處,所謂電流效率係所生成之苛性鈉之量相對於流通之電流之比率,若藉由流通之電流,雜質離子或氫氧化物離子而非鈉離子於離子交換膜中移動,則電流效率降低。電流效率係藉由一定時間所生成之苛性鈉之莫耳數除以其間流通之電流之電子之莫耳數而求出。苛性鈉之莫耳數係藉由將由電解生成之苛性鈉回收於聚合物槽中,對其質量進行測定而求出。苛性鈉中食鹽濃度表示將苛性鈉濃度換算為50%所得之值。 再者,將實施例、比較例中所使用之電極及饋電體之規格示於表1。 (11)觸媒層之厚度、電解用電極基材、電極之厚度測定 電解用電極基材之厚度係使用電子數顯厚度計(Mitutoyo股份有限公司製造,最少顯示0.001 mm)於面內均勻地測定10點並算出平均值。以此作為電解用電極基材之厚度(量規厚度)。電極之厚度係與電極基材同樣地藉由電子數顯厚度計於面內均勻地測定10點並算出平均值。以此作為電極之厚度(量規厚度)。觸媒層之厚度係藉由電極之厚度減去電解用電極基材之厚度而求出。(12)電極之彈性變形試驗 將[方法(i)]中製作之離子交換膜A(隔膜)及電極切割成110 mm見方之尺寸。將離子交換膜於純水中浸漬12小時以上後用於試驗。於溫度23±2℃、相對濕度30±5%之條件下,將離子交換膜與電極重疊而製作積層體後,如圖14所示般以不產生間隙之方式捲繞至外徑f32 mm、長度20 cm之PVC製管。為了避免捲繞之積層體從PVC製管剝離或鬆動,而使用聚乙烯製之捆束帶加以固定。於該狀態下保持6小時。其後,去除捆束帶,將積層體從PVC製管解捲。僅將電極置於平台上,測定從平台隆起之部分之高度L1 、L2 並求出平均值。以該值作為電極變形之指標。即,值較小意指難以變形。 再者,於使用多孔金屬之情形時,於捲繞時存在SW方向、LW方向之兩種。於本試驗中係沿SW方向捲繞。 又,對於產生變形之電極(未恢復為原來平坦之狀態之電極),藉由如圖15所示之方法對塑性變形後之柔軟程度進行評價。即,將產生變形之電極置於在純水中充分浸漬之隔膜上,將一端固定,將浮起之相反之端部壓抵於隔膜,將力解除,對產生變形之電極是否追隨隔膜進行評價。 (13)膜損傷評價 使用下述之離子交換膜B作為隔膜。 作為強化芯材,使用為聚四氟乙烯(PTFE)且將100丹尼之帶狀紗線以900次/m撚絞而製成紗狀者(以下稱為PTFE紗)。作為經紗之犧牲紗,使用將35丹尼、8根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。又,作為緯紗之犧牲紗,使用將35丹尼、8根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗。首先,以將PTFE紗以24根/英吋配置、將犧牲紗於鄰接之PTFE紗間配置2根之方式進行平織,而獲得厚度100 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.92 mg當量/g之乾燥樹脂之聚合物(A1)、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.10 mg當量/g之乾燥樹脂之聚合物(B1)。使用該等聚合物(A1)及(B1),藉由共擠出T模法獲得聚合物(A1)層之厚度為25 μm、聚合物(B1)層之厚度為89 μm之2層膜X。再者,各聚合物之離子交換容量表示將各聚合物之離子交換基前驅物水解而轉換為離子交換基時之離子交換容量。 又,另行準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.10 mg當量/g之乾燥樹脂之聚合物(B2)。將該聚合物單層擠出而獲得20 μm之膜Y。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙、膜Y、補強材及膜X,於加熱板溫度225℃、減壓度0.022 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)與氫氧化鉀(KOH)之水溶液中浸漬1小時而進行皂化後,於0.5 N之NaOH中浸漬1小時,將離子交換基所附離子取代為Na,繼而進行水洗。進而於60℃下加以乾燥。 又,將以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.05 mg當量/g之乾燥樹脂之聚合物(B3)水解後,藉由鹽酸使其成為酸型。於將該酸型之聚合物(B3')以5質量%之比率溶解於水及乙醇之50/50(質量比)混合液中而成之溶液中,以聚合物(B3')與氧化鋯粒子之質量比成為20/80之方式添加一次粒子之平均粒徑為0.02 μm之氧化鋯粒子。其後,藉由球磨機使其於氧化鋯粒子之懸浮液中分散而獲得懸浮液。 利用噴射法將該懸浮液塗佈於離子交換膜之兩表面並加以乾燥,藉此獲得具有含有聚合物(B3')與氧化鋯粒子之塗佈層之離子交換膜B。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.35 mg/cm2 。 陽極係使用與(9)電解評價相同者。 陰極係使用各實施例、比較例所記載者。陰極室之集電體、墊及饋電體係使用與(9)電解評價相同者。即,以Ni網作為饋電體,利用作為金屬彈性體之墊之反彈力而成為零間距結構。墊片亦使用與(9)電解評價相同者。作為隔膜,使用藉由上述方法所製作之離子交換膜B。即,除了將離子交換膜B與電解用電極之積層體夾持於一對墊片間以外,準備與(9)相同之電解槽。 使用上述電解池進行食鹽之電解。陽極室之鹽水濃度(氯化鈉濃度)係調整為205 g/L。陰極室之氫氧化鈉濃度係調整為32質量%。以各電解池內之溫度成為70℃之方式調節陽極室及陰極室之各溫度。於電流密度8 kA/m2 下實施食鹽電解。從電解開始起12小時後停止電解,取出離子交換膜B並觀察損傷狀態。 「0」意指無損傷。「1至3」意指存在損傷,數字越大,意指損傷之程度越大。 (14)電極之通氣阻力 使用通氣性試驗機KES-F8(商品名,Kato Tech股份有限公司)測定電極之通氣阻力。通氣阻力值之單位為kPa・s/m。將測定實施5次,將其平均值記載於表2。測定係於以下之兩個條件下實施。再者,測定室之溫度設為24℃,相對濕度設為32%。 ・測定條件1(通氣阻力1) 活塞速度:0.2 cm/s 通氣量:0.4 cc/cm2 /s 測定範圍:SENSE L(低) 樣品尺寸:50 mm×50 mm ・測定條件2(通氣阻力2) 活塞速度:2 cm/s 通氣量:4 cc/cm2 /s 測定範圍:SENSE M(中)或H(高) 樣品尺寸:50 mm×50 mm [實施例1] 作為陰極電解用電極基材,準備量規厚度為16 μm之電解鎳箔。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 藉由打孔加工於該鎳箔開出圓形之孔而製成多孔箔。開孔率為49%。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。實施例1中所製作之電極之厚度為24 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。塗層亦形成於未經粗面化之面。又,為氧化釕與氧化鈰之合計厚度。 將藉由上述方法所製作之電極之接著力之測定結果示於表2。觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 為了將藉由上述方法所製作之電極用於電解評價而將其切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之[方法(i)]中所製作之離子交換膜A(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向,藉由水溶液之表面張力使其等密接。 即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極剝落或偏離之情況。又,即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極剝落或偏離之情況。 將上述膜一體電極以附著有電極之面成為陰極室側之方式夾於陽極池與陰極池之間。剖面結構係從陰極室側起依序排列集電體、墊、鎳網饋電體、電極、膜、陽極而形成零間距結構。 對所獲得之電極進行電解評價。將其結果示於表2。 表現出較低之電壓、較高之電流效率及較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF(螢光X射線分析)測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例2] 實施例2係使用量規厚度為22 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.96 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為44%。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為29 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0033(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例3] 實施例3係使用量規厚度為30 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為1.38 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為44%。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為38 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例4] 實施例4係使用量規厚度為16 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為75%。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為24 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0023(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例5] 實施例5係準備量規厚度為20 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之兩面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.96 μm。兩面均為相同之粗糙度。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為49%。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為30 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0023(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則兩面均殘存大致100%塗層。若對比實施例1~4進行考慮,則說明即使不與膜相對向之相反面中塗層較少或不存在,亦能夠發揮出良好之電解性能。 [實施例6] 實施例6除了藉由離子鍍敷實施對陰極電解用電極基材之塗佈以外,與實施例1同樣地實施評價,並將結果示於表2。再者,離子鍍敷係於加熱溫度200℃下使用Ru金屬靶,於氬氣/氧氣環境下以成膜壓力7×10-2 Pa進行製膜。所形成之塗層為氧化釕。 電極之厚度為26 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例7] 實施例7係藉由電成形法製作陰極電解用電極基材。光罩之形狀係設為將0.485 mm×0.485 mm之正方形以0.15 mm為間隔縱、橫排列而成之形狀。藉由依序實施曝光、顯影、電鍍,獲得量規厚度為20 μm、開孔率56%之鎳多孔箔。表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為37 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為17 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0032(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例8] 實施例8中作為陰極電解用電極基材,係藉由電成形法製作,量規厚度為50 μm,開孔率為56%。表面之算術平均粗糙度Ra為0.73 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為60 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0032(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例9] 實施例9係使用量規厚度為150 μm、空隙率為76%之鎳不織布(NIKKO TECHNO股份有限公司製造)作為陰極電解用電極基材。不織布之鎳纖維直徑約為40 μm,單位面積重量為300 g/m2 。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為165 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為15 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為29 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0612(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例10] 實施例10係使用量規厚度為200 μm、空隙率為72%之鎳不織布(NIKKO TECHNO股份有限公司製造)作為陰極電解用電極基材。不織布之鎳纖維直徑約為40 μm,單位面積重量為500 g/m2 。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為215 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為15 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為40 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0164(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例11] 實施例11係使用量規厚度為200 μm、空隙率為72%之發泡鎳(Mitsubishi Materials股份有限公司製造)作為陰極電解用電極基材。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 又,電極之厚度為210 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為17 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0402(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例12] 實施例12係使用線徑50 μm、200目、量規厚度為100 μm、開孔率為37%之鎳網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。即使實施噴擊處理,開孔率亦不變化。由於難以測定金屬絲網表面之粗糙度,因此於實施例12中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。1根金屬絲網之算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為110 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0154(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例13] 實施例13係使用線徑65 μm、150目、量規厚度為130 μm、開孔率為38%之鎳網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。即使實施噴擊處理,開孔率亦不變化。由於難以測定金屬絲網表面之粗糙度,因此於實施例13中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.66 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施上述評價,並將結果示於表2。 電極之厚度為133 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為3 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為6.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0124(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價亦為「0」而較良好。 [實施例14] 實施例14係使用與實施例3相同之基材(量規厚度30 μm、開孔率44%)作為陰極電解用電極基材。除了未設置鎳網饋電體以外,以與實施例1相同之構成實施電解評價。即,電解池之剖面結構係從陰極室側起依序排列集電體、墊、膜一體電極、陽極而形成零間距結構,墊作為饋電體發揮功能。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例15] 實施例15係使用與實施例3相同之基材(量規厚度30 μm、開孔率44%)作為陰極電解用電極基材。設置參考例1中使用之劣化且電解電壓變高之陰極代替鎳網饋電體。除此以外,以與實施例1相同之構成實施電解評價。即,電解池之剖面結構係從陰極室側起依序排列集電體、墊、劣化且電解電壓變高之陰極(作為饋電體發揮功能)、電解用電極(陰極)、隔膜、陽極而形成零間距結構,劣化且電解電壓變高之陰極作為饋電體發揮功能。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例16] 作為陽極電解用電極基材,準備量規厚度為20 μm之鈦箔。對鈦箔之兩面實施粗面化處理。對該鈦箔實施打孔加工,開出圓形之孔而製成多孔箔。孔之直徑為1 mm,開孔率為14%。表面之算術平均粗糙度Ra為0.37 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素、銥元素及鈦元素之莫耳比成為0.25:0.25:0.5之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、銥濃度為100 g/L之氯化銥(田中貴金屬工業股份有限公司)、四氯化鈦(和光純藥工業股份有限公司)加以混合。將該混合液充分攪拌,以其作為陽極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。於鈦多孔箔塗佈上述塗佈液後,於60℃下實施10分鐘之乾燥,於475℃下實施10分鐘之燒成。重複實施該等塗佈、乾燥、預燒成、燒成之一系列之操作後,於520℃下進行1小時之燒成。 為了將藉由上述方法所製作之電極用於電解評價而將其切成縱95 mm、橫110 mm之尺寸。藉由水溶液之表面張力使其密接於利用0.1 N之NaOH水溶液平衡之[方法(i)]中製作之離子交換膜A(尺寸為160 mm×160 mm)之磺酸層側的大致中央之位置。 陰極係按照以下之順序製備。首先,準備線徑150 μm、40目之鎳製金屬絲網作為基材。作為預處理而藉由氧化鋁實施噴擊處理後,於6 N之鹽酸中浸漬5分鐘,並利用純水充分洗淨、乾燥。 繼而,以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、氯化鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於300℃下實施3分鐘之預燒成,於550℃下實施10分鐘之燒成。其後,於550℃下實施1小時之燒成。重複進行該等塗佈、乾燥、預燒成、燒成之一系列之操作。 作為陰極室之集電體,使用鎳製多孔金屬。集電體之尺寸為縱95 mm×橫110 mm。作為金屬彈性體,使用以鎳細線編織而成之墊。將作為金屬彈性體之墊置於集電體上。於其上覆蓋藉由上述方法製作之陰極,藉由利用鐵氟龍(註冊商標)製作之繩將網之四角固定於集電體。 即使抓持膜與陽極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極剝落或偏離之情況。又,即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極剝落或偏離之情況。 藉由焊接將參考例3中所使用之劣化且電解電壓變高之陽極固定於陽極池,將上述膜一體電極以附著有電極之面成為陽極室側之方式夾於陽極池與陰極池之間。即,電解池之剖面結構係從陰極室側起依序排列集電體、墊、陰極、隔膜、電解用電極(鈦多孔箔陽極)、劣化且電解電壓變高之陽極,形成零間距結構。劣化且電解電壓變高之陽極作為饋電體發揮功能。再者,鈦多孔箔陽極與劣化且電解電壓變高之陽極之間僅係物理接觸,並未藉由焊接進行固定。 藉由該構成,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為26 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為6 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為4 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0060(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例17] 實施例17係使用量規厚度20 μm、開孔率30%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.37 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例16同樣地實施評價,並將結果示於表2。 電極之厚度為30 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0030(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例18] 實施例18係使用量規厚度20 μm、開孔率42%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.38 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例16同樣地實施評價,並將結果示於表2。 電極之厚度為32 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為12 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為2.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0022(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例19] 實施例19係使用量規厚度50 μm、開孔率47%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.40 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例16同樣地實施評價,並將結果示於表2。 電極之厚度為69 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為19 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為8 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0024(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例20] 實施例20係使用量規厚度100 μm、鈦纖維直徑約為20 μm、單位面積重量為100 g/m2 、開孔率78%之鈦不織布作為陽極電解用電極基材。除此以外,與實施例16同樣地實施評價,並將結果示於表2。 電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為2 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0228(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例21] 實施例21係使用量規厚度120 μm、鈦纖維直徑約為60 μm、150目之鈦金屬絲網作為陽極電解用電極基材。開孔率為42%。藉由粒編號320之氧化鋁實施噴擊處理。由於難以測定金屬絲網表面之粗糙度,因此於實施例21中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.60 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例16同樣地實施評價,並將結果示於表2。 電極之厚度為140 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為20 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為10 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0132(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例22] 實施例22係與實施例16同樣地使用劣化且電解電壓變高之陽極作為陽極饋電體,使用與實施例20相同之鈦不織布作為陽極。與實施例15同樣地使用劣化且電解電壓變高之陰極作為陰極饋電體,使用與實施例3相同之鎳箔電極作為陰極。電解池之剖面結構係從陰極室側起,依序排列集電體、墊、劣化且電壓變高之陰極、鎳多孔箔陰極、隔膜、鈦不織布陽極、劣化且電解電壓變高之陽極而形成零間距結構,劣化且電解電壓變高之陰極及陽極作為饋電體發揮功能。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極(陽極)之厚度為114 μm,觸媒層之厚度係電極(陽極)之厚度減去電解用電極基材之厚度而為14 μm。又,電極(陰極)之厚度為38 μm,觸媒層之厚度係電極(陰極)之厚度減去電解用電極基材之厚度而為8 μm。 於陽極及陰極均觀測到充分之接著力。 實施電極(陽極)之變形試驗,結果L1 、L2 之平均值為2 mm。實施電極(陰極)之變形試驗,結果L1 、L2 之平均值為0 mm。 測定電極(陽極)之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0228(kPa・s/m)。測定電極(陰極)之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。陽極及陰極中膜損傷評價均亦為「0」而較良好。再者,於實施例22中,於隔膜之單面貼附陰極,於相反之面貼附陽極,將陰極及陽極組合進行膜損傷評價。 [實施例23] 於實施例23中係使用Agfa公司製造之微多孔膜「Zirfon Perl UTP 500」。 Zirfon膜係於純水中浸漬12小時以上後用於試驗。除此以外,與實施例3同樣地實施上述評價,並將結果示於表2。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 與使用離子交換膜作為隔膜時相同,觀測到充分之接著力,微多孔膜與電極藉由表面張力而密接,操作性為「1」而較良好。 [實施例24] 作為陰極電解用電極基材,準備量規厚度為566 μm之紡織碳纖維而成之碳布。按照以下之順序製備用以於該碳布形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088(商品名),厚度10 mm)而成之塗佈滾筒與上述塗佈液始終相接之方式設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。所製作之電極之厚度為570 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為4 μm。觸媒層之厚度為氧化釕與氧化鈰之合計厚度。 對所獲得之電極進行電解評價。將其結果示於表2。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。 測定電極之通氣阻力,結果於測定條件1下為0.19(kPa・s/m),於測定條件2下為0.176(kPa・s/m)。 又,操作性為「2」,可判斷能夠作為大型積層體進行操作。 電壓較高,膜損傷評價為「1」,確認到膜損傷。認為其原因在於:由於實施例24之電極之通氣阻力較大,因此電極中產生之NaOH滯留於電極與隔膜之界面而成為高濃度。 [參考例1] 於參考例1中,作為陰極而使用於大型電解槽中使用8年、劣化且電解電壓變高之陰極。於陰極室之墊上設置上述陰極代替鎳網饋電體,隔著[方法(i)]中製作之離子交換膜A實施電解評價。於參考例1中不使用膜一體電極,電解池之剖面結構係從陰極室側起,依序排列集電體、墊、劣化且電解電壓變高之陰極、離子交換膜A、陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.04 V,電流效率為97.0%,苛性鈉中食鹽濃度(50%換算值)為20 ppm。由於陰極劣化,因此結果為電壓較高 [參考例2] 於參考例2中,使用鎳網饋電體作為陰極。即,藉由未形成觸媒塗層之鎳網實施電解。 將鎳網陰極設置於陰極室之墊上,隔著[方法(i)]中製作之離子交換膜A實施電解評價。參考例2之電池之剖面結構係從陰極室側起,依序排列集電體、墊、鎳網、離子交換膜A、陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.38 V,電流效率為97.7%,苛性鈉中食鹽濃度(50%換算值)為24 ppm。由於未塗佈陰極觸媒,因此結果為電壓較高。 [參考例3] 於參考例3中,作為陽極而使用於大型電解槽中使用約8年、劣化且電解電壓變高之陽極。 參考例3之電解池之剖面結構係從陰極室側起,依序排列集電體、墊、陰極、[方法(i)]中製作之離子交換膜A、劣化且電解電壓變高之陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.18 V,電流效率為97.0%,苛性鈉中食鹽濃度(50%換算值)為22 ppm。由於陽極劣化,因此結果為電壓較高。 [比較例1] 於比較例1中,使用全滾筒加工後之量規厚度100 μm、開孔率33%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於比較例1中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.68 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 每單位面積之質量為67.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.05(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為64%,直徑145 mm圓柱捲繞評價(3)之結果為22%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為13 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0168(kPa・s/m)。 [比較例2] 於比較例2中,使用全滾筒加工後之量規厚度100 μm、開孔率16%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於比較例2中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為107 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。 每單位面積之質量為78.1(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.04(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為37%,直徑145 mm圓柱捲繞評價(3)之結果為25%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為18.5 mm。測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0176(kPa・s/m)。 [比較例3] 比較例3係使用全滾筒加工後之量規厚度為100 μm、開孔率為40%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於比較例3中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.70 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。對電解用電極基材之塗佈係藉由與實施例6同樣之離子鍍敷實施。除此以外,與實施例1同樣地實施評價,並將結果示於表2。 電極之厚度為110 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 每單位質量·單位面積所承受之力(1)為0.07(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為80%,直徑145 mm圓柱捲繞評價(3)之結果為32%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「3」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為11 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0030(kPa・s/m)。 [比較例4] 比較例4係使用全滾筒加工後之量規厚度為100 μm、開孔率為58%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於比較例4中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施評價,將結果示於表2。 電極之厚度為109 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為9 μm。 每單位質量·單位面積所承受之力(1)為0.06(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為69%,直徑145 mm圓柱捲繞評價(3)之結果為39%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「3」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為11.5 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 [比較例5] 比較例5係使用量規厚度為300 μm、開孔率為56%之鎳金屬絲網作為陰極電解用電極基材。由於難以測定金屬絲網之表面粗糙度,因此於比較例5中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施評價,將結果示於表2。 電極之厚度為308 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為49.2(mg/cm2 )。因此,直徑280 mm圓柱捲繞評價(2)之結果為88%,直徑145 mm圓柱捲繞評價(3)之結果為42%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況,操作性為「3」,存在問題。實際中以大型尺寸進行操作,可評價為「3」。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為23 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0034(kPa・s/m)。 [比較例6] 於比較例6中使用量規厚度200 μm、開孔率37%之鎳金屬絲網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定金屬絲網之表面粗糙度,因此於比較例6中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.65 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例1同樣地實施電極電解評價、接著力之測定結果、密接性。將結果示於表2。 電極之厚度為210 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 每單位面積之質量為56.4 mg/cm2 。因此,直徑145 mm圓柱捲繞評價方法(3)之結果為63%,電極與隔膜之密接性較差。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況,操作性為「3」,存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為19 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0096(kPa・s/m)。 [比較例7] 於比較例7中使用全滾筒加工後之量規厚度500 μm、開孔率17%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於比較例7中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.60 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例16同樣地實施評價,並將結果示於表2。 又,電極之厚度為508 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為152.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0072(kPa・s/m)。 [比較例8] 於比較例8中,使用全滾筒加工後之量規厚度800 μm、開孔率8%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於比較例8中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.61 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例16同樣地實施上述評價,並將結果示於表2。 電極之厚度為808 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為251.3(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0172(kPa・s/m)。 [比較例9] 於比較例9中,使用全滾筒加工後之量規厚度1000 μm、開孔率46%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於比較例9中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.59 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例16同樣地實施上述評價,並將結果示於表2。 又,電極之厚度為1011 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為11 μm。 每單位面積之質量為245.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 [比較例10] 於比較例10中,以先前文獻(日本專利特開昭58-48686之實施例)為參考,製作將電極熱壓接於隔膜而成之膜電極接合體。 使用量規厚度100 μm、開孔率33%之鎳多孔金屬作為陰極電解用電極基材,與實施例1同樣地實施電極塗佈。其後,按照下述之順序對電極之單面實施惰性化處理。於電極之單面貼附聚醯亞胺黏著帶(中興化成股份有限公司),於相反面塗佈PTFE分散液(DuPont-Mitsui Fluorochemicals股份有限公司,31-JR(商品名)),於120℃之馬弗爐中乾燥10分鐘。將聚醯亞胺膠帶剝離,於設定為380℃之馬弗爐中實施10分鐘燒結處理。將該操作重複2次,對電極之單面進行惰性化處理。 製作由末端官能基為「-COOCH3 」之全氟碳聚合物(C聚合物)與末端基為「-SO2 F」之全氟碳聚合物(S聚合物)之2層所形成之膜。C聚合物層之厚度為3密耳(mil),S聚合物層之厚度為4密耳(mil)。對該2層膜實施皂化處理,藉由水解對聚合物之末端導入離子交換基。C聚合物末端被水解為羧酸基,S聚合物末端被水解為磺基。以磺酸基計之離子交換容量為1.0 meq/g,以羧酸基計之離子交換容量為0.9 meq/g。 使具有羧酸基作為離子交換基之面與經惰性化之電極面相對向,並實施熱壓製,而將離子交換膜與電極一體化。熱壓接後電極之單面亦為露出之狀態,不存在電極貫通膜之部分。 其後,為了抑制電解中產生之氣泡對膜之附著,將導入有氧化鋯與磺基之全氟碳聚合物混合物塗佈於兩面。由此製作比較例10之膜電極接合體。 使用該膜電極接合體,測定每單位質量·單位面積所承受之力(1),結果由於藉由熱壓接將電極與膜強力接合,因此電極未向上方移動。因此,以不移動離子交換膜與鎳板之方式進行固定,藉由更強之力將電極向上方拉拽,結果於承受1.50(N/mg・cm2 )之力時,膜之一部分破裂。比較例10之膜電極接合體之每單位質量·單位面積所承受之力(1)至少為1.50(N/mg・cm2 ),被強力地接合。 實施直徑280 mm圓柱捲繞評價(1),結果與塑膠製管之接觸面積未達5%。另一方面,實施直徑280 mm圓柱捲繞評價(2),結果雖然電極與膜100%接合,但最初隔膜並未捲繞至圓柱。直徑145 mm圓柱捲繞評價(3)之結果亦相同。該結果意指膜之操作性因一體化之電極而受損,而難以捲繞為滾筒狀、或加以彎折。操作性為「3」,存在問題。膜損傷評價為「0」。又,實施電解評價,結果電壓變高,電流效率變低,苛性鈉中之食鹽濃度(50%換算值)變高,電解性能變差。 又,電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 實施電極之變形試驗,結果L1 、L2 之平均值為13 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0168(kPa・s/m)。 [比較例11] 比較例11係使用線徑150 μm、40目、量規厚度300 μm、開孔率58%之鎳網作為陰極電解用電極基材。除此以外,與比較例10同樣地製作膜電極接合體。 使用該膜電極接合體,測定每單位質量·單位面積所承受之力(1),結果由於藉由熱壓接將電極與膜強力接合,因此電極未向上方移動。因此,以不移動離子交換膜與鎳板之方式進行固定,藉由更強之力將電極向上方拉拽,結果於承受1.60(N/mg・cm2 )之力時,膜之一部分破裂。比較例11之膜電極接合體之每單位質量·單位面積所承受之力(1)至少為1.60(N/mg・cm2 ),被強力地接合。 使用該膜電極接合體實施直徑280 mm圓柱捲繞評價(1),結果與塑膠製管之接觸面積未達5%。另一方面,實施直徑280 mm圓柱捲繞評價(2),結果雖然電極與膜100%接合,但最初隔膜並未捲繞至圓柱。直徑145 mm圓柱捲繞評價(3)之結果亦相同。該結果意指膜之操作性因一體化之電極而受損,而難以捲繞為滾筒狀、或加以彎折。操作性為「3」,存在問題。又,實施電解評價,結果電壓變高,電流效率變低,苛性鈉中之食鹽濃度變高,電解性能變差。 又,電極之厚度為308 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 實施電極之變形試驗,結果L1 、L2 之平均值為23 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0034(kPa・s/m)。 [比較例12] (觸媒之製備) 將硝酸銀(和光純藥股份有限公司)0.728 g、硝酸鈰6水合物(和光純藥股份有限公司)1.86 g添加至純水150 ml中,製作金屬鹽水溶液。於15%氫氧化四甲基銨水溶液(和光純藥股份有限公司)100 g中添加純水240 g而製作鹼性溶液。一邊使用磁攪拌器攪拌鹼性溶液,一邊使用滴定管以5 ml/分鐘滴加添加上述金屬鹽水溶液。對含有所生成之金屬氫氧化物微粒之懸浮液進行抽氣過濾後,進行水洗而去除鹼性成分。其後,將過濾物轉移至200 ml之2-丙醇(Kishida Chemical股份有限公司)中,藉由超音波分散機(US-600T,日本精機製作所股份有限公司)再分散10分鐘,而獲得均勻之懸浮液。 將疏水性碳黑(DENKA BLACK(註冊商標)AB-7(商品名),電氣化學工業股份有限公司)0.36 g、親水性碳黑(科琴黑(註冊商標)EC-600JD(商品名),三菱化學股份有限公司)0.84 g分散於2-丙醇100 ml中,藉由超音波分散機分散10分鐘,而獲得碳黑之懸浮液。將金屬氫氧化物前驅物之懸浮液與碳黑之懸浮液混合,藉由超音波分散機分散10分鐘。將該懸浮液進行抽氣過濾,於室溫下乾燥半天,而獲得分散固定有金屬氫氧化物前驅物之碳黑。繼而,使用惰性氣體燒成爐(VMF165型,山田電機股份有限公司),於氮氣環境、400℃下進行1小時之燒成,而獲得將電極觸媒分散固定化之碳黑A。 (反應層用之粉末製作) 於將電極觸媒分散固定化之碳黑A 1.6 g中添加利用純水稀釋為20重量%之界面活性劑Triton(註冊商標)X-100(商品名,ICN Biomedical公司)0.84 ml、純水15 ml,藉由超音波分散機分散10分鐘。於該分散液中添加PTFE(聚四氟乙烯)分散液(PTFE30J(商品名),DuPont-Mitsui Fluorochemicals股份有限公司)0.664 g,並攪拌5分鐘後,進行抽氣過濾。進而,於乾燥機中在80℃下乾燥1小時,藉由研磨機進行粉碎,而獲得反應槽用粉末A。 (氣體擴散層用粉末之製作) 藉由超音波分散機將疏水性碳黑(DENKA BLACK(註冊商標)AB-7(商品名))20 g、利用純水稀釋為20重量%之界面活性劑Triton(註冊商標)X-100(商品名)50 ml、純水360 ml分散10分鐘。於所獲得之分散液中添加PTFE分散液22.32 g,並攪拌5分鐘後,進行過濾。進而,於80℃之乾燥機中乾燥1小時,藉由研磨機實施粉碎,而獲得氣體擴散層用粉末A。 (氣體擴散電極之製作) 於氣體擴散層用粉末A 4 g中添加乙醇8.7 ml,進行混練而製成飴狀。藉由滾筒成形機將該製成飴狀之氣體擴散層用粉末成形為片狀,埋入銀網(SW=1,LW=2,厚度=0.3 mm)作為集電體,最終成形為1.8 mm之片狀。於反應層用粉末A 1 g中添加乙醇2.2 ml,進行混練而製成飴狀。藉由滾筒成形機將該製成飴狀之反應層用粉末成形為厚度0.2 mm之片狀。進而,將所製作之使用氣體擴散層用粉末A所獲得之片材及使用反應層用粉末A所獲得之片材之2片片材進行積層,藉由滾筒成形機成形為1.8 mm之片狀。將該積層而成之片材於室溫下乾燥一晝夜,而將乙醇去除。進而,為了將殘存之界面活性劑去除,於空氣中在300℃下進行1小時之熱分解處理。包於鋁箔中,藉由熱壓機(SA303(商品名),TESTER SANGYO股份有限公司),於360℃下以50 kgf/cm2 進行1分鐘熱壓,而獲得氣體擴散電極。氣體擴散電極之厚度為412 μm。 使用所獲得之電極,進行電解評價。電解池之剖面結構係從陰極室側起依序排列集電體、墊、鎳網饋電體、電極、膜、陽極而形成零間距結構。將其結果示於表2。 實施電極之變形試驗,結果L1 、L2 之平均值為19 mm。 測定電極之通氣阻力,結果於測定條件1下為25.88(kPa・s/m)。 又,操作性為「3」,存在問題。又,實施電解評價,結果電流效率變低,苛性鈉中之食鹽濃度變高,電解性能顯著變差。膜損傷評價為「3」,亦存在問題。 根據該等結果可知,若使用比較例12中獲得之氣體擴散電極,則電解性能顯著較差。又,於離子交換膜之大致整個面確認到損傷。認為其原因在於:由於比較例12之氣體擴散電極之通氣阻力顯著較大,因此電極中產生之NaOH滯留於電極與隔膜之界面而成為高濃度。 [比較例13] 準備量規厚度為150 μm之鎳線作為陰極電解用電極基材。實施利用該鎳線之粗面化處理。由於難以測定鎳線之表面粗糙度,因此於比較例13中於噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為鎳線之表面粗糙度。藉由粒編號320之氧化鋁實施噴擊處理。算術平均粗糙度Ra為0.64 μm。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088(商品名),厚度10 mm)而成之塗佈滾筒與上述塗佈液始終相接之方式設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。比較例13中所製作之鎳線1根之厚度為158 μm。 將藉由上述方法所製作之鎳線切成110 mm及95 mm之長度。如圖16所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由瞬間接著劑(Aron Alpha(註冊商標),東亞合成股份有限公司)將交點部分接著而製作電極。對電極實施評價,將其結果示於表2。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為99.7%。 電極之每單位面積之質量為0.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為15 mm。 測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力值為0.0002(kPa・s/m)。 又,對於電極,使用圖17所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓成為3.16 V,較高。 [比較例14] 於比較例14中,使用比較例13中所製作之電極,如圖18所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由瞬間接著劑(Aron Alpha(註冊商標),東亞合成股份有限公司)將交點部分接著而製作電極。對電極實施評價,將其結果示於表2。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為99.4%。 電極之每單位面積之質量為0.9(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為16 mm。 測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力為0.0004(kPa・s/m)。 又,對於電極,使用圖19所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓為3.18 V,較高。 [比較例15] 於比較例15中,使用比較例13中所製作之電極,如圖20所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由瞬間接著劑(Aron Alpha(註冊商標),東亞合成股份有限公司)將交點部分接著而製作電極。對電極實施評價,將其結果示於表2。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為98.8%。 電極之每單位面積之質量為1.9(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為14 mm。 又,測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力為0.0005(kPa・s/m)。 又,對於電極,使用圖21所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓為3.18 V,較高。 [表1] [表2] 於表2中,全部樣品於「每單位質量·單位面積所承受之力(1)」及「每單位質量·單位面積所承受之力(2)」之測定前可藉由表面張力而自立(即,不存在下垂之情況)。 比較例1、2、7~9由於每單位面積之質量較大,每單位質量·單位面積所承受之力(1)較小,因此與隔膜之密接性較差。因此,對於大型電解槽尺寸(例如,縱1.5 m、橫3 m),於操作作為高分子膜之隔膜時,必然存在鬆弛之情況,此時電極剝落,無法承受實用。 比較例3、4由於每單位質量·單位面積所承受之力(1)較小,因此與隔膜之密接性較差。因此,對於大型電解槽尺寸(例如,縱1.5 m、橫3 m),操作作為高分子膜之隔膜時,必然存在鬆弛之情況,此時電極剝落,無法承受實用。 比較例5、6每單位面積之質量較大,與隔膜之密接性較差。因此,對於大型電解槽尺寸(例如,縱1.5 m、橫3 m),操作作為高分子膜之隔膜時,必然存在鬆弛之情況,此時電極剝落,無法承受實用。 比較例10、11由於藉由熱壓製將膜與電極強力地接合,因此不存在如比較例1、2、7~9般於操作時從膜發生剝離之情況。然而,由於與電極強力地接合,因此喪失高分子膜之柔軟性,難以捲繞成滾筒狀、或加以彎折,操作性較差,無法承受實用。 進而,比較例10、11中電解性能大幅地變差。認為電壓大幅上升之原因在於:因成為將電極埋入至離子交換膜中之狀態,導致離子之流動受到阻礙。認為電流效率之降低、苛性鈉中食鹽濃度變差之原因在於如下要因:因將電極埋入至具有表現出較高之電流效率、離子選擇性之效果之羧酸層中,導致產生羧酸層之厚度不均,埋入羧酸層之一部分之電極發生貫通等。 進而,於比較例10、11中,於隔膜或電極之某一者產生問題而必須更換之情形時,由於強力地接合,故而無法僅更換其中一者,導致成本變高。 比較例12中電解性能大幅地變差。認為電壓大幅上升之原因在於產物滯留於隔膜與電極之界面。 比較例13~15由於每單位質量·單位面積所承受之力(1)及(2)均較小(為測定下限以下),因此與隔膜之密接性較差。因此,對於大型電解槽尺寸(例如,縱1.5 m、橫3 m),操作作為高分子膜之隔膜時,必然存在鬆弛之情況,此時電極剝落,無法承受實用。 本實施形態中,膜與電極藉由適度之力密接於表面,因此操作中不存在電極剝離等問題,不存在阻礙膜內之離子流動之情況,因此表現出良好之電解性能。 <第2實施形態之驗證> 如下所述準備與第2實施形態相對應之實驗例(於以下之<第2實施形態之驗證>之項中簡稱為「實施例」)、及不與第2實施形態相對應之實驗例(於以下之<第2實施形態之驗證>之項中簡稱為「比較例」),藉由以下方法對該等進行評價。一邊適當參照圖31~42一邊對其詳細內容進行說明。 [評價方法] (1)開孔率 將電極切成130 mm×100 mm之尺寸。使用電子數顯厚度計(Mitutoyo股份有限公司製造,最少顯示0.001 mm)於面內均勻地測定10點,並算出平均值。以其作為電極之厚度(量規厚度)而算出體積。其後,利用電子天平測定質量,根據金屬之比重(鎳之比重=8.908 g/cm3 、鈦之比重=4.506 g/cm3 )算出開孔率或空隙率。 開孔率(空隙率)(%)=(1-(電極質量)/(電極體積×金屬之比重))×100 (2)每單位面積之質量(mg/cm2 ) 將電極切成130 mm×100 mm之尺寸,利用電子天平測定質量。用該值除以面積(130 mm×100 mm)而算出每單位面積之質量。 (3)每單位質量·單位面積所承受之力(1)(接著力)(N/mg・cm2 )) [方法(i)] 測定係使用拉伸壓縮試驗機(今田製作所股份有限公司,試驗機本體:SDT-52NA型 拉伸壓縮試驗機,負荷計:SL-6001型負荷計)。 利用粒編號320之氧化鋁對厚度1.2 mm、200 mm見方之鎳板實施噴擊加工。噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.7 μm。此處,表面粗糙度測定係使用觸針式之表面粗糙度測定機SJ-310(Mitutoyo股份有限公司)。將測定樣品設置於與地面平行之平台上,於下述之測定條件下測定算術平均粗糙度Ra。將測定實施6次時,記載其平均值。 <觸針之形狀>圓錐,錐角度=60°,前端半徑=2 μm,靜態測定力=0.75 mN <粗糙度標準>JIS2001 <評價曲線>R <濾波>GAUSS <臨界值 λc>0.8 mm <臨界值 λs>2.5 μm <區間數>5 <前掃、後掃>有 將該鎳板以成為鉛直之方式固定於拉伸壓縮試驗機之下側之夾頭。 使用下述之離子交換膜A作為隔膜。 作為強化芯材,使用聚四氟乙烯(PTFE)製且90丹尼之單絲(以下稱為PTFE紗)。作為犧牲紗,使用35丹尼、6根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。首先,以沿TD及MD之兩方向之各方向以24根/英吋配置PTFE紗、且於鄰接之PTFE紗間配置2根犧牲紗之方式進行平織而獲得織布。藉由滾筒將所獲得之織布進行壓接而獲得厚度70 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.85 mg當量/g之乾燥樹脂之樹脂A、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之乾燥樹脂之樹脂B。 使用該等樹脂A及B,藉由共擠出T模法獲得樹脂A層之厚度為15 μm、樹脂B層之厚度為104 μm之2層膜X。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙(高度50 μm之圓錐形狀之壓紋加工)、補強材及膜X,於加熱板表面溫度223℃、減壓度0.067 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。 藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)30質量%、氫氧化鉀(KOH)15質量%之80℃之水溶液中浸漬20分鐘而進行皂化。其後,於含有氫氧化鈉(NaOH)0.5 N之50℃之水溶液中浸漬1小時,將離子交換基之抗衡離子置換為Na,繼而進行水洗。進而於60℃下加以乾燥。 進而,於樹脂B之酸型樹脂之5質量%乙醇溶液中添加1次粒徑1 μm之氧化鋯20質量%並使其分散而調製懸浮液,藉由懸浮液噴射法對上述複合膜之兩面進行噴霧,於複合膜之表面形成氧化鋯之塗層,而獲得離子交換膜A。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.5 mg/cm2 。再者,平均粒徑係利用粒度分佈計(島津製作所製造之「SALD(註冊商標)2200」)進行測定。 將上述所獲得之離子交換膜(隔膜)於純水中浸漬12小時以上後用於試驗。使其與以純水充分濡濕之上述鎳板接觸,藉由水之張力進行接著。此時,以鎳板與離子交換膜之上端之位置對齊之方式設置。 測定所使用之電解用電極樣品(電極)係切成130 mm見方。離子交換膜A係切成170 mm見方。以2塊不鏽鋼板(厚度1 mm、縱9 mm、橫170 mm)夾著電極之一邊,以不鏽鋼板、電極之中心對齊之方式對位後,藉由4個夾具均勻地固定。將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。此時,將對試驗機承受之荷重設為0 N。暫時從拉伸壓縮試驗機卸下不鏽鋼板、電極、夾具一體物,為了利用純水將電極充分濡濕,而浸漬於裝有純水之槽中。其後,再次將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。 使拉伸壓縮試驗機之上側夾頭下降,利用純水之表面張力使電解用電極樣品接著於離子交換膜表面。此時之接著面係橫130 mm、縱110 mm。將裝入至洗瓶中之純水吹送至電極及離子交換膜整體,製成隔膜、電極再次充分濡濕之狀態。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從上向下滾動,從而將多餘之純水去除。輥僅施加1次。 以10 mm/分鐘之速度使電極上升,開始負荷測定,記錄電極與隔膜之重疊部分成為橫130 mm、縱100 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極與離子交換膜之重疊部分之面積、及與離子交換膜重疊之部分之電極質量,而算出每單位質量·單位面積所承受之力(1)。與離子交換膜重疊之部分之電極質量係根據上述(2)之每單位面積之質量(mg/cm2 )中所獲得之值,藉由比例計算而求出。 測定室之環境係溫度23±2℃、相對濕度30±5%。 再者,實施例、比較例中所使用之電極於接著於藉由表面張力接著於鉛直地固定之鎳板之離子交換膜時,可不下垂或剝離而獨立地接著。 再者,將承受力(1)之評價方法之模式圖示於圖31。 再者,拉伸試驗機之測定下限為0.01(N)。 (4)每單位質量·單位面積所承受之力(2)(接著力)(N/mg・cm2 )) [方法(ii)] 測定係使用拉伸壓縮試驗機(今田製作所股份有限公司,試驗機本體:SDT-52NA型 拉伸壓縮試驗機,負荷計:SL-6001型負荷計)。 將與方法(i)相同之鎳板以成為鉛直之方式固定於拉伸壓縮試驗機之下側之夾頭。 測定所使用之電解用電極樣品(電極)係切成130 mm見方。離子交換膜A係切成170 mm見方。以2塊不鏽鋼板(厚度1 mm、縱9 mm、橫170 mm)夾著電極之一邊,以不鏽鋼板、電極之中心對齊之方式對位後,藉由4個夾具均勻地固定。將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。此時,將對試驗機承受之荷重設為0 N。暫時從拉伸壓縮試驗機卸下不鏽鋼板、電極、夾具一體物,為了利用純水將電極充分濡濕,而浸漬於裝有純水之槽中。其後,再次將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。 使拉伸壓縮試驗機之上側夾頭下降,藉由溶液之表面張力使電解用電極樣品接著於鎳板表面。此時之接著面係橫130 mm、縱110 mm。將裝入至洗瓶中之純水吹送至電極及鎳板整體,製成鎳板、電極再次充分濡濕之狀態。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從上向下滾動,從而將多餘之溶液去除。輥僅施加1次。 以10 mm/分鐘之速度使電極上升,開始負荷測定,記錄電極與鎳板之縱向之重疊部分成為100 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極與鎳板之重疊部分之面積、及與鎳板重疊之部分之電極質量,而算出每單位質量·單位面積所承受之力(2)。與隔膜重疊之部分之電極質量係根據上述(2)之每單位面積之質量(mg/cm2 )中所獲得之值,藉由比例計算而求出。 又,測定室之環境係溫度23±2℃、相對濕度30±5%。 再者,實施例、比較例中所使用之電極於藉由表面張力接著於鉛直地固定之鎳板時,可不下垂或剝離而獨立地接著。 再者,拉伸試驗機之測定下限為0.01(N)。 (5)直徑280 mm圓柱捲繞評價方法(1)(%) (膜與圓柱) 按照以下之順序實施評價方法(1)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸。將離子交換膜於純水中浸漬12小時以上後用於試驗。比較例1及2中電極藉由熱壓製而與離子交換膜成為一體,因此準備離子交換膜與電極之一體物(電極係130 mm見方)。將離子交換膜於純水中充分浸漬後,置於外徑280 mm之塑膠(聚乙烯)製之管之曲面上。其後,藉由將厚度5 mm之獨立發泡型之EPDM海綿橡膠捲繞於氯乙烯管(外徑38 mm)而成之輥將多餘之溶液去除。輥係從圖32所示之模式圖之左側向右側於離子交換膜上滾動。輥僅施加1次。1分鐘後,測定離子交換膜與外徑280 mm之塑膠製之管電極密接之部分之比率。 (6)直徑280 mm圓柱捲繞評價方法(2)(%) (膜與電極) 按照以下之順序實施評價方法(2)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成130 mm見方。將離子交換膜於純水中浸漬12小時以上後用於試驗。將離子交換膜與電極於純水中充分浸漬後進行積層。將該積層體以電極成為外側之方式置於外徑280 mm之塑膠(聚乙烯)製之管之曲面上。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從圖33所示之模式圖之左側向右側滾動,從而將多餘之溶液去除。輥僅施加1次。1分鐘後,測定離子交換膜與電極密接之部分之比率。 (7)直徑145 mm圓柱捲繞評價方法(3)(%) (膜與電極) 按照以下之順序實施評價方法(3)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成130 mm見方。將離子交換膜於純水中浸漬12小時以上後用於試驗。將離子交換膜與電極於純水中充分浸漬後進行積層。將該積層體以電極成為外側之方式置於外徑145 mm之塑膠(聚乙烯)製之管之曲面上。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從圖34所示之模式圖之左側向右側滾動,從而將多餘之溶液去除。輥僅施加1次。1分鐘後,測定離子交換膜與電極密接之部分之比率。 (8)操作性(感應評價) (A)將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成95×110 mm。將離子交換膜於純水中浸漬12小時以上後用於試驗。於各實施例中將離子交換膜與電極於碳酸氫鈉水溶液、0.1 N之NaOH水溶液、純水之三種溶液中充分浸漬後進行積層,靜置於鐵氟龍板上。將電解評價所使用之陽極池與陰極池之間隔設為約3 cm,提起靜置之積層體而實施插入並夾於其間之操作。於實施該操作時一邊操作一邊確認電極是否偏離、掉落。 (B)將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成95×110 mm。將離子交換膜於純水中浸漬12小時以上後用於試驗。於各實施例中將離子交換膜與電極於碳酸氫鈉水溶液、0.1 N之NaOH水溶液、純水之三種溶液中充分浸漬後進行積層,靜置於鐵氟龍板上。手持積層體之膜部分之相鄰的兩處之角,以積層體成為鉛直之方式提起。從該狀態起,以將手持之兩處之角靠近之方式移動,使膜成為凸狀、凹狀。將該操作再重複1次,確認電極對膜之追隨性。基於以下之指標,按照1~4之4個等級對該結果進行評價。 1:操作良好 2:能夠操作 3:操作困難 4:大體無法操作 此處,對於比較例2-5之樣品,以與電極為1.3 m×2.5 m、離子交換膜為1.5 m×2.8 m之尺寸之大型電解池相同之尺寸實施操作。比較例5之評價結果(如下文所述為「3」)係作為對上述(A)、(B)之評價與製成大型尺寸時之不同進行評價之指標。即,於對小型之積層體進行評價所獲得之結果為「1」、「2」之情形時,評價為即使於製成大型尺寸之情形時操作性亦無問題。 (9)電解評價(電壓(V)、電流效率(%)、苛性鈉中食鹽濃度(ppm,50%換算)) 藉由下述電解實驗評價電解性能。 使具有設置有陽極之陽極室之鈦製的陽極池(陽極終端池)與具有設置有陰極之鎳製的陰極室(陰極終端池)之陰極池相對。於池間配置一對墊片,將積層體(離子交換膜A與電解用電極之積層體)夾於一對墊片間。然後,使陽極池、墊片、積層體、墊片及陰極密接而獲得電解池,準備包含該電解池之電解槽。 作為陽極,係藉由將氯化釕、氯化銥及四氯化鈦之混合溶液塗佈於已實施噴擊及酸蝕刻處理作為預處理之鈦基材上並進行乾燥、燒成而製作。陽極係藉由焊接而固定於陽極室。作為陰極,使用各實施例、比較例所記載者。作為陰極室之集電體,使用鎳製多孔金屬。集電體之尺寸為縱95 mm×橫110 mm。作為金屬彈性體,使用以鎳細線編織而成之墊。將作為金屬彈性體之墊置於集電體上。於其上覆蓋以40目之網眼將直徑150 μm之鎳線平織而成之鎳網,藉由利用鐵氟龍(註冊商標)製作之繩將Ni網之四角固定於集電體。以該Ni網作為饋電體。於該電解池中,利用作為金屬彈性體之墊之反彈力而成為零間距結構。作為墊片,使用EPDM(乙烯丙烯二烯)製之橡膠墊片。作為隔膜,使用[方法(i)]中製作之離子交換膜A(160 mm見方)。 使用上述電解池進行食鹽之電解。陽極室之鹽水濃度(氯化鈉濃度)係調整為205 g/L。陰極室之氫氧化鈉濃度係調整為32質量%。以各電解池內之溫度成為90℃之方式調節陽極室及陰極室之各溫度。於電流密度6 kA/m2 下實施食鹽電解,測定電壓、電流效率、苛性鈉中食鹽濃度。此處,所謂電流效率係所生成之苛性鈉之量相對於流通之電流之比率,若藉由流通之電流,雜質離子或氫氧化物離子而非鈉離子於離子交換膜中移動,則電流效率降低。電流效率係藉由一定時間所生成之苛性鈉之莫耳數除以其間流通之電流之電子之莫耳數而求出。苛性鈉之莫耳數係藉由將由電解生成之苛性鈉回收於聚合物槽中,對其質量進行測定而求出。苛性鈉中食鹽濃度表示將苛性鈉濃度換算為50%所得之值。 再者,將實施例、比較例中所使用之電極及饋電體之規格示於表3。 (11)觸媒層之厚度、電解用電極基材、電極之厚度測定 電解用電極基材之厚度係使用電子數顯厚度計(Mitutoyo股份有限公司製造,最少顯示0.001 mm)於面內均勻地測定10點並算出平均值。以此作為電解用電極基材之厚度(量規厚度)。電極之厚度係與電極基材同樣地藉由電子數顯厚度計於面內均勻地測定10點並算出平均值。以此作為電極之厚度(量規厚度)。觸媒層之厚度係藉由電極之厚度減去電解用電極基材之厚度而求出。(12)電極之彈性變形試驗 將[方法(i)]中製作之離子交換膜A(隔膜)及電極切割成110 mm見方之尺寸。將離子交換膜於純水中浸漬12小時以上後用於試驗。於溫度23±2℃、相對濕度30±5%之條件下,將離子交換膜與電極重疊而製作積層體後,如圖35所示般以不產生間隙之方式捲繞至外徑f32 mm、長度20 cm之PVC製管。為了避免捲繞之積層體從PVC製管剝離或鬆動,而使用聚乙烯製之捆束帶加以固定。於該狀態下保持6小時。其後,去除捆束帶,將積層體從PVC製管解捲。僅將電極置於平台上,測定從平台隆起之部分之高度L1 、L2 並求出平均值。以該值作為電極變形之指標。即,值較小意指難以變形。 再者,於使用多孔金屬之情形時,於捲繞時存在SW方向、LW方向之兩種。於本試驗中係沿SW方向捲繞。 又,對於產生變形之電極(未恢復為原來平坦之狀態之電極),藉由如圖36所示之方法對塑性變形後之柔軟程度進行評價。即,將產生變形之電極置於在純水中充分浸漬之隔膜上,將一端固定,將浮起之相反之端部壓抵於隔膜,將力解除,對產生變形之電極是否追隨隔膜進行評價。 (13)膜損傷評價 使用下述之離子交換膜B作為隔膜。 作為強化芯材,使用為聚四氟乙烯(PTFE)且將100丹尼之帶狀紗線以900次/m撚絞而製成紗狀者(以下稱為PTFE紗)。作為經紗之犧牲紗,使用將35丹尼、8根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。又,作為緯紗之犧牲紗,使用將35丹尼、8根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗。首先,以將PTFE紗以24根/英吋配置、將犧牲紗於鄰接之PTFE紗間配置2根之方式進行平織,而獲得厚度100 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.92 mg當量/g之乾燥樹脂之聚合物(A1)、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.10 mg當量/g之乾燥樹脂之聚合物(B1)。使用該等聚合物(A1)及(B1),藉由共擠出T模法獲得聚合物(A1)層之厚度為25 μm、聚合物(B1)層之厚度為89 μm之2層膜X。再者,各聚合物之離子交換容量表示將各聚合物之離子交換基前驅物水解而轉換為離子交換基時之離子交換容量。 又,另行準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.10 mg當量/g之乾燥樹脂之聚合物(B2)。將該聚合物單層擠出而獲得20 μm之膜Y。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙、膜Y、補強材及膜X,於加熱板溫度225℃、減壓度0.022 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)與氫氧化鉀(KOH)之水溶液中浸漬1小時而進行皂化後,於0.5 N之NaOH中浸漬1小時,將離子交換基所附離子取代為Na,繼而進行水洗。進而於60℃下加以乾燥。 又,將以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.05 mg當量/g之乾燥樹脂之聚合物(B3)水解後,藉由鹽酸使其成為酸型。於將該酸型之聚合物(B3')以5質量%之比率溶解於水及乙醇之50/50(質量比)混合液中而成之溶液中,以聚合物(B3')與氧化鋯粒子之質量比成為20/80之方式添加一次粒子之平均粒徑為0.02 μm之氧化鋯粒子。其後,藉由球磨機使其於氧化鋯粒子之懸浮液中分散而獲得懸浮液。 利用噴射法將該懸浮液塗佈於離子交換膜之兩表面並加以乾燥,藉此獲得具有含有聚合物(B3')與氧化鋯粒子之塗佈層之離子交換膜B。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.35 mg/cm2 。 陽極係使用與(9)電解評價相同者。 陰極係使用各實施例、比較例所記載者。陰極室之集電體、墊及饋電體係使用與(9)電解評價相同者。即,以Ni網作為饋電體,利用作為金屬彈性體之墊之反彈力而成為零間距結構。墊片亦使用與(9)電解評價相同者。作為隔膜,使用藉由上述方法所製作之離子交換膜B。即,除了將離子交換膜B與電解用電極之積層體夾持於一對墊片間以外,準備與(9)相同之電解槽。 使用上述電解池進行食鹽之電解。陽極室之鹽水濃度(氯化鈉濃度)係調整為205 g/L。陰極室之氫氧化鈉濃度係調整為32質量%。以各電解池內之溫度成為70℃之方式調節陽極室及陰極室之各溫度。於電流密度8 kA/m2 下實施食鹽電解。從電解開始起12小時後停止電解,取出離子交換膜B並觀察損傷狀態。 「0」意指無損傷。「1至3」意指存在損傷,數字越大,意指損傷之程度越大。 (14)電極之通氣阻力 使用通氣性試驗機KES-F8(商品名,Kato Tech股份有限公司)測定電極之通氣阻力。通氣阻力值之單位為kPa・s/m。將測定實施5次,將其平均值記載於表4。測定係於以下之兩個條件下實施。再者,測定室之溫度設為24℃,相對濕度設為32%。 ・測定條件1(通氣阻力1) 活塞速度:0.2 cm/s 通氣量:0.4 cc/cm2 /s 測定範圍:SENSE L(低) 樣品尺寸:50 mm×50 mm ・測定條件2(通氣阻力2) 活塞速度:2 cm/s 通氣量:4 cc/cm2 /s 測定範圍:SENSE M(中)或H(高) 樣品尺寸:50 mm×50 mm [實施例2-1] 作為陰極電解用電極基材,準備量規厚度為16 μm之電解鎳箔。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 藉由打孔加工於該鎳箔開出圓形之孔而製成多孔箔。開孔率為49%。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。實施例2-1中所製作之電極之厚度為24 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。塗層亦形成於未經粗面化之面。又,為氧化釕與氧化鈰之合計厚度。 將藉由上述方法所製作之電極之接著力之測定結果示於表4。觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 為了將藉由上述方法所製作之電極用於電解評價而將其切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之[方法(i)]中所製作之離子交換膜A(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向,藉由水溶液之表面張力使其等密接。 即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極剝落或偏離之情況。又,即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極剝落或偏離之情況。 將上述膜一體電極以附著有電極之面成為陰極室側之方式夾於陽極池與陰極池之間。剖面結構係從陰極室側起依序排列集電體、墊、鎳網饋電體、電極、膜、陽極而形成零間距結構。 對所獲得之電極進行電解評價。將其結果示於表4。 表現出較低之電壓、較高之電流效率及較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF(螢光X射線分析)測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例2-2] 實施例2-2係使用量規厚度為22 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.96 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為44%。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為29 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0033(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例2-3] 實施例2-3係使用量規厚度為30 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為1.38 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為44%。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為38 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例2-4] 實施例2-4係使用量規厚度為16 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為75%。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為24 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0023(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例2-5] 實施例2-5係準備量規厚度為20 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之兩面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.96 μm。兩面均為相同之粗糙度。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為49%。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為30 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0023(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則兩面均殘存大致100%塗層。若對比實施例2-1~2-4進行考慮,則說明即使不與膜相對向之相反面中塗層較少或不存在,亦能夠發揮出良好之電解性能。 [實施例2-6] 實施例2-6除了藉由離子鍍敷實施對陰極電解用電極基材之塗佈以外,與實施例2-1同樣地實施評價,並將結果示於表4。再者,離子鍍敷係於加熱溫度200℃下使用Ru金屬靶,於氬氣/氧氣環境下以成膜壓力7×10-2 Pa進行製膜。所形成之塗層為氧化釕。 電極之厚度為26 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-7] 實施例2-7係藉由電成形法製作陰極電解用電極基材。光罩之形狀係設為將0.485 mm×0.485 mm之正方形以0.15 mm為間隔縱、橫排列而成之形狀。藉由依序實施曝光、顯影、電鍍,獲得量規厚度為20 μm、開孔率56%之鎳多孔箔。表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為37 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為17 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0032(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-8] 實施例2-8中作為陰極電解用電極基材,係藉由電成形法製作,量規厚度為50 μm,開孔率為56%。表面之算術平均粗糙度Ra為0.73 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為60 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0032(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-9] 實施例2-9係使用量規厚度為150 μm、空隙率為76%之鎳不織布(NIKKO TECHNO股份有限公司製造)作為陰極電解用電極基材。不織布之鎳纖維直徑約為40 μm,單位面積重量為300 g/m2 。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為165 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為15 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為29 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0612(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例2-10] 實施例2-10係使用量規厚度為200 μm、空隙率為72%之鎳不織布(NIKKO TECHNO股份有限公司製造)作為陰極電解用電極基材。不織布之鎳纖維直徑約為40 μm,單位面積重量為500 g/m2 。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為215 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為15 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為40 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0164(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例2-11] 實施例2-11係使用量規厚度為200 μm、空隙率為72%之發泡鎳(Mitsubishi Materials股份有限公司製造)作為陰極電解用電極基材。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 又,電極之厚度為210 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為17 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0402(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例2-12] 實施例2-12係使用線徑50 μm、200目、量規厚度為100 μm、開孔率為37%之鎳網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。即使實施噴擊處理,開孔率亦不變化。由於難以測定金屬絲網表面之粗糙度,因此於實施例2-12中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。1根金屬絲網之算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為110 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0154(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-13] 實施例2-13係使用線徑65 μm、150目、量規厚度為130 μm、開孔率為38%之鎳網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。即使實施噴擊處理,開孔率亦不變化。由於難以測定金屬絲網表面之粗糙度,因此於實施例2-13中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.66 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施上述評價,並將結果示於表4。 電極之厚度為133 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為3 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為6.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0124(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價亦為「0」而較良好。 [實施例2-14] 實施例2-14係使用與實施例2-3相同之基材(量規厚度30 μm,開孔率44%)作為陰極電解用電極基材。除了未設置鎳網饋電體以外,以與實施例2-1相同之構成實施電解評價。即,電解池之剖面結構係從陰極室側起依序排列集電體、墊、膜一體電極、陽極而形成零間距結構,墊作為饋電體發揮功能。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-15] 實施例2-15係使用與實施例2-3相同之基材(量規厚度30 μm,開孔率44%)作為陰極電解用電極基材。設置參考例1中使用之劣化且電解電壓變高之陰極代替鎳網饋電體。除此以外,以與實施例2-1相同之構成實施電解評價。即,電解池之剖面結構係從陰極室側起依序排列集電體、墊、劣化且電解電壓變高之陰極(作為饋電體發揮功能)、電解用電極(陰極)、隔膜、陽極而形成零間距結構,劣化且電解電壓變高之陰極作為饋電體發揮功能。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-16] 作為陽極電解用電極基材,準備量規厚度為20 μm之鈦箔。對鈦箔之兩面實施粗面化處理。對該鈦箔實施打孔加工,開出圓形之孔而製成多孔箔。孔之直徑為1 mm,開孔率為14%。表面之算術平均粗糙度Ra為0.37 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素、銥元素及鈦元素之莫耳比成為0.25:0.25:0.5之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、銥濃度為100 g/L之氯化銥(田中貴金屬工業股份有限公司)、四氯化鈦(和光純藥工業股份有限公司)加以混合。將該混合液充分攪拌,以其作為陽極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。於鈦多孔箔塗佈上述塗佈液後,於60℃下實施10分鐘之乾燥,於475℃下實施10分鐘之燒成。重複實施該等塗佈、乾燥、預燒成、燒成之一系列之操作後,於520℃下進行1小時之燒成。 為了將藉由上述方法所製作之電極用於電解評價而將其切成縱95 mm、橫110 mm之尺寸。藉由水溶液之表面張力使其密接於利用0.1 N之NaOH水溶液平衡之[方法(i)]中製作之離子交換膜A(尺寸為160 mm×160 mm)之磺酸層側的大致中央之位置。 陰極係按照以下之順序製備。首先,準備線徑150 μm、40目之鎳製金屬絲網作為基材。作為預處理而藉由氧化鋁實施噴擊處理後,於6 N之鹽酸中浸漬5分鐘,並利用純水充分洗淨、乾燥。 繼而,以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、氯化鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於300℃下實施3分鐘之預燒成,於550℃下實施10分鐘之燒成。其後,於550℃下實施1小時之燒成。重複進行該等塗佈、乾燥、預燒成、燒成之一系列之操作。 作為陰極室之集電體,使用鎳製多孔金屬。集電體之尺寸為縱95 mm×橫110 mm。作為金屬彈性體,使用以鎳細線編織而成之墊。將作為金屬彈性體之墊置於集電體上。於其上覆蓋藉由上述方法製作之陰極,藉由利用鐵氟龍(註冊商標)製作之繩將網之四角固定於集電體。 即使抓持膜與陽極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極剝落或偏離之情況。又,即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極剝落或偏離之情況。 藉由焊接將參考例3中所使用之劣化且電解電壓變高之陽極固定於陽極池,將上述膜一體電極以附著有電極之面成為陽極室側之方式夾於陽極池與陰極池之間。即,電解池之剖面結構係從陰極室側起依序排列集電體、墊、陰極、隔膜、電解用電極(鈦多孔箔陽極)、劣化且電解電壓變高之陽極,形成零間距結構。劣化且電解電壓變高之陽極作為饋電體發揮功能。再者,鈦多孔箔陽極與劣化且電解電壓變高之陽極之間僅係物理接觸,並未藉由焊接進行固定。 藉由該構成,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為26 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為6 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為4 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0060(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-17] 實施例2-17係使用量規厚度20 μm、開孔率30%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.37 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-16同樣地實施評價,並將結果示於表4。 電極之厚度為30 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0030(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-18] 實施例2-18係使用量規厚度20 μm、開孔率42%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.38 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-16同樣地實施評價,並將結果示於表4。 電極之厚度為32 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為12 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為2.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0022(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-19] 實施例2-19係使用量規厚度50 μm、開孔率47%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.40 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-16同樣地實施評價,並將結果示於表4。 電極之厚度為69 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為19 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為8 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0024(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-20] 實施例2-20係使用量規厚度100 μm、鈦纖維直徑約為20 μm、單位面積重量為100 g/m2 、開孔率78%之鈦不織布作為陽極電解用電極基材。除此以外,與實施例2-16同樣地實施評價,並將結果示於表4。 電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為2 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0228(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-21] 實施例2-21係使用量規厚度120 μm、鈦纖維直徑約為60 μm、150目之鈦金屬絲網作為陽極電解用電極基材。開孔率為42%。藉由粒編號320之氧化鋁實施噴擊處理。由於難以測定金屬絲網表面之粗糙度,因此於實施例2-21中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.60 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-16同樣地實施評價,並將結果示於表4。 電極之厚度為140 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為20 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為10 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0132(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例2-22] 實施例2-22係與實施例2-16同樣地使用劣化且電解電壓變高之陽極作為陽極饋電體,使用與實施例2-20相同之鈦不織布作為陽極。與實施例2-15同樣地使用劣化且電解電壓變高之陰極作為陰極饋電體,使用與實施例2-3相同之鎳箔電極作為陰極。電解池之剖面結構係從陰極室側起,依序排列集電體、墊、劣化且電壓變高之陰極、鎳多孔箔陰極、隔膜、鈦不織布陽極、劣化且電解電壓變高之陽極而形成零間距結構,劣化且電解電壓變高之陰極及陽極作為饋電體發揮功能。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極(陽極)之厚度為114 μm,觸媒層之厚度係電極(陽極)之厚度減去電解用電極基材之厚度而為14 μm。又,電極(陰極)之厚度為38 μm,觸媒層之厚度係電極(陰極)之厚度減去電解用電極基材之厚度而為8 μm。 於陽極及陰極均觀測到充分之接著力。 實施電極(陽極)之變形試驗,結果L1 、L2 之平均值為2 mm。實施電極(陰極)之變形試驗,結果L1 、L2 之平均值為0 mm。 測定電極(陽極)之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0228(kPa・s/m)。測定電極(陰極)之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。陽極及陰極中膜損傷評價均亦為「0」而較良好。再者,於實施例2-22中,於隔膜之單面貼附陰極,於相反之面貼附陽極,將陰極及陽極組合進行膜損傷評價。 [實施例2-23] 於實施例2-23中係使用Agfa公司製造之微多孔膜「Zirfon Perl UTP 500」。 Zirfon膜係於純水中浸漬12小時以上後用於試驗。除此以外,與實施例2-3同樣地實施上述評價,並將結果示於表4。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 與使用離子交換膜作為隔膜時相同,觀測到充分之接著力,微多孔膜與電極藉由表面張力而密接,操作性為「1」而較良好。 [實施例2-24] 作為陰極電解用電極基材,準備量規厚度為566 μm之紡織碳纖維而成之碳布。按照以下之順序製備用以於該碳布形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088(商品名),厚度10 mm)而成之塗佈滾筒與上述塗佈液始終相接之方式設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。所製作之電極之厚度為570 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為4 μm。觸媒層之厚度為氧化釕與氧化鈰之合計厚度。 對所獲得之電極進行電解評價。將其結果示於表4。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。 測定電極之通氣阻力,結果於測定條件1下為0.19(kPa・s/m),於測定條件2下為0.176(kPa・s/m)。 又,操作性為「2」,可判斷能夠作為大型積層體進行操作。 電壓較高,膜損傷評價為「1」,確認到膜損傷。認為其原因在於:由於實施例2-24之電極之通氣阻力較大,因此電極中產生之NaOH滯留於電極與隔膜之界面而成為高濃度。 [參考例1] 於參考例1中,作為陰極而使用於大型電解槽中使用8年、劣化且電解電壓變高之陰極。於陰極室之墊上設置上述陰極代替鎳網饋電體,隔著[方法(i)]中製作之離子交換膜A實施電解評價。於參考例1中不使用膜一體電極,電解池之剖面結構係從陰極室側起,依序排列集電體、墊、劣化且電解電壓變高之陰極、離子交換膜A、陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.04 V,電流效率為97.0%,苛性鈉中食鹽濃度(50%換算值)為20 ppm。由於陰極劣化,因此結果為電壓較高 [參考例2] 於參考例2中,使用鎳網饋電體作為陰極。即,藉由未形成觸媒塗層之鎳網實施電解。 將鎳網陰極設置於陰極室之墊上,隔著[方法(i)]中製作之離子交換膜A實施電解評價。參考例2之電池之剖面結構係從陰極室側起,依序排列集電體、墊、鎳網、離子交換膜A、陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.38 V,電流效率為97.7%,苛性鈉中食鹽濃度(50%換算值)為24 ppm。由於未塗佈陰極觸媒,因此結果為電壓較高。 [參考例3] 於參考例3中,作為陽極而使用於大型電解槽中使用約8年、劣化且電解電壓變高之陽極。 參考例3之電解池之剖面結構係從陰極室側起,依序排列集電體、墊、陰極、[方法(i)]中製作之離子交換膜A、劣化且電解電壓變高之陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.18 V,電流效率為97.0%,苛性鈉中食鹽濃度(50%換算值)為22 ppm。由於陽極劣化,因此結果為電壓較高。 [實施例2-25] 於實施例2-25中,使用全滾筒加工後之量規厚度100 μm、開孔率33%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例2-25中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.68 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 每單位面積之質量為67.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.05(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為64%,直徑145 mm圓柱捲繞評價(3)之結果為22%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為13 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0168(kPa・s/m)。 [實施例2-26] 於實施例2-26中,使用全滾筒加工後之量規厚度100 μm、開孔率16%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例2-26中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為107 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。 每單位面積之質量為78.1(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.04(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為37%,直徑145 mm圓柱捲繞評價(3)之結果為25%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為18.5 mm。測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0176(kPa・s/m)。 [實施例2-27] 實施例2-27係使用全滾筒加工後之量規厚度為100 μm、開孔率為40%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例2-27中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.70 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。對電解用電極基材之塗佈係藉由與實施例2-6同樣之離子鍍敷實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為110 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 每單位質量·單位面積所承受之力(1)為0.07(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為80%,直徑145 mm圓柱捲繞評價(3)之結果為32%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「3」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為11 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0030(kPa・s/m)。 [實施例2-28] 實施例2-28係使用全滾筒加工後之量規厚度為100 μm、開孔率為58%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例2-28中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為109 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為9 μm。 每單位質量·單位面積所承受之力(1)為0.06(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為69%,直徑145 mm圓柱捲繞評價(3)之結果為39%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「3」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為11.5 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 [實施例2-29] 實施例2-29係使用量規厚度為300 μm、開孔率為56%之鎳金屬絲網作為陰極電解用電極基材。由於難以測定金屬絲網之表面粗糙度,因此於實施例2-29中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施評價,並將結果示於表4。 電極之厚度為308 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為49.2(mg/cm2 )。因此,直徑280 mm圓柱捲繞評價(2)之結果為88%,直徑145 mm圓柱捲繞評價(3)之結果為42%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況,操作性為「3」,存在問題。實際中以大型尺寸進行操作,可評價為「3」。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為23 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0034(kPa・s/m)。 [實施例2-30] 於實施例2-30中使用量規厚度200 μm、開孔率37%之鎳金屬絲網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定金屬絲網之表面粗糙度,因此於實施例2-30中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.65 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-1同樣地實施電極電解評價、接著力之測定結果、密接性。將結果示於表4。 電極之厚度為210 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 每單位面積之質量為56.4 mg/cm2 。因此,直徑145 mm圓柱捲繞評價方法(3)之結果為63%,電極與隔膜之密接性較差。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況,操作性為「3」,存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為19 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0096(kPa・s/m)。 [實施例2-31] 於實施例2-31中使用全滾筒加工後之量規厚度500 μm、開孔率17%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例2-31中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.60 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-16同樣地實施評價,並將結果示於表4。 又,電極之厚度為508 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為152.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0072(kPa・s/m)。 [實施例2-32] 於實施例2-32中,使用全滾筒加工後之量規厚度800 μm、開孔率8%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例2-32中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.61 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-16同樣地實施上述評價,並將結果示於表4。 電極之厚度為808 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為251.3(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0172(kPa・s/m)。 [實施例2-33] 於實施例2-33中,使用全滾筒加工後之量規厚度1000 μm、開孔率46%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例2-33中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.59 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例2-16同樣地實施上述評價,並將結果示於表4。 又,電極之厚度為1011 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為11 μm。 每單位面積之質量為245.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 [實施例2-34] 準備量規厚度為150 μm之鎳線作為陰極電解用電極基材。實施利用該鎳線之粗面化處理。由於難以測定鎳線之表面粗糙度,因此於實施例2-34中於噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為鎳線之表面粗糙度。藉由粒編號320之氧化鋁實施噴擊處理。算術平均粗糙度Ra為0.64 μm。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088(商品名),厚度10 mm)而成之塗佈滾筒與上述塗佈液始終相接之方式設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。實施例2-34中所製作之鎳線1根之厚度為158 μm。 將藉由上述方法所製作之鎳線切成110 mm及95 mm之長度。如圖37所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由瞬間接著劑(Aron Alpha(註冊商標),東亞合成股份有限公司)將交點部分接著而製作電極。對電極實施評價,將其結果示於表4。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為99.7%。 電極之每單位面積之質量為0.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為15 mm。 測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力值為0.0002(kPa・s/m)。 又,對於電極,使用圖38所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓成為3.16 V,較高。 [實施例2-35] 於實施例2-35中,使用實施例2-34中所製作之電極,如圖39所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由瞬間接著劑(Aron Alpha(註冊商標),東亞合成股份有限公司)將交點部分接著而製作電極。對電極實施評價,將其結果示於表4。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為99.4%。 電極之每單位面積之質量為0.9(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為16 mm。 測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力為0.0004(kPa・s/m)。 又,對於電極,使用圖40所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓為3.18 V,較高。 [實施例2-36] 於實施例2-36中,使用實施例2-34中所製作之電極,如圖41所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由瞬間接著劑(Aron Alpha(註冊商標),東亞合成股份有限公司)將交點部分接著而製作電極。對電極實施評價,將其結果示於表4。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為98.8%。 電極之每單位面積之質量為1.9(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為14 mm。 又,測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力為0.0005(kPa・s/m)。 又,對於電極,使用圖42所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓為3.18 V,較高。 [比較例2-1] 於比較例2-1中以先前文獻(日本專利特開昭58-48686之實施例)作為參考,製作將電極熱壓接於隔膜之熱壓接接合體。 使用量規厚度100 μm、開孔率33%之鎳多孔金屬作為陰極電解用電極基材,與實施例2-1同樣地實施電極塗佈。其後,按照下述之順序對電極之單面實施惰性化處理。於電極之單面貼附聚醯亞胺黏著帶(中興化成股份有限公司),於相反面塗佈PTFE分散液(DuPont-Mitsui Fluorochemicals股份有限公司,31-JR(商品名)),於120℃之馬弗爐中乾燥10分鐘。將聚醯亞胺膠帶剝離,於設定為380℃之馬弗爐中實施10分鐘燒結處理。將該操作重複2次,對電極之單面進行惰性化處理。 製作由末端官能基為「-COOCH3 」之全氟碳聚合物(C聚合物)與末端基為「-SO2 F」之全氟碳聚合物(S聚合物)之2層所形成之膜。C聚合物層之厚度為3密耳(mil),S聚合物層之厚度為4密耳(mil)。對該2層膜實施皂化處理,藉由水解對聚合物之末端導入離子交換基。C聚合物末端被水解為羧酸基,S聚合物末端被水解為磺基。以磺酸基計之離子交換容量為1.0 meq/g,以羧酸基計之離子交換容量為0.9 meq/g。 使具有羧酸基作為離子交換基之面與經惰性化之電極面相對向,並實施熱壓製,而將離子交換膜與電極一體化。熱壓接後電極之單面亦為露出之狀態,不存在電極貫通膜之部分。 其後,為了抑制電解中產生之氣泡對膜之附著,將導入有氧化鋯與磺基之全氟碳聚合物混合物塗佈於兩面。由此製作比較例2-1之熱壓接接合體。 使用該熱壓接接合體,測定每單位質量·單位面積所承受之力(1),結果由於藉由熱壓接將電極與膜強力接合,因此電極未向上方移動。因此,以不移動離子交換膜與鎳板之方式進行固定,藉由更強之力將電極向上方拉拽,結果於承受1.50(N/mg・cm2 )之力時,膜之一部分破裂。比較例2-1之熱壓接接合體之每單位質量·單位面積所承受之力(1)至少為1.50(N/mg・cm2 ),被強力地接合。 實施直徑280 mm圓柱捲繞評價(1),結果與塑膠製管之接觸面積未達5%。另一方面,實施直徑280 mm圓柱捲繞評價(2),結果雖然電極與膜100%接合,但最初隔膜並未捲繞至圓柱。直徑145 mm圓柱捲繞評價(3)之結果亦相同。該結果意指膜之操作性因一體化之電極而受損,而難以捲繞為滾筒狀、或加以彎折。操作性為「3」,存在問題。膜損傷評價為「0」。又,實施電解評價,結果電壓變高,電流效率變低,苛性鈉中之食鹽濃度(50%換算值)變高,電解性能變差。 又,電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 實施電極之變形試驗,結果L1 、L2 之平均值為13 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0168(kPa・s/m)。 [比較例2-2] 比較例2-2係使用線徑150 μm、40目、量規厚度300 μm、開孔率58%之鎳網作為陰極電解用電極基材。除此以外,與比較例2-1同樣地製作熱壓接接合體。 使用該熱壓接接合體,測定每單位質量·單位面積所承受之力(1),結果由於藉由熱壓接將電極與膜強力接合,因此電極未向上方移動。因此,以不移動離子交換膜與鎳板之方式進行固定,藉由更強之力將電極向上方拉拽,結果於承受1.60(N/mg・cm2 )之力時,膜之一部分破裂。比較例2-2之熱壓接接合體之每單位質量·單位面積所承受之力(1)至少為1.60(N/mg・cm2 ),被強力地接合。 使用該熱壓接接合體實施直徑280 mm圓柱捲繞評價(1),結果與塑膠製管之接觸面積未達5%。另一方面,實施直徑280 mm圓柱捲繞評價(2),結果雖然電極與膜100%接合,但最初隔膜並未捲繞至圓柱。直徑145 mm圓柱捲繞評價(3)之結果亦相同。該結果意指膜之操作性因一體化之電極而受損,而難以捲繞為滾筒狀、或加以彎折。操作性為「3」,存在問題。又,實施電解評價,結果電壓變高,電流效率變低,苛性鈉中之食鹽濃度變高,電解性能變差。 又,電極之厚度為308 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 實施電極之變形試驗,結果L1 、L2 之平均值為23 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0034(kPa・s/m)。 [表3] [表4] 於表4中,全部樣品於「每單位質量·單位面積所承受之力(1)」及「每單位質量·單位面積所承受之力(2)」之測定前可藉由表面張力而自立(即,不存在下垂之情況)。 <第3實施形態之驗證> 如下所述準備與第3實施形態相對應之實驗例(於以下之<第3實施形態之驗證>之項中簡稱為「實施例」)、及不與第3實施形態相對應之實驗例(於以下之<第3實施形態之驗證>之項中簡稱為「比較例」),藉由以下方法對該等進行評價。一邊適當參照圖57~62一邊對其詳細內容進行說明。 (1)電解評價(電壓(V)、電流效率(%)) 藉由下述電解實驗評價電解性能。 使具有設置有陽極之陽極室之鈦製的陽極池(陽極終端池)與具有設置有陰極之鎳製的陰極室(陰極終端池)之陰極池相對。於池間配置一對墊片,將離子交換膜夾於一對墊片間。然後,使陽極池、墊片、離子交換膜、墊片及陰極密接而獲得電解池。 作為陽極,係藉由將氯化釕、氯化銥及四氯化鈦之混合溶液塗佈於已實施噴擊及酸蝕刻處理作為預處理之鈦基材上並進行乾燥、燒成而製作。陽極係藉由焊接而固定於陽極室。作為陰極,使用各實施例、比較例所記載者。作為陰極室之集電體,使用鎳製多孔金屬。集電體之尺寸為縱95 mm×橫110 mm。作為金屬彈性體,使用以鎳細線編織而成之墊。將作為金屬彈性體之墊置於集電體上。於其上覆蓋以40目之網眼將直徑150 μm之鎳線平織而成之鎳網,藉由利用鐵氟龍(註冊商標)製作之繩將Ni網之四角固定於集電體。以該Ni網作為饋電體。於該電解池中,利用作為金屬彈性體之墊之反彈力而設為零間距結構。作為墊片,使用EPDM(乙烯丙烯二烯)製之橡膠墊片。作為隔膜,使用下述之離子交換膜。 作為強化芯材,使用聚四氟乙烯(PTFE)製且90丹尼之單絲(以下稱為PTFE紗)。作為犧牲紗,使用35丹尼、6根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗。首先,以沿TD及MD之兩方向之各方向以24根/英吋配置PTFE紗、且於鄰接之PTFE紗間配置2根犧牲紗之方式進行平織而獲得織布。藉由滾筒將所獲得之織布進行壓接而獲得厚度70 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.85 mg當量/g之乾燥樹脂之樹脂A、以CF2 =CF2 與CF2 =CFOCF2 CF(CF2 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之乾燥樹脂之樹脂B。 使用該等樹脂A及B,藉由共擠出T模法獲得樹脂A層之厚度為15 μm、樹脂B層之厚度為104 μm之2層膜X。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙(高度50 μm之圓錐形狀之壓紋加工)、補強材及膜X,於加熱板表面溫度223℃、減壓度0.067 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。 藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)30質量%、氫氧化鉀(KOH)15質量%之80℃之水溶液中浸漬20分鐘而進行皂化。其後,於含有氫氧化鈉(NaOH)0.5 N之50℃之水溶液中浸漬1小時,將離子交換基之抗衡離子置換為Na,繼而進行水洗。進而於60℃下加以乾燥。 進而,於樹脂B之酸型樹脂之5質量%乙醇溶液添加平均粒徑(1次粒子徑)1 μm之氧化鋯20質量%並使其分散而調製懸浮液,藉由懸浮液噴射法對上述複合膜之兩面進行噴霧,於複合膜之表面形成氧化鋯之塗層,而獲得離子交換膜。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.5 mg/cm2 。再者,平均粒徑係利用粒度分佈計(例如,島津製作所製造之「SALD(註冊商標)2200」)進行測定。 使用上述電解池進行食鹽之電解。陽極室之鹽水濃度(氯化鈉濃度)係調整為205 g/L。陰極室之氫氧化鈉濃度係調整為32質量%。以各電解池內之溫度成為90℃之方式調節陽極室及陰極室之各溫度。於電流密度6 kA/m2 下實施食鹽電解,測定電壓、電流效率。此處,所謂電流效率係所生成之苛性鈉之量相對於流通之電流之比率,若藉由流通之電流,雜質離子或氫氧化物離子而非鈉離子於離子交換膜中移動,則電流效率降低。電流效率係藉由一定時間所生成之苛性鈉之莫耳數除以其間流通之電流之電子之莫耳數而求出。苛性鈉之莫耳數係藉由將由電解生成之苛性鈉回收於聚合物槽中,對其質量進行測定而求出。 (2)操作性(感應評價) (A)將上文所述之離子交換膜(隔膜)切割成170 mm見方之尺寸,將下文所述之實施例及比較例中獲得之電極切割成95×110 mm。將離子交換膜與電極積層,靜置於鐵氟龍板上。將電解評價所使用之陽極池與陰極池之間隔設為約3 cm,提起靜置之積層體而實施插入並夾於其間之操作。於實施該操作時一邊操作一邊確認電極是否偏離、掉落。 (B)與上述(A)同樣地將積層體靜置於鐵氟龍板上。手持積層體之膜部分之相鄰的兩處之角,以積層體成為鉛直之方式提起。從該狀態起,以將手持之兩處之角靠近之方式移動,使膜成為凸狀、凹狀。將該操作再重複1次,確認電極對膜之追隨性。基於以下之指標,按照1~4之4個等級對該結果進行評價。 1:操作良好 2:能夠操作 3:操作困難 4:大體無法操作 此處,對於實施例3-4、3-6之樣品,如下文所述,即使為與大型電解池相同之尺寸亦對操作性進行評價。實施例3-4、3-6之評價結果係作為對上述(A)、(B)之評價與製成大型尺寸時之不同進行評價之指標。即,於對小型之積層體進行評價所獲得之結果為「1」、「2」之情形時,評價為即使於製成大型尺寸之情形時操作性亦良好。 (3)固定區域之比率 以離子交換膜中之與電解用電極相反之面之面積(與通電面相對應之部分及與非通電面相對應之部分之合計)作為面積S1而算出。繼而,以電解用電極之面積作為通電面之面積S2而算出。面積S1及S2係以從電解用電極側觀察離子交換膜與電解用電極之積層體時(參照圖57)之面積特定出。再者,由於電解用電極之形狀即使具有開孔,開孔率亦未達90%,因此將該電解用電極視為平板(開孔部分亦算入面積)。 關於固定區域之面積S3,亦如圖57般作為俯視積層體時之面積而特定出(僅與通電面相對應之部分之面積S3'亦同樣)。再者,於將下文所述之PTFE膠帶作為固定用構件進行固定之情形時,膠帶之重複部分並不算入面積中。又,於將下文所述之PTFE紗或接著劑作為固定用構件進行固定之情形時,亦將存在於電極、隔膜之背面側之面積包含在內算入面積中。 如上所述,作為離子交換膜中之固定區域之面積相對於與電解用電極相反之面之面積的比率α(%),算出100×(S3/S1)。進而,作為固定區域之僅與通電面相對應之部分之面積相對於通電面之面積之比率β,算出100×S3'/S2。[實施例3-1] 準備量規厚度為22 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.96 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 藉由打孔加工於該鎳箔開出圓形之孔而製成多孔箔。開孔率為44%。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。實施例3-1中所製作之電極之厚度為24 μm。含有氧化釕與氧化鈰之觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。塗層亦形成於未經粗面化之面。 為了將藉由上述方法所製作之電極用於電解評價而將其切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之離子交換膜(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向而配置。使用PTFE膠帶(日東電工製造),如圖57所示般(但圖57僅為用以說明之概要圖,尺寸未必準確。以下之圖亦同樣),以夾著離子交換膜與電極之方式將4邊固定。於實施例3-1中,PTFE膠帶係固定用構件,比率α為60%,比率β為1.0%。 即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極剝落或偏離之情況。又,即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極剝落或偏離之情況。 將上述膜一體電極以附著有電極之面成為陰極室側之方式夾於陽極池與陰極池之間。剖面結構係從陰極室側起依序排列集電體、墊、鎳網饋電體、電極、膜、陽極而形成零間距結構。 對所獲得之電極進行評價。將其結果示於表5。 表現出較低之電壓、較高之電流效率。操作性亦為「2」而相對較良好。 [實施例3-2] 如圖58所示,除了增加PTFE膠帶重疊於電解面之面積以外,與實施例3-1同樣地實施評價。即,於實施例3-2中,由於設為PTFE膠帶之面積沿電解用電極之面內方向增加,因此電解用電極中之電解面之面積與實施例3-1相比有所減少。於實施例3-2中,比率α為69%,比率β為23%。將評價之結果示於表5。 表現出較低之電壓、較高之電流效率。操作性亦為「1」而較良好。 [實施例3-3] 如圖59所示,除了增加PTFE膠帶重疊於電解面之面積以外,與實施例3-1同樣地實施評價。即,於實施例3-3中,由於設為PTFE膠帶之面積沿電解用電極之面內方向增加,因此電解用電極中之電解面之面積與實施例3-1相比有所減少。於實施例3-3中,比率α為87%,比率β為67%。將評價之結果示於表5。 表現出較低之電壓、較高之電流效率。操作性亦為「1」而較良好。 [實施例3-4] 準備與實施例3-1相同之電極,為了用於電解評價而切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之離子交換膜(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向而配置。使用PTFE製之紗,如圖60所示,以使電極之左側縱向延伸之方式縫製離子交換膜與電極。從距電極之角部縱向10 mm、橫向10 mm之部分起,使PTFE紗從圖60之紙面背面側向正面側貫通,於縱向35 mm、橫向10 mm之部分從紙面正面側向背面側貫通,於縱向60 mm、橫向10 mm之部分再次使紗從紙面背面側向正面側貫通,於縱向85 mm、橫向10 mm之部分從紙面正面側向背面側貫通。於紗貫通離子交換膜之部分塗佈將以CF2 =CF2 與CF2 =CFOCF2 CF(CF2 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之樹脂之酸型樹脂S以成為5質量%之方式分散於乙醇中而成之溶液。 如上所述,於實施例3-4中,比率α為0.35%,比率β為0.86%。 即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極掉落之情況。即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極掉落之情況。 對所獲得之電極進行評價。將其結果示於表5。 表現出較低之電壓、較高之電流效率。操作性亦為「2」而相對較良好。 進而,於實施例3-4中,準備變更為大型尺寸之離子交換膜、電極。準備4片縱1.5 m、橫2.5 m之離子交換膜、及縱0.3 m、橫2.4 m之陰極。以無間隙之方式將陰極排列於離子交換膜之羧酸層側,藉由PTFE紗將陰極與離子交換膜接著而製作積層體。於該例中,比率α為0.013%,比率β為0.017%。 實施將膜與電極成為一體之膜一體電極安裝於大型電解槽之操作,能夠順利地安裝。[實施例3-5] 準備與實施例3-1相同之電極,為了用於電解評價而切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之離子交換膜(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向而配置。使用圖61所示之聚丙烯製之固定用樹脂,將離子交換膜與電極加以固定。即,設置於距電極之角部縱向20 mm、橫向20 mm之部分中1處、距位於其下方之角部縱向20 mm、橫向20 mm之部分中進而1處之合計2處。於固定用樹脂貫通離子交換膜之部分塗佈與實施例3-4相同之溶液。 如上所述,於實施例3-5中,固定用樹脂及樹脂S成為固定用構件,比率α為0.47%,比率β為1.1%。 即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極掉落之情況。即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極掉落之情況。 對所獲得之電極進行評價。將其結果示於表5。 表現出較低之電壓、較高之電流效率。操作性亦為「2」而相對較良好。[實施例3-6] 準備與實施例3-1相同之電極,為了用於電解評價而切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之離子交換膜(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向而配置。如圖62所示,使用氰基丙烯酸酯系接著劑(商品名:Aron Alpha,東亞合成股份有限公司),將離子交換膜與電極加以固定。即,藉由接著劑於電極之縱向之1邊中5處(均為等間隔)、及電極之橫向之1邊中8處(均為等間隔)進行固定。 如上所述,於實施例3-6中,接著劑成為固定用構件,比率α為0.78%,比率β為1.9%。即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極掉落之情況。即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極掉落之情況。 對所獲得之電極進行評價。將其結果示於表5。 表現出較低之電壓、較高之電流效率。操作性為「1」,亦相對較良好。進而,於實施例3-6中,準備變更為大型尺寸之離子交換膜、電極。準備4片縱1.5 m、橫2.5 m之離子交換膜、及縱0.3 m、橫2.4 m之陰極。藉由上述接著劑將4片陰極之橫向之1邊彼此之緣部分相連,製成1片大型陰極(縱1.2 m、橫2.4 m)。藉由Aron Alpha將該大型陰極接著於離子交換膜之羧酸層側中央部分而製作積層體。即,與圖62同樣地,藉由接著劑於電極之縱向之1邊中5處(均為等間隔)、及於電極之橫向之1邊中8處(均為等間隔)進行固定。於該例中,比率α為0.019%,比率β為0.024%。 實施將膜與電極成為一體之膜一體電極安裝於大型電解槽之操作,能夠順利地安裝。[實施例3-7] 準備與實施例3-1相同之電極,為了用於電解評價而切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之離子交換膜(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向而配置。塗佈與實施例3-4相同之溶液,將離子交換膜與電極固定。即,設置於距電極之角部縱向20 mm、橫向20 mm之部分中1處、距位於其下方之角部縱向20 mm、橫向20 mm之部分進而1處之合計2處(參照圖61)。 如上所述,於實施例3-7中,樹脂S成為固定用構件,比率α為2.0%,比率β為4.8%。即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極掉落之情況。即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極掉落之情況。 對所獲得之電極進行評價。將其結果示於表5。 表現出較低之電壓、較高之電流效率。操作性亦為「2」而相對較良好。 [比較例3-1] 除了增加PTFE膠帶重疊於電解面之面積以外,與實施例3-1同樣地實施評價。即,於比較例3-1中,由於設為PTFE膠帶之面積沿電解用電極之面內方向增加,因此電解用電極中之電解面之面積與實施例3-1相比有所減少。於比較例3-1中,比率α為93%,比率β為83%。將評價之結果示於表5。 電壓較高,電流效率亦較低。操作性為「1」,較良好。 [比較例3-2] 除了增加PTFE膠帶重疊於電解面之面積以外,與實施例3-1同樣地實施評價。將評價之結果示於表5。即,於比較例3-2中,使PTFE膠帶之面積沿電解用電極之面內方向增加。 於比較例3-2中,比率α及比率β為100%,電解面整個面為由PTFE覆蓋之固定區域,因此無法供給電解液而無法進行電解。操作性為「1」,較良好。 [比較例3-3] 除了不使用PTFE膠帶、即比率α及比率β為0%以外,與實施例3-1同樣地實施評價。將評價之結果示於表5。 表現出較低之電壓、較高之電流效率。另一方面,由於不存在隔膜與電極之固定區域,因此無法將隔膜與電極作為積層體(一體物)進行處理,操作性為「4」。 將實施例3-1~7及比較例3-1~3之評價結果合併示於下述之表5。 [表5] <第4實施形態之驗證> 如下所述準備與第4實施形態相對應之實驗例(於以下之<第4實施形態之驗證>之項中簡稱為「實施例」)、及不與第4實施形態相對應之實驗例(於以下之<第4實施形態之驗證>之項中簡稱為「比較例」),藉由以下方法對該等進行評價。一邊適當參照圖79~90一邊對其詳細內容進行說明。 [評價方法] (1)開孔率 將電極切成130 mm×100 mm之尺寸。使用電子數顯厚度計(Mitutoyo股份有限公司製造,最少顯示0.001 mm)於面內均勻地測定10點,並算出平均值。以其作為電極之厚度(量規厚度)而算出體積。其後,利用電子天平測定質量,根據金屬之比重(鎳之比重=8.908 g/cm3 、鈦之比重=4.506 g/cm3 )算出開孔率或空隙率。 開孔率(空隙率)(%)=(1-(電極質量)/(電極體積×金屬之比重))×100 (2)每單位面積之質量(mg/cm2 ) 將電極切成130 mm×100 mm之尺寸,利用電子天平測定質量。用該值除以面積(130 mm×100 mm)而算出每單位面積之質量。 (3)每單位質量·單位面積所承受之力(1)(接著力)(N/mg・cm2 )) [方法(i)] 測定係使用拉伸壓縮試驗機(今田製作所股份有限公司,試驗機本體:SDT-52NA型 拉伸壓縮試驗機,負荷計:SL-6001型負荷計)。 藉由粒編號320之氧化鋁對厚度1.2 mm、200 mm見方之鎳板實施噴擊加工。噴擊處理後之鎳板之算術平均表面粗糙度(Ra)為0.7 μm。此處,表面粗糙度測定係使用觸針式之表面粗糙度測定機SJ-310(Mitutoyo股份有限公司)。將測定樣品設置於與地面平行之平台上,於下述之測定條件下測定算術平均粗糙度Ra。將測定實施6次時,記載其平均值。 <觸針之形狀>圓錐,錐角度=60°,前端半徑=2 μm,靜態測定力=0.75 mN <粗糙度標準>JIS2001 <評價曲線>R <濾波>GAUSS <臨界值 λc>0.8 mm <臨界值 λs>2.5 μm <區間數>5 <前掃、後掃>有 將該鎳板以成為鉛直之方式固定於拉伸壓縮試驗機之下側之夾頭。 使用下述之離子交換膜A作為隔膜。 作為強化芯材,使用聚四氟乙烯(PTFE)製且90丹尼之單絲(以下稱為PTFE紗)。作為犧牲紗,使用35丹尼、6根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。首先,以沿TD及MD之兩方向之各方向以24根/英吋配置PTFE紗、且於鄰接之PTFE紗間配置2根犧牲紗之方式進行平織而獲得織布。藉由滾筒將所獲得之織布進行壓接而獲得厚度70 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.85 mg當量/g之乾燥樹脂之樹脂A、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之乾燥樹脂之樹脂B。 使用該等樹脂A及B,藉由共擠出T模法獲得樹脂A層之厚度為15 μm、樹脂B層之厚度為104 μm之2層膜X。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙(高度50 μm之圓錐形狀之壓紋加工)、補強材及膜X,於加熱板表面溫度223℃、減壓度0.067 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。 藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)30質量%、氫氧化鉀(KOH)15質量%之80℃之水溶液中浸漬20分鐘而進行皂化。其後,於含有氫氧化鈉(NaOH)0.5 N之50℃之水溶液中浸漬1小時,將離子交換基之抗衡離子置換為Na,繼而進行水洗。進而於60℃下加以乾燥。 進而,於樹脂B之酸型樹脂之5質量%乙醇溶液中添加1次粒徑1 μm之氧化鋯20質量%並使其分散而調製懸浮液,藉由懸浮液噴射法對上述複合膜之兩面進行噴霧,於複合膜之表面形成氧化鋯之塗層,而獲得離子交換膜A。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.5 mg/cm2 。再者,平均粒徑係利用粒度分佈計(島津製作所製造之「SALD(註冊商標)2200」)進行測定。 將上述所獲得之離子交換膜(隔膜)於純水中浸漬12小時以上後用於試驗。使其與以純水充分濡濕之上述鎳板接觸,藉由水之張力進行接著。此時,以鎳板與離子交換膜之上端之位置對齊之方式設置。 測定所使用之電解用電極樣品(電極)係切成130 mm見方。離子交換膜A係切成170 mm見方。以2塊不鏽鋼板(厚度1 mm、縱9 mm、橫170 mm)夾著電極之一邊,以不鏽鋼板、電極之中心對齊之方式對位後,藉由4個夾具均勻地固定。將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。此時,將對試驗機承受之荷重設為0 N。暫時從拉伸壓縮試驗機卸下不鏽鋼板、電極、夾具一體物,為了利用純水將電極充分濡濕,而浸漬於裝有純水之槽中。其後,再次將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。 使拉伸壓縮試驗機之上側夾頭下降,利用純水之表面張力使電解用電極樣品接著於離子交換膜表面。此時之接著面係橫130 mm、縱110 mm。將裝入至洗瓶中之純水吹送至電極及離子交換膜整體,製成隔膜、電極再次充分濡濕之狀態。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從上向下滾動,從而將多餘之純水去除。輥僅施加1次。 以10 mm/分鐘之速度使電極上升,開始負荷測定,記錄電極與隔膜之重疊部分成為橫130 mm、縱100 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極與離子交換膜之重疊部分之面積、及與離子交換膜重疊之部分之電極質量,而算出每單位質量·單位面積所承受之力(1)。與離子交換膜重疊之部分之電極質量係根據上述(2)之每單位面積之質量(mg/cm2 )中所獲得之值,藉由比例計算而求出。 測定室之環境係溫度23±2℃、相對濕度30±5%。 再者,實施例、比較例中所使用之電極於接著於藉由表面張力接著於鉛直地固定之鎳板之離子交換膜時,可不下垂或剝離而獨立地接著。 再者,將承受力(1)之評價方法之模式圖示於圖79。 再者,拉伸試驗機之測定下限為0.01(N)。 (4)每單位質量·單位面積所承受之力(2)(接著力)(N/mg・cm2 )) [方法(ii)] 測定係使用拉伸壓縮試驗機(今田製作所股份有限公司,試驗機本體:SDT-52NA型 拉伸壓縮試驗機,負荷計:SL-6001型負荷計)。 將與方法(i)相同之鎳板以成為鉛直之方式固定於拉伸壓縮試驗機之下側之夾頭。 測定所使用之電解用電極樣品(電極)係切成130 mm見方。離子交換膜A係切成170 mm見方。以2塊不鏽鋼板(厚度1 mm、縱9 mm、橫170 mm)夾著電極之一邊,以不鏽鋼板、電極之中心對齊之方式對位後,藉由4個夾具均勻地固定。將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。此時,將對試驗機承受之荷重設為0 N。暫時從拉伸壓縮試驗機卸下不鏽鋼板、電極、夾具一體物,為了利用純水將電極充分濡濕,而浸漬於裝有純水之槽中。其後,再次將不鏽鋼板之中心夾於拉伸壓縮試驗機之上側之夾頭,將電極懸掛。 使拉伸壓縮試驗機之上側夾頭下降,藉由溶液之表面張力使電解用電極樣品接著於鎳板表面。此時之接著面係橫130 mm、縱110 mm。將裝入至洗瓶中之純水吹送至電極及鎳板整體,製成鎳板、電極再次充分濡濕之狀態。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從上向下滾動,從而將多餘之溶液去除。輥僅施加1次。 以10 mm/分鐘之速度使電極上升,開始負荷測定,記錄電極與鎳板之縱向之重疊部分成為100 mm時之負荷。將該測定實施3次並算出平均值。 該平均值除以電極與鎳板之重疊部分之面積、及與鎳板重疊之部分之電極質量,而算出每單位質量·單位面積所承受之力(2)。與隔膜重疊之部分之電極質量係根據上述(2)之每單位面積之質量(mg/cm2 )中所獲得之值,藉由比例計算而求出。 又,測定室之環境係溫度23±2℃、相對濕度30±5%。 再者,實施例、比較例中所使用之電極於藉由表面張力接著於鉛直地固定之鎳板時,可不下垂或剝離而獨立地接著。 再者,拉伸試驗機之測定下限為0.01(N)。 (5)直徑280 mm圓柱捲繞評價方法(1)(%) (膜與圓柱) 按照以下之順序實施評價方法(1)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸。將離子交換膜於純水中浸漬12小時以上後用於試驗。實施例33及34中電極藉由熱壓製而與離子交換膜成為一體,因此準備離子交換膜與電極之一體物(電極係130 mm見方)。將離子交換膜於純水中充分浸漬後,置於外徑280 mm之塑膠(聚乙烯)製之管之曲面上。其後,藉由將厚度5 mm之獨立發泡型之EPDM海綿橡膠捲繞於氯乙烯管(外徑38 mm)而成之輥將多餘之溶液去除。輥係從圖80所示之模式圖之左側向右側於離子交換膜上滾動。輥僅施加1次。1分鐘後,測定離子交換膜與外徑280 mm之塑膠製之管電極密接之部分之比率。 (6)直徑280 mm圓柱捲繞評價方法(2)(%) (膜與電極) 按照以下之順序實施評價方法(2)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成130 mm見方。將離子交換膜於純水中浸漬12小時以上後用於試驗。將離子交換膜與電極於純水中充分浸漬後進行積層。將該積層體以電極成為外側之方式置於外徑280 mm之塑膠(聚乙烯)製之管之曲面上。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從圖81所示之模式圖之左側向右側滾動,從而將多餘之溶液去除。輥僅施加1次。1分鐘後,測定離子交換膜與電極密接之部分之比率。 (7)直徑145 mm圓柱捲繞評價方法(3)(%) (膜與電極) 按照以下之順序實施評價方法(3)。 將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成130 mm見方。將離子交換膜於純水中浸漬12小時以上後用於試驗。將離子交換膜與電極於純水中充分浸漬後進行積層。將該積層體以電極成為外側之方式置於外徑145 mm之塑膠(聚乙烯)製之管之曲面上。其後,將於氯乙烯管(外徑38 mm)捲繞厚度5 mm之獨立發泡型之EPDM海綿橡膠而成之輥從電極上方輕輕按壓,並且從圖82所示之模式圖之左側向右側滾動,從而將多餘之溶液去除。輥僅施加1次。1分鐘後,測定離子交換膜與電極密接之部分之比率。 (8)操作性(感應評價) (A)將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成95×110 mm。將離子交換膜於純水中浸漬12小時以上後用於試驗。於各實施例中將離子交換膜與電極於碳酸氫鈉水溶液、0.1 N之NaOH水溶液、純水之三種溶液中充分浸漬後進行積層,靜置於鐵氟龍板上。將電解評價所使用之陽極池與陰極池之間隔設為約3 cm,提起靜置之積層體而實施插入並夾於其間之操作。於實施該操作時一邊操作一邊確認電極是否偏離、掉落。 (B)將[方法(i)]中製作之離子交換膜A(隔膜)切割成170 mm見方之尺寸,將電極切割成95×110 mm。將離子交換膜於純水中浸漬12小時以上後用於試驗。於各實施例中將離子交換膜與電極於碳酸氫鈉水溶液、0.1 N之NaOH水溶液、純水之三種溶液中充分浸漬後進行積層,靜置於鐵氟龍板上。手持積層體之膜部分之相鄰的兩處之角,以積層體成為鉛直之方式提起。從該狀態起,以將手持之兩處之角靠近之方式移動,使膜成為凸狀、凹狀。將該操作再重複1次,確認電極對膜之追隨性。基於以下之指標,按照1~4之4個等級對該結果進行評價。 1:操作良好 2:能夠操作 3:操作困難 4:大體無法操作 此處,對於實施例4-28之樣品,以與電極為1.3 m×2.5 m、離子交換膜為1.5 m×2.8 m之尺寸之大型電解池相同之尺寸實施操作。實施例28之評價結果(如下文所述為「3」)係作為對上述(A)、(B)之評價與製成大型尺寸時之不同進行評價之指標。即,於對小型之積層體進行評價所獲得之結果為「1」、「2」之情形時,評價為即使於製成大型尺寸之情形時操作性亦無問題。 (9)電解評價(電壓(V)、電流效率(%)、苛性鈉中食鹽濃度(ppm,50%換算)) 藉由下述電解實驗評價電解性能。 使具有設置有陽極之陽極室之鈦製的陽極池(陽極終端池)與具有設置有陰極之鎳製的陰極室(陰極終端池)之陰極池相對。於池間配置一對墊片,將積層體(離子交換膜A與電解用電極之積層體)夾於一對墊片間。此處,使離子交換膜A與電解用電極之兩者直接夾於墊片間。然後,使陽極池、墊片、積層體、墊片及陰極密接而獲得電解池,準備包含該電解池之電解槽。 作為陽極,係藉由將氯化釕、氯化銥及四氯化鈦之混合溶液塗佈於已實施噴擊及酸蝕刻處理作為預處理之鈦基材上並進行乾燥、燒成而製作。陽極係藉由焊接而固定於陽極室。作為陰極,使用各實施例、比較例所記載者。作為陰極室之集電體,使用鎳製多孔金屬。集電體之尺寸為縱95 mm×橫110 mm。作為金屬彈性體,使用以鎳細線編織而成之墊。將作為金屬彈性體之墊置於集電體上。於其上覆蓋以40目之網眼將直徑150 μm之鎳線平織而成之鎳網,藉由利用鐵氟龍(註冊商標)製作之繩將Ni網之四角固定於集電體。以該Ni網作為饋電體。於該電解池中,利用作為金屬彈性體之墊之反彈力而成為零間距結構。作為墊片,使用EPDM(乙烯丙烯二烯)製之橡膠墊片。作為隔膜,使用[方法(i)]中製作之離子交換膜A(160 mm見方)。 使用上述電解池進行食鹽之電解。陽極室之鹽水濃度(氯化鈉濃度)係調整為205 g/L。陰極室之氫氧化鈉濃度係調整為32質量%。以各電解池內之溫度成為90℃之方式調節陽極室及陰極室之各溫度。於電流密度6 kA/m2 下實施食鹽電解,測定電壓、電流效率、苛性鈉中食鹽濃度。此處,所謂電流效率係所生成之苛性鈉之量相對於流通之電流之比率,若藉由流通之電流,雜質離子或氫氧化物離子而非鈉離子於離子交換膜中移動,則電流效率降低。電流效率係藉由一定時間所生成之苛性鈉之莫耳數除以其間流通之電流之電子之莫耳數而求出。苛性鈉之莫耳數係藉由將由電解生成之苛性鈉回收於聚合物槽中,對其質量進行測定而求出。苛性鈉中食鹽濃度表示將苛性鈉濃度換算為50%所得之值。 再者,將實施例、比較例中所使用之電極及饋電體之規格示於表6。 (11)觸媒層之厚度、電解用電極基材、電極之厚度測定 電解用電極基材之厚度係使用電子數顯厚度計(Mitutoyo股份有限公司製造,最少顯示0.001 mm)於面內均勻地測定10點並算出平均值。以此作為電解用電極基材之厚度(量規厚度)。電極之厚度係與電極基材同樣地藉由電子數顯厚度計於面內均勻地測定10點並算出平均值。以此作為電極之厚度(量規厚度)。觸媒層之厚度係藉由電極之厚度減去電解用電極基材之厚度而求出。(12)電極之彈性變形試驗 將[方法(i)]中製作之離子交換膜A(隔膜)及電極切割成110 mm見方之尺寸。將離子交換膜於純水中浸漬12小時以上後用於試驗。於溫度23±2℃、相對濕度30±5%之條件下,將離子交換膜與電極重疊而製作積層體後,如圖83所示般以不產生間隙之方式捲繞至外徑f32 mm、長度20 cm之PVC製管。為了避免捲繞之積層體從PVC製管剝離或鬆動,而使用聚乙烯製之捆束帶加以固定。於該狀態下保持6小時。其後,去除捆束帶,將積層體從PVC製管解捲。僅將電極置於平台上,測定從平台隆起之部分之高度L1 、L2 並求出平均值。以該值作為電極變形之指標。即,值較小意指難以變形。 再者,於使用多孔金屬之情形時,於捲繞時存在SW方向、LW方向之兩種。於本試驗中係沿SW方向捲繞。 又,對於產生變形之電極(未恢復為原來平坦之狀態之電極),藉由如圖84所示之方法對塑性變形後之柔軟程度進行評價。即,將產生變形之電極置於在純水中充分浸漬之隔膜上,將一端固定,將浮起之相反之端部壓抵於隔膜,將力解除,對產生變形之電極是否追隨隔膜進行評價。 (13)膜損傷評價 使用下述之離子交換膜B作為隔膜。 作為強化芯材,使用為聚四氟乙烯(PTFE)且將100丹尼之帶狀紗線以900次/m撚絞而製成紗狀者(以下稱為PTFE紗)。作為經紗之犧牲紗,使用將35丹尼、8根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。又,作為緯紗之犧牲紗,使用將35丹尼、8根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗。首先,以將PTFE紗以24根/英吋配置、將犧牲紗於鄰接之PTFE紗間配置2根之方式進行平織,而獲得厚度100 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.92 mg當量/g之乾燥樹脂之聚合物(A1)、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.10 mg當量/g之乾燥樹脂之聚合物(B1)。使用該等聚合物(A1)及(B1),藉由共擠出T模法獲得聚合物(A1)層之厚度為25 μm、聚合物(B1)層之厚度為89 μm之2層膜X。再者,各聚合物之離子交換容量表示將各聚合物之離子交換基前驅物水解而轉換為離子交換基時之離子交換容量。 又,另行準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.10 mg當量/g之乾燥樹脂之聚合物(B2)。將該聚合物單層擠出而獲得20 μm之膜Y。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙、膜Y、補強材及膜X,於加熱板溫度225℃、減壓度0.022 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)與氫氧化鉀(KOH)之水溶液中浸漬1小時而進行皂化後,於0.5 N之NaOH中浸漬1小時,將離子交換基所附離子取代為Na,繼而進行水洗。進而於60℃下加以乾燥。 又,將以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.05 mg當量/g之乾燥樹脂之聚合物(B3)水解後,藉由鹽酸使其成為酸型。於將該酸型之聚合物(B3')以5質量%之比率溶解於水及乙醇之50/50(質量比)混合液中而成之溶液中,以聚合物(B3')與氧化鋯粒子之質量比成為20/80之方式添加一次粒子之平均粒徑為0.02 μm之氧化鋯粒子。其後,藉由球磨機使其於氧化鋯粒子之懸浮液中分散而獲得懸浮液。 利用噴射法將該懸浮液塗佈於離子交換膜之兩表面並加以乾燥,藉此獲得具有含有聚合物(B3')與氧化鋯粒子之塗佈層之離子交換膜B。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.35 mg/cm2 。 陽極係使用與(9)電解評價相同者。 陰極係使用各實施例、比較例所記載者。陰極室之集電體、墊及饋電體係使用與(9)電解評價相同者。即,以Ni網作為饋電體,利用作為金屬彈性體之墊之反彈力而成為零間距結構。墊片亦使用與(9)電解評價相同者。作為隔膜,使用藉由上述方法所製作之離子交換膜B。即,除了將離子交換膜B與電解用電極之積層體夾持於一對墊片間以外,準備與(9)相同之電解槽。 使用上述電解池進行食鹽之電解。陽極室之鹽水濃度(氯化鈉濃度)係調整為205 g/L。陰極室之氫氧化鈉濃度係調整為32質量%。以各電解池內之溫度成為70℃之方式調節陽極室及陰極室之各溫度。於電流密度8 kA/m2 下實施食鹽電解。從電解開始起12小時後停止電解,取出離子交換膜B並觀察損傷狀態。 「○」意指無損傷。「×」意指於離子交換膜之大致整個面存在損傷。 (14)電極之通氣阻力 使用通氣性試驗機KES-F8(商品名,Kato Tech股份有限公司)測定電極之通氣阻力。通氣阻力值之單位為kPa・s/m。將測定實施5次,將其平均值記載於表7。測定係於以下之兩個條件下實施。再者,測定室之溫度設為24℃,相對濕度設為32%。 ・測定條件1(通氣阻力1) 活塞速度:0.2 cm/s 通氣量:0.4 cc/cm2 /s 測定範圍:SENSE L(低) 樣品尺寸:50 mm×50 mm ・測定條件2(通氣阻力2) 活塞速度:2 cm/s 通氣量:4 cc/cm2 /s 測定範圍:SENSE M(中)或H(高) 樣品尺寸:50 mm×50 mm [實施例4-1] 作為陰極電解用電極基材,準備量規厚度為16 μm之電解鎳箔。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 藉由打孔加工於該鎳箔開出圓形之孔而製成多孔箔。開孔率為49%。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。實施例4-1中所製作之電極之厚度為24 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。塗層亦形成於未經粗面化之面。又,為氧化釕與氧化鈰之合計厚度。 將藉由上述方法所製作之電極之接著力之測定結果示於表7。觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 為了將藉由上述方法所製作之電極用於電解評價而將其切成縱95 mm、橫110 mm之尺寸。使電極之經粗面化之面與利用0.1 N之NaOH水溶液平衡之[方法(i)]中所製作之離子交換膜A(尺寸為160 mm×160 mm)之羧酸層側的大致中央之位置相對向,藉由水溶液之表面張力使其等密接。 即使抓持膜與電極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極剝落或偏離之情況。又,即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極剝落或偏離之情況。 將上述膜一體電極以附著有電極之面成為陰極室側之方式夾於陽極池與陰極池之間。剖面結構係從陰極室側起依序排列集電體、墊、鎳網饋電體、電極、膜、陽極而形成零間距結構。 對所獲得之電極進行電解評價。將其結果示於表7。 表現出較低之電壓、較高之電流效率及較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF(螢光X射線分析)測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例4-2] 實施例4-2係使用量規厚度為22 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.96 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為44%。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為29 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0033(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例4-3] 實施例4-3係使用量規厚度為30 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為1.38 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為44%。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為38 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例4-4] 實施例4-4係使用量規厚度為16 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為75%。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為24 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0023(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則經粗面化之面中殘存大致100%塗層,未經粗面化之面中塗層減少。由此說明,與膜相對向之面(經粗面化之面)有助於電解,即使不與膜相對向之相反面中塗層較少或不存在亦能夠發揮出良好之電解性能。 [實施例4-5] 實施例4-5係準備量規厚度為20 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之兩面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.96 μm。兩面均為相同之粗糙度。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。開孔率為49%。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為30 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。塗層亦形成於未經粗面化之面。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0023(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 又,若藉由XRF測定電解後之塗佈量,則兩面均殘存大致100%塗層。若對比實施例4-1~4-4進行考慮,則說明即使不與膜相對向之相反面中塗層較少或不存在,亦能夠發揮出良好之電解性能。 [實施例4-6] 實施例4-6除了藉由離子鍍敷實施對陰極電解用電極基材之塗佈以外,與實施例4-1同樣地實施評價,並將結果示於表7。再者,離子鍍敷係於加熱溫度200℃下使用Ru金屬靶,於氬氣/氧氣環境下以成膜壓力7×10-2 Pa進行製膜。所形成之塗層為氧化釕。 電極之厚度為26 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-7] 實施例4-7係藉由電成形法製作陰極電解用電極基材。光罩之形狀係設為將0.485 mm×0.485 mm之正方形以0.15 mm為間隔縱、橫排列而成之形狀。藉由依序實施曝光、顯影、電鍍,獲得量規厚度為20 μm、開孔率56%之鎳多孔箔。表面之算術平均粗糙度Ra為0.71 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為37 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為17 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0032(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-8] 實施例4-8中作為陰極電解用電極基材,係藉由電成形法製作,量規厚度為50 μm,開孔率為56%。表面之算術平均粗糙度Ra為0.73 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為60 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0032(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-9] 實施例4-9係使用量規厚度為150 μm、空隙率為76%之鎳不織布(NIKKO TECHNO股份有限公司製造)作為陰極電解用電極基材。不織布之鎳纖維直徑約為40 μm,單位面積重量為300 g/m2 。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為165 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為15 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為29 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0612(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例4-10] 實施例4-10係使用量規厚度為200 μm、空隙率為72%之鎳不織布(NIKKO TECHNO股份有限公司製造)作為陰極電解用電極基材。不織布之鎳纖維直徑約為40 μm,單位面積重量為500 g/m2 。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為215 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為15 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為40 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0164(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例4-11] 實施例4-11係使用量規厚度為200 μm、空隙率為72%之發泡鎳(Mitsubishi Materials股份有限公司製造)作為陰極電解用電極基材。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 又,電極之厚度為210 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為17 mm,未恢復為原來平坦之狀態。因此,對塑性變形後之柔軟程度進行評價,結果電極藉由表面張力而追隨隔膜。由此確認,即使經塑性變形,亦能夠藉由較小之力使其與隔膜接觸,該電極之操作性良好。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0402(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價為「0」而較良好。 [實施例4-12] 實施例4-12係使用線徑50 μm、200目、量規厚度為100 μm、開孔率為37%之鎳網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。即使實施噴擊處理,開孔率亦不變化。由於難以測定金屬絲網表面之粗糙度,因此於實施例4-12中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。1根金屬絲網之算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為110 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0154(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-13] 實施例4-13係使用線徑65 μm、150目、量規厚度為130 μm、開孔率為38%之鎳網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。即使實施噴擊處理,開孔率亦不變化。由於難以測定金屬絲網表面之粗糙度,因此於實施例4-13中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.66 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施上述評價,並將結果示於表7。 電極之厚度為133 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為3 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為6.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0124(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性為「2」,可判斷能夠作為大型積層體進行操作。膜損傷評價亦為「0」而較良好。 [實施例4-14] 實施例4-14係使用與實施例4-3相同之基材(量規厚度30 μm,開孔率44%)作為陰極電解用電極基材。除了未設置鎳網饋電體以外,以與實施例4-1相同之構成實施電解評價。即,電解池之剖面結構係從陰極室側起依序排列集電體、墊、膜一體電極、陽極而形成零間距結構,墊作為饋電體發揮功能。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-15] 實施例4-15係使用與實施例4-3相同之基材(量規厚度30 μm,開孔率44%)作為陰極電解用電極基材。設置參考例1中使用之劣化且電解電壓變高之陰極代替鎳網饋電體。除此以外,以與實施例4-1相同之構成實施電解評價。即,電解池之剖面結構從陰極室側起,依序排列集電體、墊、劣化且電解電壓變高之陰極(作為饋電體發揮功能)、陰極、隔膜、陽極而形成零間距結構,劣化且電解電壓變高之陰極作為饋電體發揮功能。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-16] 作為陽極電解用電極基材,準備量規厚度為20 μm之鈦箔。對鈦箔之兩面實施粗面化處理。對該鈦箔實施打孔加工,開出圓形之孔而製成多孔箔。孔之直徑為1 mm,開孔率為14%。表面之算術平均粗糙度Ra為0.37 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素、銥元素及鈦元素之莫耳比成為0.25:0.25:0.5之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、銥濃度為100 g/L之氯化銥(田中貴金屬工業股份有限公司)、四氯化鈦(和光純藥工業股份有限公司)加以混合。將該混合液充分攪拌,以其作為陽極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。於鈦多孔箔塗佈上述塗佈液後,於60℃下實施10分鐘之乾燥,於475℃下實施10分鐘之燒成。重複實施該等塗佈、乾燥、預燒成、燒成之一系列之操作後,於520℃下進行1小時之燒成。 為了將藉由上述方法所製作之電極用於電解評價而將其切成縱95 mm、橫110 mm之尺寸。藉由水溶液之表面張力使其密接於利用0.1 N之NaOH水溶液平衡之[方法(i)]中製作之離子交換膜A(尺寸為160 mm×160 mm)之磺酸層側的大致中央之位置。 陰極係按照以下之順序製備。首先,準備線徑150 μm、40目之鎳製金屬絲網作為基材。作為預處理而藉由氧化鋁實施噴擊處理後,於6 N之鹽酸中浸漬5分鐘,並利用純水充分洗淨、乾燥。 繼而,以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、氯化鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於300℃下實施3分鐘之預燒成,於550℃下實施10分鐘之燒成。其後,於550℃下實施1小時之燒成。重複進行該等塗佈、乾燥、預燒成、燒成之一系列之操作。 作為陰極室之集電體,使用鎳製多孔金屬。集電體之尺寸為縱95 mm×橫110 mm。作為金屬彈性體,使用以鎳細線編織而成之墊。將作為金屬彈性體之墊置於集電體上。於其上覆蓋藉由上述方法製作之陰極,藉由利用鐵氟龍(註冊商標)製作之繩將網之四角固定於集電體。 即使抓持膜與陽極成為一體之膜一體電極之膜部分之四角,使電極成為地面側而將膜一體電極以與地面平行之方式懸吊,亦不存在電極剝落或偏離之情況。又,即使抓持1邊之兩端而將膜一體電極以垂直於地面之方式懸吊,亦不存在電極剝落或偏離之情況。 藉由焊接將參考例3中所使用之劣化且電解電壓變高之陽極固定於陽極池,將上述膜一體電極以附著有電極之面成為陽極室側之方式夾於陽極池與陰極池之間。即,電解池之剖面結構係從陰極室側起,依序排列集電體、墊、陰極、隔膜、鈦多孔箔陽極、劣化且電解電壓變高之陽極,形成零間距結構。劣化且電解電壓變高之陽極作為饋電體發揮功能。再者,鈦多孔箔陽極與劣化且電解電壓變高之陽極之間僅係物理接觸,並未藉由焊接進行固定。 藉由該構成,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為26 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為6 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為4 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0060(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-17] 實施例4-17係使用量規厚度20 μm、開孔率30%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.37 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-16同樣地實施評價,並將結果示於表7。 電極之厚度為30 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0030(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-18] 實施例4-18係使用量規厚度20 μm、開孔率42%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.38 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-16同樣地實施評價,並將結果示於表7。 電極之厚度為32 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為12 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為2.5 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0022(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-19] 實施例4-19係使用量規厚度50 μm、開孔率47%之鈦箔作為陽極電解用電極基材。表面之算術平均粗糙度Ra為0.40 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-16同樣地實施評價,並將結果示於表7。 電極之厚度為69 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為19 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為8 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0024(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-20] 實施例4-20係使用量規厚度100 μm、鈦纖維直徑約為20 μm、單位面積重量為100 g/m2 、開孔率78%之鈦不織布作為陽極電解用電極基材。除此以外,與實施例4-16同樣地實施評價,並將結果示於表7。 電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為2 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0228(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-21] 實施例4-21係使用量規厚度120 μm、鈦纖維直徑約為60 μm、150目之鈦金屬絲網作為陽極電解用電極基材。開孔率為42%。藉由粒編號320之氧化鋁實施噴擊處理。由於難以測定金屬絲網表面之粗糙度,因此於實施例4-21中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.60 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-16同樣地實施評價,並將結果示於表7。 電極之厚度為140 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為20 μm。 觀測到充分之接著力。 實施電極之變形試驗,結果L1 、L2 之平均值為10 mm。可知為彈性變形區域較廣之電極。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0132(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。膜損傷評價亦為「0」而較良好。 [實施例4-22] 實施例4-22係與實施例4-16同樣地使用劣化且電解電壓變高之陽極作為陽極饋電體,使用與實施例4-20相同之鈦不織布作為陽極。與實施例4-15同樣地使用劣化且電解電壓變高之陰極作為陰極饋電體,使用與實施例4-3相同之鎳箔電極作為陰極。電解池之剖面結構係從陰極室側起,依序排列集電體、墊、劣化且電壓變高之陰極、鎳多孔箔陰極、隔膜、鈦不織布陽極、劣化且電解電壓變高之陽極而形成零間距結構,劣化且電解電壓變高之陰極及陽極作為饋電體發揮功能。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極(陽極)之厚度為114 μm,觸媒層之厚度係電極(陽極)之厚度減去電解用電極基材之厚度而為14 μm。又,電極(陰極)之厚度為38 μm,觸媒層之厚度係電極(陰極)之厚度減去電解用電極基材之厚度而為8 μm。 於陽極及陰極均觀測到充分之接著力。 實施電極(陽極)之變形試驗,結果L1 、L2 之平均值為2 mm。實施電極(陰極)之變形試驗,結果L1 、L2 之平均值為0 mm。 測定電極(陽極)之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0228(kPa・s/m)。測定電極(陰極)之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 又,表現出較低之電壓、較高之電流效率、較低之苛性中食鹽濃度。操作性亦為「1」而較良好。陽極及陰極中膜損傷評價均亦為「0」而較良好。再者,於實施例4-22中,於隔膜之單面貼附陰極,於相反之面貼附陽極,將陰極及陽極組合進行膜損傷評價。 [實施例4-23] 於實施例4-23中係使用Agfa公司製造之微多孔膜「Zirfon Perl UTP 500」。 Zirfon膜係於純水中浸漬12小時以上後用於試驗。除此以外,與實施例4-3同樣地實施上述評價,並將結果示於表7。 實施電極之變形試驗,結果L1 、L2 之平均值為0 mm。可知為彈性變形區域較廣之電極。 與使用離子交換膜作為隔膜時相同,觀測到充分之接著力,微多孔膜與電極藉由表面張力而密接,操作性為「1」而較良好。 [參考例1] 於參考例1中,作為陰極而使用於大型電解槽中使用8年、劣化且電解電壓變高之陰極。於陰極室之墊上設置上述陰極代替鎳網饋電體,隔著[方法(i)]中製作之離子交換膜A實施電解評價。於參考例1中不使用膜一體電極,電解池之剖面結構係從陰極室側起,依序排列集電體、墊、劣化且電解電壓變高之陰極、離子交換膜A、陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.04 V,電流效率為97.0%,苛性鈉中食鹽濃度(50%換算值)為20 ppm。由於陰極劣化,因此結果為電壓較高 [參考例2] 於參考例2中,使用鎳網饋電體作為陰極。即,藉由未形成觸媒塗層之鎳網實施電解。 將鎳網陰極設置於陰極室之墊上,隔著[方法(i)]中製作之離子交換膜A實施電解評價。參考例2之電池之剖面結構係從陰極室側起,依序排列集電體、墊、鎳網、離子交換膜A、陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.38 V,電流效率為97.7%,苛性鈉中食鹽濃度(50%換算值)為24 ppm。由於未塗佈陰極觸媒,因此結果為電壓較高。 [參考例3] 於參考例3中,作為陽極而使用於大型電解槽中使用約8年、劣化且電解電壓變高之陽極。 參考例3之電解池之剖面結構係從陰極室側起,依序排列集電體、墊、陰極、[方法(i)]中製作之離子交換膜A、劣化且電解電壓變高之陽極而形成零間距結構。 藉由該構成實施電解評價,結果電壓為3.18 V,電流效率為97.0%,苛性鈉中食鹽濃度(50%換算值)為22 ppm。由於陽極劣化,因此結果為電壓較高。 [實施例4-24] 於實施例4-24中,使用全滾筒加工後之量規厚度100 μm、開孔率33%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例4-24中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.68 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 每單位面積之質量為67.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.05(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為64%,直徑145 mm圓柱捲繞評價(3)之結果為22%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為13 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0168(kPa・s/m)。 [實施例4-25] 於實施例4-25中,使用全滾筒加工後之量規厚度100 μm、開孔率16%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例4-25中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為107 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。 每單位面積之質量為78.1(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.04(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為37%,直徑145 mm圓柱捲繞評價(3)之結果為25%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為18.5 mm。測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0176(kPa・s/m)。 [實施例4-26] 實施例4-26係使用全滾筒加工後之量規厚度為100 μm、開孔率為40%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例4-26中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.70 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。對電解用電極基材之塗佈係藉由與實施例4-6同樣之離子鍍敷實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為110 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 每單位質量·單位面積所承受之力(1)為0.07(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為80%,直徑145 mm圓柱捲繞評價(3)之結果為32%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「3」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為11 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0030(kPa・s/m)。 [實施例4-27] 實施例4-27係使用全滾筒加工後之量規厚度為100 μm、開孔率為58%之鎳多孔金屬作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例4-27中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為109 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為9 μm。 每單位質量·單位面積所承受之力(1)為0.06(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果為69%,直徑145 mm圓柱捲繞評價(3)之結果為39%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等問題。操作性為「3」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為11.5 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0028(kPa・s/m)。 [實施例4-28] 實施例4-28係使用量規厚度為300 μm、開孔率為56%之鎳金屬絲網作為陰極電解用電極基材。由於難以測定金屬絲網之表面粗糙度,因此於實施例4-28中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。算術平均粗糙度Ra為0.64 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施評價,並將結果示於表7。 電極之厚度為308 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為49.2(mg/cm2 )。因此,直徑280 mm圓柱捲繞評價(2)之結果為88%,直徑145 mm圓柱捲繞評價(3)之結果為42%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況,操作性為「3」,存在問題。實際中以大型尺寸進行操作,可評價為「3」。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為23 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0034(kPa・s/m)。 [實施例4-29] 於實施例4-29中使用量規厚度200 μm、開孔率37%之鎳金屬絲網作為陰極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定金屬絲網之表面粗糙度,因此於實施例4-29中在噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.65 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-1同樣地實施電極電解評價、接著力之測定結果、密接性。將結果示於表7。 電極之厚度為210 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為10 μm。 每單位面積之質量為56.4 mg/cm2 。因此,直徑145 mm圓柱捲繞評價方法(3)之結果為63%,電極與隔膜之密接性較差。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況,操作性為「3」,存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為19 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0096(kPa・s/m)。 [實施例4-30] 於實施例4-30中使用全滾筒加工後之量規厚度500 μm、開孔率17%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例4-30中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.60 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-16同樣地實施評價,並將結果示於表7。 又,電極之厚度為508 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為152.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0072(kPa・s/m)。 [實施例4-31] 於實施例4-31中,使用全滾筒加工後之量規厚度800 μm、開孔率8%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例4-31中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.61 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-16同樣地實施上述評價,並將結果示於表7。 電極之厚度為808 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 每單位面積之質量為251.3(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0172(kPa・s/m)。 [實施例4-32] 於實施例4-32中,使用全滾筒加工後之量規厚度1000 μm、開孔率46%之鈦多孔金屬作為陽極電解用電極基材。藉由粒編號320之氧化鋁實施噴擊處理。噴擊處理後開孔率亦未變化。由於難以測定多孔金屬之表面粗糙度,因此於實施例4-32中在噴擊時同時對厚度1 mm之鈦板進行噴擊處理,以該鈦板之表面粗糙度作為金屬絲網之表面粗糙度。算術平均粗糙度Ra為0.59 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。除此以外,與實施例4-16同樣地實施上述評價,並將結果示於表7。 又,電極之厚度為1011 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為11 μm。 每單位面積之質量為245.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)為0.01(N/mg・cm2 ),為較小之值。因此,直徑280 mm圓柱捲繞評價(2)之結果未達5%,直徑145 mm圓柱捲繞評價(3)之結果未達5%,將電極與隔膜剝離之部分變多。其存在於處理膜一體電極時,電極容易被剝離,於操作中電極從膜剝離掉落等情況。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果電極係捲曲為PVC製管之形狀之狀態而未恢復,無法測定L1 、L2 之值。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0027(kPa・s/m)。 [實施例4-33] 實施例4-33中,以先前文獻(日本專利特開昭58-48686之實施例)為參考,製作將電極熱壓接於隔膜而成之膜電極接合體。 使用量規厚度100 μm、開孔率33%之鎳多孔金屬作為陰極電解用電極基材,與實施例4-1同樣地實施電極塗佈。其後,按照下述之順序對電極之單面實施惰性化處理。於電極之單面貼附聚醯亞胺黏著帶(中興化成股份有限公司),於相反面塗佈PTFE分散液(DuPont-Mitsui Fluorochemicals股份有限公司,31-JR(商品名)),於120℃之馬弗爐中乾燥10分鐘。將聚醯亞胺膠帶剝離,於設定為380℃之馬弗爐中實施10分鐘燒結處理。將該操作重複2次,對電極之單面進行惰性化處理。 製作由末端官能基為「-COOCH3 」之全氟碳聚合物(C聚合物)與末端基為「-SO2 F」之全氟碳聚合物(S聚合物)之2層所形成之膜。C聚合物層之厚度為3密耳(mil),S聚合物層之厚度為4密耳(mil)。對該2層膜實施皂化處理,藉由水解對聚合物之末端導入離子交換基。C聚合物末端被水解為羧酸基,S聚合物末端被水解為磺基。以磺酸基計之離子交換容量為1.0 meq/g,以羧酸基計之離子交換容量為0.9 meq/g。 使具有羧酸基作為離子交換基之面與經惰性化之電極面相對向,並實施熱壓製,而將離子交換膜與電極一體化。熱壓接後電極之單面亦為露出之狀態,不存在電極貫通膜之部分。 其後,為了抑制電解中產生之氣泡對膜之附著,將導入有氧化鋯與磺基之全氟碳聚合物混合物塗佈於兩面。由此製作實施例4-33之膜電極接合體。 使用該膜電極接合體,測定每單位質量·單位面積所承受之力(1),結果由於藉由熱壓接將電極與膜強力接合,因此電極未向上方移動。因此,以不移動離子交換膜與鎳板之方式進行固定,藉由更強之力將電極向上方拉拽,結果於承受1.50(N/mg・cm2 )之力時,膜之一部分破裂。實施例4-33之膜電極接合體之每單位質量·單位面積所承受之力(1)至少為1.50(N/mg・cm2 ),被強力地接合。 實施直徑280 mm圓柱捲繞評價(1),結果與塑膠製管之接觸面積未達5%。另一方面,實施直徑280 mm圓柱捲繞評價(2),結果雖然電極與膜100%接合,但最初隔膜並未捲繞至圓柱。直徑145 mm圓柱捲繞評價(3)之結果亦相同。該結果意指膜之操作性因一體化之電極而受損,而難以捲繞為滾筒狀、或加以彎折。操作性為「3」,存在問題。膜損傷評價為「0」。又,實施電解評價,結果電壓變高,電流效率變低,苛性鈉中之食鹽濃度(50%換算值)變高,電解性能變差。 又,電極之厚度為114 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為14 μm。 實施電極之變形試驗,結果L1 、L2 之平均值為13 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0168(kPa・s/m)。 [實施例4-34] 實施例4-34係使用線徑150 μm、40目、量規厚度300 μm、開孔率58%之鎳網作為陰極電解用電極基材。除此以外,與實施例4-33同樣地製作膜電極接合體。 使用該膜電極接合體,測定每單位質量·單位面積所承受之力(1),結果由於藉由熱壓接將電極與膜強力接合,因此電極未向上方移動。因此,以不移動離子交換膜與鎳板之方式進行固定,藉由更強之力將電極向上方拉拽,結果於承受1.60(N/mg・cm2 )之力時,膜之一部分破裂。實施例4-34之膜電極接合體之每單位質量·單位面積所承受之力(1)至少為1.60(N/mg・cm2 ),被強力地接合。 使用該膜電極接合體實施直徑280 mm圓柱捲繞評價(1),結果與塑膠製管之接觸面積未達5%。另一方面,實施直徑280 mm圓柱捲繞評價(2),結果雖然電極與膜100%接合,但最初隔膜並未捲繞至圓柱。直徑145 mm圓柱捲繞評價(3)之結果亦相同。該結果意指膜之操作性因一體化之電極而受損,而難以捲繞為滾筒狀、或加以彎折。操作性為「3」,存在問題。又,實施電解評價,結果電壓變高,電流效率變低,苛性鈉中之食鹽濃度變高,電解性能變差。 又,電極之厚度為308 μm。觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為8 μm。 實施電極之變形試驗,結果L1 、L2 之平均值為23 mm。 測定電極之通氣阻力,結果於測定條件1下為0.07(kPa・s/m)以下,於測定條件2下為0.0034(kPa・s/m)。 [實施例4-35] 準備量規厚度為150 μm之鎳線作為陰極電解用電極基材。實施利用該鎳線之粗面化處理。由於難以測定鎳線之表面粗糙度,因此於實施例4-35中於噴擊時同時對厚度1 mm之鎳板進行噴擊處理,以該鎳板之表面粗糙度作為鎳線之表面粗糙度。藉由粒編號320之氧化鋁實施噴擊處理。算術平均粗糙度Ra為0.64 μm。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088(商品名),厚度10 mm)而成之塗佈滾筒與上述塗佈液始終相接之方式設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。實施例4-35中所製作之鎳線1根之厚度為158 μm。 將藉由上述方法所製作之鎳線切成110 mm及95 mm之長度。如圖85所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由Aron Alpha將交點部分接著而製作電極。對電極實施評價,將其結果示於表7。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為99.7%。 電極之每單位面積之質量為0.5(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為15 mm。 測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力值為0.0002(kPa・s/m)。 又,對於電極,使用圖86所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓成為3.16 V,較高。 [實施例4-36] 於實施例4-36中,使用實施例4-35中所製作之電極,如圖87所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由Aron Alpha將交點部分接著而製作電極。對電極實施評價,將其結果示於表7。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為99.4%。 電極之每單位面積之質量為0.9(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為16 mm。 測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力為0.0004(kPa・s/m)。 又,對於電極,使用圖88所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓為3.18 V,較高。 [實施例4-37] 於實施例4-37中,使用實施例4-35中所製作之電極,如圖89所示,以110 mm之鎳線與95 mm之鎳線於各鎳線之中心垂直重疊之方式放置,藉由Aron Alpha將交點部分接著而製作電極。對電極實施評價,將其結果示於表7。 電極中鎳線重疊之部分最厚,電極之厚度為306 μm。觸媒層之厚度為6 μm。開孔率為98.8%。 電極之每單位面積之質量為1.9(mg/cm2 )。每單位質量·單位面積所承受之力(1)及(2)均為拉伸試驗機之測定下限以下。因此,直徑280 mm圓柱捲繞評價(1)之結果未達5%,將電極與隔膜剝離之部分變多。操作性為「4」,亦存在問題。膜損傷評價為「0」。 實施電極之變形試驗,結果L1 、L2 之平均值為14 mm。 又,測定電極之通氣阻力,結果於測定條件2下為0.001(kPa・s/m)以下。於測定條件2下,將通氣阻力測定裝置之SENSE(測定範圍)設為H(高)進行測定,結果通氣阻力為0.0005(kPa・s/m)。 又,對於電極,使用圖90所示之結構體,將電極(陰極)設置於Ni網饋電體上,藉由(9)電解評價所記載之方法實施電解評價。其結果為,電壓為3.18 V,較高。 [比較例4-1] (觸媒之製備) 將硝酸銀(和光純藥股份有限公司)0.728 g、硝酸鈰6水合物(和光純藥股份有限公司)1.86 g添加至純水150 ml中,製作金屬鹽水溶液。於15%氫氧化四甲基銨水溶液(和光純藥股份有限公司)100 g中添加純水240 g而製作鹼性溶液。一邊使用磁攪拌器攪拌鹼性溶液,一邊使用滴定管以5 ml/分鐘滴加添加上述金屬鹽水溶液。對含有所生成之金屬氫氧化物微粒之懸浮液進行抽氣過濾後,進行水洗而去除鹼性成分。其後,將過濾物轉移至200 ml之2-丙醇(Kishida Chemical股份有限公司)中,藉由超音波分散機(US-600T,日本精機製作所股份有限公司)再分散10分鐘,而獲得均勻之懸浮液。 將疏水性碳黑(DENKA BLACK(註冊商標)AB-7(商品名),電氣化學工業股份有限公司)0.36 g、親水性碳黑(科琴黑(註冊商標)EC-600JD(商品名),三菱化學股份有限公司)0.84 g分散於2-丙醇100 ml中,藉由超音波分散機分散10分鐘,而獲得碳黑之懸浮液。將金屬氫氧化物前驅物之懸浮液與碳黑之懸浮液混合,藉由超音波分散機分散10分鐘。將該懸浮液進行抽氣過濾,於室溫下乾燥半天,而獲得分散固定有金屬氫氧化物前驅物之碳黑。繼而,使用惰性氣體燒成爐(VMF165型,山田電機股份有限公司),於氮氣環境、400℃下進行1小時之燒成,而獲得將電極觸媒分散固定化之碳黑A。 (反應層用之粉末製作) 於將電極觸媒分散固定化之碳黑A 1.6 g中添加利用純水稀釋為20重量%之界面活性劑Triton(註冊商標)X-100(商品名,ICN Biomedical公司)0.84 ml、純水15 ml,藉由超音波分散機分散10分鐘。於該分散液中添加PTFE(聚四氟乙烯)分散液(PTFE30J(商品名),DuPont-Mitsui Fluorochemicals股份有限公司)0.664 g,並攪拌5分鐘後,進行抽氣過濾。進而,於乾燥機中在80℃下乾燥1小時,藉由研磨機進行粉碎,而獲得反應槽用粉末A。 (氣體擴散層用粉末之製作) 藉由超音波分散機將疏水性碳黑(DENKA BLACK(註冊商標)AB-7(商品名))20 g、利用純水稀釋為20重量%之界面活性劑Triton(註冊商標)X-100(商品名)50 ml、純水360 ml分散10分鐘。於所獲得之分散液中添加PTFE分散液22.32 g,並攪拌5分鐘後,進行過濾。進而,於80℃之乾燥機中乾燥1小時,藉由研磨機實施粉碎,而獲得氣體擴散層用粉末A。 (氣體擴散電極之製作) 於氣體擴散層用粉末A 4 g中添加乙醇8.7 ml,進行混練而製成飴狀。藉由滾筒成形機將該製成飴狀之氣體擴散層用粉末成形為片狀,埋入銀網(SW=1,LW=2,厚度=0.3 mm)作為集電體,最終成形為1.8 mm之片狀。於反應層用粉末A 1 g中添加乙醇2.2 ml,進行混練而製成飴狀。藉由滾筒成形機將該製成飴狀之反應層用粉末成形為厚度0.2 mm之片狀。進而,將所製作之使用氣體擴散層用粉末A所獲得之片材及使用反應層用粉末A所獲得之片材之2片片材進行積層,藉由滾筒成形機成形為1.8 mm之片狀。將該積層而成之片材於室溫下乾燥一晝夜,而將乙醇去除。進而,為了將殘存之界面活性劑去除,於空氣中在300℃下進行1小時之熱分解處理。包於鋁箔中,藉由熱壓機(SA303(商品名),TESTER SANGYO股份有限公司),於360℃下以50 kgf/cm2 進行1分鐘熱壓,而獲得氣體擴散電極。氣體擴散電極之厚度為412 μm。 使用所獲得之電極,進行電解評價。電解池之剖面結構係從陰極室側起依序排列集電體、墊、鎳網饋電體、電極、膜、陽極而形成零間距結構。將其結果示於表7。 實施電極之變形試驗,結果L1 、L2 之平均值為19 mm。 測定電極之通氣阻力,結果於測定條件1下為25.88(kPa・s/m)。 又,操作性為「3」,存在問題。又,實施電解評價,結果電流效率變低,苛性鈉中之食鹽濃度變高,電解性能顯著變差。膜損傷評價為「3」,亦存在問題。 根據該等結果可知,若使用比較例4-1中獲得之氣體擴散電極,則電解性能顯著較差。又,於離子交換膜之大致整個面確認到損傷。認為其原因在於:由於比較例4-1之氣體擴散電極之通氣阻力顯著較大,因此電極中產生之NaOH滯留於電極與隔膜之界面而成為高濃度。 [表6] [表7] 於表7中,全部樣品於「每單位質量·單位面積所承受之力(1)」及「每單位質量·單位面積所承受之力(2)」之測定前可藉由表面張力而自立(即,不存在下垂之情況)。 <第5實施形態之驗證> 如下所述準備與第5實施形態相對應之實驗例(於以下之<第5實施形態之驗證>之項中簡稱為「實施例」)、及不與第5實施形態相對應之實驗例(於以下之<第5實施形態之驗證>之項中簡稱為「比較例」),藉由以下方法對該等進行評價。一邊適當參照圖93~94,100~102一邊對其詳細內容進行說明。 使用以下述方式製造之離子交換膜A作為隔膜。 作為強化芯材,使用聚四氟乙烯(PTFE)製且90丹尼之單絲(以下稱為PTFE紗)。作為犧牲紗,使用35丹尼、6根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。首先,以沿TD及MD之兩方向之各方向以24根/英吋配置PTFE紗、且於鄰接之PTFE紗間配置2根犧牲紗之方式進行平織而獲得織布。藉由滾筒將所獲得之織布進行壓接而獲得厚度70 μm之織布。 其次,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.85 mg當量/g之乾燥樹脂之樹脂A、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之乾燥樹脂之樹脂B。 使用該等樹脂A及B,藉由共擠出T模法獲得樹脂A層之厚度為15 μm、樹脂B層之厚度為104 μm之2層膜X。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙(高度50 μm之圓錐形狀之壓紋加工)、補強材及膜X,於加熱板表面溫度223℃、減壓度0.067 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。 藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)30質量%、氫氧化鉀(KOH)15質量%之80℃之水溶液中浸漬20分鐘而進行皂化。其後,於含有氫氧化鈉(NaOH)0.5 N之50℃之水溶液中浸漬1小時,將離子交換基之抗衡離子置換為Na,繼而進行水洗。進而於60℃下加以乾燥。 進而,於樹脂B之酸型樹脂之5質量%乙醇溶液中添加1次粒徑1 μm之氧化鋯20質量%並使其分散,而調製懸浮液,藉由懸浮液噴射法對上述複合膜之兩面進行噴霧,於複合膜之表面形成氧化鋯之塗層,而獲得離子交換膜A。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.5 mg/cm2 。此處,平均粒徑係利用粒度分佈計(島津製作所製造之「SALD(註冊商標)2200」)進行測定。 使用下述之陰極、陽極作為電極。 準備量規厚度為22 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.95 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 藉由打孔加工於該鎳箔開出圓形之孔而製成多孔箔。開孔率為44%。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。所製作之電極之厚度為29 μm。含有氧化釕與氧化鈰之觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。塗層亦形成於未經粗面化之面。 使用量規厚度100 μm、鈦纖維直徑約為20 μm、單位面積重量為100 g/m2 、開孔率78%之鈦不織布作為陽極電解用電極基材。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素、銥元素及鈦元素之莫耳比成為0.25:0.25:0.5之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、銥濃度為100 g/L之氯化銥(田中貴金屬工業股份有限公司)、四氯化鈦(和光純藥工業股份有限公司)加以混合。將該混合液充分攪拌,以其作為陽極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。於鈦多孔箔塗佈上述塗佈液後,於60℃下實施10分鐘之乾燥,於475℃下實施10分鐘之燒成。重複實施該等塗佈、乾燥、預燒成、燒成之一系列之操作後,於520℃下進行1小時之燒成。 [實施例5-1] (使用陰極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備縱1.5 m、橫2.5 m之離子交換膜。又,藉由上述所記載之方法,準備4片縱0.3 m、橫2.4 m之陰極。 將離子交換膜於2%之碳酸氫鈉溶液中浸漬一晝夜後,將陰極無間隙地排列於羧酸層側,而製作陰極與離子交換膜之積層體(參照圖100)。若將陰極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陰極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。如圖101所示,將所獲得之積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。捲繞體之尺寸成為外徑84 mm、長度1.7 m之圓柱形狀,能夠減小積層體之尺寸。 繼而,於既有之大型電解槽(具有與圖93、94所示者相同之結構之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陰極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。若於電解運轉中預先準備積層體之捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例5-2] (使用陽極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備縱1.5 m、橫2.5 m之離子交換膜。又,藉由上述所記載之方法準備4片縱0.3 m、橫2.4 m之陽極。 將離子交換膜於2%之碳酸氫鈉溶液中浸漬一晝夜後,按照與實施例5-1相同之要領將陽極無間隙地排列於磺酸層側,而製作陽極與離子交換膜之積層體。若將陰極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陰極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。按照與實施例5-1相同之要領將所獲得之積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。捲繞體之尺寸成為外徑86 mm、長度1.7 m之圓柱形狀,能夠減小積層體之尺寸。 繼而,於既有之大型電解槽(與實施例5-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。若於電解運轉中預先準備積層體之捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例5-3] (使用陽極/陰極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備縱1.5 m、橫2.5 m之離子交換膜。又,藉由上述所記載之方法各準備4片縱0.3 m、橫2.4 m之陽極及陽極。 將離子交換膜於2%之碳酸氫鈉溶液中浸漬一晝夜後,按照與實施例5-1相同之要領,將陰極無間隙地排列於羧酸層側,將陽極無間隙地排列於磺酸層側,而製作陰極、陽極與離子交換膜之積層體。若將陰極、陽極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陰極、陽極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。按照與實施例5-1相同之要領將所獲得之積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。捲繞體之尺寸成為外徑88 mm、長度1.7 m之圓柱形狀,能夠減小積層體之尺寸。 繼而,於既有之大型電解槽(與實施例5-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。若於電解運轉中預先準備積層體之捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例5-4] (使用陰極之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法,準備4片縱0.3 m、橫2.4 m之陰極。以成為縱1.2 m、橫2.4 m之尺寸之方式將4片陰極無間隙地排列。為了避免陰極彼此分開,如圖102所示般,使PTFE繩通過陰極之開孔部分(未圖示),藉此將相鄰之陰極彼此繫結而加以固定。於該操作中,不施加壓力,溫度為23℃。按照與實施例5-1相同之要領將該陰極捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。捲繞體之尺寸成為外徑78 mm、長度1.7 m之圓柱形狀,能夠減小積層體之尺寸。 繼而,於既有之大型電解槽(與實施例5-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之陰極之方式解除捲繞狀態。此時,係將陰極維持為大致垂直於地面,但不存在陰極剝落等情況。繼而,將陰極插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換陰極。若於電解運轉中預先準備陰極捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成陰極之更新。 [實施例5-5] (使用陽極之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備4片縱0.3 m、橫2.4 m之陽極。以成為縱1.2 m、橫2.4 m之尺寸之方式將4片陽極無間隙地排列。為了避免陽極彼此分開,按照與實施例5-4相同之要領,藉由PTFE繩將相鄰之陽極彼此繫結而加以固定。於該操作中,不施加壓力,溫度為23℃。按照與實施例5-1相同之要領將該陽極捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。捲繞體之尺寸成為外徑81 mm、長度1.7 m之圓柱形狀,能夠減小積層體之尺寸。 繼而,於既有之大型電解槽(與實施例5-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之陽極之方式解除捲繞狀態。此時,係將陽極維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將陽極插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換陽極。若於電解運轉中預先準備陽極捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成陽極之更新。 [比較例5-1] (先前之電極更新) 於既有之大型電解槽(與實施例5-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,藉由升降機從大型電解槽吊起電解池。將取出之電解池搬運至能夠進行焊接施工之工場。 將藉由焊接固定於電解池之肋部之陽極剝離取下後,使用磨機等研磨所剝離取下之部分之毛邊等,使其變得平滑。關於陰極,將折入集電體中並固定之部分去除而剝離陰極。 其後,於陽極室之肋部上設置新陽極,藉由點焊將新陽極固定於電解池。關於陰極,亦同樣地將新陰極設置於陰極側,折入集電體中並加以固定。 將完成更新之電解池搬運至大型電解槽之場所,使用升降機將電解池放回電解槽中。 從將電解池及離子交換膜之固定狀態解除起至再次固定電解池所需之時間為1天以上。 <第6實施形態之驗證> 如下所述準備與第6實施形態相對應之實驗例(於以下之<第6實施形態之驗證>之項中簡稱為「實施例」)、及不與第6實施形態相對應之實驗例(於以下之<第6實施形態之驗證>之項中簡稱為「比較例」),藉由以下方法對該等進行評價。一邊適當參照圖105~106一邊對其詳細內容進行說明。 使用以下述方式製造之離子交換膜b作為隔膜。 作為強化芯材,使用聚四氟乙烯(PTFE)製且90丹尼之單絲(以下稱為PTFE紗)。作為犧牲紗,使用35丹尼、6根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。首先,以沿TD及MD之兩方向之各方向以24根/英吋配置PTFE紗、且於鄰接之PTFE紗間配置2根犧牲紗之方式進行平織而獲得織布。藉由滾筒將所獲得之織布進行壓接而獲得厚度70 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.85 mg當量/g之乾燥樹脂之樹脂A、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之乾燥樹脂之樹脂B。 使用該等樹脂A及B,藉由共擠出T模法獲得樹脂A層之厚度為15 μm、樹脂B層之厚度為104 μm之2層膜X。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙(高度50 μm之圓錐形狀之壓紋加工)、補強材及膜X,於加熱板表面溫度223℃、減壓度0.067 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。 藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)30質量%、氫氧化鉀(KOH)15質量%之80℃之水溶液中浸漬20分鐘而進行皂化。其後,於含有氫氧化鈉(NaOH)0.5 N之50℃之水溶液中浸漬1小時,將離子交換基之抗衡離子置換為Na,繼而進行水洗。進而於60℃下加以乾燥。 進而,於樹脂B之酸型樹脂之5質量%乙醇溶液中添加1次粒徑1 μm之氧化鋯20質量%並使其分散而調製懸浮液,藉由懸浮液噴射法對上述複合膜之兩面進行噴霧,於複合膜之表面形成氧化鋯之塗層,而獲得離子交換膜A。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.5 mg/cm2 。此處,平均粒徑係利用粒度分佈計(島津製作所製造之「SALD(註冊商標)2200」)進行測定。 使用下述之陰極、陽極作為電極。 準備量規厚度為22 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.95 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 藉由打孔加工於該鎳箔開出圓形之孔而製成多孔箔。開孔率為44%。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。所製作之電極之厚度為29 μm。含有氧化釕與氧化鈰之觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。塗層亦形成於未經粗面化之面。 使用量規厚度100 μm、鈦纖維直徑約為20 μm、單位面積重量為100 g/m2 、開孔率78%之鈦不織布作為陽極電解用電極基材。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素、銥元素及鈦元素之莫耳比成為0.25:0.25:0.5之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、銥濃度為100 g/L之氯化銥(田中貴金屬工業股份有限公司)、四氯化鈦(和光純藥工業股份有限公司)加以混合。將該混合液充分攪拌,以其作為陽極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。於鈦多孔箔塗佈上述塗佈液後,於60℃下實施10分鐘之乾燥,於475℃下實施10分鐘之燒成。重複實施該等塗佈、乾燥、預燒成、燒成之一系列之操作後,於520℃下進行1小時之燒成。 [實施例6-1] (使用陰極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法,準備縱1.5 m、橫2.5 m之離子交換膜b。又,藉由上述所記載之方法,準備4片縱0.3 m、橫2.4 m之陰極。 將離子交換膜b於2%之碳酸氫鈉溶液中浸漬一晝夜後,將陰極無間隙地排列於羧酸層側,而製作陰極與離子交換膜b之積層體。若將陰極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陰極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。將該積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。再者,為了將離子交換膜b熔融,必須為200℃以上,於本實施例中進行一體化時離子交換膜不熔融。 繼而,於既有之大型電解槽(具有與圖105、106所示者相同之結構之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陰極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例6-2] (使用陽極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法,準備縱1.5 m、橫2.5 m之離子交換膜b。又,藉由上述所記載之方法準備4片縱0.3 m、橫2.4 m之陽極。 將離子交換膜b於2%之碳酸氫鈉溶液中浸漬一晝夜後,將陽極無間隙地排列於磺酸層側,而製作陽極與離子交換膜之積層體。若將陽極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陽極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。將該積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。 繼而,於既有之大型電解槽(與實施例6-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例6-3] (使用陽極/陰極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法,準備縱1.5 m、橫2.5 m之離子交換膜b。又,藉由上述所記載之方法各準備4片縱0.3 m、橫2.4 m之陽極及陽極。 將離子交換膜b於2%之碳酸氫鈉溶液中浸漬一晝夜後,將陰極無間隙地排列於羧酸層側,將陽極無間隙地排列於磺酸層側,而製作陰極、陽極與離子交換膜b之積層體。若將陰極、陽極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陰極、陽極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。將該積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。 繼而,於既有之大型電解槽(與實施例6-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [比較例6-1] 如下所述,以日本專利特開昭58-48686號公報之實施例作為參考,製作將電極熱壓接於隔膜而成之膜電極積層體。 使用量規厚度100 μm、開孔率33%之鎳多孔金屬作為陰極電解用電極基材,與實施例6-1同樣地實施電極塗佈。電極之尺寸為200 mm×200 mm,片數為72片。其後,按照下述之順序對電極之單面實施惰性化處理。於電極之單面貼附聚醯亞胺黏著帶(中興化成股份有限公司),於相反面塗佈PTFE分散液(DuPont-Mitsui Fluorochemicals股份有限公司,31-JR(商品名)),於120℃之馬弗爐中乾燥10分鐘。將聚醯亞胺膠帶剝離,於設定為380℃之馬弗爐中實施10分鐘燒結處理。將該操作重複2次,對電極之單面進行惰性化處理。 製作由末端官能基為「-COOCH3 」之全氟碳聚合物(C聚合物)與末端基為「-SO2 F」之全氟碳聚合物(S聚合物)之2層所形成之膜。C聚合物層之厚度為3密耳(mil),S聚合物層之厚度為4密耳(mil)。對該2層膜實施皂化處理,藉由水解對聚合物之末端導入離子交換基。C聚合物末端被水解為羧酸基,S聚合物末端被水解為磺基。以磺酸基計之離子交換容量為1.0 meq/g,以羧酸基計之離子交換容量為0.9 meq/g。所獲得之離子交換膜之大小與實施例6-1相同。 使具有羧酸基作為離子交換基之面與上述電極之經惰性化之電極面相對向,並實施熱壓製(熱壓接),而將離子交換膜與電極一體化。即,於離子交換膜熔融之溫度下,對1片縱1500 mm、橫2500 mm之離子交換膜進行200 mm見方之電極72片之一體化。熱壓接後電極之單面亦為露出之狀態,不存在電極貫通膜之部分。 於1500 mm×2500 mm之大型尺寸下,藉由熱壓接將離子交換膜與電極進行一體化之步驟需要一天以上之時間。即,於電極更新及隔膜之更換時,於比較例6-1中評價為需要多於實施例之時間。<第7實施形態之驗證> 如下所述準備與第7實施形態相對應之實驗例(於以下之<第7實施形態之驗證>之項中簡稱為「實施例」)、及不與第7實施形態相對應之實驗例(於以下之<第7實施形態之驗證>之項中簡稱為「比較例」),藉由以下方法對該等進行評價。一邊適當參照圖114~115一邊對其詳細內容進行說明。 使用以下述方式製造之離子交換膜作為隔膜。 作為強化芯材,使用聚四氟乙烯(PTFE)製且90丹尼之單絲(以下稱為PTFE紗)。作為犧牲紗,使用35丹尼、6根長絲之聚對苯二甲酸乙二酯(PET)以200次/m撚絞而成之紗(以下稱為PET紗)。首先,以沿TD及MD之兩方向之各方向以24根/英吋配置PTFE紗、且於鄰接之PTFE紗間配置2根犧牲紗之方式進行平織而獲得織布。藉由滾筒將所獲得之織布進行壓接而獲得厚度70 μm之織布。 繼而,準備以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 COOCH3 之共聚物計離子交換容量為0.85 mg當量/g之乾燥樹脂之樹脂A、以CF2 =CF2 與CF2 =CFOCF2 CF(CF3 )OCF2 CF2 SO2 F之共聚物計離子交換容量為1.03 mg當量/g之乾燥樹脂之樹脂B。 使用該等樹脂A及B,藉由共擠出T模法獲得樹脂A層之厚度為15 μm、樹脂B層之厚度為104 μm之2層膜X。 繼而,於內部具有加熱源及真空源、其表面具有微細孔之加熱板上依序積層脫模紙(高度50 μm之圓錐形狀之壓紋加工)、補強材及膜X,於加熱板表面溫度223℃、減壓度0.067 MPa之條件下加熱減壓2分鐘後,去除脫模紙,藉此獲得複合膜。 藉由將所獲得之複合膜於含有二甲基亞碸(DMSO)30質量%、氫氧化鉀(KOH)15質量%之80℃之水溶液中浸漬20分鐘而進行皂化。其後,於含有氫氧化鈉(NaOH)0.5 N之50℃之水溶液中浸漬1小時,將離子交換基之抗衡離子置換為Na,繼而進行水洗。進而於60℃下加以乾燥。 進而,於樹脂B之酸型樹脂之5質量%乙醇溶液中添加1次粒徑1 μm之氧化鋯20質量%並使其分散而調製懸浮液,藉由懸浮液噴射法對上述複合膜之兩面進行噴霧,於複合膜之表面形成氧化鋯之塗層,而獲得離子交換膜A。藉由螢光X射線測定對氧化鋯之塗佈密度進行測定,結果為0.5 mg/cm2 。此處,平均粒徑係利用粒度分佈計(島津製作所製造之「SALD(註冊商標)2200」)進行測定。 使用下述之陰極、陽極作為電極。 準備量規厚度為22 μm之電解鎳箔作為陰極電解用電極基材。對該鎳箔之單面實施利用電解鍍鎳之粗面化處理。經粗面化之表面之算術平均粗糙度Ra為0.95 μm。表面粗糙度之測定係於與實施噴擊處理之鎳板之表面粗糙度測定相同之條件下實施。 藉由打孔加工於該鎳箔開出圓形之孔而製成多孔箔。開孔率為44%。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素與鈰元素之莫耳比成為1:0.25之方式將釕濃度為100 g/L之硝酸釕溶液(FURUYA METAL股份有限公司)、硝酸鈰(Kishida Chemical股份有限公司)加以混合。將該混合液充分攪拌,以其作為陰極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。其後,於50℃下實施10分鐘之乾燥,於150℃下實施3分鐘之預燒成,於350℃下實施10分鐘之燒成。重複該等塗佈、乾燥、預燒成、燒成之一系列之操作直至成為特定之塗佈量為止。所製作之電極之厚度為29 μm。含有氧化釕與氧化鈰之觸媒層之厚度係電極之厚度減去電解用電極基材之厚度而為7 μm。塗層亦形成於未經粗面化之面。 使用量規厚度100 μm、鈦纖維直徑約為20 μm、單位面積重量為100 g/m2 、開孔率78%之鈦不織布作為陽極電解用電極基材。 按照以下之順序製備用以形成電極觸媒之塗佈液。以釕元素、銥元素及鈦元素之莫耳比成為0.25:0.25:0.5之方式將釕濃度為100 g/L之氯化釕溶液(田中貴金屬工業股份有限公司)、銥濃度為100 g/L之氯化銥(田中貴金屬工業股份有限公司)、四氯化鈦(和光純藥工業股份有限公司)加以混合。將該混合液充分攪拌,以其作為陽極塗佈液。 於滾筒塗佈裝置之最下部設置裝有上述塗佈液之槽。以於PVC(聚氯乙烯)製之筒上捲繞有獨立氣泡型之發泡EPDM(乙烯-丙烯-二烯橡膠)製之橡膠(Inoac Corporation,E-4088,厚度10 mm)之塗佈滾筒與塗佈液始終相接之方式進行設置。於其上部設置同樣捲繞有EPDM之塗佈滾筒,進而於其上設置PVC製之輥。使電極基材通過第2個塗佈滾筒與最上部之PVC製之輥之間而塗佈塗佈液(滾筒塗佈法)。於鈦多孔箔塗佈上述塗佈液後,於60℃下實施10分鐘之乾燥,於475℃下實施10分鐘之燒成。重複實施該等塗佈、乾燥、預燒成、燒成之一系列之操作後,於520℃下進行1小時之燒成。 [實施例7-1] (使用陰極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備縱1.5 m、橫2.5 m之離子交換膜。又,藉由上述所記載之方法,準備4片縱0.3 m、橫2.4 m之陰極。 將離子交換膜於2%之碳酸氫鈉溶液中浸漬一晝夜後,將陰極無間隙地排列於羧酸層側,而製作陰極與離子交換膜之積層體。若將陰極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陰極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。將該積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。 繼而,於既有之大型電解槽(具有與圖114、115所示者相同之結構之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陰極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。若於電解運轉中預先準備積層體之捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例7-2] (使用陽極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備縱1.5 m、橫2.5 m之離子交換膜。又,藉由上述所記載之方法準備4片縱0.3 m、橫2.4 m之陽極。 將離子交換膜於2%之碳酸氫鈉溶液中浸漬一晝夜後,將陽極無間隙地排列於磺酸層側,而製作陽極與離子交換膜之積層體。若將陽極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陽極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。將該積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。 繼而,於既有之大型電解槽(與實施例7-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。若於電解運轉中預先準備積層體之捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例7-3] (使用陽極/陰極-膜積層體之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備縱1.5 m、橫2.5 m之離子交換膜。又,藉由上述所記載之方法各準備4片縱0.3 m、橫2.4 m之陽極及陽極。 將離子交換膜於2%之碳酸氫鈉溶液中浸漬一晝夜後,將陰極無間隙地排列於羧酸層側,將陽極無間隙地排列於磺酸層側,而製作陰極、陽極與離子交換膜之積層體。若將陰極、陽極置於膜上,則因與碳酸氫鈉水溶液之接觸,界面張力發揮作用,陰極、陽極與膜以吸附之方式成為一體。於以上述方式進行一體化時不施加壓力。又,一體化時之溫度為23℃。將該積層體捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。 繼而,於既有之大型電解槽(與實施例7-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之積層體之方式解除捲繞狀態。此時,係將積層體維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將積層體插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換電極、隔膜。若於電解運轉中預先準備積層體之捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成電極更新及隔膜更換。 [實施例7-4] (使用陰極之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法,準備4片縱0.3 m、橫2.4 m之陰極。以成為縱1.2 m、橫2.4 m之尺寸之方式將4片陰極無間隙地排列。為了避免陰極彼此分開,藉由PTFE繩將相鄰之陰極繫結而加以固定。於該操作中,不施加壓力,溫度為23℃。將該陰極捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。 繼而,於既有之大型電解槽(與實施例7-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之陰極之方式解除捲繞狀態。此時,係將陰極維持為大致垂直於地面,但不存在陰極剝落等情況。繼而,將陰極插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換陰極。若於電解運轉中預先準備陰極捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成陰極之更新。 [實施例7-5] (使用陽極之例) 以下述方式預先製作捲繞體。首先,藉由上述所記載之方法準備4片縱0.3 m、橫2.4 m之陽極。以成為縱1.2 m、橫2.4 m之尺寸之方式將4片陽極無間隙地排列。為了避免陽極彼此分開,藉由PTFE繩將相鄰之陽極繫結而加以固定。於該操作中,不施加壓力,溫度為23℃。將該陽極捲繞於外徑76 mm、長度1.7 m之聚氯乙烯(PVC)管而製作捲繞體。 繼而,於既有之大型電解槽(與實施例7-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,將上述捲繞體搬運至大型電解槽上。於大型電解槽上,從立設PVC管之狀態,以拉出所捲繞之陽極之方式解除捲繞狀態。此時,係將陽極維持為大致垂直於地面,但不存在陽極剝落等情況。繼而,將陽極插入至電解池間後,移動電解池,利用電解池彼此將該積層體夾住。 與先前相比,能夠容易地更換陽極。若於電解運轉中預先準備陽極捲繞體,則評價為對於每個電解池,能夠於數十分鐘左右完成陽極之更新。 [比較例7-1] (先前之電極更新) 於既有之大型電解槽(與實施例7-1相同之電解槽)中,將利用壓製器所形成之鄰接之電解池及離子交換膜之固定狀態加以解除,取出既有隔膜而成為電解池間有空隙之狀態。其後,藉由升降機從大型電解槽吊起電解池。將取出之電解池搬運至能夠進行焊接施工之工場。 將藉由焊接固定於電解池之肋部之陽極剝離取下後,使用磨機等研磨所剝離取下之部分之毛邊等,使其變得平滑。關於陰極,將折入集電體中並固定之部分去除而剝離陰極。 其後,於陽極室之肋部上設置新陽極,藉由點焊將新陽極固定於電解池。關於陰極,亦同樣地將新陰極設置於陰極側,折入集電體中並加以固定。 將完成更新之電解池搬運至大型電解槽之場所,使用升降機將電解池放回電解槽中。 從將電解池及離子交換膜之固定狀態解除起至再次固定電解池所需之時間為1天以上。 本申請案係基於2017年3月22日提出申請之日本專利申請案(日本專利特願2017-056524號及日本專利特願2017-056525號)、以及2018年3月20日提出申請之日本專利申請案(日本專利特願2018-053217號、日本專利特願2018-053146號、日本專利特願2018-053144號、日本專利特願2018-053231號、日本專利特願2018-053145號、日本專利特願2018-053149號及日本專利特願2018-053139號),該等之內容係作為參照而併入至本文。Hereinafter, the embodiment of the present invention (hereinafter also referred to as the present embodiment) will be described in detail with reference to the drawings, the first embodiment to the seventh embodiment, as necessary, with reference to the drawings. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following. The accompanying drawings show an example of the embodiment, and the embodiment is not limited to the explanation. The present invention can be appropriately modified and implemented within the scope of the gist thereof. In addition, unless otherwise specified, positional relationships such as up, down, left, and right in the drawings are based on the positional relationships shown in the drawings. The dimensions and ratios of the drawings are not limited to those shown. <First Embodiment> Here, a first embodiment of the present invention will be described in detail with reference to FIGS. 1 to 21. [Electrolysis electrode] The electrode for electrolysis in the first embodiment (hereinafter referred to as "this embodiment" in the following "first embodiment") can obtain good operability, and can be used with separators such as ion exchange membranes or microporous membranes. , Degraded electrodes, and feeders without a catalyst coating, etc. have good adhesion. Furthermore, from the viewpoint of economics, the mass per unit area is 48 mg / cm2 the following. In addition, in the above aspect, it is preferably 30 mg / cm2 Below, more preferably 20 mg / cm2 In the following, from the viewpoint of combining the operability, adhesiveness, and economy, 15 mg / cm is preferred.2 the following. The lower limit value is not particularly limited, for example, 1 mg / cm2 about. The above-mentioned mass per unit area can be set to the above range, for example, by appropriately adjusting the opening ratio and thickness of the electrode described below. More specifically, for example, if the thickness is the same, the mass per unit area tends to become smaller if the opening ratio is increased, and the mass per unit area tends to be larger if the opening ratio is decreased. . The electrode for electrolysis in this embodiment can obtain good operability, and has a good adhesion with a separator such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a power supply body without a catalyst coating. In other words, the force per unit mass and area is 0.08 N / (mg · cm2 )the above. In addition, in the above aspect, it is preferably 0.1 N / (mg · cm2 Above), more preferably 0.14 N / (mg · cm2 ) Above, from the viewpoint of easier handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The upper limit value is not particularly limited, but is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. If the electrode for electrolysis in this embodiment is an electrode with a wide elastic deformation area, better operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and those without a catalyst coating. From the viewpoint that the power supply and the like have better adhesion, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, still more preferably 170 μm or less, and even more preferably 150 μm or less. It is particularly preferably 145 μm or less, more preferably 140 μm or less, even more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. In addition, in this embodiment, "the elastic deformation area is wide" means that the electrode for electrolysis is wound into a wound body, and warping caused by winding is unlikely to occur after the wound state is released. When the thickness of the electrode for electrolysis includes a catalyst layer described below, it means the thickness of the electrode substrate for electrolysis and the thickness of the catalyst layer. With the electrode for electrolysis of this embodiment, as described above, it has a good adhesion to a separator such as an ion-exchange membrane or a microporous membrane, a deteriorated electrode, and a power supply body without a catalyst coating layer, and can exchange with ions. A separator such as a membrane or a microporous membrane is integrated and used. Therefore, it is not necessary to accompany complicated replacement work such as peeling off the electrode fixed to the electrolytic cell when the electrode is updated, and the electrode can be updated by the same simple operation as that of the diaphragm, so the operation efficiency is greatly improved. In addition, even when the new electrolytic cell is provided only with a power source (that is, an electrode without a catalyst layer), the electrode for electrolysis in this embodiment can be attached to the power source only. It functions as an electrode, so the catalyst coating can be greatly reduced, or even no catalyst coating. Furthermore, with the electrode for electrolysis of this embodiment, the electrolytic performance can be made the same as or improved in the new product. The electrode for electrolysis of this embodiment can be wound around a tube made of vinyl chloride (for example, roll-shaped) for storage, transportation to a customer, and the like, and handling is greatly facilitated. The withstand force can be measured by the following method (i) or (ii). Specifically, it is as described in the examples. As for the bearing capacity, the value obtained by the measurement of the method (i) (also referred to as "bearing capacity (1)") and the value obtained by the measurement of the method (ii) (also referred to as "bearing capacity (2) ) ") Can be the same or different, but any value is 0.08 N / (mg ・ cm2 )the above. The above-mentioned bearing force can be set to the above range, for example, by appropriately adjusting a porosity, an electrode thickness, an arithmetic average surface roughness, and the like described below. More specifically, for example, if the opening ratio is increased, the bearing force tends to be small, and if the opening ratio is decreased, the bearing force tends to be large. [Method (i)] A nickel plate (thickness: 1.2 mm, 200 mm square) obtained by spraying with alumina of grain number 320 was laminated in order, and the perfluorocarbon polymer film with an ion exchange group was introduced. Ion-exchange membrane (170 mm square, with details of the so-called ion-exchange membrane as described in the examples) and inorganic electrode samples (130 mm square) coated on both sides with inorganic particles and binders. After sufficient immersion in water, excess water adhering to the surface of the laminate was removed to obtain a sample for measurement. Furthermore, the arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment was 0.7 μm. The specific calculation method of the arithmetic average surface roughness (Ra) is as described in the examples. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample for electrolysis in the measurement sample was raised vertically at 10 mm / min to measure the electrode for electrolysis. Load when the sample is raised 10 mm vertically. This measurement was performed three times and the average value was calculated. This average value is divided by the area of the overlapping part of the electrode sample for electrolysis and the ion-exchange membrane and the mass of the electrode sample for electrolysis of the part overlapping the ion-exchange membrane to calculate the force per unit mass and unit area (1) ( N / mg ・ cm2 ). With the force (1) per unit mass and unit area obtained by method (i), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating. From the viewpoint that the layer power supply has a good adhesion, it is 0.08 N / (mg · cm2 ) Or more, preferably 0.1 N / (mg · cm2 ) Above, from the viewpoint of easier handling at a large size (for example, a size of 1.5 m × 2.5 m), more preferably 0.2 N / (mg · cm2 )the above. The upper limit value is not particularly limited, but is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. If the electrode for electrolysis in this embodiment satisfies the bearing capacity (1), it can be integrated with, for example, an ion-exchange membrane or a microporous membrane, and it is not necessary to fix the electrode to the electrolytic cell by welding or other methods when updating the electrode The replacement and attachment of the cathode and anode greatly improves the operation efficiency. Moreover, by using the electrode for electrolysis of this embodiment as an electrode integrated with an ion exchange membrane, the electrolytic performance can be made the same as or improved in the new product. When a new electrolytic cell is shipped, a catalyst coating was previously applied to the electrode fixed to the electrolytic cell, but it can only be used by combining the electrode without a catalytic coating with the electrode for electrolysis of this embodiment. As an electrode, the amount of manufacturing steps or catalysts used to form the catalyst coating can be greatly reduced or even none of these exist. The previous electrode with a greatly reduced or absent catalyst coating layer is electrically connected to the electrode for electrolysis in this embodiment, so that it can function as a current feeder. [Method (ii)] A nickel plate (thickness 1.2 mm, 200 mm square, the same nickel plate as in the above method (i)) and an electrode sample for electrolysis were sequentially stacked on the nickel plate with alumina of grain number 320 and spray processing. (130 mm square), the laminated body was sufficiently immersed in pure water, and then excess water adhered to the surface of the laminated body was removed to obtain a sample for measurement. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample for electrolysis in the measurement sample was raised vertically at 10 mm / min to measure the electrode for electrolysis Load when the sample is raised 10 mm vertically. This measurement was performed three times and the average value was calculated. The average value is divided by the area of the overlapping portion of the electrode sample for electrolysis and the nickel plate, and the mass of the electrode sample for electrolysis in the portion overlapping the nickel plate, and the adhesion force per unit mass and unit area (2) (N / mg・ Cm2 ). With the force (2) per unit mass and unit area obtained by method (ii), good operability can be obtained. It can be used with membranes such as ion exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating. From the viewpoint that the layer power supply has a good adhesion, it is 0.08 N / (mg · cm2 ) Or more, preferably 0.1 N / (mg · cm2 ) Above, from the viewpoint of easier handling at a large size (for example, a size of 1.5 m × 2.5 m), more preferably 0.14 N / (mg · cm2 )the above. The upper limit value is not particularly limited, but is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. If the electrode for electrolysis of this embodiment satisfies the withstand force (2), it can be wound, for example, in the state (roller-like) of a pipe made of vinyl chloride for storage, transportation to a customer, etc., and the operation is greatly facilitated. In addition, by attaching the electrode for electrolysis of this embodiment to the deteriorated electrode, the electrolytic performance can be made the same as or improved in the new product. In this embodiment, the liquid existing between a separator such as an ion exchange membrane or a microporous membrane, and an electrode for electrolysis, or a power supply (a deteriorated electrode or an electrode without a catalyst coating layer), and an electrode for electrolysis only For the surface tension of water, organic solvents, etc., any liquid can be used. The greater the surface tension of the liquid, the greater the force on the diaphragm and the electrode for electrolysis, or the metal plate and the electrode for electrolysis. Therefore, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the values in parentheses are the surface tension of the liquid). Hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m), water (72.76 mN / m) In the case of a liquid having a large surface tension, the separator is integrated with the electrode for electrolysis, or the porous metal plate or metal plate (feeder) is integrated with the electrode for electrolysis (laminated body), and electrode replacement becomes easy. The amount of liquid between the separator and the electrode for electrolysis, or the porous metal plate or metal plate (feeder), and the electrode for electrolysis may be such that the amount of liquid adheres to each other by surface tension. As a result, the amount of liquid is small. Therefore, even if the laminated body is placed in an electrolytic cell and mixed into the electrolytic solution, it will not affect the electrolysis itself. From a practical point of view, as the liquid, a liquid having a surface tension of 20 mN / m to 80 mN / m such as ethanol, ethylene glycol, and water is preferably used. Particularly preferred is water or a caustic soda, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, etc. dissolved in water to make an alkaline aqueous solution. Moreover, you may adjust surface tension by making these liquids contain a surfactant. By including a surfactant, the adhesion between the separator and the electrode for electrolysis, or the metal plate and the electrode for electrolysis changes, and the operability can be adjusted. The surfactant is not particularly limited, and any of an ionic surfactant and a nonionic surfactant can be used. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, and good operability can be obtained. It can be used with separators such as ion-exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating. The electric body has a good adhesive force, can be appropriately wound into a roll shape, and can be bent well. From the viewpoint of easy handling in a large size (for example, a size of 1.5 m × 2.5 m), 300 μm is preferred. Below, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and still more preferably 100 μm or less. From the viewpoint of performance and economy, it is more preferably 50 μm or less. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It has good adhesion to separators such as ion-exchange membranes or microporous membranes, degraded electrodes, and power supply bodies without a catalyst coating. From the viewpoint of force, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and further, for a large size (for example, a size of 1.5 m × 2.5 m) From the viewpoint of easy handling, it is more preferably 95% or more. The upper limit is 100%. [Method (2)] An ion exchange membrane (170 mm square) and an electrode sample for electrolysis (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body is placed on the curved surface of a polyethylene tube (outer diameter of 280 mm) in such a way that the sample of the electrode for electrolysis in the laminated body becomes the outside. The laminated body and the tube were fully impregnated with pure water to remove excess water adhered to the surface of the laminated body and the tube. After 1 minute, the portion of the ion exchange membrane (170 mm square) closely contacting the electrode electrode for electrolysis The area ratio (%) was measured. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It has good adhesion to separators such as ion-exchange membranes or microporous membranes, degraded electrodes, and feed bodies without a catalyst coating. From the viewpoint that the force can be appropriately wound into a roll shape and bent well, the ratio measured by the following method (3) is preferably 75% or more, more preferably 80% or more, and From the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 90% or more. The upper limit is 100%. [Method (3)] An ion exchange membrane (170 mm square) and an electrode sample for electrolysis (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body is placed on the curved surface of a polyethylene pipe (145 mm in outer diameter) so that the sample of the electrode for electrolysis in the laminated body becomes the outer side. The laminated body and the tube were fully impregnated with pure water to remove excess water adhered to the surface of the laminated body and the tube. After 1 minute, the portion of the ion exchange membrane (170 mm square) in close contact with the electrode electrode for electrolysis was removed. The area ratio (%) was measured. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It has good adhesion to separators such as ion-exchange membranes or microporous membranes, degraded electrodes, and feed bodies without a catalyst coating. From the viewpoint of preventing the retention of gas generated during electrolysis, a porous structure is preferred, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80%, and more preferably 20 to 75%. The open porosity is the ratio of the perforated portion per unit volume. There are various calculation methods for the opening part according to the submicron order or only the openings that can be seen visually. In this embodiment, the volume V is calculated from the values of the gauge thickness, width, and length of the electrode, and the weight W is measured. Then, the aperture ratio A is calculated by the following formula. A = (1- (W / (V × ρ)) × 100 ρ Density of electrode material (g / cm3 ). E.g. in the case of nickel 8.908 g / cm3 In the case of titanium is 4.506 g / cm3 . The adjustment of the opening ratio is appropriately adjusted by the following methods: if it is a punched metal, change the area of the punched metal per unit area; if it is a porous metal, change SW (short diameter), LW (long diameter), Feed value; if it is a wire mesh, change the wire diameter and mesh number of the metal fiber; if it is electroforming, change the pattern of the photoresist used; if it is a non-woven fabric, change the metal fiber diameter and fiber density; In the case of a foamed metal, a template or the like for forming a void is changed. From the viewpoint of operability, the electrode for electrolysis in this embodiment is preferably 40 mm or less, more preferably 29 mm or less, and even more preferably 10 mm or less by the following method (A). , And more preferably 6.5 mm or less. The specific measurement method is as described in the examples. [Method (A)] Under the conditions of a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, a sample formed by laminating an ion exchange membrane and the above-mentioned electrode for electrolysis was wound and fixed to a vinyl chloride product having an outer diameter of f32 mm. On the curved surface of the core material, after standing for 6 hours, the electrode for electrolysis was separated and placed on a horizontal plate. At this time, the height L of the two ends of the electrode for electrolysis in the vertical direction was measured.1 And L2 Take the average of these as the measured value. The electrode for electrolysis in the present embodiment is preferably set to a size of 50 mm × 50 mm and a temperature of 24 ° C., a relative humidity of 32%, a piston speed of 0.2 cm / s, and a ventilation volume of 0.4 cc / cm.2 In the case of / s (hereinafter also referred to as "measurement condition 1"), the ventilation resistance (hereinafter also referred to as "ventilation resistance 1") is 24 kPa · s / m or less. Large ventilation resistance means that the air is difficult to flow, and refers to a state with a high density. In this state, the product of electrolysis stays in the electrode, and the reaction matrix is difficult to diffuse into the electrode, so the electrolytic performance (voltage, etc.) tends to deteriorate. Moreover, there exists a tendency for the density | concentration of the film surface to increase. Specifically, there is a tendency that the caustic concentration on the cathode side increases and the supply property of the brine on the anode side decreases. As a result, since the product stays at the interface between the separator and the electrode at a high concentration, the separator tends to be damaged, and the voltage on the cathode surface and the membrane damage and the anode surface tend to be damaged. In this embodiment, in order to prevent such abnormalities, it is preferable to set the ventilation resistance to 24 kPa · s / m or less. From the same viewpoint as described above, it is more preferably less than 0.19 kPa · s / m, still more preferably 0.15 kPa · s / m or less, and still more preferably 0.07 kPa · s / m or less. Furthermore, in this embodiment, if the ventilation resistance is larger than a certain degree, the NaOH generated in the electrode tends to stay at the interface between the electrode and the separator and becomes a high concentration in the case of the cathode. In the case of the anode, the tendency is high. The tendency of the salt water supply to decrease and the concentration of the salt water to become low, in order to prevent damage to the diaphragm that may occur due to such retention, it is preferably less than 0.19 kPa · s / m, more preferably 0.15 kPa · s / m or less, more preferably 0.07 kPa · s / m or less. On the other hand, when the ventilation resistance is low, since the area of the electrode becomes smaller, the electrolytic area tends to become smaller and the electrolytic performance (voltage, etc.) tends to deteriorate. When the ventilation resistance is zero, since no electrode for electrolysis is provided, there is a tendency that the power supply body functions as an electrode, and the electrolytic performance (voltage, etc.) tends to be significantly deteriorated. In this respect, the preferable lower limit value specified as the ventilation resistance 1 is not particularly limited, but preferably exceeds 0 kPa · s / m, more preferably 0.0001 kPa · s / m or more, and more preferably 0.001 kPa · s / m or more. In addition, in terms of measurement method, if the ventilation resistance 1 is 0.07 kPa · s / m or less, sufficient measurement accuracy may not be obtained. From this viewpoint, it is also possible to realize the ventilation resistance (hereinafter referred to as "measurement condition 2") obtained by the following measurement method (hereinafter also referred to as "measurement condition 2") with respect to an electrode for electrolysis whose ventilation resistance 1 is 0.07 kPa · s / m or less Also called "ventilation resistance 2"). That is, the ventilation resistance 2 is set to a size of 50 mm × 50 mm for the electrode for electrolysis, and the temperature is 24 ° C, the relative humidity is 32%, the piston speed is 2 cm / s, and the ventilation volume is 4 cc / cm.2 / s in the case of ventilation resistance. Specific measurement methods of the ventilation resistances 1 and 2 are described in the examples. The above-mentioned ventilation resistances 1 and 2 can be set to the above-mentioned range, for example, by appropriately adjusting the opening ratio and the thickness of the electrodes described below. More specifically, for example, if the thickness is the same, if the opening rate is increased, the ventilation resistances 1 and 2 tend to decrease, and if the opening rate is decreased, the ventilation resistances 1 and 2 tend to be large. . Hereinafter, one embodiment of an electrode for electrolysis according to this embodiment will be described. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer is described below, and may include a plurality of layers or a single-layer structure. As shown in FIG. 1, the electrode 100 for electrolysis according to this embodiment includes an electrode substrate 10 for electrolysis, and a first layer 20 covering one of both surfaces of the electrode substrate 10 for electrolysis. The first layer 20 preferably covers the entire electrode base material 10 for electrolysis. This makes it easy to improve the catalyst activity and durability of the electrode. Furthermore, the first layer 20 may be formed only on one surface area of the electrode base material 10 for electrolysis. As shown in FIG. 1, the surface of the first layer 20 may be covered by the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, the second layer 30 may be laminated on only one surface of the first layer 20. (Electrode base material for electrolysis) The electrode base material 10 for electrolysis is not particularly limited. For example, nickel, nickel alloy, stainless steel, and valve metal typified by titanium or the like can be used. Preferably, it contains at least one element selected from the group consisting of nickel (Ni) and titanium (Ti). That is, it is preferable that the electrode substrate for electrolysis contains at least one element selected from nickel (Ni) and titanium (Ti). When stainless steel is used in a high-concentration alkaline aqueous solution, considering the elution of iron and chromium, and the conductivity of stainless steel is about 1/10 of that of nickel, it is preferable to use a substrate containing nickel (Ni) as the base material. Electrode substrate for electrolysis. In addition, when the electrode base material 10 for electrolysis is used in a chlorine gas generating environment in a high-concentration saline solution, the material is preferably titanium with high corrosion resistance. The shape of the electrode substrate 10 for electrolysis is not particularly limited, and a suitable shape can be selected according to the purpose. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. Among them, punched metal or porous metal is preferred. In addition, the so-called electroforming is a technique for producing a precise patterned metal thin film by combining a photolithographic process and an electroplating method. It is a method for obtaining a metal thin film by forming a pattern on a substrate with a photoresist, and performing electroplating on a portion not protected by the photoresist. Regarding the shape of the electrode substrate for electrolysis, there are suitable specifications according to the distance between the anode and the cathode in the electrolytic cell. There is no particular limitation. When the anode and the cathode have a limited distance, porous metal and punched metal shapes can be used. In the case of a so-called zero-pitch electrolytic cell where the ion exchange membrane is connected to the electrode, a braided thin wire can be used. The finished woven mesh, foamed metal, metal non-woven fabric, porous metal, punched metal, metal porous foil, etc. Examples of the electrode base material 10 for electrolysis include metal foil, wire mesh, metal nonwoven fabric, punched metal, porous metal, or foamed metal. As a sheet material before being processed into a punched metal or a porous metal, a sheet material formed by rolling and an electrolytic foil are preferred. The electrolytic foil is preferably subjected to a plating treatment with the same element as the base material as a post-treatment to form unevenness on the surface. As described above, the thickness of the electrode base material 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, even more preferably 155 μm or less, even more preferably 135 μm or less, and even more preferably 125. μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, and further more preferably 50 μm or less in terms of operability and economy. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the electrode base material for electrolysis, it is preferable to reduce the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing environment. Further, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, it is preferable to use steel sand and alumina sand to form unevenness on the surface, and then increase the surface area by acid treatment. It is preferable to increase the surface area by applying a plating treatment to the same element as the substrate. In order to bring the first layer 20 into close contact with the surface of the electrode base material 10 for electrolysis, it is preferable that the surface area of the electrode base material 10 for electrolysis is increased. Examples of the treatment for increasing the surface area include a shot treatment using cut wire shot, steel grit, alumina sand, etc., an acid treatment using sulfuric acid or hydrochloric acid, and a plating treatment using the same element as the substrate. . The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 5 μm. Next, a case where the electrode for electrolysis of this embodiment is used as an anode for salt electrolysis will be described. (First layer) In FIG. 1, the first layer 20 as a catalyst layer contains at least one of ruthenium oxide, iridium oxide, and titanium oxide. Examples of the ruthenium oxide include RuO2 Wait. Examples of the iridium oxide include IrO2 Wait. Examples of the titanium oxide include TiO2 Wait. The first layer 20 is preferably two oxides containing ruthenium oxide and titanium oxide, or three oxides containing ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and further, the adhesion with the second layer 30 is further improved. In the case where the first layer 20 contains two oxides of ruthenium oxide and titanium oxide, the titanium oxide contained in the first layer 20 is better than 1 mol of the ruthenium oxide contained in the first layer 20 It is 1 to 9 moles, more preferably 1 to 4 moles. By setting the composition ratio of the two oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains three oxides of ruthenium oxide, iridium oxide, and titanium oxide, the iridium oxide contained in the first layer 20 is 1 mole relative to the ruthenium oxide contained in the first layer 20 The amount is preferably 0.2 to 3 moles, and more preferably 0.3 to 2.5 moles. In addition, the titanium oxide contained in the first layer 20 is preferably 0.3 to 8 moles, and more preferably 1 to 7 moles relative to 1 mole of the ruthenium oxide contained in the first layer 20. By setting the composition ratio of the three oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains at least two oxides selected from the group consisting of ruthenium oxide, iridium oxide, and titanium oxide, these oxides preferably form a solid solution. By forming an oxide solid solution, the electrode 100 for electrolysis exhibits excellent durability. In addition to the above composition, as long as it contains at least one of ruthenium oxide, iridium oxide, and titanium oxide, various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like called DSA (registered trademark) may be used as the first layer 20. The first layer 20 need not be a single layer, and may include a plurality of layers. For example, the first layer 20 may include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. (Second layer) The second layer 30 preferably contains ruthenium and titanium. This can further reduce the chlorine overvoltage immediately after electrolysis. The second layer 30 is preferably a palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. This can further reduce the chlorine overvoltage immediately after electrolysis. The thicker the second layer 30 is, the longer the time during which the electrolytic performance can be maintained. From the viewpoint of economy, the thickness is preferably 0.05 to 3 μm. Next, a case where the electrode for electrolysis of this embodiment is used as a cathode for salt electrolysis will be described. (First layer) The components of the first layer 20 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals, and oxides or hydroxides of these metals. In the case of containing at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal, a platinum group metal, a platinum group metal oxide, and a platinum group metal hydroxide are preferred. The alloy containing a platinum group metal contains at least one platinum group metal of platinum, palladium, rhodium, ruthenium, and iridium. The platinum group metal preferably contains platinum. The platinum group metal oxide is preferably a ruthenium oxide. The platinum group metal hydroxide is preferably a ruthenium hydroxide. The platinum group metal alloy is preferably an alloy containing platinum and nickel, iron, and cobalt. It is preferable to further contain an oxide or hydroxide of a lanthanoid as a second component as necessary. Accordingly, the electrode 100 for electrolysis exhibits excellent durability. The lanthanide oxide or hydroxide preferably contains at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, and praseodymium. It is preferable to further contain an oxide or hydroxide of a transition metal as a third component as necessary. By adding the third component, the electrode 100 for electrolysis can exhibit more excellent durability and reduce the electrolytic voltage. Examples of preferred combinations include ruthenium, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + osmium, ruthenium + rhenium + platinum, ruthenium + rhenium + Platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur , Ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + osmium, ruthenium + rhenium + manganese, ruthenium + 钐 + iron, ruthenium + rhenium + cobalt, ruthenium + 钐 + zinc, ruthenium + 钐+ Gallium, Ruthenium + 钐 + Sulfur, Ruthenium + 钐 + Lead, Ruthenium + 钐 + Ni, Pt + Ce, Pt + Pd + Ce, Pt + Pd + La + Ce, Pt + Ir, Pt + Pd, Pt + I + Palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, alloys of platinum and nickel, alloys of platinum and cobalt, alloys of platinum and iron, etc. When the platinum group metal, platinum group metal oxide, platinum group metal hydroxide, and platinum group metal-containing alloy are not contained, the main component of the catalyst is preferably nickel. Preferably, it contains at least one of nickel metal, oxide, and hydroxide. As a second component, a transition metal may be added. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon. Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, and the like. If necessary, an intermediate layer may be provided between the first layer 20 and the electrode base material 10 for electrolysis. By providing the intermediate layer, the durability of the electrode 100 for electrolysis can be improved. The intermediate layer is preferably one having an affinity for both the first layer 20 and the electrode base material 10 for electrolysis. The intermediate layer is preferably a nickel oxide, a platinum group metal, a platinum group metal oxide, or a platinum group metal hydroxide. The intermediate layer can be formed by coating and firing a solution containing the components forming the intermediate layer, or heat-treating the substrate at a temperature of 300 to 600 ° C in an air environment to form a surface oxide layer. . In addition, it can be formed by a known method such as a thermal spray method or an ion plating method. (Second layer) The components of the first layer 30 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals, and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. Examples of preferred combinations of the elements contained in the second layer include the combinations listed in the first layer. The combination of the first layer and the second layer may be a combination with the same composition but a different composition ratio, or a combination with a different composition. As the thickness of the catalyst layer, the thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 μm to 20 μm. When it is 0.01 μm or more, it can fully function as a catalyst. If it is 20 μm or less, it is less likely to fall off from the substrate, and a strong catalyst layer can be formed. More preferably, it is 0.05 μm to 15 μm. More preferably, it is 0.1 μm to 10 μm. It is more preferably 0.2 μm to 8 μm. The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer, is preferably 315 μm or less, more preferably 220 μm or less, and further preferably 170 μm in terms of the operability of the electrode. Below, still more preferably 150 μm or less, even more preferably 145 μm or less, even more preferably 140 μm or less, even more preferably 138 μm or less, and even more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. The thickness of the electrode can be determined by measuring with an electronic digital thickness gauge (Mitutoyo Co., Ltd., at least 0.001 mm). The thickness of the electrode substrate for electrolysis was measured in the same manner as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. (Manufacturing method of the electrode for electrolysis) Next, one Embodiment of the manufacturing method of the electrode 100 for electrolysis is demonstrated in detail. In this embodiment, the first layer 20 is formed on the electrode substrate for electrolysis by using a method such as firing (thermal decomposition) of a coating film under an oxygen environment, or ion plating, plating, or thermal spraying. The second layer 30 is preferably used to produce the electrode 100 for electrolysis. Among them, a thermal decomposition method, a plating method, and an ion plating method are preferable because they can suppress the deformation of the electrode substrate for electrolysis and form a catalyst layer. From the viewpoint of productivity, a plating method and a thermal decomposition method are more preferred. Such a manufacturing method according to this embodiment can achieve high productivity of the electrode 100 for electrolysis. Specifically, in the thermal decomposition method, the electrode substrate for electrolysis is subjected to a coating step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. Form a catalyst layer. The term "thermal decomposition" means heating a metal salt that becomes a precursor to decompose it into a metal or a metal oxide and a gaseous substance. Decomposition products differ depending on the type of metal used, the type of salt, and the environment in which thermal decomposition is performed, but most metals tend to form oxides easily in an oxidizing environment. In the industrial manufacturing process of electrolytic electrodes, thermal decomposition is usually performed in the air, and in most cases, metal oxides or metal hydroxides are formed. (Formation of the first layer of the anode) (Coating step) The first layer 20 is a solution (first coating liquid) in which a salt of at least one metal among ruthenium, iridium, and titanium is dissolved, and is applied to an electrode base for electrolysis. It is obtained by thermal decomposition (baking) in the presence of oxygen. The contents of ruthenium, iridium, and titanium in the first coating liquid are approximately equal to those of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 100 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of the second layer of the anode) The second layer 30 is formed as necessary. For example, a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second coating solution) is applied to the first The layer 20 is obtained by thermal decomposition in the presence of oxygen. (Formation of the first layer of the cathode by thermal decomposition method) (Coating step) The first layer 20 is a solution (first coating solution) in which metal salts of various combinations are dissolved on the electrode substrate for electrolysis , Obtained by thermal decomposition (firing) in the presence of oxygen. The content ratio of the metal in the first coating liquid is substantially equal to that of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and water, alcohols such as ethanol and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 10 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if it is fired for a longer period of time as required, and then heated in the range of 350 ° C to 650 ° C for 1 minute to 90 minutes, the stability of the first layer 20 can be further improved. (Formation of Intermediate Layer) The intermediate layer is formed as necessary. For example, a solution (second coating solution) containing a palladium compound or a platinum compound is coated on a substrate, and then obtained by thermal decomposition in the presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the base material by heating the base material in the range of 300 ° C to 580 ° C for 1 minute to 60 minutes without applying the solution. (Formation of the first layer of the cathode using ion plating) The first layer 20 may also be formed by ion plating. As an example, the method of fixing a base material in a chamber and irradiating an electron beam with a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma environment is argon and oxygen. Ruthenium is deposited on the substrate in the form of ruthenium oxide. (Formation of the first layer using a plated cathode) The first layer 20 may also be formed by a plating method. As an example, if a substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed. (Formation of the first layer of the cathode using thermal spraying) The first layer 20 can also be formed by a thermal spraying method. As an example, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed by plasma-spraying nickel oxide particles onto a substrate. The electrode for electrolysis of this embodiment can be used by being integrated with a separator such as an ion exchange membrane or a microporous membrane. Therefore, it can be used as a membrane-integrated electrode, and the replacement and attachment of the cathode and the anode when the electrode is not required to be replaced, the operation efficiency is greatly improved. The electrode for electrolysis of this embodiment is formed into a laminated body with a separator such as an ion-exchange membrane or a microporous membrane, and is made into one body of the separator and the electrode, so that the electrolytic performance is the same as or improved in the new product. The separator is not particularly limited as long as it can be laminated with an electrode, and will be described in detail below. [Ion exchange membrane] An ion exchange membrane has a membrane body containing a hydrocarbon polymer or a fluorinated polymer having an ion exchange group, and a coating layer provided on at least one side of the membrane body. The coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1 to 10 m.2 / g. The gas produced by the ion exchange membrane of this structure during electrolysis has less influence on the electrolytic performance, and can exhibit stable electrolytic performance. The ion-exchange membrane includes a sulfonate-derived ion-exchange group (as -SO3 - Sulfonic acid layer and sulfonic acid layer derived from a carboxyl group (with -CO2 - The group represented by this is any of the carboxylic acid layers (hereinafter also referred to as "carboxylic acid groups"). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforced core material. Hereinafter, the inorganic particles and the binder will be described in detail in the description of the coating layer. Fig. 2 is a schematic sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 includes a membrane body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and coating layers 11 a and 11 b formed on both sides of the membrane body 10. In the ion exchange membrane 1, the membrane body 10 includes a sulfonic acid layer 3 and a carboxylic acid layer 2, and the strength and dimensional stability are strengthened by a reinforcing core material 4. Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it can be suitably used as an ion exchange membrane. The ion exchange membrane may include only one of a sulfonic acid layer and a carboxylic acid layer. The ion exchange membrane is not necessarily reinforced by a reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example shown in FIG. 2. (Membrane Body) First, the membrane body 10 constituting the ion exchange membrane 1 will be described. The membrane body 10 may be any one having a function of selectively transmitting cations and containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group. The structure or material is not particularly limited, and an appropriate one can be appropriately selected. The hydrocarbon-based polymer or fluorine-containing polymer having an ion-exchange group in the membrane body 10 can be obtained, for example, from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group precursor that can become an ion-exchange group by hydrolysis or the like. . Specifically, for example, a polymer containing a fluorinated hydrocarbon in the main chain, a group which can be converted into an ion-exchange group by hydrolysis, or the like (ion-exchange group precursor) as a pendant side chain and capable of being melt-processed (hereinafter referred to as a case may be referred to “Fluorine-containing polymer (a)”) After preparing the precursor of the membrane body 10, the precursor of the ion exchange group is converted into an ion exchange group, whereby the membrane body 10 can be obtained. The fluorine-containing polymer (a) can be copolymerized, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. Manufacturing. Moreover, it can also manufacture by homopolymerizing 1 type of monomer selected from any of the following 1st group, the following 2nd group, and the following 3rd group. Examples of the monomers of the first group include fluoroethylene compounds. Examples of the fluoroethylene compound include fluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether. Especially when an ion exchange membrane is used as a membrane for alkaline electrolysis, the fluoroethylene compound is preferably a perfluoro monomer, and is preferably selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Perfluoro monomer in the group. Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid-type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include CF.2 = CF (OCF2 CYF)s -O (CZF)t -COOR and other monomers (here, s represents an integer from 0 to 2, t represents an integer from 1 to 12, and Y and Z each independently represent F or CF3 R represents a lower alkyl group. Lower alkyl is, for example, an alkyl group having 1 to 3 carbon atoms. Of these, CF is preferred2 = CF (OCF2 CYF)n -O (CF2 )m -COOR. Here, n is an integer of 0 to 2, m is an integer of 1 to 4, and Y is F or CF.3 , R represents CH3 , C2 H5 , Or C3 H7 . When an ion-exchange membrane is used as a cation-exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. The alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms. As the monomer of the second group, among the above, the monomers described below are more preferred. CF2 = CFOCF2 -CF (CF3 OCF2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )2 COOCH3 , CF2 = CF [OCF2 -CF (CF3 )]2 O (CF2 )2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )3 COOCH3 , CF2 = CFO (CF2 )2 COOCH3 , CF2 = CFO (CF2 )3 COOCH3 . Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfonic acid-type ion exchange group (sulfonic acid group). As the vinyl compound having a functional group convertible to a sulfonic acid group, for example, CF is preferably used.2 = CFO-X-CF2 -SO2 A monomer represented by F (here, X represents perfluoroalkylene). Specific examples of these include the monomers shown below. CF2 = CFOCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, CF2 = CF (CF2 )2 SO2 F, CF2 = CFO [CF2 CF (CF3 ) O]2 CF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF2 OCF3 OCF2 CF2 SO2 F. Of these, CF is more preferred2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, and CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F. Copolymers obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of vinyl fluoride, especially a common polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, an inert solvent such as perfluorocarbon or chlorofluorocarbon can be used, in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, at a temperature of 0 to 200 ° C. Polymerization is carried out under a pressure of 0.1 to 20 MPa. In the above-mentioned copolymerization, the type and ratio of the combination of the above-mentioned monomers are not particularly limited, and are selected and determined according to the type and amount of functional groups to be imparted to the obtained fluorine-containing polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is produced, at least one monomer may be selected from the above-mentioned first group and the second group for copolymerization. When a fluorinated polymer containing only a sulfonic acid group is produced, at least one monomer may be selected from the monomers of the first group and the third group and copolymerized. Furthermore, when a fluorinated polymer having a carboxylic acid group and a sulfonic acid group is prepared, at least one monomer is selected from the monomers of the first group, the second group, and the third group and copolymerized. Just fine. In this case, the copolymer containing the first group and the second group and the copolymer containing the first group and the third group are separately polymerized, and then the target fluorine-containing polymerization can be obtained by mixing them. Thing. The mixing ratio of each monomer is not particularly limited. When the amount of functional groups per unit of polymer is increased, the ratio of the monomers selected from the second group and the third group may be increased. The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of the exchange group per unit weight of the dry resin, and can be measured by neutralization titration or the like. In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. The membrane body 10 having such a layer structure can further improve the selective permeability of cations such as sodium ions. When the ion exchange membrane 1 is arranged in the electrolytic cell, the sulfonic acid layer 3 is usually arranged on the anode side of the electrolytic cell and the carboxylic acid layer 2 is arranged on the cathode side of the electrolytic cell. The sulfonic acid layer 3 is preferably made of a material having a low electrical resistance, and from the viewpoint of film strength, it is preferable that its film thickness is thicker than that of the carboxylic acid layer 2. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, and more preferably 3 to 15 times. The carboxylic acid layer 2 is preferably one having high anion repellency even if the film thickness is thin. Here, the anion repellency refers to a property that prevents anion from penetrating into or passing through the ion exchange membrane 1. In order to improve anion repellency, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity in the sulfonic acid layer. As the fluorine-containing polymer used in the sulfonic acid layer 3, for example, CF is suitably used.2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 A polymer obtained by using F as a monomer of group 3. As the fluorine-containing polymer used in the carboxylic acid layer 2, for example, CF is suitably used.2 = CFOCF2 CF (CF2 ) O (CF2 )2 COOCH3 A polymer obtained as a monomer of Group 2. (Coating layer) The ion exchange membrane has a coating layer on at least one side of the membrane body. As shown in FIG. 2, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively. The coating layer contains inorganic particles and a binder. The average particle diameter of the inorganic particles is more preferably 0.90 μm or more. When the average particle diameter of the inorganic particles is 0.90 μm or more, not only the durability against gas adhesion is greatly improved, but also the durability against impurities is greatly improved. That is, a particularly significant effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the value of the specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by pulverizing raw stones can be used. Inorganic particles obtained by pulverizing raw stones are preferably used suitably. The average particle diameter of the inorganic particles may be 2 μm or less. When the average particle diameter of the inorganic particles is 2 μm or less, the film can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm. Here, the average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation). The shape of the inorganic particles is preferably irregular. Resistance to impurities is further improved. The particle size distribution of the inorganic particles is preferably wide. The inorganic particles preferably contain at least one inorganic substance selected from the group consisting of an oxide of a Group IV element of the periodic table, a nitride of a group IV element of the periodic table, and a carbide of a group IV element of the periodic table. From the viewpoint of durability, zirconia particles are more preferred. The inorganic particles are preferably inorganic particles produced by pulverizing rough particles of the inorganic particles, or spherical particles having uniform particle diameters by melting and refining the rough particles of the inorganic particles as the inorganic particles. There are no particular restrictions on the method of crushing the rough stone, and examples thereof include a ball mill, a bead mill, a colloid mill, a cone mill, a disc mill, a roller mill, a powder mill, a hammer mill, a granulator, and a VSI mill. (Vertical shaft impactor mill), Wiley mill, roll mill, jet mill, etc. Moreover, it is preferable to wash it after crushing, and as a washing method at this time, acid treatment is preferred. This makes it possible to reduce impurities such as iron adhering to the surfaces of the inorganic particles. The coating layer preferably contains a binder. The binder is a component that holds inorganic particles on the surface of the ion exchange membrane and forms a coating layer. From the viewpoint of resistance to an electrolytic solution or an electrolytic product, the binder preferably contains a fluorine-containing polymer. As the binder, a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group is more preferred from the viewpoints of resistance to an electrolytic solution or a product of electrolysis and adhesion to the surface of an ion exchange membrane. When a coating layer is provided on a layer (sulfonic acid layer) containing a fluorinated polymer having a sulfonic acid group, it is more preferable to use a fluorine-containing type having a sulfonic acid group as a binding agent for the coating layer. polymer. When a coating layer is provided on a layer (carboxylic acid layer) containing a fluorinated polymer having a carboxylic acid group, it is more preferable to use a compound having a carboxylic acid group as a binder for the coating layer. Fluoropolymer. The content of the inorganic particles in the coating layer is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. The content of the binder is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass. The distribution density of the coating layer in the ion exchange membrane is preferably per 1 cm2 It is 0.05 ~ 2 mg. When the ion exchange membrane has a concave-convex shape on the surface, the distribution density of the coating layer is preferably 1 cm2 It is 0.5 to 2 mg. The method for forming the coating layer is not particularly limited, and a known method can be used. For example, a method of applying a coating liquid in which inorganic particles are dispersed in a solution containing a binder by spraying or the like can be cited. (Reinforced core material) The ion exchange membrane preferably has a reinforced core material disposed inside the membrane body. The reinforced core material is a member that strengthens the strength or dimensional stability of the ion exchange membrane. By disposing the reinforced core material inside the membrane body, the expansion and contraction of the ion exchange membrane can be controlled to a desired range, in particular. This ion-exchange membrane does not expand or contract more than necessary during electrolysis or the like, and can maintain excellent dimensional stability for a long period of time. The structure of the reinforcing core material is not particularly limited, and for example, a yarn called a reinforcing yarn may be formed by spinning. The so-called reinforcing yarn is a member constituting a reinforcing core material, and refers to a yarn capable of imparting required dimensional stability and mechanical strength to an ion exchange membrane and stably existing in the ion exchange membrane. By using a reinforced core material spun from this reinforcing yarn, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane. The material for reinforcing the core material and the reinforcing yarn used therefor is not particularly limited. It is preferably a material resistant to acids or alkalis. In terms of long-term heat resistance and chemical resistance, it is preferable to include Fiber of fluoropolymer. Examples of the fluorine-containing polymer used as the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). ), Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, from the viewpoint of heat resistance and chemical resistance, it is preferred to use a fiber containing polytetrafluoroethylene. The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The textile density (the number of weaves per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited. For example, a woven fabric, a non-woven fabric, a knitted fabric, or the like can be used, and a woven fabric form is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, and more preferably 30 to 150 μm. Woven or knitted fabrics can use monofilament, multifilament or similar yarns, slit yarns, etc. The weaving method can use plain weaving, leno weaving, knitting, rib weaving, and crepe stripe weaving. ) And other textile methods. The spinning method and configuration of the reinforced core material in the membrane body are not particularly limited, and the appropriate size can be appropriately set in consideration of the size or shape of the ion exchange membrane, the physical properties required for the ion exchange membrane, and the use environment. For example, the reinforced core material may be arranged along a specific direction of the film body. From the viewpoint of dimensional stability, it is preferable to arrange the reinforced core material along a specific first direction, and along a second substantially perpendicular to the first direction. Orientation with other reinforced core materials. By arranging a plurality of reinforcing core materials in a substantially lined manner inside the longitudinal film body of the film body, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. For example, a configuration in which a reinforced core material (longitudinal yarn) arranged in the longitudinal direction and a reinforced core material (horizontal yarn) arranged in the horizontal direction is preferably woven into the surface of the film body. From the viewpoints of dimensional stability, mechanical strength, and ease of manufacture, it is more preferable to produce a plain weave fabric in which longitudinal and transverse yarns are alternately woven one by one, or twisted with two warp yarns and one side yarn. Interwoven leno weaves, twill weave woven by weaving the same number of cross yarns in every 2 or more parallel yarns. It is particularly preferable to arrange the reinforced core material in two directions of the MD direction (Machine Direction) and the TD direction (Transverse Direction) of the ion exchange membrane. That is, it is preferable to perform plain weaving in the MD direction and the TD direction. Here, the MD direction refers to a direction (traveling direction) in which the membrane body or various core materials (for example, a reinforced core material, a reinforced yarn, a sacrificial yarn described below, etc.) are transported in the manufacturing steps of the ion exchange membrane described below ), The TD direction refers to a direction substantially perpendicular to the MD direction. In addition, the yarn woven in the MD direction is referred to as an MD yarn, and the yarn woven in the TD direction is referred to as a TD yarn. Generally, the ion exchange membrane used in electrolysis is rectangular, and the length direction is MD direction and the width direction is TD direction. By weaving a reinforced core material as MD yarn and a reinforced core material as TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. The arrangement interval of the reinforced core material is not particularly limited, and an appropriate arrangement may be appropriately set in consideration of physical properties required for the ion exchange membrane and use environment. The opening ratio of the reinforced core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane. The so-called aperture ratio of the reinforced core material refers to the total area (B) of the surface through which any substance such as ions (the electrolyte and its cations (for example, sodium ions)) can pass through. Ratio (B / A). The total area (B) of the surface through which substances such as ions can pass may refer to the total area of areas in the ion exchange membrane that are not blocked by the reinforced core material or the like contained in the ion exchange membrane. FIG. 3 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 3 is an enlarged view of a part of the ion exchange membrane, and only the arrangement of the reinforced core materials 21 and 22 in the area is illustrated, and other components are omitted. The total area of the reinforced core material is subtracted from the area (A) of the area surrounded by the reinforced core material 21 arranged in the longitudinal direction and the reinforced core material 22 arranged in the horizontal direction, which also includes the area of the reinforced core material ( C). The total area (B) of the area (A) through which substances such as ions can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I). Opening ratio = (B) / (A) = ((A)-(C)) / (A)… (I) In the reinforced core material, it is particularly preferable from the viewpoint of chemical resistance and heat resistance The morphology is a tape-like yarn or high-alignment monofilament containing PTFE. Specifically, it is more preferable to use a reinforced core material which uses a band-shaped yarn obtained by cutting a high-strength porous sheet containing PTFE into a band shape, or 50 to 300 of a highly-oriented monofilament containing PTFE. Denim plain weave fabric with a textile density of 10 to 50 per inch, with a thickness in the range of 50 to 100 μm. The aperture ratio of the ion-exchange membrane containing the reinforced core material is more preferably 60% or more. Examples of the shape of the reinforcing yarn include round yarn and ribbon yarn. (Communication hole) The ion exchange membrane preferably has a communication hole inside the membrane body. The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, the so-called communication hole is a tubular hole formed inside the membrane body, and is formed by dissolving a sacrificial core material (or sacrificial yarn) described below. The shape or diameter of the communication hole can be controlled by selecting the shape or diameter of the sacrificial core material (sacrificial yarn). By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured during electrolysis. The shape of the communication hole is not particularly limited. According to the manufacturing method described below, the shape of the sacrificial core material used for forming the communication hole can be made. The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With this structure, in the portion where the communication hole is formed on the cathode side of the reinforced core material, ions (for example, sodium ions) transported through the electrolyte filled with the communication hole can also flow to the cathode side of the reinforced core material. As a result, since the flow of cations is not blocked, the resistance of the ion exchange membrane can be further reduced. The communication hole may be formed only in one specific direction of the membrane body constituting the ion exchange membrane. From the viewpoint of exhibiting more stable electrolytic performance, it is preferably formed in both the longitudinal direction and the lateral direction of the membrane body. [Manufacturing Method] As a suitable method for manufacturing the ion exchange membrane, a method having the following steps (1) to (6) can be mentioned. (1) Step: a step of producing a fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted to an ion-exchange group by hydrolysis. (2) Step: by weaving at least a plurality of reinforcing core materials and sacrificial yarns that have properties of dissolving in acid or alkali and forming communicating holes to obtain reinforcements of sacrificial yarns arranged between adjacent reinforcing core materials. Material steps. (3) Step: a step of membrane-forming the above-mentioned fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted into an ion-exchange group by hydrolysis. (4) Step: a step of burying the above-mentioned reinforcing material in the above-mentioned film to obtain a film body in which the above-mentioned reinforcing material is internally arranged as necessary. (5) Step: a step of hydrolyzing the membrane body obtained in step (4) (hydrolysis step). (6) Step: a step (coating step) of providing a coating layer on the film body obtained in step (5). Each step will be described in detail below. (1) Step: Step for producing fluoropolymer In step (1), a fluoropolymer is produced using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the monomers of the raw materials may be adjusted in the production of the fluorine-containing polymer forming each layer. (2) Step: Manufacturing steps of reinforcing material The so-called reinforcing material is a woven fabric of textile reinforcing yarn. A reinforcing core material is formed by embedding a reinforcing material in the film. When making an ion exchange membrane with communicating holes, sacrificial yarns are also woven into the reinforcing material together. In this case, the blending amount of the sacrificial yarn is preferably 10 to 80% by mass of the entire reinforcing material, and more preferably 30 to 70% by mass. By weaving the sacrificial yarn, the reinforcing core material can be prevented from being detached. Sacrificial yarns are soluble in the manufacturing steps of the film or in an electrolytic environment. Rhenium, polyethylene terephthalate (PET), cellulose, and polyamide can be used. In addition, polyvinyl alcohol having a thickness of 20 to 50 denier, monofilament or multifilament is also preferred. Furthermore, in step (2), the aperture ratio or the arrangement of the communication holes can be controlled by adjusting the configuration of the reinforced core material or the sacrificial yarn. (3) Step: Film formation step In the step (3), the fluorinated polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single-layer structure, as described above, a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or a multilayer structure of three or more layers. As a method of film formation, the following are mentioned, for example. A method of separately forming a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group into a membrane. A method for making a composite film from a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group by coextrusion. Moreover, the film may be plural. In addition, coextrusion of a heterogeneous film is preferred because it improves the bonding strength at the interface. (4) Step: the step of obtaining the film body In step (4), the reinforcing material obtained in step (2) is embedded in the inside of the film obtained in step (3) to obtain the reinforcing material inside. Membrane body. As a preferred method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) on the cathode side by a coextrusion method (hereinafter, The layer containing it is called the first layer) and a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonium fluoride functional group) (hereinafter, the layer containing it is referred to as a second layer). It is necessary to use a heating source and a vacuum source to separate the breathable and heat-resistant release paper, and sequentially laminate the reinforcing material and the second / first layer composite film on a flat plate or a drum with a large number of fine holes on the surface. At the melting temperature of each polymer, the method of integration is performed while removing the air between the layers by decompression; (ii) Different from the second / first layer composite film, the The fluorine-containing polymer (third layer) is separately formed into a film, and if necessary, a heating source and a vacuum source are used to separate the third layer film, the reinforced core material, Layer / first layer of composite film is sequentially laminated on a plate or drum with a large number of fine holes on the surface, Each of the polymer melt temperature, while removed under reduced pressure by the air between the layers while the integration method. Here, coextrusion of the first layer and the second layer helps to improve the bonding strength of the interface. In addition, the method of integrating under reduced pressure has a feature that the thickness of the third layer on the reinforcing material is larger than that of the pressure pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane body, it has a property capable of sufficiently maintaining the mechanical strength of the ion exchange membrane. In addition, the variation of the laminate described here is an example. The required layer structure or physical properties of the film body may be considered, and an appropriate laminate pattern (for example, a combination of layers) may be appropriately selected and then co-extruded. Furthermore, in order to further improve the electrical performance of the ion exchange membrane, a fluorine-containing polymer containing both a carboxylic acid group precursor and a sulfonic acid group precursor may be further interposed between the first layer and the second layer. Instead of the second layer, a fourth layer containing a fluorinated polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is used. The formation method of the fourth layer may be a method of separately manufacturing a fluorinated polymer having a carboxylic acid group precursor and a fluorinated polymer having a sulfonic acid group precursor and then mixing them. A method in which a monomer of a precursor is copolymerized with a monomer having a sulfonic acid group precursor. When the fourth layer is made into an ion-exchange membrane, the co-extruded film of the first layer and the fourth layer can be formed, and the third layer and the second layer can be separately formed into a membrane. The method described herein is laminated, and the three layers of the first layer / the fourth layer / the second layer can also be co-extruded to form a film. In this case, the direction of travel of the extruded film is the MD direction. As a result, a film body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material. Moreover, it is preferable that the ion exchange membrane has a protruding portion, that is, a protruding portion containing a fluorinated polymer having a sulfonic acid group on the surface side including the sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming a convex portion on the surface of a resin can be adopted. Specifically, the method of embossing the surface of a film main body is mentioned, for example. For example, when the composite film is integrated with a reinforcing material or the like, the convex portion can be formed by using a release paper that has been embossed in advance. When the convex portion is formed by embossing, the height of the convex portion or the arrangement density can be controlled by controlling the transferred embossed shape (shape of the release paper). (5) Hydrolysis step In step (5), a step of hydrolyzing the membrane body obtained in step (4) to convert an ion-exchange group precursor to an ion-exchange group (hydrolysis step) is performed. In step (5), a dissolution hole can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body by using an acid or an alkali. In addition, the sacrificial yarn may not be completely dissolved and removed, but may remain in the communication hole. In addition, the sacrificial yarn remaining in the communication hole can be removed by dissolving the electrolytic solution when the ion exchange membrane is supplied for electrolysis. Sacrificial yarns are those which are soluble in acids or alkalis in the manufacturing steps of ion exchange membranes or in an electrolytic environment. The sacrificial yarns are dissolved to form communication holes in this part. Step (5) can be carried out by immersing the film body obtained in step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (Dimethyl sulfoxide) can be used. The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35 mass% of DMSO. The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the thicker the apparent thickness. It is more preferably 75 to 100 ° C. The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes. Here, the step of forming the communication hole by dissolving the sacrificial yarn will be described in more detail. 4 (a) and 4 (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane. In Figs. 4 (a) and 4 (b), only the reinforcing yarn 52, the sacrificial yarn 504a, and the communication hole 504 formed by the sacrificial yarn 504a are shown, and other members such as the film body are not shown. First, a knitting-reinforcing material is made from the reinforcing yarn 52 constituting the reinforcing core material in the ion-exchange membrane and the sacrificial yarn 504a used to form the communication hole 504 in the ion-exchange membrane. Then, in step (5), the communication hole 504 is formed by dissolving the sacrificial yarn 504a. According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a can be adjusted according to how the reinforcing core material and the communication hole are arranged in the membrane body of the ion exchange membrane, which is relatively simple. In FIG. 4 (a), the flat woven reinforcing material woven with the reinforcing yarn 52 and the sacrificial yarn 504a in the longitudinal direction and the transverse direction of the paper surface is exemplified. The configuration of the reinforcing yarn 52 and the sacrificial yarn 504a in the reinforcing material may be changed as necessary. . (6) Coating step In step (6), a coating liquid containing inorganic particles obtained by pulverizing or melting the raw stone and a binder is prepared, and the coating liquid is applied to the ion exchange obtained in step (5). The surface of the film is dried to form a coating layer. As the binding agent, it is preferred that the fluorine-containing polymer having an ion-exchange group precursor is hydrolyzed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to ion-exchange. Substitute counter ion for H+ The resulting binding agent (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group). This makes it easy to dissolve in water or ethanol described below, and is therefore preferred. This binding agent was dissolved in a solution obtained by mixing water and ethanol. Furthermore, the preferred volume ratio of water to ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1 to 1: 2. The coating liquid was obtained by dispersing the inorganic particles in the dissolving liquid thus obtained by a ball mill. At this time, the average particle diameter of the particles and the like can also be adjusted by adjusting the time during dispersion and the rotation speed. Moreover, the preferable blending amount of the inorganic particles and the binder is as described above. The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, and it is preferable to make a thin coating liquid. Thereby, the surface of an ion exchange membrane can be apply | coated uniformly. When dispersing the inorganic particles, a surfactant may be added to the dispersion liquid. The surfactant is preferably a nonionic surfactant, and examples thereof include HS-210, NS-210, P-210, and E-212 manufactured by Nippon Oil Corporation. An ion exchange membrane can be obtained by applying the obtained coating solution to the surface of an ion exchange membrane by spray coating or roll coating. [Microporous membrane] The microporous membrane of this embodiment is not particularly limited as long as it can be laminated with an electrode for electrolysis as described above, and various microporous membranes can be applied. The porosity of the microporous membrane of this embodiment is not particularly limited, and it can be set to, for example, 20 to 90, and preferably 30 to 85. The porosity can be calculated by the following formula, for example. Porosity = (1-(film weight in dry state) / (weight calculated from the volume calculated from the thickness, width, and length of the film and the density of the film material)) × 100 average pore diameter of the microporous membrane of this embodiment It is not particularly limited, and may be, for example, 0.01 μm to 10 μ, and preferably 0.05 μm to 5 μm. The average pore diameter is, for example, a case where the film is vertically cut in the thickness direction, and the cut surface is observed with a field emission-scanning electron microscope (FE-SEM). The average pore diameter can be determined by measuring the diameter of the observed pores at about 100 points and obtaining an average value. The thickness of the microporous membrane in this embodiment is not particularly limited, and it can be set to, for example, 10 μm to 1,000 μm, and preferably 50 μm to 600 μm. The thickness can be measured, for example, using a micrometer (manufactured by Mitutoyo Co., Ltd.). As specific examples of the microporous membrane described above, there can be mentioned Zilfon Perl UTP 500 (also referred to as a Zilfon membrane in this embodiment) manufactured by Agfa, International Publication No. 2013-183584, and International Publication No. 2016-203701. No., etc. [Laminated Body] The laminated body according to this embodiment includes the electrode for electrolysis according to this embodiment, and a separator or a power source connected to the electrode for electrolysis. Due to the structure described above, the laminated body of this embodiment can improve the work efficiency when the electrodes in the electrolytic cell are renewed, and can also exhibit excellent electrolytic performance after the renewal. That is, with the laminated body of this embodiment, when the electrode is updated, the complicated operation such as peeling and fixing the electrode fixed to the electrolytic cell is not necessary, and the electrode can be updated by the same simple operation as that of the diaphragm. Therefore, the operation efficiency is greatly improved. . Furthermore, with the laminated body of the present invention, it is possible to maintain or improve the electrolytic performance when the new product is used. In addition, even when the new electrolytic cell is provided only with a power source (that is, an electrode without a catalyst layer), the electrode for electrolysis in this embodiment can be attached to the power source only. Because it functions as an electrode, it can also greatly reduce the catalyst coating or even the catalystless coating. The laminated body of this embodiment can be wound, for example, in the state (roller-like) of a pipe made of vinyl chloride, etc. for storage, conveyance to a customer, etc., and handling is greatly facilitated. In addition, as the power feeder in this embodiment, various substrates described below, such as a deteriorated electrode (that is, an existing electrode) or an electrode without a catalyst coating layer, can be applied. In the multilayer body of this embodiment, it is preferable that the force per unit mass and unit area of the above-mentioned electrode for electrolysis with respect to the separator or the power supply unit is 0.08 N / (mg · cm2 ) Or more, more preferably 0.1 N / (mg · cm2 ), More preferably 0.14 N / (mg · cm2 ) Above, from the viewpoint of easier handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The upper limit value is not particularly limited, but is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. [Wound body] The wound body of this embodiment includes an electrode for electrolysis of this embodiment or a laminated body of this embodiment. That is, the winding system of this embodiment is a product obtained by winding the electrode for electrolysis of this embodiment or the laminated body of this embodiment. Like the wound body of the present embodiment, the workability can be further improved by winding and reducing the size of the electrode for electrolysis of the present embodiment or the laminated body of the present embodiment. [Electrolytic Cell] The electrolytic cell of this embodiment includes an electrode for electrolysis of this embodiment. Hereinafter, an embodiment of an electrolytic cell will be described in detail using a case where salt electrolysis is performed using an ion exchange membrane as a separator. [Electrolytic Cell] FIG. 5 is a sectional view of the electrolytic cell 1. FIG. The electrolytic cell 1 includes an anode chamber 10, a cathode chamber 20, a partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, an anode 11 provided in the anode chamber 10, and a cathode 21 provided in the cathode chamber 20. If necessary, a reverse current absorber 18 having a base material 18a and a reverse current absorbing layer 18b formed on the base material 18a and provided in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 provided in the cathode chamber 20, and a reverse current absorber 18 provided in the cathode chamber 20. The reverse current absorber 18 has a base material 18a and is formed on the cathode as shown in FIG. The reverse current absorbing layer 18b on the substrate 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the current collector 23 and the cathode 21. The support 24 is provided between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via a metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be indirectly connected through a current collector, a support, a metal elastomer, or a partition wall. The entire surface of the cathode 21 is preferably covered with a catalyst layer for reduction reaction. In addition, the form of electrical connection may be to directly install the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22, and laminate the cathode 21 on the metal elastic body 22, respectively. The form. Examples of a method for directly mounting the respective constituent members to each other include welding and the like. The reverse current sink 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40. FIG. 6 is a cross-sectional view of two adjacent electrolytic cells 1 in the electrolytic cell 4. FIG. 7 shows the electrolytic cell 4. FIG. 8 shows the steps of assembling the electrolytic cell 4. As shown in FIG. 6, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are sequentially arranged in series. An ion exchange membrane 2 is arranged between the anode chamber of one of the two electrolytic cells adjacent to the electrolytic cell and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are separated by the cation exchange membrane 2. As shown in FIG. 7, the electrolytic cell 4 includes a plurality of electrolytic cells 1 connected in series through a dielectric exchange membrane 2. That is, the electrolytic cell 4 is a bipolar electrolytic cell having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 8, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series through a dielectric exchange membrane 2 and connecting them with a press 5. The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. Among the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4, the anode 11 of the electrolytic cell 1 located at the extreme end is electrically connected to the anode terminal 7. The cathode 21 of the electrolytic cell at the end opposite to the anode terminal 7 of the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 to the cathode terminal 6 through the anode and cathode of each electrolytic cell 1. Furthermore, an electrolytic cell having only an anode chamber (anode terminal cell) and an electrolytic cell having only a cathode chamber (cathode terminal cell) may be disposed at both ends of the connected electrolytic cells 1. In this case, the anode terminal 7 is connected to an anode terminal cell disposed at one end thereof, and the cathode terminal 6 is connected to a cathode terminal cell disposed at the other end. When electrolysis of brine is performed, brine is supplied to each anode chamber 10 and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid system is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (omitted from the figure) through an electrolytic solution supply hose (omitted from the figure). In addition, the electrolytic solution and the products of electrolysis are recovered by an electrolytic solution recovery tube (omitted from the figure). During the electrolysis, the sodium ions in the brine start from the anode chamber 10 of an electrolytic cell 1 and pass through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Accordingly, the current in the electrolysis flows in a direction in which the electrolytic cells 1 are connected in series. That is, a current flows from the anode chamber 10 to the cathode chamber 20 through the cation exchange membrane 2. Along with the electrolysis of brine, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen are generated on the cathode 21 side. (Anode Chamber) The anode chamber 10 includes an anode 11 or an anode power source 11. When the electrolytic electrode of this embodiment is inserted into the anode side, 11 functions as an anode power source. When the electrolytic electrode of this embodiment is not inserted on the anode side, 11 functions as an anode. The anode chamber 10 preferably includes an anode-side electrolytic solution supply unit that supplies an electrolytic solution to the anode chamber 10, and a baffle plate that is disposed above the anode-side electrolytic solution supply unit and is disposed substantially parallel or inclined to the partition wall 30. And an anode-side gas-liquid separation portion disposed above the baffle and separating gas from an electrolyte mixed with the gas. (Anode) When the electrode for electrolysis of this embodiment is not inserted on the anode side, an anode 11 is provided in the frame of the anode chamber 10. As the anode 11, a metal electrode such as a so-called DSA (registered trademark) can be used. The so-called DSA is an electrode with a titanium substrate covered with an oxide containing ruthenium, iridium, and titanium as components. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode Feeder) When the electrode for electrolysis of this embodiment is inserted on the anode side, an anode feed member 11 is provided in the frame of the anode chamber 10. As the anode power source 11, a metal electrode such as a so-called DSA (registered trademark) may be used, or titanium without a catalyst coating layer may be used. Alternatively, a DSA having a thinner catalyst coating thickness may be used. Furthermore, a used anode can also be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode-side electrolytic solution supply unit) The anode-side electrolytic solution supply unit is a person that supplies an electrolytic solution to the anode chamber 10 and is connected to an electrolytic solution supply pipe. The anode-side electrolytic solution supply portion is preferably arranged below the anode chamber 10. As the anode-side electrolytic solution supply portion, for example, a tube (dispersion tube) having an opening formed on the surface can be used. The tube is more preferably arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies an electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is transported into the electrolytic cell 1 through the tube, and is supplied into the anode chamber 10 from an opening provided on the surface of the tube. Since the tube is arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell, the electrolyte can be uniformly supplied to the inside of the anode chamber 10, which is preferable. (Anode-side gas-liquid separation section) The anode-side gas-liquid separation section is preferably disposed above the baffle. In electrolysis, the anode-side gas-liquid separator has a function of separating a generated gas such as chlorine gas from the electrolytic solution. In addition, unless otherwise specified, the so-called upper means the upper direction in the electrolytic cell 1 in FIG. 5, and the lower means the lower direction in the electrolytic cell 1 in FIG. 5. During the electrolysis, if the generated gas generated in the electrolytic cell 1 and the electrolyte become mixed phase (gas-liquid mixed phase) and are discharged out of the system, there will be physical damage to the ion exchange membrane due to vibration caused by pressure fluctuations inside the electrolytic cell 1. Situation. In order to suppress this situation, it is preferable to provide an anode-side gas-liquid separation unit for separating gas from liquid in the electrolytic cell 1 of this embodiment. It is preferable to provide a defoaming plate for eliminating bubbles in the anode-side gas-liquid separation section. The gas and liquid mixed phase flow can be separated into the electrolyte and the gas by breaking the bubbles when passing through the defoaming plate. As a result, vibration during electrolysis can be prevented. (Baffle) The baffle is preferably disposed above the anode-side electrolytic solution supply portion, and is disposed substantially parallel or inclined to the partition wall 30. The baffle is a partition that controls the flow of the electrolyte in the anode chamber 10. By providing the baffle, the electrolyte (brine, etc.) can be circulated inside the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle is preferably arranged to separate a space near the anode 11 from a space near the partition wall 30. From this viewpoint, the baffle is preferably provided so as to face the respective surfaces of the anode 11 and the partition wall 30. In the space near the anode separated by the baffle, by performing electrolysis, the concentration of the electrolyte (brine concentration) is reduced, and a gas such as chlorine gas is generated. As a result, a difference in gas-liquid specific gravity occurs between the space near the anode 11 separated by the baffle and the space near the partition wall 30. With this situation, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform. Although not shown in FIG. 5, a current collector may be separately provided inside the anode chamber 10. The current collector may be made of the same material or structure as the current collector of the cathode chamber described below. Moreover, in the anode chamber 10, the anode 11 itself can also be made to function as a current collector. (Partition Wall) The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes referred to as a spacer, and divides the anode chamber 10 and the cathode chamber 20. As the partition wall 30, those known as separators for electrolysis can be used, and examples thereof include partition walls in which a plate containing nickel is welded on the cathode side, and a plate containing titanium is welded on the anode side. (Cathode Room) When the cathode electrode 20 is inserted into the cathode side of the present embodiment, 21 functions as a cathode power supply. When the electrode for electrolytic use of the present embodiment is not inserted into the cathode side, 21 Functions as a cathode. When there is a reverse current sink, the cathode or the cathode power source 21 is electrically connected to the reverse current sink system. The cathode chamber 20 preferably includes a cathode-side electrolytic solution supply unit and a cathode-side gas-liquid separation unit similarly to the anode chamber 10. It should be noted that, among the parts constituting the cathode chamber 20, the same descriptions as the parts constituting the anode chamber 10 are omitted. (Cathode) When the electrode for electrolysis in this embodiment is not inserted on the cathode side, a cathode 21 is provided in the frame of the cathode chamber 20. The cathode 21 is preferably a catalyst layer having a nickel substrate and a coated nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include: Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals, and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD (chemical vapor deposition), PVD (physical vapor deposition), and thermal decomposition And shot. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. If necessary, a reduction treatment is performed on the cathode 21. In addition, as the base material of the cathode 21, nickel, a nickel alloy, or nickel-plated iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Cathode Feeder) When the electrode for electrolysis of this embodiment is inserted on the cathode side, a cathode feed member 21 is provided in the frame of the cathode chamber 20. The cathode feed body 21 may be covered with a catalyst component. This catalyst component can be used as a cathode and remain. Examples of the components of the catalyst layer include Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals, and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. In addition, as a base material of the cathode power supply body 21, nickel, a nickel alloy, or nickel plating on iron or stainless steel can be used. In addition, as the power feeder 21, nickel, a nickel alloy, and iron or stainless steel plated with nickel without a catalyst coating layer may be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Reverse current absorbing layer) As the material of the reverse current absorbing layer, a material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected. Examples include nickel and iron. (Current Collector) The cathode chamber 20 preferably includes a current collector 23. This improves the current collection effect. In this embodiment, the current collector 23 is preferably a porous plate, and is arranged so as to be substantially parallel to the surface of the cathode 21. The current collector 23 is preferably composed of a conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, an alloy, or a composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a mesh shape. (Metal Elastomer) By providing the metal elastomer 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, each anode 11 and each cathode The distance between 21 becomes shorter, and the voltage applied to the plurality of electrolytic cells 1 connected in series can be reduced. By reducing the voltage, power consumption can be reduced. In addition, when the metal elastic body 22 is provided, when the laminated body containing the electrolytic electrode of the present invention is installed in an electrolytic cell, the pressure of the metal elastic body 22 can stably maintain the electrode for electrolysis. Starting position. As the metal elastic body 22, a spring member such as a coil spring or a coil, a cushioning pad, or the like can be used. As the metal elastic body 22, it is possible to use a suitable one in consideration of the stress against the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side or on the surface of the partition wall on the anode chamber 10 side. Generally, the two compartments are divided such that the cathode compartment 20 is smaller than the anode compartment 10. Therefore, in terms of the strength of the frame, it is preferable that the metal elastic body 22 is disposed between the current collector 23 and the cathode 21 of the cathode compartment 20. The metal elastic body 23 is preferably made of a conductive metal such as nickel, iron, copper, silver, or titanium. (Support) The cathode chamber 20 is preferably provided with a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently. The support 24 preferably contains a conductive metal such as nickel, iron, copper, silver, and titanium. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a mesh shape. The support 24 is, for example, a plate. The plurality of support bodies 24 are arranged between the partition wall 30 and the current collector 23. The plurality of support bodies 24 are arranged so that their respective faces are parallel to each other. The support 24 is disposed so as to be substantially perpendicular to the partition wall 30 and the current collector 23. (Anode-Side Gasket, Cathode-Side Gasket) The anode-side gasket is preferably arranged on the surface of the frame constituting the anode chamber 10. The cathode-side gasket is preferably disposed on a surface of a frame constituting the cathode chamber 20. The anode-side gasket provided in one electrolytic cell and the cathode-side gasket of an adjacent electrolytic cell are connected to each other by sandwiching the ion exchange membrane 2 (see FIGS. 5 and 6). With these gaskets, when a plurality of electrolytic cells 1 are connected in series through the dielectric exchange membrane 2, airtightness can be imparted to the connection points. The so-called gasket is a seal between the ion exchange membrane and the electrolytic cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. The gasket is required to be resistant to corrosive electrolytes or generated gases, and can be used for a long time. Therefore, in terms of chemical resistance or hardness, generally, ethylene-propylene-diene rubber (EPDM rubber), ethylene-propylene rubber (EPM rubber) sulfide or peroxide crosslinked material can be used as a mat. sheet. In addition, if necessary, a gasket covering a region (liquid-contacting portion) in contact with the liquid may be coated with a fluorine resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). . These gaskets may have openings so as not to hinder the flow of the electrolytic solution, and their shapes are not particularly limited. For example, a frame-shaped gasket is attached to the periphery of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20 with an adhesive or the like. In addition, for example, when two dielectric cells 1 are connected to the dielectric separator exchange membrane 2 (see FIG. 6), the dielectric separator exchange membrane 2 may fasten each electrolytic cell 1 to which a gasket is attached. This makes it possible to prevent the electrolytic solution, alkali metal hydroxide, chlorine gas, hydrogen gas, and the like from being leaked to the outside of the electrolytic cell 1. (Ion exchange membrane 2) As the ion exchange membrane 2, it is as described in the item of the said ion exchange membrane. (Water Electrolysis) The electrolytic cell in the case of performing water electrolysis in this embodiment has a structure in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis described above is changed to a microporous membrane. In addition, the electrolyzer is different from the case where the salt electrolysis is performed in the point that the supplied raw material is water. Regarding other configurations, the electrolytic cell in the case of performing water electrolysis may also have the same configuration as the electrolytic cell in the case of performing salt electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. In the case of water electrolysis, only oxygen is generated in the anode chamber, so the same material as the cathode chamber can be used. Examples include nickel. The anode coating is preferably a catalyst coating for generating oxygen. Examples of the catalyst coating layer include metals, oxides, hydroxides, and the like of platinum group metals and transition metal groups. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used. <Second Embodiment> Here, a second embodiment of the present invention will be described in detail with reference to FIGS. 22 to 42. [Laminated Body] The laminated body of the second embodiment (hereinafter simply referred to as "this embodiment" in the item of "Second Embodiment") includes an electrode for electrolysis, and a separator or a power source connected to the electrode for electrolysis. The force per unit mass and unit area of the above-mentioned electrode for electrolysis for the above-mentioned separator or power supply unit does not reach 1.5 N / mg · cm2 . Due to the structure described above, the laminated body of this embodiment can improve the working efficiency when the electrodes in the electrolytic cell are renewed, and can also exhibit excellent electrolytic performance after the renewal. That is, with the laminated body of this embodiment, when the electrodes are renewed, there is no need to perform complicated operations such as peeling the existing electrodes fixed to the electrolytic cell, and the electrodes can be renewed by the same simple operation as that of the diaphragm. Therefore, the operation efficiency is improved. A substantial increase. Furthermore, with the laminated body of the present invention, it is possible to maintain or improve the electrolytic performance when the new product is used. Therefore, the electrode fixed to the previous new electrolytic cell and functioning as the anode and the cathode can only function as the power feeder, which can greatly reduce the catalyst coating or even the catalyst-free coating. The laminated body of this embodiment can be wound, for example, in the state (roller-like) of a pipe made of vinyl chloride, etc. for storage, conveyance to a customer, etc., and handling is greatly facilitated. In addition, as the power feeder in this embodiment, various substrates described below such as a deteriorated electrode (that is, an existing electrode) or an electrode not formed with a catalyst coating layer can be applied. Moreover, as long as the laminated body of this embodiment has the said structure, it can be a part which has a fixed part. That is, when the laminated body of this embodiment has a fixed part, the part without the fixed part is used for measurement, and the force per unit mass and unit area of the obtained electrode for electrolysis is less than 1.5 N / mg ・ cm2 Just fine. [Electrolysis electrode] The electrolysis electrode of this embodiment can obtain good operability, and can be used with separators such as ion exchange membranes or microporous membranes, and power supply bodies (degraded electrodes and electrodes without a catalyst coating layer), etc. From the viewpoint of good adhesion, the force per unit mass and unit area does not reach 1.5 N / mg · cm2 , Preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Still more preferably 1.1 N / mg ・ cm2 Hereinafter, it is more preferably 1.10 N / mg · cm2 Below, more preferably 1.0 N / mg · cm2 Below, more preferably 1.00 N / mg · cm2 the following. From the viewpoint of further improving electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ) Above, and more preferably 0.1 N / mg · cm2 Above, more preferably 0.14 N / (mg · cm2 )the above. From the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The above-mentioned bearing force can be set to the above range, for example, by appropriately adjusting a porosity, an electrode thickness, an arithmetic average surface roughness, and the like described below. More specifically, for example, if the opening ratio is increased, the bearing force tends to be small, and if the opening ratio is decreased, the bearing force tends to be large. In addition, from the viewpoint of obtaining good operability, it has good adhesion to separators such as ion-exchange membranes or microporous membranes, deteriorated electrodes, and feeders without a catalyst coating, and so on in terms of economy. From a viewpoint, the mass per unit area is preferably 48 mg / cm2 Below, more preferably 30 mg / cm2 Below, more preferably 20 mg / cm2 In the following, from the viewpoint of combining the operability, adhesiveness, and economy, 15 mg / cm is preferred.2 the following. The lower limit value is not particularly limited, for example, 1 mg / cm2 about. The above-mentioned mass per unit area can be set to the above range, for example, by appropriately adjusting the opening ratio and thickness of the electrode described below. More specifically, for example, if the thickness is the same, the mass per unit area tends to become smaller if the opening ratio is increased, and the mass per unit area tends to be larger if the opening ratio is decreased. . The withstand force can be measured by the following method (i) or (ii). Specifically, it is as described in the examples. As for the bearing capacity, the value obtained by the measurement of the method (i) (also referred to as "bearing capacity (1)") and the value obtained by the measurement of the method (ii) (also referred to as "bearing capacity (2) ) ") May be the same or different, but none of them has reached 1.5 N / mg · cm2 . [Method (i)] A nickel plate (thickness: 1.2 mm, 200 mm square) obtained by spraying with alumina of grain number 320 was laminated in order, and the perfluorocarbon polymer film with an ion exchange group was introduced. Ion-exchange membrane (170 mm square, details of the so-called ion-exchange membrane as described in the examples) and electrode samples (130 mm square) coated with inorganic particles and binders on both sides. After sufficient immersion, excess moisture adhering to the surface of the laminated body was removed to obtain a sample for measurement. In addition, the arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment is 0.5 to 0.8 μm. The specific calculation method of the arithmetic average surface roughness (Ra) is as described in the examples. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. This average value is divided by the area of the overlapped part of the electrode sample and the ion-exchange membrane and the mass of the electrode sample of the overlapped part of the ion-exchange membrane to calculate the force per unit mass and unit area (1) (N / mg · cm2 ). With the force (1) per unit mass and unit area obtained by method (i), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layered feeder has good adhesion, it is less than 1.5 N / mg · cm2 , Preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 Hereinafter, it is more preferably 1.1 N / mg · cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, more preferably 1.0 N / mg · cm2 Below, more preferably 1.00 N / mg · cm2 the following. From the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 ), More preferably 0.2 N / (mg ・ cm2 )the above. If the electrode for electrolysis in this embodiment satisfies the bearing capacity (1), it can be integrated with, for example, an ion exchange membrane or a microporous membrane or a power supply (ie, made into a multilayer body). Therefore, when the electrode is updated, There is no need to replace and attach the cathode and anode fixed to the electrolytic cell by welding or other methods, and the operation efficiency is greatly improved. In addition, by using the electrode for electrolysis of this embodiment as a laminated body integrated with an ion exchange membrane, a microporous membrane, or a power feeder, the electrolytic performance can be the same as or improved in the new product. . When a new electrolytic cell is shipped, a catalyst coating was previously applied to the electrode fixed to the electrolytic cell, but it can only be used by combining the electrode without a catalytic coating with the electrode for electrolysis of this embodiment. As an electrode, the amount of manufacturing steps or catalysts used to form the catalyst coating can be greatly reduced or even none of these exist. The previous electrode with a greatly reduced or absent catalyst coating layer is electrically connected to the electrode for electrolysis in this embodiment, so that it can function as a current feeder. [Method (ii)] A nickel plate (thickness 1.2 mm, 200 mm square, the same nickel plate as in the above method (i)) and an electrode sample (130 mm square), and the laminated body is sufficiently immersed in pure water, and then excess water adhered to the surface of the laminated body is removed to obtain a sample for measurement. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate and the mass of the electrode sample in the overlapped portion of the nickel plate to calculate the adhesion force per unit mass and unit area (2) (N / mg · cm2 ). With the force (2) per unit mass and unit area obtained by method (ii), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layered feeder has good adhesion, it is less than 1.5 N / mg · cm2 , Preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 Hereinafter, it is more preferably 1.1 N / mg · cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, more preferably 1.0 N / mg · cm2 Below, more preferably 1.00 N / mg · cm2 the following. From the viewpoint of further improving electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 )the above. If the electrode for electrolysis of this embodiment satisfies the withstand force (2), it can be wound, for example, in the state (roller-like) of a pipe made of vinyl chloride for storage, transportation to a customer, etc., and the operation is greatly facilitated. In addition, by laminating the deteriorated existing electrode to the electrolytic electrode of the present embodiment to form a laminated body, the electrolytic performance can be the same as or improved in the new product. If the electrode for electrolysis in this embodiment is an electrode with a wide elastic deformation area, better operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and those without a catalyst coating. From the viewpoint that the power supply and the like have better adhesion, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, still more preferably 170 μm or less, and even more preferably 150 μm or less. It is particularly preferably 145 μm or less, more preferably 140 μm or less, even more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. In addition, in this embodiment, "the elastic deformation area is wide" means that the electrode for electrolysis is wound into a wound body, and warping caused by winding is unlikely to occur after the wound state is released. When the thickness of the electrode for electrolysis includes a catalyst layer described below, it means the thickness of the electrode substrate for electrolysis and the thickness of the catalyst layer. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, and good operability can be obtained. It can be used in contact with separators such as ion exchange membranes or microporous membranes, degraded electrodes (feeders), and non-formed The electrode (feeder) of the dielectric coating has good adhesion, can be wound into a roll shape and bent well, and it is easy to handle at a large size (for example, 1.5 m × 2.5 m). In particular, it is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and even more It is preferably 100 μm or less, and from the viewpoint of operability and economy, it is more preferably 50 μm or less. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In this embodiment, a metal porous plate or a metal plate (i.e., a power supply body) such as a separator and an electrode such as an ion exchange membrane or a microporous membrane, or a deteriorated existing electrode or an electrode without a catalyst coating layer (i.e., a power supply body) ) And a liquid are interposed between the electrodes for electrolysis. Any liquid can be used as long as the liquid has surface tension such as water or an organic solvent. The greater the surface tension of the liquid, the greater the force it will withstand between the separator and the electrode for electrolysis, or the porous metal plate or metal plate and the electrode for electrolysis. Therefore, a liquid with a larger surface tension is preferred. Examples of the liquid include the following (the values in parentheses are the surface tension of the liquid at 20 ° C). Hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m), water (72.76 mN / m), if As a liquid with a large surface tension, the separator is integrated with the electrode for electrolysis, or the metal porous plate or metal plate (feeder) is integrated with the electrode for electrolysis (laminated body), and the electrode is easily renewed. The amount of liquid between the separator and the electrode for electrolysis, or the porous metal plate or metal plate (feeder), and the electrode for electrolysis may be such that the amount of liquid adheres to each other by surface tension. As a result, the amount of liquid is small. Therefore, even if the laminated body is placed in an electrolytic cell and mixed into the electrolytic solution, it will not affect the electrolysis itself. From a practical point of view, as the liquid, a liquid having a surface tension of 24 mN / m to 80 mN / m such as ethanol, ethylene glycol, and water is preferably used. Particularly preferred is water or a caustic soda, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, etc. dissolved in water to make an alkaline aqueous solution. Moreover, you may adjust surface tension by making these liquids contain a surfactant. By including a surfactant, the adhesion between the separator and the electrode for electrolysis, or the porous metal plate or metal plate (feeder) and the electrode for electrolysis is changed, and the operability can be adjusted. The surfactant is not particularly limited, and any of an ionic surfactant and a nonionic surfactant can be used. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating ( From the viewpoint of having good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and further, for a large size (for example, a size From the viewpoint of easy handling at 1.5 m × 2.5 m), it is more preferably 95% or more. The upper limit is 100%. [Method (2)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 280 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating ( (Feeder) has a good adhesive force, and can be appropriately wound into a roll shape and bent well, the ratio measured by the following method (3) is preferably 75% or more, more preferably It is 80% or more, and from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 90% or more. The upper limit is 100%. [Method (3)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 145 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating ( From the viewpoint of having a good adhesive force and preventing the retention of gas generated during electrolysis, a porous structure is preferred, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80%, and more preferably 20 to 75%. The open porosity is the ratio of the perforated portion per unit volume. There are various calculation methods for the opening part according to the submicron order or only the openings that can be seen visually. In this embodiment, the volume V is calculated from the values of the gauge thickness, width, and length of the electrode, and the weight W is measured. Then, the aperture ratio A is calculated by the following formula. A = (1- (W / (V × ρ)) × 100 ρ Density of electrode material (g / cm3 ). E.g. in the case of nickel 8.908 g / cm3 In the case of titanium is 4.506 g / cm3 . The adjustment of the opening ratio is appropriately adjusted by the following methods: if it is a punched metal, change the area of the punched metal per unit area; if it is a porous metal, change SW (short diameter), LW (long diameter), Feed value; if it is a wire mesh, change the wire diameter and mesh number of the metal fiber; if it is electroforming, change the pattern of the photoresist used; if it is a non-woven fabric, change the metal fiber diameter and fiber density; In the case of a foamed metal, a template or the like for forming a void is changed. From the viewpoint of operability, the electrode for electrolysis in this embodiment is preferably 40 mm or less, more preferably 29 mm or less, and even more preferably 10 mm or less by the following method (A). , And more preferably 6.5 mm or less. The specific measurement method is as described in the examples. [Method (A)] Under the conditions of a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, a sample formed by laminating an ion exchange membrane and the above-mentioned electrode for electrolysis was wound and fixed to a vinyl chloride product having an outer diameter of f32 mm. On the curved surface of the core material, after standing for 6 hours, the electrode for electrolysis was separated and placed on a horizontal plate. At this time, the height L of the two ends of the electrode for electrolysis in the vertical direction was measured.1 And L2 Take the average of these as the measured value. The electrode for electrolysis in the present embodiment is preferably set to a size of 50 mm × 50 mm and a temperature of 24 ° C., a relative humidity of 32%, a piston speed of 0.2 cm / s, and a ventilation volume of 0.4 cc / cm.2 In the case of / s (hereinafter also referred to as "measurement condition 1"), the ventilation resistance (hereinafter also referred to as "ventilation resistance 1") is 24 kPa · s / m or less. Large ventilation resistance means that the air is difficult to flow, and refers to a state with a high density. In this state, the product of electrolysis stays in the electrode, and the reaction matrix is difficult to diffuse into the electrode, so the electrolytic performance (voltage, etc.) tends to deteriorate. Moreover, there exists a tendency for the density | concentration of the film surface to increase. Specifically, there is a tendency that the caustic concentration on the cathode side increases and the supply property of the brine on the anode side decreases. As a result, since the product stays at the interface between the separator and the electrode at a high concentration, the separator tends to be damaged, and the voltage on the cathode surface and the membrane damage and the anode surface tend to be damaged. In this embodiment, in order to prevent such abnormalities, it is preferable to set the ventilation resistance to 24 kPa · s / m or less. From the same viewpoint as described above, it is more preferably less than 0.19 kPa · s / m, still more preferably 0.15 kPa · s / m or less, and still more preferably 0.07 kPa · s / m or less. Furthermore, in this embodiment, if the ventilation resistance is larger than a certain degree, the NaOH generated in the electrode tends to stay at the interface between the electrode and the separator and becomes a high concentration in the case of the cathode. In the case of the anode, the tendency is high. The tendency of the salt water supply to decrease and the concentration of the salt water to become low, in order to prevent damage to the diaphragm that may occur due to such retention, it is preferably less than 0.19 kPa · s / m, more preferably 0.15 kPa · s / m or less, more preferably 0.07 kPa · s / m or less. On the other hand, when the ventilation resistance is low, since the area of the electrode becomes smaller, the electrolytic area tends to become smaller and the electrolytic performance (voltage, etc.) tends to deteriorate. When the ventilation resistance is zero, since no electrode for electrolysis is provided, there is a tendency that the power supply body functions as an electrode, and the electrolytic performance (voltage, etc.) tends to be significantly deteriorated. In this respect, the preferable lower limit value specified as the ventilation resistance 1 is not particularly limited, but preferably exceeds 0 kPa · s / m, more preferably 0.0001 kPa · s / m or more, and more preferably 0.001 kPa · s / m or more. In addition, in terms of measurement method, if the ventilation resistance 1 is 0.07 kPa · s / m or less, sufficient measurement accuracy may not be obtained. From this viewpoint, it is also possible to realize the ventilation resistance (hereinafter referred to as "measurement condition 2") obtained by the following measurement method (hereinafter also referred to as "measurement condition 2") with respect to an electrode for electrolysis whose ventilation resistance 1 is 0.07 kPa · s / m or less Also called "ventilation resistance 2"). That is, the ventilation resistance 2 is set to a size of 50 mm × 50 mm for the electrode for electrolysis, and the temperature is 24 ° C, the relative humidity is 32%, the piston speed is 2 cm / s, and the ventilation volume is 4 cc / cm.2 / s in the case of ventilation resistance. Specific measurement methods of the ventilation resistances 1 and 2 are described in the examples. The above-mentioned ventilation resistances 1 and 2 can be set to the above-mentioned range, for example, by appropriately adjusting the opening ratio and the thickness of the electrodes described below. More specifically, for example, if the thickness is the same, if the opening rate is increased, the ventilation resistances 1 and 2 tend to decrease, and if the opening rate is decreased, the ventilation resistances 1 and 2 tend to be large. . The electrode for electrolysis in this embodiment is as described above, and the force per unit mass and unit area of the above-mentioned electrode for electrolysis with respect to the separator or the power supply does not reach 1.5 N / mg · cm2 . Therefore, the electrode for electrolysis of this embodiment can be configured to be connected to the separator or the power supply by contacting the separator or the power supply (for example, an existing anode or cathode in an electrolytic cell) with a moderate bonding force. Of laminated body. That is, there is no need to firmly attach the separator or the power supply to the electrode for electrolysis by a complicated method such as thermocompression bonding. The relatively weak force also becomes a laminated body, so the laminated body can be easily constituted regardless of the scale. Furthermore, such a laminated body exhibits excellent electrolytic performance. Therefore, the laminated body of this embodiment is suitable for electrolytic use, and for example, it can be particularly preferably used for a component related to an electrolytic cell or a replacement of the component. Hereinafter, one embodiment of an electrode for electrolysis according to this embodiment will be described. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer is described below, and may include a plurality of layers or a single-layer structure. As shown in FIG. 22, the electrode 100 for electrolysis according to this embodiment includes an electrode base material 10 for electrolysis, and a first layer 20 covering one of both surfaces of the electrode base material 10 for electrolysis. The first layer 20 preferably covers the entire electrode base material 10 for electrolysis. As a result, the catalyst activity and durability of the electrode for electrolysis can be easily improved. Furthermore, the first layer 20 may be formed only on one surface area of the electrode base material 10 for electrolysis. As shown in FIG. 22, the surface of the first layer 20 may be covered by the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, the second layer 30 may be laminated on only one surface of the first layer 20. (Electrode base material for electrolysis) The electrode base material 10 for electrolysis is not particularly limited, and for example, nickel, nickel alloy, stainless steel, or a valve metal typified by titanium can be used, and it is preferably selected from nickel (Ni) And at least one element of titanium (Ti). When stainless steel is used in a high-concentration alkaline aqueous solution, considering the elution of iron and chromium, and the conductivity of stainless steel is about 1/10 of that of nickel, it is preferable to use a substrate containing nickel (Ni) as the base material. Electrode substrate for electrolysis. In addition, when the electrode base material 10 for electrolysis is used in a chlorine gas generating environment in a high-concentration saline solution, the material is preferably titanium with high corrosion resistance. The shape of the electrode substrate 10 for electrolysis is not particularly limited, and a suitable shape can be selected according to the purpose. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. Among them, punched metal or porous metal is preferred. In addition, the so-called electroforming is a technique for producing a precise patterned metal thin film by combining a photolithographic process and an electroplating method. It is a method for obtaining a metal thin film by forming a pattern on a substrate with a photoresist, and performing electroplating on a portion not protected by the photoresist. Regarding the shape of the electrode substrate for electrolysis, there are suitable specifications according to the distance between the anode and the cathode in the electrolytic cell. There is no particular limitation. When the anode and the cathode have a limited distance, porous metal and punched metal shapes can be used. In the case of a so-called zero-pitch electrolytic cell where the ion exchange membrane is connected to the electrode, a braided thin wire can be used. The finished woven mesh, metal mesh, foamed metal, metal non-woven fabric, porous metal, punched metal, metal porous foil, etc. Examples of the electrode base material 10 for electrolysis include a porous metal foil, a metal wire mesh, a metal nonwoven fabric, a punched metal, a porous metal, or a foamed metal. As a sheet material before being processed into a punched metal or a porous metal, a sheet material formed by rolling and an electrolytic foil are preferred. The electrolytic foil is preferably further subjected to a plating treatment using the same element as the base material as a post-treatment to form unevenness on one or both sides. As described above, the thickness of the electrode base material 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, even more preferably 155 μm or less, even more preferably 135 μm or less, and even more preferably 125. μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, and further more preferably 50 μm or less in terms of operability and economy. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the electrode base material for electrolysis, it is preferable to reduce the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing environment. In addition, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, it is preferable to use steel sand and alumina powder to form unevenness on the surface, and then increase the surface area by acid treatment. Alternatively, it is preferable to increase the surface area by applying a plating treatment to the same element as the substrate. In order to bring the first layer 20 into close contact with the surface of the electrode base material 10 for electrolysis, it is preferable that the surface area of the electrode base material 10 for electrolysis is increased. Examples of the treatment for increasing the surface area include blasting treatment using steel wire grain, steel sand, alumina sand, etc., acid treatment using sulfuric acid or hydrochloric acid, and plating treatment using the same element as the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm. Next, a case where the electrode for electrolysis of this embodiment is used as an anode for salt electrolysis will be described. (First layer) In FIG. 22, the first layer 20 as a catalyst layer contains at least one of ruthenium oxide, iridium oxide, and titanium oxide. Examples of the ruthenium oxide include RuO2 Wait. Examples of the iridium oxide include IrO2 Wait. Examples of the titanium oxide include TiO2 Wait. The first layer 20 is preferably two oxides containing ruthenium oxide and titanium oxide, or three oxides containing ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and further, the adhesion with the second layer 30 is further improved. In the case where the first layer 20 contains two oxides of ruthenium oxide and titanium oxide, the titanium oxide contained in the first layer 20 is better than 1 mol of the ruthenium oxide contained in the first layer 20 It is 1 to 9 moles, more preferably 1 to 4 moles. By setting the composition ratio of the two oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains three oxides of ruthenium oxide, iridium oxide, and titanium oxide, the iridium oxide contained in the first layer 20 is 1 mole relative to the ruthenium oxide contained in the first layer 20 The amount is preferably 0.2 to 3 moles, and more preferably 0.3 to 2.5 moles. In addition, the titanium oxide contained in the first layer 20 is preferably 0.3 to 8 moles, and more preferably 1 to 7 moles relative to 1 mole of the ruthenium oxide contained in the first layer 20. By setting the composition ratio of the three oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains at least two oxides selected from the group consisting of ruthenium oxide, iridium oxide, and titanium oxide, these oxides preferably form a solid solution. By forming an oxide solid solution, the electrode 100 for electrolysis exhibits excellent durability. In addition to the above composition, as long as it contains at least one of ruthenium oxide, iridium oxide, and titanium oxide, various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like called DSA (registered trademark) may be used as the first layer 20. The first layer 20 need not be a single layer, and may include a plurality of layers. For example, the first layer 20 may include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. (Second layer) The second layer 30 preferably contains ruthenium and titanium. This can further reduce the chlorine overvoltage immediately after electrolysis. The second layer 30 is preferably a palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. This can further reduce the chlorine overvoltage immediately after electrolysis. The thicker the second layer 30 is, the longer the time during which the electrolytic performance can be maintained. From the viewpoint of economy, the thickness is preferably 0.05 to 3 μm. Next, a case where the electrode for electrolysis of this embodiment is used as a cathode for salt electrolysis will be described. (First layer) The components of the first layer 20 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. In the case of containing at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal, a platinum group metal, a platinum group metal oxide, and a platinum group metal hydroxide are preferred. The alloy containing a platinum group metal contains at least one platinum group metal of platinum, palladium, rhodium, ruthenium, and iridium. The platinum group metal preferably contains platinum. The platinum group metal oxide is preferably a ruthenium oxide. The platinum group metal hydroxide is preferably a ruthenium hydroxide. The platinum group metal alloy is preferably an alloy containing platinum and nickel, iron, and cobalt. It is preferable to further contain an oxide or hydroxide of a lanthanoid as a second component as necessary. Accordingly, the electrode 100 for electrolysis exhibits excellent durability. The lanthanide oxide or hydroxide preferably contains at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, and praseodymium. It is preferable to further contain an oxide or hydroxide of a transition metal as a third component as necessary. By adding the third component, the electrode 100 for electrolysis can exhibit more excellent durability and reduce the electrolytic voltage. Examples of preferred combinations include ruthenium, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + osmium, ruthenium + rhenium + platinum, ruthenium + rhenium + Platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur , Ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + osmium, ruthenium + rhenium + manganese, ruthenium + 钐 + iron, ruthenium + rhenium + cobalt, ruthenium + 钐 + zinc, ruthenium + 钐+ Gallium, Ruthenium + 钐 + Sulfur, Ruthenium + 钐 + Lead, Ruthenium + 钐 + Ni, Pt + Ce, Pt + Pd + Ce, Pt + Pd + La + Ce, Pt + Ir, Pt + Pd, Pt + I + Palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, alloys of platinum and nickel, alloys of platinum and cobalt, alloys of platinum and iron, etc. When the platinum group metal, platinum group metal oxide, platinum group metal hydroxide, and platinum group metal-containing alloy are not contained, the main component of the catalyst is preferably nickel. Preferably, it contains at least one of nickel metal, oxide, and hydroxide. As a second component, a transition metal may be added. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon. Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, and the like. If necessary, an intermediate layer may be provided between the first layer 20 and the electrode base material 10 for electrolysis. By providing the intermediate layer, the durability of the electrode 100 for electrolysis can be improved. The intermediate layer is preferably one having an affinity for both the first layer 20 and the electrode base material 10 for electrolysis. The intermediate layer is preferably a nickel oxide, a platinum group metal, a platinum group metal oxide, or a platinum group metal hydroxide. The intermediate layer can be formed by coating and firing a solution containing the components forming the intermediate layer, or heat-treating the substrate at a temperature of 300 to 600 ° C in an air environment to form a surface oxide layer. . In addition, it can be formed by a known method such as a thermal spray method or an ion plating method. (Second layer) The components of the first layer 30 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. Examples of preferred combinations of the elements contained in the second layer include the combinations listed in the first layer. The combination of the first layer and the second layer may be a combination with the same composition but a different composition ratio, or a combination with a different composition. As the thickness of the catalyst layer, the thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 μm to 20 μm. When it is 0.01 μm or more, it can fully function as a catalyst. If it is 20 μm or less, it is less likely to fall off from the substrate, and a strong catalyst layer can be formed. More preferably, it is 0.05 μm to 15 μm. More preferably, it is 0.1 μm to 10 μm. It is more preferably 0.2 μm to 8 μm. As the thickness of the electrode for electrolysis, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer, in terms of operability of the electrode for electrolysis, it is preferably 315 μm or less, more preferably 220 μm or less, It is preferably 170 μm or less, more preferably 150 μm or less, even more preferably 145 μm or less, more preferably 140 μm or less, still more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. The thickness of the electrode can be determined by measuring with an electronic digital thickness gauge (Mitutoyo Co., Ltd., showing a minimum of 0.001 mm). The thickness of the electrode substrate for electrolysis can be measured in the same manner as the thickness of the electrode for electrolysis. The thickness of the catalyst layer can be obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode for electrolysis. (Manufacturing method of the electrode for electrolysis) Next, one Embodiment of the manufacturing method of the electrode 100 for electrolysis is demonstrated in detail. In this embodiment, the first layer 20 is formed on the electrode substrate for electrolysis by using a method such as firing (thermal decomposition) of a coating film under an oxygen environment, or ion plating, plating, or thermal spraying. The second layer 30 is preferably used to produce the electrode 100 for electrolysis. Such a manufacturing method according to this embodiment can achieve high productivity of the electrode 100 for electrolysis. Specifically, a catalyst layer is formed on an electrode substrate for electrolysis by a coating step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. The term "thermal decomposition" means heating a metal salt that becomes a precursor to decompose it into a metal or a metal oxide and a gaseous substance. Decomposition products differ depending on the type of metal used, the type of salt, and the environment in which thermal decomposition is performed, but most metals tend to form oxides easily in an oxidizing environment. In the industrial manufacturing process of electrodes, thermal decomposition is usually performed in air, and in most cases, metal oxides or metal hydroxides are formed. (Formation of the first layer of the anode) (Coating step) The first layer 20 is a solution (first coating liquid) in which a salt of at least one metal among ruthenium, iridium, and titanium is dissolved, and is applied to an electrode base for electrolysis. It is obtained by thermal decomposition (baking) in the presence of oxygen. The contents of ruthenium, iridium, and titanium in the first coating liquid are approximately equal to those of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 100 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of the second layer) The second layer 30 is formed as necessary, for example, a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (a second coating solution) is applied to the first layer 20 It is obtained by thermal decomposition in the presence of oxygen. (Formation of the first layer of the cathode by thermal decomposition method) (Coating step) The first layer 20 is a solution (first coating solution) in which metal salts of various combinations are dissolved on the electrode substrate for electrolysis , Obtained by thermal decomposition (firing) in the presence of oxygen. The content ratio of the metal in the first coating liquid is substantially equal to that of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 10 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of Intermediate Layer) The intermediate layer is formed as necessary. For example, a solution (second coating solution) containing a palladium compound or a platinum compound is coated on a substrate, and then obtained by thermal decomposition in the presence of oxygen. Alternatively, instead of applying the solution, only the substrate is heated, thereby forming a nickel oxide intermediate layer on the surface of the substrate. (Formation of the first layer of the cathode using ion plating) The first layer 20 may also be formed by ion plating. As an example, the method of fixing a base material in a chamber and irradiating an electron beam with a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma environment is argon and oxygen. Ruthenium is deposited on the substrate in the form of ruthenium oxide. (Formation of the first layer using a plated cathode) The first layer 20 may also be formed by a plating method. As an example, if a substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed. (Formation of the first layer of the cathode using thermal spraying) The first layer 20 can also be formed by a thermal spraying method. As an example, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed by plasma-spraying nickel oxide particles onto a substrate. The electrode for electrolysis of this embodiment can be used by being integrated with a separator such as an ion exchange membrane or a microporous membrane. Therefore, it can be used as a membrane-integrated electrode, and the replacement and attachment of the cathode and the anode when the electrode is not required to be replaced, the operation efficiency is greatly improved. In addition, by using a bulk electrode such as an ion exchange membrane or a microporous membrane, the electrolytic performance can be the same as or improved in the new product. Hereinafter, the ion exchange membrane will be described in detail. [Ion exchange membrane] An ion exchange membrane has a membrane body containing a hydrocarbon polymer or a fluorinated polymer having an ion exchange group, and a coating layer provided on at least one side of the membrane body. The coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1 to 10 m.2 / g. The gas produced by the ion exchange membrane of this structure during electrolysis has less influence on the electrolytic performance, and can exhibit stable electrolytic performance. The above-mentioned membrane system of a perfluorocarbon polymer to which an ion exchange group is introduced is provided with an ion exchange group (as -SO3 - Sulfonic acid layer and sulfonic acid layer derived from a carboxyl group (with -CO2 - The group represented by this is any of the carboxylic acid layers (hereinafter also referred to as "carboxylic acid groups"). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforced core material. Hereinafter, the inorganic particles and the binder will be described in detail in the description of the coating layer. Fig. 23 is a schematic sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 includes a membrane body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and coating layers 11 a and 11 b formed on both sides of the membrane body 10. In the ion-exchange membrane 1, the membrane body 10 is provided with an ion-exchange group (as -SO3 - The sulfonic acid layer 3, which is also referred to as a "sulfonic acid group" hereinafter, and an ion-exchange group (with -CO2 - The carboxylic acid layer 2 shown below is also referred to as a "carboxylic acid group", and the strength and dimensional stability are strengthened by the reinforcing core material 4. Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it can be suitably used as a cation exchange membrane. The ion exchange membrane may include only one of a sulfonic acid layer and a carboxylic acid layer. The ion exchange membrane is not necessarily reinforced by a reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example shown in FIG. 23. (Membrane Body) First, the membrane body 10 constituting the ion exchange membrane 1 will be described. The membrane body 10 may be any one having a function of selectively transmitting cations and containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group. The structure or material is not particularly limited, and an appropriate one can be appropriately selected. The hydrocarbon-based polymer or fluorine-containing polymer having an ion-exchange group in the membrane body 10 can be obtained, for example, from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group precursor that can become an ion-exchange group by hydrolysis or the like. . Specifically, for example, a polymer containing a fluorinated hydrocarbon in the main chain, a group which can be converted into an ion-exchange group by hydrolysis, or the like (ion-exchange group precursor) as a pendant side chain and capable of being melt-processed (hereinafter referred to as a case may be referred to “Fluorine-containing polymer (a)”) After preparing the precursor of the membrane body 10, the precursor of the ion exchange group is converted into an ion exchange group, whereby the membrane body 10 can be obtained. The fluorine-containing polymer (a) can be copolymerized, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. Manufacturing. Moreover, it can also manufacture by homopolymerizing 1 type of monomer selected from any of the following 1st group, the following 2nd group, and the following 3rd group. Examples of the monomers of the first group include fluoroethylene compounds. Examples of the fluoroethylene compound include fluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether. Especially when an ion exchange membrane is used as a membrane for alkaline electrolysis, the fluoroethylene compound is preferably a perfluoro monomer, and is preferably selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Perfluoro monomer in the group. Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid-type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include CF.2 = CF (OCF2 CYF)s -O (CZF)t -COOR and other monomers (here, s represents an integer from 0 to 2, t represents an integer from 1 to 12, and Y and Z each independently represent F or CF3 R represents a lower alkyl group. Lower alkyl is, for example, an alkyl group having 1 to 3 carbon atoms. Of these, CF is preferred2 = CF (OCF2 CYF)n -O (CF2 )m -COOR. Here, n is an integer of 0 to 2, m is an integer of 1 to 4, and Y is F or CF.3 , R represents CH3 , C2 H5 , Or C3 H7 . When an ion-exchange membrane is used as a cation-exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. The alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms. As the monomer of the second group, among the above, the monomers described below are more preferred. CF2 = CFOCF2 -CF (CF3 OCF2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )2 COOCH3 , CF2 = CF [OCF2 -CF (CF3 )]2 O (CF2 )2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )3 COOCH3 , CF2 = CFO (CF2 )2 COOCH3 , CF2 = CFO (CF2 )3 COOCH3 . Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfonic acid-type ion exchange group (sulfonic acid group). As the vinyl compound having a functional group convertible to a sulfonic acid group, for example, CF is preferably used.2 = CFO-X-CF2 -SO2 A monomer represented by F (here, X represents perfluoroalkylene). Specific examples of these include the monomers shown below. CF2 = CFOCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, CF2 = CF (CF2 )2 SO2 F, CF2 = CFO [CF2 CF (CF3 ) O]2 CF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF2 OCF3 OCF2 CF2 SO2 F. Of these, CF is more preferred2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, and CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F. Copolymers obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of vinyl fluoride, especially a common polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, an inert solvent such as perfluorocarbon or chlorofluorocarbon can be used, in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, at a temperature of 0 to 200 ° C. Polymerization is carried out under a pressure of 0.1 to 20 MPa. In the above-mentioned copolymerization, the type and ratio of the combination of the above-mentioned monomers are not particularly limited, and are selected and determined according to the type and amount of functional groups to be imparted to the obtained fluorine-containing polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is produced, at least one monomer may be selected from the above-mentioned first group and the second group for copolymerization. When a fluorinated polymer containing only a sulfonic acid group is produced, at least one monomer may be selected from the monomers of the first group and the third group and copolymerized. Furthermore, when a fluorinated polymer having a carboxylic acid group and a sulfonic acid group is prepared, at least one monomer is selected from the monomers of the first group, the second group, and the third group and copolymerized. Just fine. In this case, the copolymer containing the first group and the second group and the copolymer containing the first group and the third group are separately polymerized, and then the target fluorine-containing polymerization can be obtained by mixing them. Thing. The mixing ratio of each monomer is not particularly limited. When the amount of functional groups per unit of polymer is increased, the ratio of the monomers selected from the second group and the third group may be increased. The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of the exchange group per unit weight of the dry resin, and can be measured by neutralization titration or the like. In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. The membrane body 10 having such a layer structure can further improve the selective permeability of cations such as sodium ions. When the ion exchange membrane 1 is arranged in the electrolytic cell, the sulfonic acid layer 3 is usually arranged on the anode side of the electrolytic cell and the carboxylic acid layer 2 is arranged on the cathode side of the electrolytic cell. The sulfonic acid layer 3 is preferably made of a material having a low electrical resistance, and from the viewpoint of film strength, it is preferable that its film thickness is thicker than that of the carboxylic acid layer 2. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, and more preferably 3 to 15 times. The carboxylic acid layer 2 is preferably one having high anion repellency even if the film thickness is thin. Here, the anion repellency refers to a property that prevents anion from penetrating into or passing through the ion exchange membrane 1. In order to improve anion repellency, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity in the sulfonic acid layer. As the fluorine-containing polymer used in the sulfonic acid layer 3, for example, CF is suitably used.2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 A polymer obtained by using F as a monomer of group 3. As the fluorine-containing polymer used in the carboxylic acid layer 2, for example, CF is suitably used.2 = CFOCF2 CF (CF2 ) O (CF2 )2 COOCH3 A polymer obtained as a monomer of Group 2. (Coating layer) The ion exchange membrane has a coating layer on at least one side of the membrane body. As shown in FIG. 23, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively. The coating layer contains inorganic particles and a binder. The average particle diameter of the inorganic particles is more preferably 0.90 μm or more. When the average particle diameter of the inorganic particles is 0.90 μm or more, not only the durability against gas adhesion is greatly improved, but also the durability against impurities is greatly improved. That is, a particularly significant effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the value of the specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by pulverizing raw stones can be used. Inorganic particles obtained by pulverizing raw stones are preferably used suitably. The average particle diameter of the inorganic particles may be 2 μm or less. When the average particle diameter of the inorganic particles is 2 μm or less, the film can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm. Here, the average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation). The shape of the inorganic particles is preferably irregular. Resistance to impurities is further improved. The particle size distribution of the inorganic particles is preferably wide. The inorganic particles preferably contain at least one inorganic substance selected from the group consisting of an oxide of a Group IV element of the periodic table, a nitride of a group IV element of the periodic table, and a carbide of a group IV element of the periodic table. From the viewpoint of durability, zirconia particles are more preferred. The inorganic particles are preferably inorganic particles produced by pulverizing rough particles of the inorganic particles, or spherical particles having uniform particle diameters by melting and refining the rough particles of the inorganic particles as the inorganic particles. There are no particular restrictions on the method of crushing the rough stone, and examples thereof include a ball mill, a bead mill, a colloid mill, a cone mill, a disc mill, a roller mill, a powder mill, a hammer mill, a granulator, and a VSI mill Machines, Willy mills, roll mills, jet mills, etc. Moreover, it is preferable to wash it after crushing, and as a washing method at this time, acid treatment is preferred. This makes it possible to reduce impurities such as iron adhering to the surfaces of the inorganic particles. The coating layer preferably contains a binder. The binder is a component that holds inorganic particles on the surface of the ion exchange membrane and forms a coating layer. From the viewpoint of resistance to an electrolytic solution or an electrolytic product, the binder preferably contains a fluorine-containing polymer. As the binder, a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group is more preferred from the viewpoints of resistance to an electrolytic solution or a product of electrolysis and adhesion to the surface of an ion exchange membrane. When a coating layer is provided on a layer (sulfonic acid layer) containing a fluorinated polymer having a sulfonic acid group, it is more preferable to use a fluorine-containing type having a sulfonic acid group as a binding agent for the coating layer. polymer. When a coating layer is provided on a layer (carboxylic acid layer) containing a fluorinated polymer having a carboxylic acid group, it is more preferable to use a compound having a carboxylic acid group as a binder for the coating layer. Fluoropolymer. The content of the inorganic particles in the coating layer is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. The content of the binder is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass. The distribution density of the coating layer in the ion exchange membrane is preferably per 1 cm2 It is 0.05 ~ 2 mg. When the ion exchange membrane has a concave-convex shape on the surface, the distribution density of the coating layer is preferably 1 cm2 It is 0.5 to 2 mg. The method for forming the coating layer is not particularly limited, and a known method can be used. For example, a method of applying a coating liquid in which inorganic particles are dispersed in a solution containing a binder by spraying or the like can be cited. (Reinforced core material) The ion exchange membrane preferably has a reinforced core material disposed inside the membrane body. The reinforced core material is a member that strengthens the strength or dimensional stability of the ion exchange membrane. By disposing the reinforced core material inside the membrane body, the expansion and contraction of the ion exchange membrane can be controlled to a desired range, in particular. This ion-exchange membrane does not expand or contract more than necessary during electrolysis or the like, and can maintain excellent dimensional stability for a long period of time. The structure of the reinforcing core material is not particularly limited, and for example, a yarn called a reinforcing yarn may be formed by spinning. The so-called reinforcing yarn is a member constituting a reinforcing core material, and refers to a yarn capable of imparting required dimensional stability and mechanical strength to an ion exchange membrane and stably existing in the ion exchange membrane. By using a reinforced core material spun from this reinforcing yarn, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane. The material for reinforcing the core material and the reinforcing yarn used therefor is not particularly limited. It is preferably a material resistant to acids or alkalis. In terms of long-term heat resistance and chemical resistance, it is preferable to include Fiber of fluoropolymer. Examples of the fluorine-containing polymer used as the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). ), Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, from the viewpoint of heat resistance and chemical resistance, it is preferred to use a fiber containing polytetrafluoroethylene. The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The textile density (the number of weaves per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited. For example, a woven fabric, a non-woven fabric, a knitted fabric, or the like can be used, and a woven fabric form is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, and more preferably 30 to 150 μm. Woven or knitted fabrics can use monofilament, multifilament or any of these yarns, cut yarns, etc. The weaving method can use various weaving methods such as plain weaving, leno weaving, knitting, rib weaving, thin crepe weaving, etc. The spinning method and configuration of the reinforced core material in the membrane body are not particularly limited, and the appropriate size can be appropriately set in consideration of the size or shape of the ion exchange membrane, the physical properties required for the ion exchange membrane, and the use environment. For example, the reinforced core material may be arranged along a specific direction of the film body. From the viewpoint of dimensional stability, it is preferable to arrange the reinforced core material along a specific first direction, and along a second substantially perpendicular to the first direction. Orientation with other reinforced core materials. By arranging a plurality of reinforcing core materials in a substantially lined manner inside the longitudinal film body of the film body, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. For example, a configuration in which a reinforced core material (longitudinal yarn) arranged in the longitudinal direction and a reinforced core material (horizontal yarn) arranged in the horizontal direction is preferably woven into the surface of the film body. From the viewpoints of dimensional stability, mechanical strength, and ease of manufacture, it is more preferable to produce a plain weave fabric in which longitudinal and transverse yarns are alternately woven one by one, or twisted with two warp yarns and one side yarn. Interwoven leno weaves, twill weave woven by weaving the same number of cross yarns in every 2 or more parallel yarns. It is particularly preferable to arrange the reinforced core material in two directions of the MD direction (Machine Direction) and the TD direction (Transverse Direction) of the ion exchange membrane. That is, it is preferable to perform plain weaving in the MD direction and the TD direction. Here, the MD direction refers to a direction (traveling direction) in which the membrane body or various core materials (for example, a reinforced core material, a reinforced yarn, a sacrificial yarn described below, etc.) are transported in the manufacturing steps of the ion exchange membrane described below ), The TD direction refers to a direction substantially perpendicular to the MD direction. In addition, the yarn woven in the MD direction is referred to as an MD yarn, and the yarn woven in the TD direction is referred to as a TD yarn. Generally, the ion exchange membrane used in electrolysis is rectangular, and the length direction is MD direction and the width direction is TD direction. By weaving a reinforced core material as MD yarn and a reinforced core material as TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. The arrangement interval of the reinforced core material is not particularly limited, and an appropriate arrangement may be appropriately set in consideration of physical properties required for the ion exchange membrane and use environment. The opening ratio of the reinforced core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane. The so-called aperture ratio of the reinforced core material refers to the total area (B) of the surface through which any substance such as ions (the electrolyte and its cations (for example, sodium ions)) can pass through. Ratio (B / A). The total area (B) of the surface through which substances such as ions can pass may refer to the total area of areas in the ion exchange membrane that are not blocked by the reinforced core material or the like contained in the ion exchange membrane. FIG. 24 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 24 is an enlarged view of a part of the ion exchange membrane, and only the arrangement of the reinforced core materials 21 and 22 in the area is illustrated, and other components are omitted. The total area of the reinforced core material is subtracted from the area (A) of the area surrounded by the reinforced core material 21 arranged in the longitudinal direction and the reinforced core material 22 arranged in the horizontal direction, which also includes the area of the reinforced core material ( C). The total area (B) of the area (A) through which substances such as ions can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I). Opening ratio = (B) / (A) = ((A)-(C)) / (A)… (I) In the reinforced core material, it is particularly preferable from the viewpoint of chemical resistance and heat resistance The morphology is a tape-like yarn or high-alignment monofilament containing PTFE. Specifically, it is more preferable to use a reinforced core material which uses a band-shaped yarn obtained by cutting a high-strength porous sheet containing PTFE into a band shape, or 50 to 300 of a highly-oriented monofilament containing PTFE. Denim plain weave fabric with a textile density of 10 to 50 per inch, with a thickness in the range of 50 to 100 μm. The aperture ratio of the ion-exchange membrane containing the reinforced core material is more preferably 60% or more. Examples of the shape of the reinforcing yarn include round yarn and ribbon yarn. (Communication hole) The ion exchange membrane preferably has a communication hole inside the membrane body. The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, the so-called communication hole is a tubular hole formed inside the membrane body, and is formed by dissolving a sacrificial core material (or sacrificial yarn) described below. The shape or diameter of the communication hole can be controlled by selecting the shape or diameter of the sacrificial core material (sacrificial yarn). By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured during electrolysis. The shape of the communication hole is not particularly limited. According to the manufacturing method described below, the shape of the sacrificial core material used for forming the communication hole can be made. The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With this structure, in the portion where the communication hole is formed on the cathode side of the reinforced core material, ions (for example, sodium ions) transported through the electrolyte filled with the communication hole can also flow to the cathode side of the reinforced core material. As a result, since the flow of cations is not blocked, the resistance of the ion exchange membrane can be further reduced. The communication hole may be formed only in one specific direction of the membrane body constituting the ion exchange membrane. From the viewpoint of exhibiting more stable electrolytic performance, it is preferably formed in both the longitudinal direction and the lateral direction of the membrane body. [Manufacturing Method] As a suitable method for manufacturing the ion exchange membrane, a method having the following steps (1) to (6) can be mentioned. (1) Step: a step of producing a fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted to an ion-exchange group by hydrolysis. (2) Step: by weaving at least a plurality of reinforcing core materials and sacrificial yarns that have properties of dissolving in acid or alkali and forming communicating holes to obtain reinforcements of sacrificial yarns arranged between adjacent reinforcing core materials. Material steps. (3) Step: a step of membrane-forming the above-mentioned fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted into an ion-exchange group by hydrolysis. (4) Step: a step of burying the above-mentioned reinforcing material in the above-mentioned film to obtain a film body in which the above-mentioned reinforcing material is internally arranged as necessary. (5) Step: a step of hydrolyzing the membrane body obtained in step (4) (hydrolysis step). (6) Step: a step (coating step) of providing a coating layer on the film body obtained in step (5). Each step will be described in detail below. (1) Step: Step for producing fluoropolymer In step (1), a fluoropolymer is produced using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the monomers of the raw materials may be adjusted in the production of the fluorine-containing polymer forming each layer. (2) Step: Manufacturing steps of reinforcing material The so-called reinforcing material is a woven fabric of textile reinforcing yarn. A reinforcing core material is formed by embedding a reinforcing material in the film. When making an ion exchange membrane with communicating holes, sacrificial yarns are also woven into the reinforcing material together. In this case, the blending amount of the sacrificial yarn is preferably 10 to 80% by mass of the entire reinforcing material, and more preferably 30 to 70% by mass. By weaving the sacrificial yarn, the reinforcing core material can be prevented from being detached. Sacrificial yarns are soluble in the manufacturing steps of the film or in an electrolytic environment. Rhenium, polyethylene terephthalate (PET), cellulose, and polyamide can be used. In addition, polyvinyl alcohol having a thickness of 20 to 50 denier, monofilament or multifilament is also preferred. Furthermore, in step (2), the aperture ratio or the arrangement of the communication holes can be controlled by adjusting the configuration of the reinforced core material or the sacrificial yarn. (3) Step: Film formation step In the step (3), the fluorinated polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single-layer structure, as described above, a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or a multilayer structure of three or more layers. As a method of film formation, the following are mentioned, for example. A method of separately forming a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group into a membrane. A method for making a composite film from a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group by coextrusion. Moreover, the film may be plural. In addition, coextrusion of a heterogeneous film is preferred because it improves the bonding strength at the interface. (4) Step: the step of obtaining the film body In step (4), the reinforcing material obtained in step (2) is embedded in the inside of the film obtained in step (3) to obtain the reinforcing material inside. Membrane body. As a preferred method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) on the cathode side by a coextrusion method (hereinafter, The layer containing it is called the first layer) and a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonium fluoride functional group) (hereinafter, the layer containing it is referred to as a second layer). It is necessary to use a heating source and a vacuum source to separate the breathable and heat-resistant release paper, and sequentially laminate the reinforcing material and the second / first layer composite film on a flat plate or a drum with a large number of fine holes on the surface. At the melting temperature of each polymer, the method of integration is performed while removing the air between the layers by decompression; (ii) Different from the second / first layer composite film, the The fluorine-containing polymer (third layer) is separately formed into a film, and if necessary, a heating source and a vacuum source are used to separate the third layer film, the reinforced core material, Layer / first layer of composite film is sequentially laminated on a plate or drum with a large number of fine holes on the surface, Each of the polymer melt temperature, while removed under reduced pressure by the air between the layers while the integration method. Here, coextrusion of the first layer and the second layer helps to improve the bonding strength of the interface. In addition, the method of integrating under reduced pressure has a feature that the thickness of the third layer on the reinforcing material is larger than that of the pressure pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane body, it has a property capable of sufficiently maintaining the mechanical strength of the ion exchange membrane. In addition, the variation of the laminate described here is an example. The required layer structure or physical properties of the film body may be considered, and an appropriate laminate pattern (for example, a combination of layers) may be appropriately selected and then co-extruded. Furthermore, in order to further improve the electrical performance of the ion exchange membrane, a fluorine-containing polymer containing both a carboxylic acid group precursor and a sulfonic acid group precursor may be further interposed between the first layer and the second layer. Instead of the second layer, a fourth layer containing a fluorinated polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is used. The formation method of the fourth layer may be a method of separately manufacturing a fluorinated polymer having a carboxylic acid group precursor and a fluorinated polymer having a sulfonic acid group precursor and then mixing them. A method in which a monomer of a precursor is copolymerized with a monomer having a sulfonic acid group precursor. When the fourth layer is made into an ion-exchange membrane, the co-extruded film of the first layer and the fourth layer can be formed, and the third layer and the second layer can be separately formed into a membrane. The method described herein is laminated, and the three layers of the first layer / the fourth layer / the second layer can also be co-extruded to form a film. In this case, the direction of travel of the extruded film is the MD direction. As a result, a film body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material. Moreover, it is preferable that the ion exchange membrane has a protruding portion, that is, a protruding portion containing a fluorinated polymer having a sulfonic acid group on the surface side including the sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming a convex portion on the surface of a resin can be adopted. Specifically, the method of embossing the surface of a film main body is mentioned, for example. For example, when the composite film is integrated with a reinforcing material or the like, the convex portion can be formed by using a release paper that has been embossed in advance. When the convex portion is formed by embossing, the height of the convex portion or the arrangement density can be controlled by controlling the transferred embossed shape (shape of the release paper). (5) Hydrolysis step In step (5), a step of hydrolyzing the membrane body obtained in step (4) to convert an ion-exchange group precursor to an ion-exchange group (hydrolysis step) is performed. In step (5), a dissolution hole can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body by using an acid or an alkali. In addition, the sacrificial yarn may not be completely dissolved and removed, but may remain in the communication hole. In addition, the sacrificial yarn remaining in the communication hole can be removed by dissolving the electrolytic solution when the ion exchange membrane is supplied for electrolysis. Sacrificial yarns are those which are soluble in acids or alkalis in the manufacturing steps of ion exchange membranes or in an electrolytic environment. The sacrificial yarns are dissolved to form communication holes in this part. Step (5) can be carried out by immersing the film body obtained in step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (Dimethyl sulfoxide) can be used. The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35 mass% of DMSO. The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the thicker the apparent thickness. It is more preferably 75 to 100 ° C. The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes. Here, the step of forming the communication hole by dissolving the sacrificial yarn will be described in more detail. 25 (a) and (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane. In Figs. 25 (a) and (b), only the reinforcing yarn 52, the sacrificial yarn 504a, and the communication hole 504 formed by the sacrificial yarn 504a are shown, and other members such as the film body are not shown. First, a knitting-reinforcing material is made from the reinforcing yarn 52 constituting the reinforcing core material in the ion-exchange membrane and the sacrificial yarn 504a used to form the communication hole 504 in the ion-exchange membrane. Then, in step (5), the communication hole 504 is formed by dissolving the sacrificial yarn 504a. According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a can be adjusted according to how the reinforcing core material and the communication hole are arranged in the membrane body of the ion exchange membrane, which is relatively simple. In FIG. 25 (a), the plain weaving reinforcing material woven with the reinforcing yarn 52 and the sacrificial yarn 504a in the longitudinal and transverse directions on the paper surface is illustrated. The configuration of the reinforcing yarn 52 and the sacrificial yarn 504a in the reinforcing material may be changed as required. . (6) Coating step In step (6), a coating liquid containing inorganic particles obtained by pulverizing or melting the raw stone and a binder is prepared, and the coating liquid is applied to the ion exchange obtained in step (5). The surface of the film is dried to form a coating layer. As the binding agent, it is preferred that the fluorine-containing polymer having an ion-exchange group precursor is hydrolyzed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to ion-exchange. Substitute counter ion for H+ The resulting binding agent (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group). This makes it easy to dissolve in water or ethanol described below, and is therefore preferred. This binding agent was dissolved in a solution obtained by mixing water and ethanol. Furthermore, the preferred volume ratio of water to ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1 to 1: 2. The coating liquid was obtained by dispersing the inorganic particles in the dissolving liquid thus obtained by a ball mill. At this time, the average particle diameter of the particles and the like can also be adjusted by adjusting the time during dispersion and the rotation speed. Moreover, the preferable blending amount of the inorganic particles and the binder is as described above. The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, and it is preferable to make a thin coating liquid. Thereby, the surface of an ion exchange membrane can be apply | coated uniformly. When dispersing the inorganic particles, a surfactant may be added to the dispersion liquid. The surfactant is preferably a nonionic surfactant, and examples thereof include HS-210, NS-210, P-210, and E-212 manufactured by Nippon Oil Corporation. An ion exchange membrane can be obtained by applying the obtained coating solution to the surface of an ion exchange membrane by spray coating or roll coating. [Microporous membrane] The microporous membrane of this embodiment is not particularly limited as long as it can be laminated with an electrode for electrolysis as described above, and various microporous membranes can be applied. The porosity of the microporous membrane of this embodiment is not particularly limited, and it can be set to, for example, 20 to 90, and preferably 30 to 85. The porosity can be calculated by the following formula, for example. Porosity = (1-(film weight in dry state) / (weight calculated from the volume calculated from the thickness, width, and length of the film and the density of the film material)) × 100 average pore diameter of the microporous membrane of this embodiment It is not particularly limited, and may be, for example, 0.01 μm to 10 μ, and preferably 0.05 μm to 5 μm. The said average pore diameter cuts a film | membrane perpendicularly along a thickness direction, and observes a cut surface by FE-SEM, for example. The average pore diameter can be determined by measuring the diameter of the observed pores at about 100 points and obtaining an average value. The thickness of the microporous membrane in this embodiment is not particularly limited, and it can be set to, for example, 10 μm to 1,000 μm, and preferably 50 μm to 600 μm. The thickness can be measured, for example, using a micrometer (manufactured by Mitutoyo Co., Ltd.). As specific examples of the microporous membrane described above, there can be mentioned Zilfon Perl UTP 500 (also referred to as a Zilfon membrane in this embodiment) manufactured by Agfa, International Publication No. 2013-183584, and International Publication No. 2016-203701. No., etc. The reason why the laminated body with the separator of this embodiment exhibits excellent electrolytic performance is presumed as follows. In the case where the separator and the electrode are firmly adhered by a method such as thermal compression bonding in the prior art, the electrode is physically attached in a state where the electrode is embedded in the separator. This adhering portion hinders the movement within the membrane of sodium ions, and the voltage rises significantly. On the other hand, by using a moderate bonding force as in the present embodiment, the electrode for electrolysis is connected to the separator or the power feeder, thereby eliminating the problem of hindering the movement of sodium ions in the membrane, which has been a problem in the prior art. Therefore, when the separator or the power supply and the electrode for electrolysis are in contact with each other by a moderate bonding force, the separator or the power supply and the electrode for electrolysis are one body, and can exhibit excellent electrolytic performance. [Wound body] The wound body of this embodiment includes a laminated body of this embodiment. That is, the winding system of this embodiment is a product obtained by winding the laminated body of this embodiment. Like the wound body of the present embodiment, by winding the laminated body of the present embodiment and reducing the size, the operability can be further improved. [Electrolytic Cell] The electrolytic cell according to this embodiment includes a laminated body according to this embodiment. Hereinafter, an embodiment of an electrolytic cell will be described in detail using a case where salt electrolysis is performed using an ion exchange membrane as a separator. [Electrolytic Cell] FIG. 26 is a sectional view of the electrolytic cell 1. FIG. The electrolytic cell 1 includes an anode chamber 10, a cathode chamber 20, a partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, an anode 11 provided in the anode chamber 10, and a cathode 21 provided in the cathode chamber 20. If necessary, a reverse current absorber 18 having a base material 18a and a reverse current absorbing layer 18b formed on the base material 18a and provided in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 provided in the cathode chamber 20, and a reverse current absorber 18 provided in the cathode chamber 20. The reverse current absorber 18 has a base material 18a as shown in FIG. The reverse current absorbing layer 18b on the substrate 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the current collector 23 and the cathode 21. The support 24 is provided between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via a metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be indirectly connected through a current collector, a support, a metal elastomer, or a partition wall. The entire surface of the cathode 21 is preferably covered with a catalyst layer for reduction reaction. In addition, the form of electrical connection may be to directly install the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22, and laminate the cathode 21 on the metal elastic body 22, respectively. The form. Examples of a method for directly mounting the respective constituent members to each other include welding and the like. The reverse current sink 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40. FIG. 27 is a cross-sectional view of two adjacent electrolytic cells 1 in the electrolytic cell 4. FIG. 28 shows the electrolytic cell 4. FIG. 29 shows the steps for assembling the electrolytic cell 4. As shown in FIG. 27, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are sequentially arranged in series. An ion exchange membrane 2 is arranged between the anode chamber of one of the two electrolytic cells adjacent to the electrolytic cell and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are separated by the cation exchange membrane 2. As shown in FIG. 28, the electrolytic cell 4 includes a plurality of electrolytic cells 1 connected in series via a dielectric exchange membrane 2. That is, the electrolytic cell 4 is a bipolar electrolytic cell having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 29, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via a separator exchange membrane 2 and connecting them with a press 5. The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. Among the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4, the anode 11 of the electrolytic cell 1 located at the extreme end is electrically connected to the anode terminal 7. The cathode 21 of the electrolytic cell at the end opposite to the anode terminal 7 of the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 to the cathode terminal 6 through the anode and cathode of each electrolytic cell 1. Furthermore, an electrolytic cell having only an anode chamber (anode terminal cell) and an electrolytic cell having only a cathode chamber (cathode terminal cell) may be disposed at both ends of the connected electrolytic cells 1. In this case, the anode terminal 7 is connected to an anode terminal cell disposed at one end thereof, and the cathode terminal 6 is connected to a cathode terminal cell disposed at the other end. When electrolysis of brine is performed, brine is supplied to each anode chamber 10 and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid system is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (omitted from the figure) through an electrolytic solution supply hose (omitted from the figure). In addition, the electrolytic solution and the products of electrolysis are recovered by an electrolytic solution recovery tube (omitted from the figure). During the electrolysis, the sodium ions in the brine start from the anode chamber 10 of an electrolytic cell 1 and pass through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Accordingly, the current in the electrolysis flows in a direction in which the electrolytic cells 1 are connected in series. That is, a current flows from the anode chamber 10 to the cathode chamber 20 through the cation exchange membrane 2. Along with the electrolysis of brine, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen are generated on the cathode 21 side. (Anode Chamber) The anode chamber 10 includes an anode 11 or an anode power source 11. When the electrolytic electrode of this embodiment is inserted into the anode side, 11 functions as an anode power source. When the electrolytic electrode of this embodiment is not inserted on the anode side, 11 functions as an anode. The anode chamber 10 preferably includes an anode-side electrolytic solution supply unit that supplies an electrolytic solution to the anode chamber 10, and a baffle plate that is disposed above the anode-side electrolytic solution supply unit and is disposed substantially parallel or inclined to the partition wall 30. And an anode-side gas-liquid separation portion disposed above the baffle and separating gas from an electrolyte mixed with the gas. (Anode) When the electrode for electrolysis of this embodiment is not inserted on the anode side, an anode 11 is provided in the frame of the anode chamber 10. As the anode 11, a metal electrode such as a so-called DSA (registered trademark) can be used. The so-called DSA is an electrode with a titanium substrate covered with an oxide containing ruthenium, iridium, and titanium as components. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode Feeder) When the electrode for electrolysis of this embodiment is inserted on the anode side, an anode feed member 11 is provided in the frame of the anode chamber 10. As the anode power source 11, a metal electrode such as a so-called DSA (registered trademark) may be used, or titanium without a catalyst coating layer may be used. Alternatively, a DSA having a thinner catalyst coating thickness may be used. Furthermore, a used anode can also be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode-side electrolytic solution supply unit) The anode-side electrolytic solution supply unit is a person that supplies an electrolytic solution to the anode chamber 10 and is connected to an electrolytic solution supply pipe. The anode-side electrolytic solution supply portion is preferably arranged below the anode chamber 10. As the anode-side electrolytic solution supply portion, for example, a tube (dispersion tube) having an opening formed on the surface can be used. The tube is more preferably arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies an electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is transported into the electrolytic cell 1 through the tube, and is supplied into the anode chamber 10 from an opening provided on the surface of the tube. Since the tube is arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell, the electrolyte can be uniformly supplied to the inside of the anode chamber 10, which is preferable. (Anode-side gas-liquid separation section) The anode-side gas-liquid separation section is preferably disposed above the baffle. In electrolysis, the anode-side gas-liquid separator has a function of separating a generated gas such as chlorine gas from the electrolytic solution. In addition, unless otherwise specified, the so-called upper means the upper direction in the electrolytic cell 1 of FIG. 26, and the lower means the lower direction in the electrolytic cell 1 of FIG. 26. During the electrolysis, if the generated gas generated in the electrolytic cell 1 and the electrolyte become mixed phase (gas-liquid mixed phase) and are discharged out of the system, there will be physical damage to the ion exchange membrane due to vibration caused by pressure fluctuations inside the electrolytic cell 1. Situation. In order to suppress this situation, it is preferable to provide an anode-side gas-liquid separation unit for separating gas from liquid in the electrolytic cell 1 of this embodiment. It is preferable to provide a defoaming plate for eliminating bubbles in the anode-side gas-liquid separation section. The gas and liquid mixed phase flow can be separated into the electrolyte and the gas by breaking the bubbles when passing through the defoaming plate. As a result, vibration during electrolysis can be prevented. (Baffle) The baffle is preferably disposed above the anode-side electrolytic solution supply portion, and is disposed substantially parallel or inclined to the partition wall 30. The baffle is a partition that controls the flow of the electrolyte in the anode chamber 10. By providing the baffle, the electrolyte (brine, etc.) can be circulated inside the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle is preferably arranged to separate a space near the anode 11 from a space near the partition wall 30. From this viewpoint, the baffle is preferably provided so as to face the respective surfaces of the anode 11 and the partition wall 30. In the space near the anode separated by the baffle, by performing electrolysis, the concentration of the electrolyte (brine concentration) is reduced, and a gas such as chlorine gas is generated. As a result, a difference in gas-liquid specific gravity occurs between the space near the anode 11 separated by the baffle and the space near the partition wall 30. With this situation, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform. Although not shown in FIG. 26, a current collector may be separately provided inside the anode chamber 10. The current collector may be made of the same material or structure as the current collector of the cathode chamber described below. Moreover, in the anode chamber 10, the anode 11 itself can also be made to function as a current collector. (Partition Wall) The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes referred to as a spacer, and divides the anode chamber 10 and the cathode chamber 20. As the partition wall 30, those known as separators for electrolysis can be used, and examples thereof include partition walls in which a plate containing nickel is welded on the cathode side, and a plate containing titanium is welded on the anode side. (Cathode Room) When the cathode electrode 20 is inserted into the cathode side of the present embodiment, 21 functions as a cathode power supply. When the electrode for electrolytic use of the present embodiment is not inserted into the cathode side, 21 Functions as a cathode. When there is a reverse current sink, the cathode or the cathode power source 21 is electrically connected to the reverse current sink system. The cathode chamber 20 preferably includes a cathode-side electrolytic solution supply unit and a cathode-side gas-liquid separation unit similarly to the anode chamber 10. It should be noted that, among the parts constituting the cathode chamber 20, the same descriptions as the parts constituting the anode chamber 10 are omitted. (Cathode) When the electrode for electrolysis in this embodiment is not inserted on the cathode side, a cathode 21 is provided in the frame of the cathode chamber 20. The cathode 21 is preferably a catalyst layer having a nickel substrate and a coated nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include: Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. If necessary, a reduction treatment is performed on the cathode 21. In addition, as the base material of the cathode 21, nickel, a nickel alloy, or nickel-plated iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Cathode Feeder) When the electrode for electrolysis of this embodiment is inserted on the cathode side, a cathode feed member 21 is provided in the frame of the cathode chamber 20. The cathode feed body 21 may be covered with a catalyst component. This catalyst component can be used as a cathode and remain. Examples of the components of the catalyst layer include Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. In addition, nickel, a nickel alloy, and iron or stainless steel plated with nickel without a catalyst coating can be used. In addition, as a base material of the cathode power supply body 21, nickel, a nickel alloy, or nickel plating on iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Reverse current absorbing layer) As the material of the reverse current absorbing layer, a material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected. Examples include nickel and iron. (Current Collector) The cathode chamber 20 preferably includes a current collector 23. This improves the current collection effect. In this embodiment, the current collector 23 is preferably a porous plate, and is arranged so as to be substantially parallel to the surface of the cathode 21. The current collector 23 is preferably composed of a conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, an alloy, or a composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a mesh shape. (Metal Elastomer) By providing the metal elastomer 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, each anode 11 and each cathode The distance between 21 becomes shorter, which can reduce the voltage to the whole of the electrolytic cells 1 connected in series. By reducing the voltage, power consumption can be reduced. In addition, when the metal elastic body 22 is provided, when the laminated body containing the electrolytic electrode of the present embodiment is installed in an electrolytic cell, the pressure of the metal elastic body 22 can stably maintain the electrode for electrolysis. starting point. As the metal elastic body 22, a spring member such as a coil spring or a coil, a cushioning pad, or the like can be used. As the metal elastic body 22, it is possible to use a suitable one in consideration of the stress against the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side or on the surface of the partition wall on the anode chamber 10 side. Generally, the two compartments are divided such that the cathode compartment 20 is smaller than the anode compartment 10. Therefore, in terms of the strength of the frame, it is preferable that the metal elastic body 22 is disposed between the current collector 23 and the cathode 21 of the cathode compartment 20. The metal elastic body 23 is preferably made of a conductive metal such as nickel, iron, copper, silver, or titanium. (Support) The cathode chamber 20 is preferably provided with a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently. The support 24 preferably contains a conductive metal such as nickel, iron, copper, silver, and titanium. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a mesh shape. The support 24 is, for example, a plate. The plurality of support bodies 24 are arranged between the partition wall 30 and the current collector 23. The plurality of support bodies 24 are arranged so that their respective faces are parallel to each other. The support 24 is disposed so as to be substantially perpendicular to the partition wall 30 and the current collector 23. (Anode-Side Gasket, Cathode-Side Gasket) The anode-side gasket is preferably arranged on the surface of the frame constituting the anode chamber 10. The cathode-side gasket is preferably disposed on a surface of a frame constituting the cathode chamber 20. The anode-side gasket provided in one electrolytic cell and the cathode-side gasket of an adjacent electrolytic cell connect the electrolytic cells to each other by sandwiching the ion exchange membrane 2 (see FIGS. 26 and 27). With these gaskets, when a plurality of electrolytic cells 1 are connected in series through the dielectric exchange membrane 2, airtightness can be imparted to the connection points. The so-called gasket is a seal between the ion exchange membrane and the electrolytic cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. The gasket is required to be resistant to corrosive electrolytes or generated gases, and can be used for a long time. Therefore, in terms of chemical resistance or hardness, generally, ethylene-propylene-diene rubber (EPDM rubber), ethylene-propylene rubber (EPM rubber) sulfide or peroxide crosslinked material can be used as a mat. sheet. In addition, if necessary, a gasket covering a region (liquid-contacting portion) in contact with the liquid may be coated with a fluorine resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). . These gaskets may have openings so as not to hinder the flow of the electrolytic solution, and their shapes are not particularly limited. For example, a frame-shaped gasket is attached to the periphery of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20 with an adhesive or the like. In addition, for example, in a case where two dielectric cells 1 are connected to the dielectric exchange membrane 2 (see FIG. 27), the dielectric exchange membrane 2 may fasten each electrolytic cell 1 to which a gasket is attached. This makes it possible to prevent the electrolytic solution, alkali metal hydroxide, chlorine gas, hydrogen gas, and the like from being leaked to the outside of the electrolytic cell 1. (Ion exchange membrane) As the ion exchange membrane 2, it is as described in the item of the said ion exchange membrane. (Water Electrolysis) The electrolytic cell in the case of performing water electrolysis in this embodiment has a structure in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis described above is changed to a microporous membrane. In addition, the electrolyzer is different from the case where the salt electrolysis is performed in the point that the supplied raw material is water. Regarding other configurations, the electrolytic cell in the case of performing water electrolysis may also have the same configuration as the electrolytic cell in the case of performing salt electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. In the case of water electrolysis, only oxygen is generated in the anode chamber, so the same material as the cathode chamber can be used. Examples include nickel. The anode coating is preferably a catalyst coating for generating oxygen. Examples of the catalyst coating layer include metals, oxides, hydroxides, and the like of platinum group metals and transition metal groups. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used. (Application of laminated body) As described above, the laminated body of this embodiment can improve the working efficiency when the electrodes in the electrolytic cell are renewed, and can also exhibit excellent electrolytic performance after the renewal. In other words, the laminated body of this embodiment can be suitably used as a laminated body for replacing the components of an electrolytic cell. The laminated body used in this application is particularly referred to as a "membrane electrode assembly". (Package) The laminated body of this embodiment is preferably transported in a state of being sealed in a packaging material. That is, the packaging body of this embodiment is provided with the laminated body of this embodiment, and the packaging material which packs the said laminated body. Since the packaging body of this embodiment is configured as described above, it is possible to prevent the adhesion or damage of dirt that may occur when the laminated body or the like of this embodiment is transported. When the components of the electrolytic cell are replaced, it is particularly preferable to carry them in the form of a packaging body according to this embodiment. The packaging material in this embodiment is not particularly limited, and various known packaging materials can be applied. The packaging body of the present embodiment is not limited to the following, but can be produced by, for example, packaging the laminated body of the present embodiment with a packaging material in a clean state, and then sealing it. <Third Embodiment> Here, a third embodiment of the present invention will be described in detail with reference to FIGS. 43 to 62. [Laminated body] The laminated body of the third embodiment (hereinafter referred to as "this embodiment" in the item of "Third Embodiment") has a diaphragm and at least one area (hereinafter also simply referred to as "hereinafter" "Fixed area"), and the ratio of the above-mentioned area in the surface of the separator exceeds 0% to less than 93%. Due to the structure described above, the laminated body of this embodiment can improve the working efficiency when the electrodes in the electrolytic cell are renewed, and can also exhibit excellent electrolytic performance after the renewal. That is, with the laminated body of this embodiment, when the electrodes are renewed, there is no need to perform complicated operations such as peeling the existing electrodes fixed to the electrolytic cell, and the electrodes can be renewed by the same simple operation as that of the diaphragm. Therefore, the operation efficiency is improved. A substantial increase. Furthermore, with the laminated body of this embodiment, the electrolytic performance of the existing electrolytic cell can be maintained to be the same as or improved in the performance of the new product. Therefore, an electrode fixed to an existing electrolytic cell and functioning as an anode and a cathode only needs to function as a feeder, which can greatly reduce a catalyst coating or even a catalystless coating. The term “feeder” used herein refers to an electrode that is degraded (ie, an existing electrode) or an electrode that is not formed with a catalyst coating. [Electrolysis electrode] The electrode for electrolysis in this embodiment is not particularly limited as long as it is an electrode that can be used for electrolysis. The area of the surface of the electrode facing the separator (the area of the current-carrying surface described below) (S2 corresponding) is 0.01 m2 the above. The "face opposite to the separator" means the surface on the side where the separator exists among the surfaces of the electrode for electrolysis. That is, the surface of the electrode for electrolysis that faces the separator may also be referred to as a surface that is in contact with the surface of the separator. The area of the surface facing the separator in the electrode for electrolysis is 0.01 m2 In the above cases, sufficient productivity can be ensured, and in particular, there is a tendency that sufficient productivity can be obtained in the implementation of industrial electrolysis. Therefore, from the viewpoint of ensuring sufficient productivity and practicality as a multilayer body used for renewing the electrolytic cell, the area of the surface of the electrode for electrolysis facing the separator is preferably 0.1 m2 Above, further preferably 1 m2 the above. This area can be measured, for example, by the method described in Examples. The electrode for electrolysis in this embodiment can obtain good operability, and has good adhesion to a separator such as an ion exchange membrane or a microporous membrane, and a power supply (a deteriorated electrode and an electrode without a catalyst coating layer). From the viewpoint of force, the force per unit mass and area is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ) Above, and more preferably 0.1 N / mg · cm2 Above, more preferably 0.14 N / (mg · cm2 )the above. From the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The above-mentioned bearing force can be set to the above range, for example, by appropriately adjusting a porosity, an electrode thickness, an arithmetic average surface roughness, and the like described below. More specifically, for example, if the opening ratio is increased, the bearing force tends to be small, and if the opening ratio is decreased, the bearing force tends to be large. In addition, from the viewpoint of obtaining good operability, it has good adhesion to separators such as ion-exchange membranes or microporous membranes, deteriorated electrodes, and feeders without a catalyst coating, and so on in terms of economy. From a viewpoint, the mass per unit area is preferably 48 mg / cm2 Below, more preferably 30 mg / cm2 Below, more preferably 20 mg / cm2 Hereinafter, it is 15 mg / cm from the viewpoint of a comprehensive combination of operability, adhesion and economy.2 the following. The lower limit value is not particularly limited, for example, 1 mg / cm2 about. The above-mentioned mass per unit area can be set to the above range, for example, by appropriately adjusting the opening ratio and thickness of the electrode described below. More specifically, for example, if the thickness is the same, the mass per unit area tends to become smaller if the opening ratio is increased, and the mass per unit area tends to be larger if the opening ratio is decreased. . The bearing capacity can be measured by the following method (i) or (ii), the value obtained by the measurement of the method (i) (also referred to as "bearing capacity (1)") and the value obtained by the method (ii) The value obtained by the measurement (also referred to as "endurance (2)") may be the same or different, but it is preferable that any value does not reach 1.5 N / mg · cm2 . [Method (i)] A nickel plate (thickness: 1.2 mm, 200 mm square) obtained by spraying with alumina of grain number 320 was laminated in order, and the perfluorocarbon polymer film with an ion exchange group was introduced. Ion-exchange membranes (170 mm square) and electrode samples (130 mm square) coated with inorganic particles and binders on both sides. After the laminate is fully immersed in pure water, the excess moisture attached to the surface of the laminate is removed. Thereby, a measurement sample is obtained. In addition, the arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment is 0.5 to 0.8 μm. The specific calculation method of the arithmetic average surface roughness (Ra) is as described in the examples. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. This average value is divided by the area of the overlapped part of the electrode sample and the ion-exchange membrane and the mass of the electrode sample of the overlapped part of the ion-exchange membrane to calculate the force per unit mass and unit area (1) (N / mg · cm2 ). With the force (1) per unit mass and unit area obtained by method (i), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 ), More preferably 0.2 N / (mg ・ cm2 )the above. [Method (ii)] A nickel plate (thickness 1.2 mm, 200 mm square, the same nickel plate as in the above method (i)) and an electrode sample (130 mm square), and the laminated body is sufficiently immersed in pure water, and then excess water adhered to the surface of the laminated body is removed to obtain a sample for measurement. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate and the mass of the electrode sample in the overlapped portion of the nickel plate to calculate the adhesion force per unit mass and unit area (2) (N / mg · cm2 ). With the force (2) per unit mass and unit area obtained by method (ii), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. Furthermore, from the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 )the above. The electrode for electrolysis in this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, and good operability can be obtained. It can be used in contact with separators such as ion exchange membranes or microporous membranes, degraded electrodes (feeders), and non-formed The electrode (feeder) of the dielectric coating has good adhesion, can be wound into a roll shape and bent well, and it is easy to handle at a large size (for example, 1.5 m × 2.5 m). In particular, it is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and even more It is preferably 100 μm or less, and from the viewpoint of operability and economy, it is more preferably 50 μm or less. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and further, for a large size (for example, From the viewpoint of easy handling at a size of 1.5 m × 2.5 m), it is more preferably 95% or more. The upper limit is 100%. [Method (2)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 280 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesive force and being able to be wound into a roll shape and bent well, the ratio measured by the following method (3) is preferably 75% or more. It is preferably 80% or more, and from the viewpoint of ease of handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 90% or more. The upper limit is 100%. [Method (3)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 145 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesion and preventing gas retention during electrolysis, a porous structure is preferred, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80%, and more preferably 20 to 75%. The open porosity is the ratio of the perforated portion per unit volume. There are various calculation methods for the opening part according to the submicron order or only the openings that can be seen visually. In this embodiment, the volume V is calculated from the values of the gauge thickness, width, and length of the electrode, and the weight W is measured. Then, the aperture ratio A is calculated by the following formula. A = (1- (W / (V × ρ)) × 100 ρ Density of electrode material (g / cm3 ). E.g. in the case of nickel 8.908 g / cm3 In the case of titanium is 4.506 g / cm3 . The adjustment of the opening ratio is appropriately adjusted by the following methods: if it is a punched metal, change the area of the punched metal per unit area; if it is a porous metal, change SW (short diameter), LW (long diameter), Feed value; if it is a wire mesh, change the wire diameter and mesh number of the metal fiber; if it is electroforming, change the pattern of the photoresist used; if it is a non-woven fabric, change the metal fiber diameter and fiber density; In the case of a foamed metal, a template or the like for forming a void is changed. Hereinafter, one embodiment of the electrode for electrolysis in this embodiment will be described. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer is described below, and may include a plurality of layers or a single-layer structure. As shown in FIG. 43, the electrode 100 for electrolysis according to this embodiment includes an electrode base material 10 for electrolysis, and a pair of first layers 20 covering one surface of the electrode base material 10 for electrolysis. The first layer 20 preferably covers the entire electrode base material 10 for electrolysis. As a result, the catalyst activity and durability of the electrode for electrolysis can be easily improved. Furthermore, the first layer 20 may be formed only on one surface area of the electrode base material 10 for electrolysis. As shown in FIG. 43, the surface of the first layer 20 may be covered by the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, the second layer 30 may be laminated on only one surface of the first layer 20. (Electrode base material for electrolysis) The electrode base material 10 for electrolysis is not particularly limited, and for example, nickel, nickel alloy, stainless steel, or a valve metal typified by titanium can be used, and it is preferably selected from nickel (Ni) And at least one element of titanium (Ti). When stainless steel is used in a high-concentration alkaline aqueous solution, considering the elution of iron and chromium, and the conductivity of stainless steel is about 1/10 of that of nickel, it is preferable to use a substrate containing nickel (Ni) as the base material. Electrode substrate for electrolysis. In addition, when the electrode base material 10 for electrolysis is used in a chlorine gas generating environment in a high-concentration saline solution, the material is preferably titanium with high corrosion resistance. The shape of the electrode substrate 10 for electrolysis is not particularly limited, and a suitable shape can be selected according to the purpose. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. Among them, punched metal or porous metal is preferred. In addition, the so-called electroforming is a technique for producing a precise patterned metal thin film by combining a photolithographic process and an electroplating method. It is a method for obtaining a metal thin film by forming a pattern on a substrate with a photoresist, and performing electroplating on a portion not protected by the photoresist. Regarding the shape of the electrode substrate for electrolysis, there are suitable specifications according to the distance between the anode and the cathode in the electrolytic cell. There is no particular limitation. When the anode and the cathode have a limited distance, porous metal and punched metal shapes can be used. In the case of a so-called zero-pitch electrolytic cell where the ion exchange membrane is connected to the electrode, a braided thin wire can be used. The finished woven mesh, metal mesh, foamed metal, metal non-woven fabric, porous metal, punched metal, metal porous foil, etc. Examples of the electrode base material 10 for electrolysis include a porous metal foil, a metal wire mesh, a metal nonwoven fabric, a punched metal, a porous metal, or a foamed metal. As a sheet material before being processed into a punched metal or a porous metal, a sheet material formed by rolling and an electrolytic foil are preferred. The electrolytic foil is preferably further subjected to a plating treatment using the same element as the base material as a post-treatment to form unevenness on one or both sides. As described above, the thickness of the electrode base material 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, even more preferably 155 μm or less, even more preferably 135 μm or less, and even more preferably 125. μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, and further more preferably 50 μm or less in terms of operability and economy. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the electrode base material for electrolysis, it is preferable to reduce the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing environment. In addition, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, it is preferable to use steel sand and alumina powder to form unevenness on the surface, and then increase the surface area by acid treatment. Alternatively, it is preferable to increase the surface area by applying a plating treatment to the same element as the substrate. In order to bring the first layer 20 into close contact with the surface of the electrode base material 10 for electrolysis, it is preferable that the surface area of the electrode base material 10 for electrolysis is increased. Examples of the treatment for increasing the surface area include blasting treatment using steel wire grain, steel sand, alumina sand, etc., acid treatment using sulfuric acid or hydrochloric acid, and plating treatment using the same element as the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm. Next, a case where the electrode for electrolysis in this embodiment is used as an anode for salt electrolysis will be described. (First layer) In FIG. 43, the first layer 20 as a catalyst layer contains at least one of ruthenium oxide, iridium oxide, and titanium oxide. Examples of the ruthenium oxide include RuO2 Wait. Examples of the iridium oxide include IrO2 Wait. Examples of the titanium oxide include TiO2 Wait. The first layer 20 is preferably two oxides containing ruthenium oxide and titanium oxide, or three oxides containing ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and further, the adhesion with the second layer 30 is further improved. In the case where the first layer 20 contains two oxides of ruthenium oxide and titanium oxide, the titanium oxide contained in the first layer 20 is better than 1 mol of the ruthenium oxide contained in the first layer 20 It is 1 to 9 moles, more preferably 1 to 4 moles. By setting the composition ratio of the two oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains three oxides of ruthenium oxide, iridium oxide, and titanium oxide, the iridium oxide contained in the first layer 20 is 1 mole relative to the ruthenium oxide contained in the first layer 20 The amount is preferably 0.2 to 3 moles, and more preferably 0.3 to 2.5 moles. In addition, the titanium oxide contained in the first layer 20 is preferably 0.3 to 8 moles, and more preferably 1 to 7 moles relative to 1 mole of the ruthenium oxide contained in the first layer 20. By setting the composition ratio of the three oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains at least two oxides selected from the group consisting of ruthenium oxide, iridium oxide, and titanium oxide, these oxides preferably form a solid solution. By forming an oxide solid solution, the electrode 100 for electrolysis exhibits excellent durability. In addition to the above composition, as long as it contains at least one of ruthenium oxide, iridium oxide, and titanium oxide, various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like called DSA (registered trademark) may be used as the first layer 20. The first layer 20 need not be a single layer, and may include a plurality of layers. For example, the first layer 20 may include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. (Second layer) The second layer 30 preferably contains ruthenium and titanium. This can further reduce the chlorine overvoltage immediately after electrolysis. The second layer 30 is preferably a palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. This can further reduce the chlorine overvoltage immediately after electrolysis. The thicker the second layer 30 is, the longer the time during which the electrolytic performance can be maintained. From the viewpoint of economy, the thickness is preferably 0.05 to 3 μm. Next, a case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis will be described. (First layer) The components of the first layer 20 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. In the case of containing at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal, a platinum group metal, a platinum group metal oxide, and a platinum group metal hydroxide are preferred. The alloy containing a platinum group metal contains at least one platinum group metal of platinum, palladium, rhodium, ruthenium, and iridium. The platinum group metal preferably contains platinum. The platinum group metal oxide is preferably a ruthenium oxide. The platinum group metal hydroxide is preferably a ruthenium hydroxide. The platinum group metal alloy is preferably an alloy containing platinum and nickel, iron, and cobalt. It is preferable to further contain an oxide or hydroxide of a lanthanoid as a second component as necessary. Accordingly, the electrode 100 for electrolysis exhibits excellent durability. The lanthanide oxide or hydroxide preferably contains at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, and praseodymium. It is preferable to further contain an oxide or hydroxide of a transition metal as a third component as necessary. By adding the third component, the electrode 100 for electrolysis can exhibit more excellent durability and reduce the electrolytic voltage. Examples of preferred combinations include ruthenium, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + osmium, ruthenium + rhenium + platinum, ruthenium + rhenium + Platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur , Ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + osmium, ruthenium + rhenium + manganese, ruthenium + 钐 + iron, ruthenium + rhenium + cobalt, ruthenium + 钐 + zinc, ruthenium + 钐+ Gallium, Ruthenium + 钐 + Sulfur, Ruthenium + 钐 + Lead, Ruthenium + 钐 + Ni, Pt + Ce, Pt + Pd + Ce, Pt + Pd + La + Ce, Pt + Ir, Pt + Pd, Pt + I + Palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, alloys of platinum and nickel, alloys of platinum and cobalt, alloys of platinum and iron, etc. When the platinum group metal, platinum group metal oxide, platinum group metal hydroxide, and platinum group metal-containing alloy are not contained, the main component of the catalyst is preferably nickel. Preferably, it contains at least one of nickel metal, oxide, and hydroxide. As a second component, a transition metal may be added. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon. Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, and the like. If necessary, an intermediate layer may be provided between the first layer 20 and the electrode base material 10 for electrolysis. By providing the intermediate layer, the durability of the electrode 100 for electrolysis can be improved. The intermediate layer is preferably one having an affinity for both the first layer 20 and the electrode base material 10 for electrolysis. The intermediate layer is preferably a nickel oxide, a platinum group metal, a platinum group metal oxide, or a platinum group metal hydroxide. The intermediate layer can be formed by coating and firing a solution containing the components forming the intermediate layer, or heat-treating the substrate at a temperature of 300 to 600 ° C in an air environment to form a surface oxide layer. . In addition, it can be formed by a known method such as a thermal spray method or an ion plating method. (Second layer) The components of the first layer 30 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. Examples of preferred combinations of the elements contained in the second layer include the combinations listed in the first layer. The combination of the first layer and the second layer may be a combination with the same composition but a different composition ratio, or a combination with a different composition. As the thickness of the catalyst layer, the thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 μm to 20 μm. When it is 0.01 μm or more, it can fully function as a catalyst. If it is 20 μm or less, it is less likely to fall off from the substrate, and a strong catalyst layer can be formed. More preferably, it is 0.05 μm to 15 μm. More preferably, it is 0.1 μm to 10 μm. It is more preferably 0.2 μm to 8 μm. The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer, is preferably 315 μm or less, more preferably 220 μm or less, and further preferably 170 μm in terms of the operability of the electrode. Below, still more preferably 150 μm or less, even more preferably 145 μm or less, even more preferably 140 μm or less, even more preferably 138 μm or less, and even more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. The thickness of the electrode can be determined by measuring with an electronic digital thickness gauge (Mitutoyo Co., Ltd., showing a minimum of 0.001 mm). The thickness of the electrode substrate for electrolysis was measured in the same manner as the electrode thickness. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness. In this embodiment, from the viewpoint of ensuring sufficient electrolytic performance, it is preferable that the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, and Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, At least one catalyst component in the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy. In this embodiment, if the electrode for electrolysis is an electrode with a wide elastic deformation area, better operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating is formed. From the viewpoint that the layered power supply has a better adhesion, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, still more preferably 170 μm or less, and even more preferably 150 μm. Hereinafter, it is particularly preferably 145 μm or less, more preferably 140 μm or less, even more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. In addition, in this embodiment, "the elastic deformation area is wide" means that the electrode for electrolysis is wound into a wound body, and warping caused by winding is unlikely to occur after the wound state is released. When the thickness of the electrode for electrolysis includes a catalyst layer described below, it means the thickness of the electrode substrate for electrolysis and the thickness of the catalyst layer. (Manufacturing method of the electrode for electrolysis) Next, one Embodiment of the manufacturing method of the electrode 100 for electrolysis is demonstrated in detail. In this embodiment, the first layer 20 is formed on the electrode substrate for electrolysis by using a method such as firing (thermal decomposition) of a coating film under an oxygen environment, or ion plating, plating, or thermal spraying. The second layer 30 is preferably used to produce the electrode 100 for electrolysis. Such a manufacturing method according to this embodiment can achieve high productivity of the electrode 100 for electrolysis. Specifically, a catalyst layer is formed on an electrode substrate for electrolysis by a coating step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. The term "thermal decomposition" means heating a metal salt that becomes a precursor to decompose it into a metal or a metal oxide and a gaseous substance. Decomposition products differ depending on the type of metal used, the type of salt, and the environment in which thermal decomposition is performed, but most metals tend to form oxides easily in an oxidizing environment. In the industrial manufacturing process of electrodes, thermal decomposition is usually performed in air, and in most cases, metal oxides or metal hydroxides are formed. (Formation of the first layer of the anode) (Coating step) The first layer 20 is a solution (first coating liquid) in which a salt of at least one metal among ruthenium, iridium, and titanium is dissolved, and is applied to an electrode base for electrolysis. It is obtained by thermal decomposition (baking) in the presence of oxygen. The contents of ruthenium, iridium, and titanium in the first coating liquid are approximately equal to those of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 100 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of the second layer) The second layer 30 is formed as necessary, for example, a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (a second coating solution) is applied to the first layer 20 It is obtained by thermal decomposition in the presence of oxygen. (Formation of the first layer of the cathode by thermal decomposition method) (Coating step) The first layer 20 is a solution (first coating solution) in which metal salts of various combinations are dissolved on the electrode substrate for electrolysis , Obtained by thermal decomposition (firing) in the presence of oxygen. The content ratio of the metal in the first coating liquid is substantially equal to that of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 10 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of Intermediate Layer) The intermediate layer is formed as necessary. For example, a solution (second coating solution) containing a palladium compound or a platinum compound is coated on a substrate, and then obtained by thermal decomposition in the presence of oxygen. Alternatively, instead of applying the solution, only the substrate is heated, thereby forming a nickel oxide intermediate layer on the surface of the substrate. (Formation of the first layer of the cathode using ion plating) The first layer 20 may also be formed by ion plating. As an example, the method of fixing a base material in a chamber and irradiating an electron beam with a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma environment is argon and oxygen. Ruthenium is deposited on the substrate in the form of ruthenium oxide. (Formation of the first layer using a plated cathode) The first layer 20 may also be formed by a plating method. As an example, if a substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed. (Formation of the first layer of the cathode using thermal spraying) The first layer 20 can also be formed by a thermal spraying method. As an example, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed by plasma-spraying nickel oxide particles onto a substrate. The electrode for electrolysis in this embodiment can be used by being integrated with a separator such as an ion exchange membrane or a microporous membrane. Therefore, the laminated body of this embodiment can be used as a membrane-integrated electrode, and the replacement and attaching operation of the cathode and the anode when the electrode is not required to be renewed, the operation efficiency is greatly improved. In addition, by using a bulk electrode such as an ion exchange membrane or a microporous membrane, the electrolytic performance can be the same as or improved in the new product. Hereinafter, the ion exchange membrane will be described in detail. [Ion exchange membrane] The ion exchange membrane is not particularly limited as long as it can be laminated with an electrode for electrolysis, and various ion exchange membranes can be applied. In this embodiment, an ion exchange membrane having a membrane body containing a hydrocarbon polymer or a fluorine-containing polymer having an ion exchange group and a coating layer provided on at least one side of the membrane body is preferably used. The coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is preferably 0.1 to 10 m.2 / g. The gas generated by the ion exchange membrane of this structure during electrolysis has less influence on the electrolytic performance, and tends to exhibit stable electrolytic performance. The above-mentioned membrane system of a perfluorocarbon polymer to which an ion exchange group is introduced is provided with an ion exchange group (as -SO3 - Sulfonic acid layer and sulfonic acid layer derived from a carboxyl group (with -CO2 - The group represented by this is any of the carboxylic acid layers (hereinafter also referred to as "carboxylic acid groups"). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforced core material. Hereinafter, the inorganic particles and the binder will be described in detail in the description of the coating layer. Fig. 44 is a schematic sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 includes a membrane body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and coating layers 11 a and 11 b formed on both sides of the membrane body 10. In the ion-exchange membrane 1, the membrane body 10 is provided with an ion-exchange group (as -SO3 - The sulfonic acid layer 3, which is also referred to as a "sulfonic acid group" hereinafter, and an ion-exchange group (with -CO2 - The carboxylic acid layer 2 shown below is also referred to as a "carboxylic acid group", and the strength and dimensional stability are strengthened by the reinforcing core material 4. Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it can be suitably used as a cation exchange membrane. The ion exchange membrane may include only one of a sulfonic acid layer and a carboxylic acid layer. The ion exchange membrane is not necessarily reinforced by a reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example shown in FIG. 44. (Membrane Body) First, the membrane body 10 constituting the ion exchange membrane 1 will be described. The membrane body 10 may be any one having a function of selectively transmitting cations and containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group. The structure or material is not particularly limited, and an appropriate one can be appropriately selected. The hydrocarbon-based polymer or fluorine-containing polymer having an ion-exchange group in the membrane body 10 can be obtained, for example, from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group precursor that can become an ion-exchange group by hydrolysis or the like. . Specifically, for example, a polymer containing a fluorinated hydrocarbon in the main chain, a group which can be converted into an ion-exchange group by hydrolysis, or the like (ion-exchange group precursor) as a pendant side chain and capable of being melt-processed (hereinafter referred to as a case may be referred to “Fluorine-containing polymer (a)”) After preparing the precursor of the membrane body 10, the precursor of the ion exchange group is converted into an ion exchange group, whereby the membrane body 10 can be obtained. The fluorine-containing polymer (a) can be copolymerized, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. Manufacturing. Moreover, it can also manufacture by homopolymerizing 1 type of monomer selected from any of the following 1st group, the following 2nd group, and the following 3rd group. Examples of the monomers of the first group include fluoroethylene compounds. Examples of the fluoroethylene compound include fluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether. Especially when an ion exchange membrane is used as a membrane for alkaline electrolysis, the fluoroethylene compound is preferably a perfluoro monomer, and is preferably selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Perfluoro monomer in the group. Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid-type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include CF.2 = CF (OCF2 CYF)s -O (CZF)t -COOR and other monomers (here, s represents an integer from 0 to 2, t represents an integer from 1 to 12, and Y and Z each independently represent F or CF3 R represents a lower alkyl group. Lower alkyl is, for example, an alkyl group having 1 to 3 carbon atoms. Of these, CF is preferred2 = CF (OCF2 CYF)n -O (CF2 )m -COOR. Here, n is an integer of 0 to 2, m is an integer of 1 to 4, and Y is F or CF.3 , R represents CH3 , C2 H5 , Or C3 H7 . When an ion-exchange membrane is used as a cation-exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. The alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms. As the monomer of the second group, among the above, the monomers described below are more preferred. CF2 = CFOCF2 -CF (CF3 OCF2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )2 COOCH3 , CF2 = CF [OCF2 -CF (CF3 )]2 O (CF2 )2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )3 COOCH3 , CF2 = CFO (CF2 )2 COOCH3 , CF2 = CFO (CF2 )3 COOCH3 . Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfonic acid-type ion exchange group (sulfonic acid group). As the vinyl compound having a functional group convertible to a sulfonic acid group, for example, CF is preferably used.2 = CFO-X-CF2 -SO2 A monomer represented by F (here, X represents perfluoroalkylene). Specific examples of these include the monomers shown below. CF2 = CFOCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, CF2 = CF (CF2 )2 SO2 F, CF2 = CFO [CF2 CF (CF3 ) O]2 CF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF2 OCF3 OCF2 CF2 SO2 F. Of these, CF is more preferred2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, and CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F. Copolymers obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of vinyl fluoride, especially a common polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, an inert solvent such as perfluorocarbon or chlorofluorocarbon can be used, in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, at a temperature of 0 to 200 ° C. Polymerization is carried out under a pressure of 0.1 to 20 MPa. In the above-mentioned copolymerization, the type and ratio of the combination of the above-mentioned monomers are not particularly limited, and are selected and determined according to the type and amount of functional groups to be imparted to the obtained fluorine-containing polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is produced, at least one monomer may be selected from the above-mentioned first group and the second group for copolymerization. When a fluorinated polymer containing only a sulfonic acid group is produced, at least one monomer may be selected from the monomers of the first group and the third group and copolymerized. Furthermore, when a fluorinated polymer having a carboxylic acid group and a sulfonic acid group is prepared, at least one monomer is selected from the monomers of the first group, the second group, and the third group and copolymerized. Just fine. In this case, the copolymer containing the first group and the second group and the copolymer containing the first group and the third group are separately polymerized, and then the target fluorine-containing polymerization can be obtained by mixing them. Thing. The mixing ratio of each monomer is not particularly limited. When the amount of functional groups per unit of polymer is increased, the ratio of the monomers selected from the second group and the third group may be increased. The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of the exchange group per unit weight of the dry resin, and can be measured by neutralization titration or the like. In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. The membrane body 10 having such a layer structure can further improve the selective permeability of cations such as sodium ions. When the ion exchange membrane 1 is arranged in the electrolytic cell, the sulfonic acid layer 3 is usually arranged on the anode side of the electrolytic cell and the carboxylic acid layer 2 is arranged on the cathode side of the electrolytic cell. The sulfonic acid layer 3 is preferably made of a material having a low electrical resistance, and from the viewpoint of film strength, it is preferable that its film thickness is thicker than that of the carboxylic acid layer 2. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, and more preferably 3 to 15 times. The carboxylic acid layer 2 is preferably one having high anion repellency even if the film thickness is thin. Here, the anion repellency refers to a property that prevents anion from penetrating into or passing through the ion exchange membrane 1. In order to improve anion repellency, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity in the sulfonic acid layer. As the fluorine-containing polymer used in the sulfonic acid layer 3, for example, CF is suitably used.2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 A polymer obtained by using F as a monomer of group 3. As the fluorine-containing polymer used in the carboxylic acid layer 2, for example, CF is suitably used.2 = CFOCF2 CF (CF2 ) O (CF2 )2 COOCH3 A polymer obtained as a monomer of Group 2. (Coating layer) The ion exchange membrane preferably has a coating layer on at least one side of the membrane body. As shown in FIG. 44, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively. The coating layer contains inorganic particles and a binder. The average particle diameter of the inorganic particles is more preferably 0.90 μm or more. When the average particle diameter of the inorganic particles is 0.90 μm or more, not only the durability against gas adhesion is greatly improved, but also the durability against impurities is greatly improved. That is, a particularly significant effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the value of the specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by pulverizing raw stones can be used. Inorganic particles obtained by pulverizing raw stones are preferably used suitably. The average particle diameter of the inorganic particles may be 2 μm or less. When the average particle diameter of the inorganic particles is 2 μm or less, the film can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm. Here, the average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation). The shape of the inorganic particles is preferably irregular. Resistance to impurities is further improved. The particle size distribution of the inorganic particles is preferably wide. The inorganic particles preferably contain at least one inorganic substance selected from the group consisting of an oxide of a Group IV element of the periodic table, a nitride of a group IV element of the periodic table, and a carbide of a group IV element of the periodic table. From the viewpoint of durability, zirconia particles are more preferred. The inorganic particles are preferably inorganic particles produced by pulverizing rough particles of the inorganic particles, or spherical particles having uniform particle diameters by melting and refining the rough particles of the inorganic particles as the inorganic particles. There are no particular restrictions on the method of crushing the rough stone, and examples thereof include a ball mill, a bead mill, a colloid mill, a cone mill, a disc mill, a roller mill, a powder mill, a hammer mill, a granulator, and a VSI mill Machines, Willy mills, roll mills, jet mills, etc. Moreover, it is preferable to wash it after crushing, and as a washing method at this time, acid treatment is preferred. This makes it possible to reduce impurities such as iron adhering to the surfaces of the inorganic particles. The coating layer preferably contains a binder. The binder is a component that holds inorganic particles on the surface of the ion exchange membrane and forms a coating layer. From the viewpoint of resistance to an electrolytic solution or an electrolytic product, the binder preferably contains a fluorine-containing polymer. As the binder, a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group is more preferred from the viewpoints of resistance to an electrolytic solution or a product of electrolysis and adhesion to the surface of an ion exchange membrane. When a coating layer is provided on a layer (sulfonic acid layer) containing a fluorinated polymer having a sulfonic acid group, it is more preferable to use a fluorine-containing type having a sulfonic acid group as a binding agent for the coating layer. polymer. When a coating layer is provided on a layer (carboxylic acid layer) containing a fluorinated polymer having a carboxylic acid group, it is more preferable to use a compound having a carboxylic acid group as a binder for the coating layer. Fluoropolymer. The content of the inorganic particles in the coating layer is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. The content of the binder is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass. The distribution density of the coating layer in the ion exchange membrane is preferably per 1 cm2 It is 0.05 ~ 2 mg. When the ion exchange membrane has a concave-convex shape on the surface, the distribution density of the coating layer is preferably 1 cm2 It is 0.5 to 2 mg. The method for forming the coating layer is not particularly limited, and a known method can be used. For example, a method of applying a coating liquid in which inorganic particles are dispersed in a solution containing a binder by spraying or the like can be cited. (Reinforced core material) The ion exchange membrane preferably has a reinforced core material disposed inside the membrane body. The reinforced core material is a member that strengthens the strength or dimensional stability of the ion exchange membrane. By disposing the reinforced core material inside the membrane body, the expansion and contraction of the ion exchange membrane can be controlled to a desired range, in particular. This ion-exchange membrane does not expand or contract more than necessary during electrolysis or the like, and can maintain excellent dimensional stability for a long period of time. The structure of the reinforcing core material is not particularly limited, and for example, a yarn called a reinforcing yarn may be formed by spinning. The so-called reinforcing yarn is a member constituting a reinforcing core material, and refers to a yarn capable of imparting required dimensional stability and mechanical strength to an ion exchange membrane and stably existing in the ion exchange membrane. By using a reinforced core material spun from this reinforcing yarn, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane. The material for reinforcing the core material and the reinforcing yarn used therefor is not particularly limited. It is preferably a material resistant to acids or alkalis. In terms of long-term heat resistance and chemical resistance, it is preferable to include Fiber of fluoropolymer. Examples of the fluorine-containing polymer used as the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). ), Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, from the viewpoint of heat resistance and chemical resistance, it is preferred to use a fiber containing polytetrafluoroethylene. The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The textile density (the number of weaves per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited. For example, a woven fabric, a non-woven fabric, a knitted fabric, or the like can be used, and a woven fabric form is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, and more preferably 30 to 150 μm. Woven or knitted fabrics can use monofilament, multifilament or any of these yarns, cut yarns, etc. The weaving method can use various weaving methods such as plain weaving, leno weaving, knitting, rib weaving, thin crepe weaving, etc. The spinning method and configuration of the reinforced core material in the membrane body are not particularly limited, and the appropriate size can be appropriately set in consideration of the size or shape of the ion exchange membrane, the physical properties required for the ion exchange membrane, and the use environment. For example, the reinforced core material may be arranged along a specific direction of the film body. From the viewpoint of dimensional stability, it is preferable to arrange the reinforced core material along a specific first direction, and along a second substantially perpendicular to the first direction. Orientation with other reinforced core materials. By arranging a plurality of reinforcing core materials in a substantially lined manner inside the longitudinal film body of the film body, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. For example, a configuration in which a reinforced core material (longitudinal yarn) arranged in the longitudinal direction and a reinforced core material (horizontal yarn) arranged in the horizontal direction is preferably woven into the surface of the film body. From the viewpoints of dimensional stability, mechanical strength, and ease of manufacture, it is more preferable to produce a plain weave fabric in which longitudinal and transverse yarns are alternately woven one by one, or twisted with two warp yarns and one side yarn. Interwoven leno weaves, twill weave woven by weaving the same number of cross yarns in every 2 or more parallel yarns. It is particularly preferable to arrange the reinforced core material in two directions of the MD direction (Machine Direction) and the TD direction (Transverse Direction) of the ion exchange membrane. That is, it is preferable to perform plain weaving in the MD direction and the TD direction. Here, the MD direction refers to a direction (traveling direction) in which the membrane body or various core materials (for example, a reinforced core material, a reinforced yarn, a sacrificial yarn described below, etc.) are transported in the manufacturing steps of the ion exchange membrane described below ), The TD direction refers to a direction substantially perpendicular to the MD direction. In addition, the yarn woven in the MD direction is referred to as an MD yarn, and the yarn woven in the TD direction is referred to as a TD yarn. Generally, the ion exchange membrane used in electrolysis is rectangular, and the length direction is MD direction and the width direction is TD direction. By weaving a reinforced core material as MD yarn and a reinforced core material as TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. The arrangement interval of the reinforced core material is not particularly limited, and an appropriate arrangement may be appropriately set in consideration of physical properties required for the ion exchange membrane and use environment. The opening ratio of the reinforced core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane. The so-called aperture ratio of the reinforced core material refers to the total area (B) of the surface through which any substance such as ions (the electrolyte and its cations (for example, sodium ions)) can pass through. Ratio (B / A). The total area (B) of the surface through which substances such as ions can pass may refer to the total area of areas in the ion exchange membrane that are not blocked by the reinforced core material or the like contained in the ion exchange membrane. Fig. 45 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 45 is an enlarged view of a part of the ion exchange membrane, and only the arrangement of the reinforced core materials 21 and 22 in the area is illustrated, and other components are omitted. The total area of the reinforced core material is subtracted from the area (A) of the area surrounded by the reinforced core material 21 arranged in the longitudinal direction and the reinforced core material 22 arranged in the horizontal direction, which also includes the area of the reinforced core material ( C). The total area (B) of the area (A) through which substances such as ions can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I). Opening ratio = (B) / (A) = ((A)-(C)) / (A)… (I) In the reinforced core material, it is particularly preferable from the viewpoint of chemical resistance and heat resistance The morphology is a tape-like yarn or high-alignment monofilament containing PTFE. Specifically, it is more preferable to use a reinforced core material which uses a band-shaped yarn obtained by cutting a high-strength porous sheet containing PTFE into a band shape, or 50 to 300 of a highly-oriented monofilament containing PTFE. Denim plain weave fabric with a textile density of 10 to 50 per inch, with a thickness in the range of 50 to 100 μm. The aperture ratio of the ion-exchange membrane containing the reinforced core material is more preferably 60% or more. Examples of the shape of the reinforcing yarn include round yarn and ribbon yarn. (Communication hole) The ion exchange membrane preferably has a communication hole inside the membrane body. The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, the so-called communication hole is a tubular hole formed inside the membrane body, and is formed by dissolving a sacrificial core material (or sacrificial yarn) described below. The shape or diameter of the communication hole can be controlled by selecting the shape or diameter of the sacrificial core material (sacrificial yarn). By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured during electrolysis. The shape of the communication hole is not particularly limited. According to the manufacturing method described below, the shape of the sacrificial core material used for forming the communication hole can be made. The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With this structure, in the portion where the communication hole is formed on the cathode side of the reinforced core material, ions (for example, sodium ions) transported through the electrolyte filled with the communication hole can also flow to the cathode side of the reinforced core material. As a result, since the flow of cations is not blocked, the resistance of the ion exchange membrane can be further reduced. The communication hole may be formed only in one specific direction of the membrane body constituting the ion exchange membrane. From the viewpoint of exhibiting more stable electrolytic performance, it is preferably formed in both the longitudinal direction and the lateral direction of the membrane body. [Manufacturing Method] As a suitable method for manufacturing the ion exchange membrane, a method having the following steps (1) to (6) can be mentioned. (1) Step: a step of producing a fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted to an ion-exchange group by hydrolysis. (2) Step: by weaving at least a plurality of reinforcing core materials and sacrificial yarns that have properties of dissolving in acid or alkali and forming communicating holes to obtain reinforcements of sacrificial yarns arranged between adjacent reinforcing core materials. Material steps. (3) Step: a step of membrane-forming the above-mentioned fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted into an ion-exchange group by hydrolysis. (4) Step: a step of burying the above-mentioned reinforcing material in the above-mentioned film to obtain a film body in which the above-mentioned reinforcing material is internally arranged as necessary. (5) Step: a step of hydrolyzing the membrane body obtained in step (4) (hydrolysis step). (6) Step: a step (coating step) of providing a coating layer on the film body obtained in step (5). Each step will be described in detail below. (1) Step: Step for producing fluoropolymer In step (1), a fluoropolymer is produced using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the monomers of the raw materials may be adjusted in the production of the fluorine-containing polymer forming each layer. (2) Step: Manufacturing steps of reinforcing material The so-called reinforcing material is a woven fabric of textile reinforcing yarn. A reinforcing core material is formed by embedding a reinforcing material in the film. When making an ion exchange membrane with communicating holes, sacrificial yarns are also woven into the reinforcing material together. In this case, the blending amount of the sacrificial yarn is preferably 10 to 80% by mass of the entire reinforcing material, and more preferably 30 to 70% by mass. By weaving the sacrificial yarn, the reinforcing core material can be prevented from being detached. Sacrificial yarns are soluble in the manufacturing steps of the film or in an electrolytic environment. Rhenium, polyethylene terephthalate (PET), cellulose, and polyamide can be used. In addition, polyvinyl alcohol having a thickness of 20 to 50 denier, monofilament or multifilament is also preferred. Furthermore, in step (2), the aperture ratio or the arrangement of the communication holes can be controlled by adjusting the configuration of the reinforced core material or the sacrificial yarn. (3) Step: Film formation step In the step (3), the fluorinated polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single-layer structure, as described above, a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or a multilayer structure of three or more layers. As a method of film formation, the following are mentioned, for example. A method of separately forming a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group into a membrane. A method for making a composite film from a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group by coextrusion. Moreover, the film may be plural. In addition, coextrusion of a heterogeneous film is preferred because it improves the bonding strength at the interface. (4) Step: the step of obtaining the film body In step (4), the reinforcing material obtained in step (2) is embedded in the inside of the film obtained in step (3) to obtain the reinforcing material inside. Membrane body. As a preferred method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) on the cathode side by a coextrusion method (hereinafter, The layer containing it is called the first layer) and a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonium fluoride functional group) (hereinafter, the layer containing it is referred to as a second layer). It is necessary to use a heating source and a vacuum source to separate the breathable and heat-resistant release paper, and sequentially laminate the reinforcing material and the second / first layer composite film on a flat plate or a drum with a large number of fine holes on the surface. At the melting temperature of each polymer, the method of integration is performed while removing the air between the layers by decompression; (ii) Different from the second / first layer composite film, the The fluorine-containing polymer (third layer) is separately formed into a film, and if necessary, a heating source and a vacuum source are used to separate the third layer film, the reinforced core material, Layer / first layer of composite film is sequentially laminated on a plate or drum with a large number of fine holes on the surface, Each of the polymer melt temperature, while removed under reduced pressure by the air between the layers while the integration method. Here, coextrusion of the first layer and the second layer helps to improve the bonding strength of the interface. In addition, the method of integrating under reduced pressure has a feature that the thickness of the third layer on the reinforcing material is larger than that of the pressure pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane body, it has a property capable of sufficiently maintaining the mechanical strength of the ion exchange membrane. In addition, the variation of the laminate described here is an example. The required layer structure or physical properties of the film body may be considered, and an appropriate laminate pattern (for example, a combination of layers) may be appropriately selected and then co-extruded. Furthermore, in order to further improve the electrical performance of the ion exchange membrane, a fluorine-containing polymer containing both a carboxylic acid group precursor and a sulfonic acid group precursor may be further interposed between the first layer and the second layer. Instead of the second layer, a fourth layer containing a fluorinated polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is used. The formation method of the fourth layer may be a method of separately manufacturing a fluorinated polymer having a carboxylic acid group precursor and a fluorinated polymer having a sulfonic acid group precursor and then mixing them. A method in which a monomer of a precursor is copolymerized with a monomer having a sulfonic acid group precursor. When the fourth layer is made into an ion-exchange membrane, the co-extruded film of the first layer and the fourth layer can be formed, and the third layer and the second layer can be separately formed into a membrane. The method described herein is laminated, and the three layers of the first layer / the fourth layer / the second layer can also be co-extruded to form a film. In this case, the direction of travel of the extruded film is the MD direction. As a result, a film body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material. Moreover, it is preferable that the ion exchange membrane has a protruding portion, that is, a protruding portion containing a fluorinated polymer having a sulfonic acid group on the surface side including the sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming a convex portion on the surface of a resin can be adopted. Specifically, the method of embossing the surface of a film main body is mentioned, for example. For example, when the composite film is integrated with a reinforcing material or the like, the convex portion can be formed by using a release paper that has been embossed in advance. When the convex portion is formed by embossing, the height of the convex portion or the arrangement density can be controlled by controlling the transferred embossed shape (shape of the release paper). (5) Hydrolysis step In step (5), a step of hydrolyzing the membrane body obtained in step (4) to convert an ion-exchange group precursor to an ion-exchange group (hydrolysis step) is performed. In step (5), a dissolution hole can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body by using an acid or an alkali. In addition, the sacrificial yarn may not be completely dissolved and removed, but may remain in the communication hole. In addition, the sacrificial yarn remaining in the communication hole can be removed by dissolving the electrolytic solution when the ion exchange membrane is supplied for electrolysis. Sacrificial yarns are those which are soluble in acids or alkalis in the manufacturing steps of ion exchange membranes or in an electrolytic environment. The sacrificial yarns are dissolved to form communication holes in this part. Step (5) can be carried out by immersing the film body obtained in step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (Dimethyl sulfoxide) can be used. The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35 mass% of DMSO. The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the thicker the apparent thickness. It is more preferably 75 to 100 ° C. The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes. Here, the step of forming the communication hole by dissolving the sacrificial yarn will be described in more detail. 46 (a) and (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane. In Figs. 46 (a) and (b), only the reinforcing yarn 52, the sacrificial yarn 504a, and the communication hole 504 formed by the sacrificial yarn 504a are shown, and other members such as the film body are not shown. First, a knitting-reinforcing material is made from the reinforcing yarn 52 constituting the reinforcing core material in the ion-exchange membrane and the sacrificial yarn 504a used to form the communication hole 504 in the ion-exchange membrane. Then, in step (5), the communication hole 504 is formed by dissolving the sacrificial yarn 504a. According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a can be adjusted according to how the reinforcing core material and the communication hole are arranged in the membrane body of the ion exchange membrane, which is relatively simple. In FIG. 46 (a), an example of a flat woven reinforcing material in which the reinforcing yarn 52 and the sacrificial yarn 504a are woven in the longitudinal and transverse directions of the paper surface is illustrated. The configuration of the reinforcing yarn 52 and the sacrificial yarn 504a in the reinforcing material may be changed as necessary. . (6) Coating step In step (6), a coating liquid containing inorganic particles obtained by pulverizing or melting the raw stone and a binder is prepared, and the coating liquid is applied to the ion exchange obtained in step (5). The surface of the film is dried to form a coating layer. As the binding agent, it is preferred that the fluorine-containing polymer having an ion-exchange group precursor is hydrolyzed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to ion-exchange. Substitute counter ion for H+ The resulting binding agent (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group). This makes it easy to dissolve in water or ethanol described below, and is therefore preferred. This binding agent was dissolved in a solution obtained by mixing water and ethanol. Furthermore, the preferred volume ratio of water to ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1 to 1: 2. The coating liquid was obtained by dispersing the inorganic particles in the dissolving liquid thus obtained by a ball mill. At this time, the average particle diameter of the particles and the like can also be adjusted by adjusting the time during dispersion and the rotation speed. Moreover, the preferable blending amount of the inorganic particles and the binder is as described above. The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, and it is preferable to make a thin coating liquid. Thereby, the surface of an ion exchange membrane can be apply | coated uniformly. When dispersing the inorganic particles, a surfactant may be added to the dispersion liquid. The surfactant is preferably a nonionic surfactant, and examples thereof include HS-210, NS-210, P-210, and E-212 manufactured by Nippon Oil Corporation. An ion exchange membrane can be obtained by applying the obtained coating solution to the surface of an ion exchange membrane by spray coating or roll coating. [Microporous membrane] The microporous membrane of this embodiment is not particularly limited as long as it can be laminated with an electrode for electrolysis as described above, and various microporous membranes can be applied. The porosity of the microporous membrane of this embodiment is not particularly limited, and it can be set to, for example, 20 to 90, and preferably 30 to 85. The porosity can be calculated by the following formula, for example. Porosity = (1-(film weight in dry state) / (weight calculated from the volume calculated from the thickness, width, and length of the film and the density of the film material)) × 100 average pore diameter of the microporous membrane of this embodiment It is not particularly limited, and may be, for example, 0.01 μm to 10 μ, and preferably 0.05 μm to 5 μm. The said average pore diameter cuts a film | membrane perpendicularly along a thickness direction, and observes a cut surface by FE-SEM, for example. The average pore diameter can be determined by measuring the diameter of the observed pores at about 100 points and obtaining an average value. The thickness of the microporous membrane in this embodiment is not particularly limited, and it can be set to, for example, 10 μm to 1,000 μm, and preferably 50 μm to 600 μm. The thickness can be measured, for example, using a micrometer (manufactured by Mitutoyo Co., Ltd.). As specific examples of the microporous membrane described above, there can be mentioned Zilfon Perl UTP 500 (also referred to as a Zilfon membrane in this embodiment) manufactured by Agfa, International Publication No. 2013-183584, and International Publication No. 2016-203701. No., etc. In this embodiment, the separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having an EW (ion exchange equivalent) different from the first ion exchange resin layer. The separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having a functional group different from the first ion exchange resin layer. The ion exchange equivalent can be adjusted by the introduced functional group, and the functional group that can be introduced is as described above. [Fixed area] In this embodiment, the electrode for electrolysis is fixed to at least one area on the surface of the separator. In the item of <3rd Embodiment>, one or two or more areas are also referred to as fixed areas. . The fixing region in this embodiment is not particularly limited as long as it has a function of suppressing the separation between the electrode for electrolysis and the separator and for fixing the electrode for electrolysis to the separator. For example, there is also a mechanism for fixing the electrode for electrolysis itself. In the case where the fixed area is configured, there may be a case where the fixed area is formed by a fixing member that is different from the electrode for electrolysis as a fixing mechanism. In addition, the fixed area in this embodiment may exist only at a position corresponding to a current-carrying surface during electrolysis, or may extend to a position corresponding to a non-current-carrying surface. In addition, the "current-carrying surface" corresponds to a portion designed to move the electrolyte between the anode chamber and the cathode chamber. The "non-energized surface" means a portion other than the energized surface. Furthermore, in this embodiment, the ratio of the fixed area on the surface of the separator (hereinafter also simply referred to as "ratio α") exceeds 0% and does not reach 93%. The above ratio can be obtained as the ratio of the area of the fixed area (hereinafter also simply referred to as "area S3") to the area of the surface of the separator (hereinafter also simply referred to as "area S1"). In this embodiment, the "surface of the separator" means the surface on the side where the electrode for electrolysis exists among the surfaces of the separator. The area of the surface of the separator that is not covered by the electrode for electrolysis is also counted as the area S1. From the viewpoint of being more stable as a laminate of a separator and an electrode for electrolysis, the above-mentioned ratio α (= 100 × S3 / S1) exceeds 0%, preferably 0.00000001% or more, and more preferably 0.0000001% or more. On the other hand, as in the prior art, when the entire surface of the contact surface between the separator and the electrode is firmly adhered by a method such as thermocompression bonding (that is, when the above ratio becomes 100%), it becomes The entire surface of the contact surface in the electrode is physically attached after being inserted into the separator. Such an adhering part hinders the movement within the membrane of sodium ions, and the voltage rises significantly. In this embodiment, from the viewpoint of sufficiently securing a space where ions can move freely, the above ratio is less than 93%, preferably 90% or less, more preferably 70% or less, and still more preferably 60% or less. In this embodiment, from the viewpoint of obtaining better electrolytic performance, it is preferable that the area of the area (area S3) of the fixed area only corresponds to the area corresponding to the current-carrying surface (hereinafter also referred to as "area S3 '"). ) To make adjustments. That is, it is preferable to adjust the ratio (hereinafter also simply referred to as "ratio β") of the area S3 'to the area of the energized surface (hereinafter also simply referred to as "area S2"). The area S2 can be specified as the surface area of the electrode for electrolysis (the details will be described below). Specifically, in this embodiment, the ratio β (= 100 × S3 '/ S2) is preferably more than 0% and less than 100%, more preferably 0.0000001% and less than 83%, and still more preferably 0.000001. % Or more and 70% or less, and more preferably 0.00001% or more and 25% or less. The ratios α and β can be measured, for example, as follows. First, the area S1 of the surface of the separator is calculated. Next, the area S2 of the electrode for electrolysis is calculated. Here, the areas S1 and S2 can be specified as areas when the laminated body of the separator and the electrode for electrolysis (see FIG. 57) is viewed from the electrode for electrolysis. In addition, the shape of the electrode for electrolysis is not particularly limited, and it may have openings. When the shape of the electrode has openings such as a mesh and (i) the opening ratio is less than 90%, the opening portion of S2 is It is also included in the area S2. On the other hand, when the shape has a hole such as a net shape and (ii) the hole ratio is 90% or more, the area of the hole portion is removed in order to fully ensure the electrolytic performance. Calculate S2. The so-called porosity is the value obtained by dividing the total area S 'of the openings in the electrode for electrolysis by the area S' 'in the electrode for electrolysis obtained by calculating the openings in the area (%, 100 × S '/ S' '). The area (area S3 and area S3 ') of the fixed area is described below. As described above, the ratio α (%) of the above-mentioned regions on the surface of the separator can be obtained by calculating 100 × (S3 / S1). The ratio β (%) of the area of the portion corresponding to the current-carrying surface of the fixed area to the area of the current-carrying surface can be calculated by calculating 100 × (S3 ′ / S2). More specifically, the measurement can be performed by the method described in the examples described below. The area S1 of the surface of the separator specified in the above manner is not particularly limited, but it is preferably 1 time or more and 5 times or less, more preferably 1 time or more and 4 times or less, and even more preferably 1 time. More than 3 times. In this embodiment, the fixed structure in the fixed area is not limited, but for example, the fixed structure exemplified below may be adopted. Furthermore, each fixing structure may be used alone, or may be used in combination of two or more. In this embodiment, it is preferable that at least a part of the electrode for electrolysis in the fixed area penetrates through the separator and is fixed. This aspect will be described using FIG. 47A. In FIG. 47A, at least a part of the electrode 2 for electrolysis passes through the separator 3 and is fixed. As shown in FIG. 47A, a part of the electrode 2 for electrolysis is in a state of penetrating the separator 3. FIG. 47A shows an example in which the electrode 2 for electrolysis is a porous metal electrode. That is, in FIG. 47A, the portions of the plurality of electrolysis electrodes 2 are shown independently, but the cross-sections of the metal porous electrodes connected to each other and shown as a whole are the same (the same applies to the following FIGS. 48 to 51). Under this kind of electrode structure, for example, if the diaphragm 3 at a specific position (which should be a fixed area) is pressed against the electrode 2 for electrolysis, a part of the diaphragm 3 enters into the uneven structure or hole on the surface of the electrode 2 for electrolysis. In the structure, the concave portion of the electrode surface or the convex portion around the hole penetrates the separator 3, and preferably penetrates to the outer surface 3b of the separator 3 as shown in FIG. 47A. As described above, the fixed structure of FIG. 47A can be manufactured by pressing the separator 3 against the electrode 2 for electrolysis. In this case, the pressure-bonding and heat suction are performed in a state where the separator 3 is softened by heating. . Thereby, the electrode 2 for electrolysis penetrates the separator 3. Alternatively, it may be performed while the separator 3 is melted. In this case, it is preferable to suck the separator 3 from the outer surface 2b side (back surface side) of the electrode 2 for electrolysis in the state shown in FIG. 47B. The region where the separator 3 is pressed against the electrode 2 for electrolysis constitutes a "fixed region". The fixed structure shown in FIG. 47A can be observed through a loupe, an optical microscope, or an electron microscope. In addition, the diaphragm 3 is penetrated by the electrolytic electrode 2 and the continuity inspection using a tester or the like between the outer surface 3b of the diaphragm 3 and the outer surface 2b of the electrolytic electrode 2 is used to estimate the fixed structure of FIG. In FIG. 47A, it is preferable that the electrolyte of the anode chamber and the cathode chamber separated by the separator does not pass through the through portion. Therefore, it is preferable that the pore diameter of the penetrating portion is small to such an extent that the electrolyte solution does not pass through. Specifically, it is preferable to exhibit the same performance as that of a diaphragm having no penetration portion when an electrolytic test is performed. Alternatively, it is preferable to perform a process for preventing penetration of the electrolytic solution to the penetrated portion. It is preferable to use a material that does not dissolve or decompose due to the products produced in the anode chamber electrolyte, the anode chamber electrolyte, the cathode chamber electrolyte, or the cathode chamber. For example, EPDM and fluorine-based resins are preferred. More preferred is a fluororesin having an ion-exchange group. In this embodiment, it is preferable that at least a part of the electrode for electrolysis in the fixed area is located inside the separator and fixed. This aspect will be described using FIG. 48A. As described above, the surface of the electrode 2 for electrolysis has a concave-convex structure or a hole structure. In the embodiment shown in FIG. 48A, a part of the electrode surface is inserted and fixed to the diaphragm 3 at a specific position (a position to be a fixed area). The fixed structure shown in FIG. 48A can be manufactured by pressing the separator 3 against the electrode 2 for electrolysis. In this case, it is preferable to form the fixed structure shown in FIG. 48A by thermal compression bonding and heat suction in a state where the diaphragm 3 is softened by heating. Alternatively, the diaphragm 3 may be melted to form the fixed structure shown in FIG. 48A. In this case, it is preferable to suck the separator 3 from the outer surface 2b side (back surface side) of the electrode 2 for electrolysis. The fixed structure shown in FIG. 48A can be observed through a loupe, an optical microscope, or an electron microscope. A method of making a section by a microtome and observing the sample is particularly preferred after the sample is embedded. Furthermore, in the fixed structure shown in FIG. 48A, since the electrolysis electrode 2 does not penetrate the separator 3, the continuity by the continuity check between the outer surface 3b of the separator 3 and the outer surface 2b of the electrolysis electrode 2 is not confirmed. . In this embodiment, it is preferable to further include a fixing member for fixing the separator and the electrode for electrolysis. This aspect will be described using FIGS. 49A to 49C. The fixing structure shown in FIG. 49A is a structure in which a fixing member 7 different from the electrolytic electrode 2 and the separator 3 is used, and the fixing member 7 penetrates and fixes the electrolytic electrode 2 and the separator 3. The electrode 2 for electrolysis does not necessarily have to be penetrated by the fixing member 7 and may be fixed by the fixing member 7 so as not to be separated from the separator 2. The material of the fixing member 7 is not particularly limited. As the fixing member 7, for example, a metal or a resin can be used. In the case of a metal, nickel, nickel-chromium alloy, titanium, stainless steel (SUS), etc. can be mentioned. It may also be an oxide of these. As the resin, a fluororesin (for example, PTFE (polytetrafluoroethylene), PFA (copolymer of tetrafluoroethylene and perfluoroalkoxyethylene)), ETFE (copolymer of tetrafluoroethylene and ethylene), or the following Material of the diaphragm 3 described) or PVDF (polyvinylidene fluoride), EPDM (ethylene-propylene-diene rubber), PP (polyethylene), PE (polypropylene), nylon, aromatic polyamide, and the like. In this embodiment, for example, a yarn-shaped fixing member (a yarn-like metal or resin) is used, and as shown in FIGS. 49B and 49C, a specific position between the electrolytic electrode 2 and the outer surface 2b, 3b of the separator 3 The position where it should be a fixed area) is sewn so that it can be fixed. The yarn-like resin is not particularly limited, and examples thereof include yarns made of PTFE. Alternatively, the electrolysis electrode 2 and the separator 3 may be fixed using a fixing mechanism such as a tucker. In FIGS. 49A to C, it is preferable that the electrolyte in the anode chamber and the cathode chamber separated by the separator does not pass through the penetration portion. Therefore, it is preferable that the pore diameter of the penetrating portion is small to such an extent that the electrolyte solution does not pass through. Specifically, it is preferable to exhibit the same performance as that of a diaphragm having no penetration portion when an electrolytic test is performed. Alternatively, it is preferable to perform a process for preventing penetration of the electrolytic solution to the penetrated portion. It is preferable to use a material that does not dissolve or decompose due to the products produced in the anode chamber electrolyte, the anode chamber electrolyte, the cathode chamber electrolyte, or the cathode chamber. For example, EPDM and fluorine-based resins are preferred. More preferred is a fluororesin having an ion-exchange group. The fixing structure shown in FIG. 50 is a structure in which an organic resin (adhesive layer) is fixed between the electrolytic electrode 2 and the separator 3. That is, in FIG. 50, the organic resin as the fixing member 7 is arranged at a specific position (a position that should be a fixed area) between the electrolytic electrode 2 and the separator 3, and is subsequently fixed. For example, an organic resin is applied to the inner surface 2a of the electrode 2 for electrolysis, the inner surface 3a of the separator 3, or both or one of the inner surfaces 2a, 3a of the electrode 2 for electrolysis and the separator 3. Then, the electrolytic electrode 2 and the separator 3 are bonded to each other, whereby a fixed structure shown in FIG. 50 can be formed. The material of the organic resin is not particularly limited, and for example, a fluororesin (for example, PTFE, PFA, ETFE), or the same resin as the material constituting the separator 3 described above can be used. Also, commercially available fluorine-based adhesives, PTFE dispersions, and the like can be used as appropriate. Furthermore, general-purpose vinyl acetate-based adhesives, ethylene-vinyl acetate copolymerization-based adhesives, acrylic resin-based adhesives, α-olefin-based adhesives, styrene-butadiene rubber-based latex adhesives, Vinyl chloride resin adhesive, chloroprene adhesive, nitrile rubber adhesive, urethane rubber adhesive, epoxy adhesive, silicone resin adhesive, modified silicone Adhesives, epoxy-modified polysiloxane resin-based adhesives, silylated urethane resin-based adhesives, cyanoacrylate-based adhesives, and the like. In this embodiment, an organic resin that is soluble in the electrolytic solution or dissolved and decomposed in the electrolysis can be used. The organic resin dissolved in the electrolytic solution or dissolved and decomposed in the electrolysis is not limited to the following, and examples thereof include vinyl acetate-based adhesives, ethylene-vinyl acetate copolymerization-based adhesives, and acrylic resin-based adhesives. , Α-olefin-based adhesives, styrene butadiene rubber-based latex adhesives, vinyl chloride resin-based adhesives, chloroprene-based adhesives, nitrile rubber-based adhesives, urethane rubber-based adhesives, Epoxy-based adhesive, polysiloxane-based adhesive, modified polysiloxane-based adhesive, epoxy-modified polysiloxane-based adhesive, silylated urethane resin-based adhesive, cyano Acrylate-based adhesives and the like. The fixed structure shown in FIG. 50 can be observed with an optical microscope or an electron microscope. A method of making a section by a microtome and observing the sample is particularly preferred after the sample is embedded. In this embodiment, it is preferable that at least a part of the fixing member holds the separator and the electrode for electrolysis from the outside. This aspect will be described using FIG. 51A. The fixing structure shown in FIG. 51A is a structure that holds and fixes the electrolytic electrode 2 and the separator 3 from the outside. That is, the outer surface 2b of the electrode 2 for electrolysis and the outer surface 3b of the separator 3 are clamped and fixed by the holding member serving as the fixing member 7. The fixed structure shown in FIG. 51A also includes a state in which the holding member is caught in the electrolytic electrode 2 or the separator 3. Examples of the holding member include an adhesive tape and a jig. In this embodiment, a holding member dissolved in an electrolytic solution may be used. Examples of the holding member dissolved in the electrolytic solution include a tape made of PET, a jig, a tape made of polyvinyl alcohol (polyvinyl alcohol), a jig, and the like. The fixed structure shown in FIG. 51A is different from those shown in FIGS. 47 to 50, and is not a junction of the interface between the electrolytic electrode 2 and the separator 3. The internal surfaces 2a, 3a of the electrolytic electrode 2 and the separator 3 are only in contact or facing each other. In the state, the fixed state of the electrolytic electrode 2 and the separator 3 can be released and separated by removing the holding member. FIG. 51A is not shown, but the electrolytic electrode 2 and the separator 3 may be fixed to the electrolytic cell using a holding member. For example, the separator and the electrode can be fixed by folding back a PTFE tape. In the present embodiment, it is preferable that at least a part of the fixing member fixes the separator and the electrode for electrolysis by magnetic force. This aspect will be described using FIG. 51B. The fixing structure shown in FIG. 51B is a structure that holds and fixes the electrolytic electrode 2 and the separator 3 from the outside. The difference from FIG. 51A is that a pair of magnets is used as a holding member used as a fixing member. In the state of the fixed structure shown in FIG. 51B, after the laminated body 1 is installed in the electrolytic cell, the holding member can be left directly or removed from the laminated body 1 when the electrolytic cell is running. FIG. 51B is not shown, but the electrolytic electrode 2 and the separator 3 may be fixed to the electrolytic cell using a holding member. In addition, when a magnetic material adhering to a magnet is used as a part of the material of the electrolytic cell, one kind of holding material may be provided on the diaphragm surface side, and the electrolytic cell, the electrode for electrolysis 2 and the diaphragm 3 may be clamped and fixed. Furthermore, a fixed area of a plurality of columns may be provided. In other words, 1, 2, 3,... N fixed regions can be arranged from the contour side of the laminated body 1 toward the inside. n is an integer of 1 or more. The m-th (m <n) fixed area and the L-th (m <L ≦ n) fixed area may be formed by different fixed patterns. It is preferable that the fixed area formed in the current-carrying portion has a line-symmetric shape. Thereby, there is a tendency that stress concentration can be suppressed. For example, if the two orthogonal directions are set to the X direction and the Y direction, one of the X direction and the Y direction may be arranged in each direction, or plural numbers may be arranged at equal intervals in the X direction and the Y direction. To form a fixed area. The number of fixed areas in the X direction and the Y direction is not limited, but it is preferable that the number of fixed areas in the X direction and the Y direction be 100 or less, respectively. From the viewpoint of ensuring the planarity of the current-carrying portion, the number of fixed areas in the X direction and the Y direction should be 50 or less, respectively. In the fixed area in this embodiment, when the fixed structure shown in FIG. 47A or FIG. 49 is provided, it is preferable that the film surface in the fixed area is in the viewpoint of preventing a short circuit caused by contact between the anode and cathode Apply sealant. As the sealing material, for example, the materials described in the above adhesive can be used. When a fixing member is used, when the area S3 and the area S3 'are obtained, the overlapping portion of the fixing member is not calculated in the area S3 and the area S3'. For example, when the PTFE yarn described above is fixed as a fixing member, the portion where the PTFE yarns intersect with each other is regarded as a repetition amount and is not included in the area. In addition, when the PTFE tape described above is fixed as a fixing member, a portion where the PTFE tape overlaps each other is regarded as a repetition amount and is not included in the area. When the PTFE yarn or the adhesive described above is fixed as a fixing member, the area existing on the back side of the electrode and / or separator for electrolysis is also included in the area S3 and the area S3 '. The laminated body in this embodiment may have various fixed regions at various positions as described above, but it is preferable that the electrode for electrolysis satisfies the above-mentioned "bearing force" especially in a part (non-fixed region) where no fixed region exists. That is, it is preferable that the force per unit mass and unit area in the non-fixed area of the electrode for electrolysis is less than 1.5 N / mg · cm.2 . [Electrolytic Cell] The electrolytic cell according to this embodiment includes a laminated body according to this embodiment. Hereinafter, an embodiment of an electrolytic cell will be described in detail using a case where salt electrolysis is performed using an ion exchange membrane as a separator. [Electrolytic Cell] FIG. 52 is a sectional view of the electrolytic cell 1. FIG. The electrolytic cell 1 includes an anode chamber 10, a cathode chamber 20, a partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, an anode 11 provided in the anode chamber 10, and a cathode 21 provided in the cathode chamber 20. If necessary, a reverse current absorber 18 having a base material 18a and a reverse current absorbing layer 18b formed on the base material 18a and provided in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 provided in the cathode chamber 20, and a reverse current absorber 18 provided in the cathode chamber 20. The reverse current absorber 18 has a substrate 18a and is formed on the cathode as shown in FIG. The reverse current absorbing layer 18b on the substrate 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the current collector 23 and the cathode 21. The support 24 is provided between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via a metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be indirectly connected through a current collector, a support, a metal elastomer, or a partition wall. The entire surface of the cathode 21 is preferably covered with a catalyst layer for reduction reaction. In addition, the form of electrical connection may be to directly install the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22, and laminate the cathode 21 on the metal elastic body 22, respectively. The form. Examples of a method for directly mounting the respective constituent members to each other include welding and the like. The reverse current sink 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40. FIG. 53 is a sectional view of two adjacent electrolytic cells 1 in the electrolytic cell 4. FIG. 54 shows the electrolytic cell 4. Fig. 55 shows the steps for assembling the electrolytic cell 4. As shown in FIG. 53, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are sequentially arranged in series. An ion exchange membrane 2 is arranged between the anode chamber of one of the two electrolytic cells adjacent to the electrolytic cell and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are separated by the cation exchange membrane 2. As shown in FIG. 54, the electrolytic cell 4 includes a plurality of electrolytic cells 1 connected in series through a dielectric exchange membrane 2. That is, the electrolytic cell 4 is a bipolar electrolytic cell having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 55, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series through a dielectric exchange membrane 2 and connecting them with a press 5. The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. Among the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4, the anode 11 of the electrolytic cell 1 located at the extreme end is electrically connected to the anode terminal 7. The cathode 21 of the electrolytic cell at the end opposite to the anode terminal 7 of the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 to the cathode terminal 6 through the anode and cathode of each electrolytic cell 1. Furthermore, an electrolytic cell having only an anode chamber (anode terminal cell) and an electrolytic cell having only a cathode chamber (cathode terminal cell) may be disposed at both ends of the connected electrolytic cells 1. In this case, the anode terminal 7 is connected to an anode terminal cell disposed at one end thereof, and the cathode terminal 6 is connected to a cathode terminal cell disposed at the other end. When electrolysis of brine is performed, brine is supplied to each anode chamber 10 and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid system is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (omitted from the figure) through an electrolytic solution supply hose (omitted from the figure). In addition, the electrolytic solution and the products of electrolysis are recovered by an electrolytic solution recovery tube (omitted from the figure). During the electrolysis, the sodium ions in the brine start from the anode chamber 10 of an electrolytic cell 1 and pass through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Accordingly, the current in the electrolysis flows in a direction in which the electrolytic cells 1 are connected in series. That is, a current flows from the anode chamber 10 to the cathode chamber 20 through the cation exchange membrane 2. Along with the electrolysis of brine, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen are generated on the cathode 21 side. (Anode Chamber) The anode chamber 10 includes an anode 11 or an anode power source 11. When the electrode for electrolysis in this embodiment is inserted on the anode side, 11 functions as an anode power source. When the electrode for electrolysis in this embodiment is not inserted on the anode side, 11 functions as an anode. The anode chamber 10 preferably includes an anode-side electrolytic solution supply unit that supplies an electrolytic solution to the anode chamber 10, and a baffle plate that is disposed above the anode-side electrolytic solution supply unit and is disposed substantially parallel or inclined to the partition wall 30. And an anode-side gas-liquid separation portion disposed above the baffle and separating gas from an electrolyte mixed with the gas. (Anode) When the electrode for electrolysis in this embodiment is not inserted on the anode side, the anode 11 is provided in the frame of the anode chamber 10. As the anode 11, a metal electrode such as a so-called DSA (registered trademark) can be used. The so-called DSA is an electrode with a titanium substrate covered with an oxide containing ruthenium, iridium, and titanium as components. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode Feeder) When the electrode for electrolysis in the present embodiment is inserted on the anode side, an anode feeder 11 is provided in the frame of the anode chamber 10. As the anode power source 11, a metal electrode such as a so-called DSA (registered trademark) may be used, or titanium without a catalyst coating layer may be used. Alternatively, a DSA having a thinner catalyst coating thickness may be used. Furthermore, a used anode can also be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode-side electrolytic solution supply unit) The anode-side electrolytic solution supply unit is a person that supplies an electrolytic solution to the anode chamber 10 and is connected to an electrolytic solution supply pipe. The anode-side electrolytic solution supply portion is preferably arranged below the anode chamber 10. As the anode-side electrolytic solution supply portion, for example, a tube (dispersion tube) having an opening formed on the surface can be used. The tube is more preferably arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies an electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is transported into the electrolytic cell 1 through the tube, and is supplied into the anode chamber 10 from an opening provided on the surface of the tube. Since the tube is arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell, the electrolyte can be uniformly supplied to the inside of the anode chamber 10, which is preferable. (Anode-side gas-liquid separation section) The anode-side gas-liquid separation section is preferably disposed above the baffle. In electrolysis, the anode-side gas-liquid separator has a function of separating a generated gas such as chlorine gas from the electrolytic solution. Furthermore, unless otherwise specified, the so-called upper means the upper direction in the electrolytic cell 1 of FIG. 52, and the lower means the lower direction of the electrolytic cell 1 in FIG. 52. During the electrolysis, if the generated gas generated in the electrolytic cell 1 and the electrolyte become mixed phase (gas-liquid mixed phase) and are discharged out of the system, there will be physical damage to the ion exchange membrane due to vibration caused by pressure fluctuations inside the electrolytic cell 1. Situation. In order to suppress this situation, it is preferable to provide an anode-side gas-liquid separation section in the electrolytic cell 1 in this embodiment to separate gas from liquid. It is preferable to provide a defoaming plate for eliminating bubbles in the anode-side gas-liquid separation section. The gas and liquid mixed phase flow can be separated into the electrolyte and the gas by breaking the bubbles when passing through the defoaming plate. As a result, vibration during electrolysis can be prevented. (Baffle) The baffle is preferably disposed above the anode-side electrolytic solution supply portion, and is disposed substantially parallel or inclined to the partition wall 30. The baffle is a partition that controls the flow of the electrolyte in the anode chamber 10. By providing the baffle, the electrolyte (brine, etc.) can be circulated inside the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle is preferably arranged to separate a space near the anode 11 from a space near the partition wall 30. From this viewpoint, the baffle is preferably provided so as to face the respective surfaces of the anode 11 and the partition wall 30. In the space near the anode separated by the baffle, by performing electrolysis, the concentration of the electrolyte (brine concentration) is reduced, and a gas such as chlorine gas is generated. As a result, a difference in gas-liquid specific gravity occurs between the space near the anode 11 separated by the baffle and the space near the partition wall 30. With this situation, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform. Although not shown in FIG. 52, a current collector may be separately provided inside the anode chamber 10. The current collector may be made of the same material or structure as the current collector of the cathode chamber described below. Moreover, in the anode chamber 10, the anode 11 itself can also be made to function as a current collector. (Partition Wall) The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes referred to as a spacer, and divides the anode chamber 10 and the cathode chamber 20. As the partition wall 30, those known as separators for electrolysis can be used, and examples thereof include partition walls in which a plate containing nickel is welded on the cathode side, and a plate containing titanium is welded on the anode side. (Cathode chamber) The cathode chamber 20 functions as a cathode power source when the electrode for electrolysis in this embodiment is inserted on the cathode side, and when the electrode for electrolysis in this embodiment is not inserted on the cathode side , 21 functions as a cathode. When there is a reverse current sink, the cathode or the cathode power source 21 is electrically connected to the reverse current sink system. The cathode chamber 20 preferably includes a cathode-side electrolytic solution supply unit and a cathode-side gas-liquid separation unit similarly to the anode chamber 10. It should be noted that, among the parts constituting the cathode chamber 20, the same descriptions as the parts constituting the anode chamber 10 are omitted. (Cathode) When the electrode for electrolysis in this embodiment is not inserted on the cathode side, a cathode 21 is provided in the frame of the cathode chamber 20. The cathode 21 is preferably a catalyst layer having a nickel substrate and a coated nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include: Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. If necessary, a reduction treatment is performed on the cathode 21. In addition, as the base material of the cathode 21, nickel, a nickel alloy, or nickel-plated iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Cathode Feeder) When the electrode for electrolysis in this embodiment is inserted on the cathode side, a cathode feed member 21 is provided in the frame of the cathode chamber 20. The cathode feed body 21 may be covered with a catalyst component. This catalyst component can be used as a cathode and remain. Examples of the components of the catalyst layer include Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. In addition, nickel, a nickel alloy, and iron or stainless steel plated with nickel without a catalyst coating can be used. In addition, as a base material of the cathode power supply body 21, nickel, a nickel alloy, or nickel plating on iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Reverse current absorbing layer) As the material of the reverse current absorbing layer, a material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected. Examples include nickel and iron. (Current Collector) The cathode chamber 20 preferably includes a current collector 23. This improves the current collection effect. In this embodiment, the current collector 23 is preferably a porous plate, and is arranged so as to be substantially parallel to the surface of the cathode 21. The current collector 23 is preferably composed of a conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, an alloy, or a composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a mesh shape. (Metal Elastomer) By providing the metal elastomer 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, each anode 11 and each cathode The distance between 21 becomes shorter, and the voltage applied to the plurality of electrolytic cells 1 connected in series can be reduced. By reducing the voltage, power consumption can be reduced. In addition, when the metal elastic body 22 is provided, when the laminated body containing the electrolytic electrode of the present embodiment is installed in an electrolytic cell, the pressure of the metal elastic body 22 can stably maintain the electrode for electrolysis. starting point. As the metal elastic body 22, a spring member such as a coil spring or a coil, a cushioning pad, or the like can be used. As the metal elastic body 22, it is possible to use a suitable one in consideration of the stress against the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side or on the surface of the partition wall on the anode chamber 10 side. Generally, the two compartments are divided such that the cathode compartment 20 is smaller than the anode compartment 10. Therefore, in terms of the strength of the frame, it is preferable that the metal elastic body 22 is disposed between the current collector 23 and the cathode 21 of the cathode compartment 20. The metal elastic body 23 is preferably made of a conductive metal such as nickel, iron, copper, silver, or titanium. (Support) The cathode chamber 20 is preferably provided with a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently. The support 24 preferably contains a conductive metal such as nickel, iron, copper, silver, and titanium. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a mesh shape. The support 24 is, for example, a plate. The plurality of support bodies 24 are arranged between the partition wall 30 and the current collector 23. The plurality of support bodies 24 are arranged so that their respective faces are parallel to each other. The support 24 is disposed so as to be substantially perpendicular to the partition wall 30 and the current collector 23. (Anode-Side Gasket, Cathode-Side Gasket) The anode-side gasket is preferably arranged on the surface of the frame constituting the anode chamber 10. The cathode-side gasket is preferably disposed on a surface of a frame constituting the cathode chamber 20. The anode-side gasket provided in one electrolytic cell and the cathode-side gasket of an adjacent electrolytic cell connect the electrolytic cells to each other by sandwiching the ion exchange membrane 2 (see FIGS. 52 and 53). With these gaskets, when a plurality of electrolytic cells 1 are connected in series through the dielectric exchange membrane 2, airtightness can be imparted to the connection points. The so-called gasket is a seal between the ion exchange membrane and the electrolytic cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. The gasket is required to be resistant to corrosive electrolytes or generated gases, and can be used for a long time. Therefore, in terms of chemical resistance or hardness, generally, ethylene-propylene-diene rubber (EPDM rubber), ethylene-propylene rubber (EPM rubber) sulfide or peroxide crosslinked material can be used as a mat. sheet. In addition, if necessary, a gasket covering a region (liquid-contacting portion) in contact with the liquid may be coated with a fluorine resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). . These gaskets may have openings so as not to hinder the flow of the electrolytic solution, and their shapes are not particularly limited. For example, a frame-shaped gasket is attached to the periphery of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20 with an adhesive or the like. In addition, when, for example, two dielectric cells 1 are connected to the dielectric separator exchange membrane 2 (see FIG. 53), the dielectric separator exchange membrane 2 may fasten each electrolytic cell 1 to which a gasket is attached. This makes it possible to prevent the electrolytic solution, alkali metal hydroxide, chlorine gas, hydrogen gas, and the like from being leaked to the outside of the electrolytic cell 1. (Ion exchange membrane 2) As the ion exchange membrane 2, it is as described in the item of the said ion exchange membrane. (Water Electrolysis) The electrolytic cell in the case of performing water electrolysis in this embodiment has a structure in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis described above is changed to a microporous membrane. In addition, the electrolyzer is different from the case where the salt electrolysis is performed in the point that the supplied raw material is water. Regarding other configurations, the electrolytic cell in the case of performing water electrolysis may also have the same configuration as the electrolytic cell in the case of performing salt electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. In the case of water electrolysis, only oxygen is generated in the anode chamber, so the same material as the cathode chamber can be used. Examples include nickel. The anode coating is preferably a catalyst coating for generating oxygen. Examples of the catalyst coating layer include metals, oxides, hydroxides, and the like of platinum group metals and transition metal groups. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used. <Fourth Embodiment> Here, a fourth embodiment of the present invention will be described in detail with reference to FIGS. 63 to 90. [Electrolyzer] The electrolytic cell of the fourth embodiment (hereinafter referred to as "this embodiment" in the item of "the fourth embodiment") includes an anode, an anode frame supporting the anode, and an anode side disposed on the anode frame Gasket, cathode facing the anode, cathode frame supporting the cathode, cathode side gasket disposed on the cathode frame and facing the anode side gasket, and disposed on the anode side gasket and the cathode side A laminated body between a separator and an electrode for electrolysis, and at least a part of the laminated body is sandwiched between the anode-side gasket and the cathode-side gasket, and the electrode for electrolysis is set to 50 mm × 50 mm. Dimensions and set the temperature to 24 ° C, the relative humidity to 32%, the piston speed to 0.2 cm / s, and the ventilation volume to 0.4 cc / cm2 In the case of / s, the ventilation resistance is 24 kPa · s / m or less. Since it is comprised as mentioned above, the electrolytic cell of this embodiment is excellent in electrolysis performance, and can prevent damage to a diaphragm. The electrolytic cell of the present embodiment includes the above-mentioned constituent members, in other words, an electrolytic cell. Hereinafter, an embodiment of an electrolytic cell will be described in detail using a case where salt electrolysis is performed using an ion exchange membrane as a separator. [Electrolytic Cell] First, an electrolytic cell that can be used as a constituent unit of the electrolytic cell of this embodiment will be described. Fig. 63 is a sectional view of the electrolytic cell 1. The electrolytic cell 1 includes an anode chamber 10, a cathode chamber 20, a partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, an anode 11 provided in the anode chamber 10, and a cathode 21 provided in the cathode chamber 20. If necessary, a reverse current absorber 18 having a base material 18a and a reverse current absorbing layer 18b formed on the base material 18a and provided in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 provided in the cathode chamber 20, and a reverse current absorber 18 provided in the cathode chamber 20. The reverse current absorber 18 has a base material 18a as shown in FIG. The reverse current absorbing layer 18b on the substrate 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the current collector 23 and the cathode 21. The support 24 is provided between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via a metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be indirectly connected through a current collector, a support, a metal elastomer, or a partition wall. The entire surface of the cathode 21 is preferably covered with a catalyst layer for reduction reaction. In addition, the form of electrical connection may be to directly install the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22, and laminate the cathode 21 on the metal elastic body 22, respectively. The form. Examples of a method for directly mounting the respective constituent members to each other include welding and the like. The reverse current sink 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40. Fig. 64 is a sectional view of two electrolytic cells 1 adjacent to each other in the electrolytic cell 4. FIG. 65 shows the electrolytic cell 4. Fig. 66 shows the steps for assembling the electrolytic cell 4. In the previous electrolytic cell, as shown in FIG. 64A, the electrolytic cell 1, the diaphragm (here, the cation exchange membrane) 2, and the electrolytic cell 1 are sequentially arranged in series, and one of the two electrolytic cells adjacent to each other in the electrolytic cell An ion exchange membrane 2 is arranged between the anode chamber of the electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1. That is, in the electrolytic cell, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are generally separated by a cation exchange membrane 2. On the other hand, in this embodiment, as shown in FIG. 64B, a laminated body 25 having an electrolytic cell 1, a separator (here, a cation exchange membrane) 2 and an electrode for electrolysis (here, a cathode for regeneration) 21a, The electrolytic cells 1 are sequentially arranged in series, and the laminated body 25 is sandwiched between the anode gasket 12 and the cathode gasket 13 in a part (the upper end portion in FIG. 64B). As shown in FIG. 65, the electrolytic cell 4 includes a plurality of electrolytic cells 1 connected in series through a dielectric exchange membrane 2. That is, the electrolytic cell 4 is a bipolar electrolytic cell having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 66, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series through a dielectric exchange membrane 2 and connecting them with a press 5. The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. Among the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4, the anode 11 of the electrolytic cell 1 located at the extreme end is electrically connected to the anode terminal 7. The cathode 21 of the electrolytic cell at the end opposite to the anode terminal 7 of the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 to the cathode terminal 6 through the anode and cathode of each electrolytic cell 1. Furthermore, an electrolytic cell having only an anode chamber (anode terminal cell) and an electrolytic cell having only a cathode chamber (cathode terminal cell) may be disposed at both ends of the connected electrolytic cells 1. In this case, the anode terminal 7 is connected to an anode terminal cell disposed at one end thereof, and the cathode terminal 6 is connected to a cathode terminal cell disposed at the other end. When electrolysis of brine is performed, brine is supplied to each anode chamber 10 and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid system is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (omitted from the figure) through an electrolytic solution supply hose (omitted from the figure). In addition, the electrolytic solution and the products of electrolysis are recovered by an electrolytic solution recovery tube (omitted from the figure). During the electrolysis, the sodium ions in the brine start from the anode chamber 10 of an electrolytic cell 1 and pass through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Accordingly, the current in the electrolysis flows in a direction in which the electrolytic cells 1 are connected in series. That is, a current flows from the anode chamber 10 to the cathode chamber 20 through the cation exchange membrane 2. Along with the electrolysis of brine, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen are generated on the cathode 21 side. As mentioned above, the separator, cathode and anode in the electrolytic cell usually accompany the operation of the electrolytic cell, and their performance will deteriorate. Eventually, they must be replaced with new products. In the case of only replacing the diaphragm, the existing diaphragm can be removed from the electrolytic cell. It is easy to renew by pulling out and inserting a new diaphragm between the pools. However, in the case of replacing the anode or the cathode by welding, special equipment is required, which is more complicated. On the other hand, in this embodiment, as described above, the laminated body 25 is sandwiched between the anode gasket 12 and the cathode gasket 13 in a part (the upper end portion in FIG. 64B). In particular, in the example shown in FIG. 64B, the separator (here, the cation exchange membrane) 2 and the electrode for electrolysis (here, the cathode for regeneration) 21a are at least above the end of the laminated body, and the anode The pressing of the gasket 12 toward the laminated body 25 and the pressing of the gasket 12 toward the laminated body 25 are fixed. In this case, it is not necessary to fix the laminated body 25 (especially, an electrode for electrolysis) to an existing member (for example, an existing cathode) by welding, so it is preferable. That is, when both the electrolytic electrode and the separator are sandwiched between the anode-side gasket and the above-mentioned cathode-side gasket, the working efficiency at the time of electrode renewal in the electrolytic cell tends to be improved, which is preferable. Furthermore, according to the configuration of the electrolytic cell of this embodiment, since the separator and the electrode for electrolysis are sufficiently fixed in the form of a laminate, excellent electrolytic performance can be obtained. (Anode Chamber) The anode chamber 10 includes an anode 11 or an anode power source 11. The term “feeder” used herein refers to an electrode that is degraded (ie, an existing electrode) or an electrode that is not formed with a catalyst coating. When the electrode for electrolysis in this embodiment is inserted on the anode side, 11 functions as an anode power source. When the electrode for electrolysis in this embodiment is not inserted on the anode side, 11 functions as an anode. The anode chamber 10 preferably includes an anode-side electrolytic solution supply unit that supplies an electrolytic solution to the anode chamber 10, and a baffle plate that is disposed above the anode-side electrolytic solution supply unit and is disposed substantially parallel or inclined to the partition wall 30. And an anode-side gas-liquid separation portion disposed above the baffle and separating gas from an electrolyte mixed with the gas. (Anode) When the electrode for electrolysis in this embodiment is not inserted on the anode side, an anode 11 is provided in a frame (ie, an anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as a so-called DSA (registered trademark) can be used. The so-called DSA is an electrode with a titanium substrate covered with an oxide containing ruthenium, iridium, and titanium as components. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode Feeder) When the electrode for electrolysis in the present embodiment is inserted on the anode side, an anode feeder 11 is provided in the frame of the anode chamber 10. As the anode power source 11, a metal electrode such as a so-called DSA (registered trademark) may be used, or titanium without a catalyst coating layer may be used. Alternatively, a DSA having a thinner catalyst coating thickness may be used. Furthermore, a used anode can also be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode-side electrolytic solution supply unit) The anode-side electrolytic solution supply unit is a person that supplies an electrolytic solution to the anode chamber 10 and is connected to an electrolytic solution supply pipe. The anode-side electrolytic solution supply portion is preferably arranged below the anode chamber 10. As the anode-side electrolytic solution supply portion, for example, a tube (dispersion tube) having an opening formed on the surface can be used. The tube is more preferably arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies an electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is transported into the electrolytic cell 1 through the tube, and is supplied into the anode chamber 10 from an opening provided on the surface of the tube. Since the tube is arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell, the electrolyte can be uniformly supplied to the inside of the anode chamber 10, which is preferable. (Anode-side gas-liquid separation section) The anode-side gas-liquid separation section is preferably disposed above the baffle. In electrolysis, the anode-side gas-liquid separator has a function of separating a generated gas such as chlorine gas from the electrolytic solution. In addition, unless otherwise specified, the so-called upper means the upper direction in the electrolytic cell 1 of FIG. 63, and the lower means the lower direction in the electrolytic cell 1 of FIG. 63. During the electrolysis, if the generated gas generated in the electrolytic cell 1 and the electrolyte become mixed phase (gas-liquid mixed phase) and are discharged out of the system, there will be physical damage to the ion exchange membrane due to vibration caused by pressure fluctuations inside the electrolytic cell 1. Situation. In order to suppress this situation, it is preferable to provide an anode-side gas-liquid separation section in the electrolytic cell 1 in this embodiment to separate gas from liquid. It is preferable to provide a defoaming plate for eliminating bubbles in the anode-side gas-liquid separation section. The gas and liquid mixed phase flow can be separated into the electrolyte and the gas by breaking the bubbles when passing through the defoaming plate. As a result, vibration during electrolysis can be prevented. (Baffle) The baffle is preferably disposed above the anode-side electrolytic solution supply portion, and is disposed substantially parallel or inclined to the partition wall 30. The baffle is a partition that controls the flow of the electrolyte in the anode chamber 10. By providing the baffle, the electrolyte (brine, etc.) can be circulated inside the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle is preferably arranged to separate a space near the anode 11 from a space near the partition wall 30. From this viewpoint, the baffle is preferably provided so as to face the respective surfaces of the anode 11 and the partition wall 30. In the space near the anode separated by the baffle, by performing electrolysis, the concentration of the electrolyte (brine concentration) is reduced, and a gas such as chlorine gas is generated. As a result, a difference in gas-liquid specific gravity occurs between the space near the anode 11 separated by the baffle and the space near the partition wall 30. With this situation, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform. Although not shown in FIG. 63, a current collector may be separately provided inside the anode chamber 10. The current collector may be made of the same material or structure as the current collector of the cathode chamber described below. Moreover, in the anode chamber 10, the anode 11 itself can also be made to function as a current collector. (Partition Wall) The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes referred to as a spacer, and divides the anode chamber 10 and the cathode chamber 20. As the partition wall 30, those known as separators for electrolysis can be used, and examples thereof include partition walls in which a plate containing nickel is welded on the cathode side, and a plate containing titanium is welded on the anode side. (Cathode chamber) The cathode chamber 20 functions as a cathode power source when the electrode for electrolysis in this embodiment is inserted on the cathode side, and when the electrode for electrolysis in this embodiment is not inserted on the cathode side , 21 functions as a cathode. When there is a reverse current sink, the cathode or the cathode power source 21 is electrically connected to the reverse current sink system. The cathode chamber 20 preferably includes a cathode-side electrolytic solution supply unit and a cathode-side gas-liquid separation unit similarly to the anode chamber 10. It should be noted that, among the parts constituting the cathode chamber 20, the same descriptions as the parts constituting the anode chamber 10 are omitted. (Cathode) When the electrode for electrolysis in this embodiment is not inserted on the cathode side, a cathode 21 is provided in a frame (ie, a cathode frame) of the cathode chamber 20. The cathode 21 is preferably a catalyst layer having a nickel substrate and a coated nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include: Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. If necessary, a reduction treatment is performed on the cathode 21. In addition, as the base material of the cathode 21, nickel, a nickel alloy, or nickel-plated iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Cathode Feeder) When the electrode for electrolysis in this embodiment is inserted on the cathode side, a cathode feed member 21 is provided in the frame of the cathode chamber 20. The cathode feed body 21 may be covered with a catalyst component. This catalyst component can be used as a cathode and remain. Examples of the components of the catalyst layer include Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. In addition, nickel, a nickel alloy, and iron or stainless steel plated with nickel without a catalyst coating can be used. In addition, as a base material of the cathode power supply body 21, nickel, a nickel alloy, or nickel plating on iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Reverse current absorbing layer) As the material of the reverse current absorbing layer, a material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected. Examples include nickel and iron. (Current Collector) The cathode chamber 20 preferably includes a current collector 23. This improves the current collection effect. In this embodiment, the current collector 23 is preferably a porous plate, and is arranged so as to be substantially parallel to the surface of the cathode 21. The current collector 23 is preferably composed of a conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, an alloy, or a composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a mesh shape. (Metal Elastomer) By providing the metal elastomer 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, each anode 11 and each cathode The distance between 21 becomes shorter, and the voltage applied to the plurality of electrolytic cells 1 connected in series can be reduced. By reducing the voltage, power consumption can be reduced. In addition, when the metal elastic body 22 is provided, when the laminated body including the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the pressure of the metal elastic body 22 can stably maintain the electrode for electrolysis. At the starting position. As the metal elastic body 22, a spring member such as a coil spring or a coil, a cushioning pad, or the like can be used. As the metal elastic body 22, it is possible to use a suitable one in consideration of the stress against the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side or on the surface of the partition wall on the anode chamber 10 side. Generally, the two compartments are divided such that the cathode compartment 20 is smaller than the anode compartment 10. Therefore, in terms of the strength of the frame, it is preferable that the metal elastic body 22 is disposed between the current collector 23 and the cathode 21 of the cathode compartment 20. The metal elastic body 23 is preferably made of a conductive metal such as nickel, iron, copper, silver, or titanium. (Support) The cathode chamber 20 is preferably provided with a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently. The support 24 preferably contains a conductive metal such as nickel, iron, copper, silver, and titanium. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a mesh shape. The support 24 is, for example, a plate. The plurality of support bodies 24 are arranged between the partition wall 30 and the current collector 23. The plurality of support bodies 24 are arranged so that their respective faces are parallel to each other. The support 24 is disposed so as to be substantially perpendicular to the partition wall 30 and the current collector 23. (Anode-Side Gasket, Cathode-Side Gasket) The anode-side gasket is preferably arranged on the surface of the frame constituting the anode chamber 10. The cathode-side gasket is preferably disposed on a surface of a frame constituting the cathode chamber 20. The anode-side gasket provided in one electrolytic cell and the cathode-side gasket of an adjacent electrolytic cell connect the electrolytic cells to each other by sandwiching the laminate 25 (see FIG. 64B). With these gaskets, when the plurality of electrolytic cells 1 are connected in series through the interlayer stack 25, airtightness can be imparted to the connection portion. The so-called gasket is a seal between the ion exchange membrane and the electrolytic cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. The gasket is required to be resistant to corrosive electrolytes or generated gases, and can be used for a long time. Therefore, in terms of chemical resistance or hardness, generally, ethylene-propylene-diene rubber (EPDM rubber), ethylene-propylene rubber (EPM rubber) sulfide or peroxide crosslinked material can be used as a mat. sheet. In addition, if necessary, a gasket covering a region (liquid-contacting portion) in contact with the liquid may be coated with a fluorine resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). . These gaskets may have openings so as not to hinder the flow of the electrolytic solution, and their shapes are not particularly limited. For example, a frame-shaped gasket is attached to the periphery of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20 with an adhesive or the like. By sandwiching the laminated body 25 with the anode gasket and the cathode gasket, it is possible to prevent the electrolyte solution, alkali metal hydroxide, chlorine gas, hydrogen gas, and the like from leaking to the outside of the electrolytic cell 1. [Laminated Body] The laminated body in this embodiment includes a separator and an electrode for electrolysis. The laminated body in this embodiment can improve the working efficiency when the electrodes in the electrolytic cell are renewed, and can also exhibit excellent electrolytic performance after the renewal. That is, with the laminated body in this embodiment, when the electrodes are updated, the complicated operations such as peeling off the existing electrodes fixed to the electrolytic cell are not required, and the electrodes can be updated by the same simple operation as that of the diaphragm. Significantly improved efficiency. Furthermore, with the laminated body in this embodiment, the electrolytic performance of the existing electrolytic cell can be maintained to be the same as or improved in the performance of the new product. Therefore, an electrode fixed to an existing electrolytic cell and functioning as an anode and a cathode only needs to function as a feeder, which can greatly reduce a catalyst coating or even a catalystless coating. [Electrode for Electrolysis] The electrode for electrolysis in this embodiment has a size of 50 mm × 50 mm and a temperature of 24 ° C., a relative humidity of 32%, a piston speed of 0.2 cm / s, and a ventilation volume of 0.4. cc / cm2 In the case of / s (hereinafter also referred to as "measurement condition 1"), the ventilation resistance (hereinafter also referred to as "ventilation resistance 1") is 24 kPa · s / m or less. Large ventilation resistance means that the air is difficult to flow, and refers to a state with a high density. In this state, the product of electrolysis remains in the electrode, and the reaction matrix is difficult to diffuse into the electrode, so the electrolytic performance (voltage, etc.) is deteriorated. In addition, the concentration on the surface of the film is increased. Specifically, the caustic concentration is increased on the cathode surface, and the supply of brine on the anode surface is decreased. As a result, since the product stays at the interface between the separator and the electrode at a high concentration, the separator is damaged, the voltage on the cathode surface is increased, the membrane is damaged, and the anode is damaged. In this embodiment, in order to prevent such abnormalities, the ventilation resistance is set to 24 kPa · s / m or less. Furthermore, in this embodiment, if the ventilation resistance is larger than a certain degree, the NaOH generated in the electrode tends to stay at the interface between the electrode and the separator and becomes a high concentration in the case of the cathode. In the case of the anode, the tendency is high. The tendency of the salt water supply to decrease and the concentration of the salt water to become low, in order to prevent damage to the diaphragm that may occur due to such retention, it is preferably less than 0.19 kPa · s / m, more preferably 0.15 kPa · s / m or less, more preferably 0.07 kPa · s / m or less. On the other hand, when the ventilation resistance is low, since the area of the electrode becomes smaller, the area for conducting electricity becomes smaller and the electrolytic performance (voltage, etc.) becomes poor. When the ventilation resistance is zero, since the electrode for electrolysis is not provided, the power feeder functions as an electrode, and the electrolytic performance (voltage, etc.) is significantly deteriorated. In this respect, the preferable lower limit value specified as the ventilation resistance 1 is not particularly limited, but preferably exceeds 0 kPa · s / m, more preferably 0.0001 kPa · s / m or more, and more preferably 0.001 kPa · s / m or more. In addition, in terms of measurement method, if the ventilation resistance 1 is 0.07 kPa · s / m or less, sufficient measurement accuracy may not be obtained. From this viewpoint, it is also possible to realize the ventilation resistance (hereinafter referred to as "measurement condition 2") obtained by the following measurement method (hereinafter also referred to as "measurement condition 2") with respect to an electrode for electrolysis whose ventilation resistance 1 is 0.07 kPa · s / m or less Also called "ventilation resistance 2"). That is, the ventilation resistance 2 is set to a size of 50 mm × 50 mm for the electrode for electrolysis, and the temperature is 24 ° C, the relative humidity is 32%, the piston speed is 2 cm / s, and the ventilation volume is 4 cc / cm.2 / s in the case of ventilation resistance. Specific measurement methods of the ventilation resistances 1 and 2 are described in the examples. The above-mentioned ventilation resistances 1 and 2 can be set to the above-mentioned range, for example, by appropriately adjusting the opening ratio and the thickness of the electrodes described below. More specifically, for example, if the thickness is the same, if the opening rate is increased, the ventilation resistances 1 and 2 tend to decrease, and if the opening rate is decreased, the ventilation resistances 1 and 2 tend to be large. . The electrode for electrolysis in this embodiment can obtain good operability, and has good adhesion to a separator such as an ion exchange membrane or a microporous membrane, and a power supply (a deteriorated electrode and an electrode without a catalyst coating layer). From the viewpoint of force, the force per unit mass and area is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ) Above, and more preferably 0.1 N / mg · cm2 Above, more preferably 0.14 N / (mg · cm2 )the above. From the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The above-mentioned bearing force can be set to the above range, for example, by appropriately adjusting a porosity, an electrode thickness, an arithmetic average surface roughness, and the like described below. More specifically, for example, if the opening ratio is increased, the bearing force tends to be small, and if the opening ratio is decreased, the bearing force tends to be large. In addition, from the viewpoint of obtaining good operability, it has good adhesion to separators such as ion-exchange membranes or microporous membranes, deteriorated electrodes, and feeders without a catalyst coating, and so on in terms of economy. From a viewpoint, the mass per unit area is preferably 48 mg / cm2 Below, more preferably 30 mg / cm2 Below, more preferably 20 mg / cm2 In the following, from the viewpoint of combining the operability, adhesiveness, and economy, 15 mg / cm is preferred.2 the following. The lower limit value is not particularly limited, for example, 1 mg / cm2 about. The above-mentioned mass per unit area can be set to the above range, for example, by appropriately adjusting the opening ratio and thickness of the electrode described below. More specifically, for example, if the thickness is the same, the mass per unit area tends to become smaller if the opening ratio is increased, and the mass per unit area tends to be larger if the opening ratio is decreased. . The withstand force can be measured by the following method (i) or (ii). Specifically, it is as described in the examples. As for the bearing capacity, the value obtained by the measurement of the method (i) (also referred to as "bearing capacity (1)") and the value obtained by the measurement of the method (ii) (also referred to as "bearing capacity (2) ) ") May be the same or different, but it is preferred that any value does not reach 1.5 N / mg · cm2 . [Method (i)] A nickel plate (thickness: 1.2 mm, 200 mm square) obtained by spraying with alumina of grain number 320 was laminated in order, and the perfluorocarbon polymer film with an ion exchange group was introduced. Ion-exchange membrane (170 mm square, details of the so-called ion-exchange membrane as described in the examples) and electrode samples (130 mm square) coated with inorganic particles and binders on both sides. After sufficient immersion, excess moisture adhering to the surface of the laminated body was removed to obtain a sample for measurement. In addition, the arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment is 0.5 to 0.8 μm. The specific calculation method of the arithmetic average surface roughness (Ra) is as described in the examples. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. This average value is divided by the area of the overlapped part of the electrode sample and the ion-exchange membrane and the mass of the electrode sample of the overlapped part of the ion-exchange membrane to calculate the force per unit mass and unit area (1) (N / mg · cm2 ). With the force (1) per unit mass and unit area obtained by method (i), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 ), More preferably 0.2 N / (mg ・ cm2 )the above. [Method (ii)] A nickel plate (thickness 1.2 mm, 200 mm square, the same nickel plate as in the above method (i)) and an electrode sample (130 mm square), and the laminated body is sufficiently immersed in pure water, and then excess water adhered to the surface of the laminated body is removed to obtain a sample for measurement. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate and the mass of the electrode sample in the overlapped portion of the nickel plate to calculate the adhesion force per unit mass and unit area (2) (N / mg · cm2 ). With the force (2) per unit mass and unit area obtained by method (ii), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. Furthermore, from the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 )the above. The electrode for electrolysis in this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, and good operability can be obtained. It can be used in contact with separators such as ion exchange membranes or microporous membranes, degraded electrodes (feeders), and non-formed The electrode (feeder) of the dielectric coating has good adhesion, can be wound into a roll shape and bent well, and it is easy to handle at a large size (for example, 1.5 m × 2.5 m). In particular, it is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and even more It is preferably 100 μm or less, and from the viewpoint of operability and economy, it is more preferably 50 μm or less. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and further, for a large size (for example, From the viewpoint of easy handling at a size of 1.5 m × 2.5 m), it is more preferably 95% or more. The upper limit is 100%. [Method (2)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 280 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesive force and being able to be wound into a roll shape and bent well, the ratio measured by the following method (3) is preferably 75% or more. It is preferably 80% or more, and from the viewpoint of ease of handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 90% or more. The upper limit is 100%. [Method (3)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 145 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). From the viewpoint of operability, the electrode for electrolysis in this embodiment is preferably a value measured by the following method (A) of 40 mm or less, more preferably 29 mm or less, and even more preferably 19 mm or less. . [Method (A)] Under conditions of a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the two layers of a perfluorocarbon polymer film having an ion exchange group introduced are coated with inorganic particles and a binder Ion-exchange membrane (170 mm square, detailed description of the so-called ion-exchange membrane as described in the examples) and the sample of the above electrode for electrolysis are wound and fixed on the curved surface of a vinyl chloride core material with an outer diameter of f32 mm After standing for 6 hours, the electrode for electrolysis was separated and placed on a horizontal plate. At this time, the height L in the vertical direction of both ends of the electrode for electrolysis was measured.1 And L2 Take the average of these as the measured value. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesion and preventing gas retention during electrolysis, a porous structure is preferred, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80%, and more preferably 20 to 75%. The open porosity is the ratio of the perforated portion per unit volume. There are various calculation methods for the opening part according to the submicron order or only the openings that can be seen visually. In this embodiment, the volume V is calculated from the values of the gauge thickness, width, and length of the electrode, and the weight W is measured. Then, the aperture ratio A is calculated by the following formula. A = (1- (W / (V × ρ)) × 100 ρ Density of electrode material (g / cm3 ). E.g. in the case of nickel 8.908 g / cm3 In the case of titanium is 4.506 g / cm3 . The adjustment of the opening rate can be appropriately adjusted by the following methods: if it is a punched metal, change the area of the punched metal per unit area; if it is a porous metal, change SW (short diameter), LW (long diameter), Feed value; if it is a wire mesh, change the wire diameter and mesh number of the metal fiber; if it is electroforming, change the pattern of the photoresist used; if it is a non-woven fabric, change the metal fiber diameter and fiber density; In the case of a foamed metal, a template or the like for forming a void is changed. Hereinafter, one embodiment of the electrode for electrolysis in this embodiment will be described. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer is described below, and may include a plurality of layers or a single-layer structure. As shown in FIG. 68, the electrode 100 for electrolysis according to this embodiment includes an electrode base material 10 for electrolysis and a pair of first layers 20 covering one surface of the electrode base material 10 for electrolysis. The first layer 20 preferably covers the entire electrode base material 10 for electrolysis. As a result, the catalyst activity and durability of the electrode for electrolysis can be easily improved. Furthermore, the first layer 20 may be formed only on one surface area of the electrode base material 10 for electrolysis. As shown in FIG. 68, the surface of the first layer 20 may be covered by the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, the second layer 30 may be laminated on only one surface of the first layer 20. (Electrode base material for electrolysis) The electrode base material 10 for electrolysis is not particularly limited, and for example, nickel, nickel alloy, stainless steel, or a valve metal typified by titanium can be used, and it is preferably selected from nickel (Ni) And at least one element of titanium (Ti). When stainless steel is used in a high-concentration alkaline aqueous solution, considering the elution of iron and chromium, and the conductivity of stainless steel is about 1/10 of that of nickel, it is preferable to use a substrate containing nickel (Ni) as the base material. Electrode substrate for electrolysis. In addition, when the electrode base material 10 for electrolysis is used in a chlorine gas generating environment in a high-concentration saline solution, the material is preferably titanium with high corrosion resistance. The shape of the electrode substrate 10 for electrolysis is not particularly limited, and a suitable shape can be selected according to the purpose. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. Among them, punched metal or porous metal is preferred. In addition, the so-called electroforming is a technique for producing a precise patterned metal thin film by combining a photolithographic process and an electroplating method. It is a method for obtaining a metal thin film by forming a pattern on a substrate with a photoresist, and performing electroplating on a portion not protected by the photoresist. Regarding the shape of the electrode substrate for electrolysis, there are suitable specifications according to the distance between the anode and the cathode in the electrolytic cell. There is no particular limitation. When the anode and the cathode have a limited distance, porous metal and punched metal shapes can be used. In the case of a so-called zero-pitch electrolytic cell where the ion exchange membrane is connected to the electrode, a braided thin wire can be used. The finished woven mesh, metal mesh, foamed metal, metal non-woven fabric, porous metal, punched metal, metal porous foil, etc. Examples of the electrode base material 10 for electrolysis include a porous metal foil, a metal wire mesh, a metal nonwoven fabric, a punched metal, a porous metal, or a foamed metal. As a sheet material before being processed into a punched metal or a porous metal, a sheet material formed by rolling and an electrolytic foil are preferred. The electrolytic foil is preferably further subjected to a plating treatment using the same element as the base material as a post-treatment to form unevenness on one or both sides. As described above, the thickness of the electrode base material 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, even more preferably 155 μm or less, even more preferably 135 μm or less, and even more preferably 125. μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, and further more preferably 50 μm or less in terms of operability and economy. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the electrode base material for electrolysis, it is preferable to reduce the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing environment. In addition, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, it is preferable to use steel sand and alumina powder to form unevenness on the surface, and then increase the surface area by acid treatment. Alternatively, it is preferable to increase the surface area by applying a plating treatment to the same element as the substrate. In order to bring the first layer 20 into close contact with the surface of the electrode base material 10 for electrolysis, it is preferable that the surface area of the electrode base material 10 for electrolysis is increased. Examples of the treatment for increasing the surface area include blasting treatment using steel wire grain, steel sand, alumina sand, etc., acid treatment using sulfuric acid or hydrochloric acid, and plating treatment using the same element as the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm. Next, a case where the electrode for electrolysis in this embodiment is used as an anode for salt electrolysis will be described. (First layer) In FIG. 68, the first layer 20 as a catalyst layer contains at least one of ruthenium oxide, iridium oxide, and titanium oxide. Examples of the ruthenium oxide include RuO2 Wait. Examples of the iridium oxide include IrO2 Wait. Examples of the titanium oxide include TiO2 Wait. The first layer 20 is preferably two oxides containing ruthenium oxide and titanium oxide, or three oxides containing ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and further, the adhesion with the second layer 30 is further improved. In the case where the first layer 20 contains two oxides of ruthenium oxide and titanium oxide, the titanium oxide contained in the first layer 20 is better than 1 mol of the ruthenium oxide contained in the first layer 20 It is 1 to 9 moles, more preferably 1 to 4 moles. By setting the composition ratio of the two oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains three oxides of ruthenium oxide, iridium oxide, and titanium oxide, the iridium oxide contained in the first layer 20 is 1 mole relative to the ruthenium oxide contained in the first layer 20 The amount is preferably 0.2 to 3 moles, and more preferably 0.3 to 2.5 moles. In addition, the titanium oxide contained in the first layer 20 is preferably 0.3 to 8 moles, and more preferably 1 to 7 moles relative to 1 mole of the ruthenium oxide contained in the first layer 20. By setting the composition ratio of the three oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains at least two oxides selected from the group consisting of ruthenium oxide, iridium oxide, and titanium oxide, these oxides preferably form a solid solution. By forming an oxide solid solution, the electrode 100 for electrolysis exhibits excellent durability. In addition to the above composition, as long as it contains at least one of ruthenium oxide, iridium oxide, and titanium oxide, various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like called DSA (registered trademark) may be used as the first layer 20. The first layer 20 need not be a single layer, and may include a plurality of layers. For example, the first layer 20 may include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. (Second layer) The second layer 30 preferably contains ruthenium and titanium. This can further reduce the chlorine overvoltage immediately after electrolysis. The second layer 30 is preferably a palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. This can further reduce the chlorine overvoltage immediately after electrolysis. The thicker the second layer 30 is, the longer the time during which the electrolytic performance can be maintained. From the viewpoint of economy, the thickness is preferably 0.05 to 3 μm. Next, a case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis will be described. (First layer) The components of the first layer 20 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. In the case of containing at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal, a platinum group metal, a platinum group metal oxide, and a platinum group metal hydroxide are preferred. The alloy containing a platinum group metal contains at least one platinum group metal of platinum, palladium, rhodium, ruthenium, and iridium. The platinum group metal preferably contains platinum. The platinum group metal oxide is preferably a ruthenium oxide. The platinum group metal hydroxide is preferably a ruthenium hydroxide. The platinum group metal alloy is preferably an alloy containing platinum and nickel, iron, and cobalt. It is preferable to further contain an oxide or hydroxide of a lanthanoid as a second component as necessary. Accordingly, the electrode 100 for electrolysis exhibits excellent durability. The lanthanide oxide or hydroxide preferably contains at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, and praseodymium. It is preferable to further contain an oxide or hydroxide of a transition metal as a third component as necessary. By adding the third component, the electrode 100 for electrolysis can exhibit more excellent durability and reduce the electrolytic voltage. Examples of preferred combinations include ruthenium, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + osmium, ruthenium + rhenium + platinum, ruthenium + rhenium + Platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur , Ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + osmium, ruthenium + rhenium + manganese, ruthenium + 钐 + iron, ruthenium + rhenium + cobalt, ruthenium + 钐 + zinc, ruthenium + 钐+ Gallium, Ruthenium + 钐 + Sulfur, Ruthenium + 钐 + Lead, Ruthenium + 钐 + Ni, Pt + Ce, Pt + Pd + Ce, Pt + Pd + La + Ce, Pt + Ir, Pt + Pd, Pt + I + Palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, alloys of platinum and nickel, alloys of platinum and cobalt, alloys of platinum and iron, etc. When the platinum group metal, platinum group metal oxide, platinum group metal hydroxide, and platinum group metal-containing alloy are not contained, the main component of the catalyst is preferably nickel. Preferably, it contains at least one of nickel metal, oxide, and hydroxide. As a second component, a transition metal may be added. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon. Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, and the like. If necessary, an intermediate layer may be provided between the first layer 20 and the electrode base material 10 for electrolysis. By providing the intermediate layer, the durability of the electrode 100 for electrolysis can be improved. The intermediate layer is preferably one having an affinity for both the first layer 20 and the electrode base material 10 for electrolysis. The intermediate layer is preferably a nickel oxide, a platinum group metal, a platinum group metal oxide, or a platinum group metal hydroxide. The intermediate layer can be formed by coating and firing a solution containing the components forming the intermediate layer, or heat-treating the substrate at a temperature of 300 to 600 ° C in an air environment to form a surface oxide layer. . In addition, it can be formed by a known method such as a thermal spray method or an ion plating method. (Second layer) The components of the first layer 30 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. Examples of preferred combinations of the elements contained in the second layer include the combinations listed in the first layer. The combination of the first layer and the second layer may be a combination with the same composition but a different composition ratio, or a combination with a different composition. As the thickness of the catalyst layer, the thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 μm to 20 μm. When it is 0.01 μm or more, it can fully function as a catalyst. If it is 20 μm or less, it is less likely to fall off from the substrate, and a strong catalyst layer can be formed. More preferably, it is 0.05 μm to 15 μm. More preferably, it is 0.1 μm to 10 μm. It is more preferably 0.2 μm to 8 μm. The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer, is preferably 315 μm or less, more preferably 220 μm or less, and further preferably 170 μm in terms of the operability of the electrode. Below, still more preferably 150 μm or less, even more preferably 145 μm or less, even more preferably 140 μm or less, even more preferably 138 μm or less, and even more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. The thickness of the electrode can be determined by measuring with an electronic digital thickness gauge (Mitutoyo Co., Ltd., showing a minimum of 0.001 mm). The thickness of the electrode substrate for electrolysis was measured in the same manner as the electrode thickness. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness. In this embodiment, from the viewpoint of ensuring sufficient electrolytic performance, it is preferable that the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, and Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, At least one catalyst component in the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy. In this embodiment, if the electrode for electrolysis is an electrode with a wide elastic deformation area, better operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating is formed. From the viewpoint that the layered power supply has a better adhesion, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, still more preferably 170 μm or less, and even more preferably 150 μm. Hereinafter, it is particularly preferably 145 μm or less, more preferably 140 μm or less, even more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. In addition, in this embodiment, "the elastic deformation area is wide" means that the electrode for electrolysis is wound into a wound body, and warping caused by winding is unlikely to occur after the wound state is released. When the thickness of the electrode for electrolysis includes a catalyst layer described below, it means the thickness of the electrode substrate for electrolysis and the thickness of the catalyst layer. (Manufacturing method of the electrode for electrolysis) Next, one Embodiment of the manufacturing method of the electrode 100 for electrolysis is demonstrated in detail. In this embodiment, the first layer 20 is formed on the electrode substrate for electrolysis by using a method such as firing (thermal decomposition) of a coating film under an oxygen environment, or ion plating, plating, or thermal spraying. The second layer 30 is preferably used to produce the electrode 100 for electrolysis. Such a manufacturing method according to this embodiment can achieve high productivity of the electrode 100 for electrolysis. Specifically, a catalyst layer is formed on an electrode substrate for electrolysis by a coating step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. The term "thermal decomposition" means heating a metal salt that becomes a precursor to decompose it into a metal or a metal oxide and a gaseous substance. Decomposition products differ depending on the type of metal used, the type of salt, and the environment in which thermal decomposition is performed, but most metals tend to form oxides easily in an oxidizing environment. In the industrial manufacturing process of electrodes, thermal decomposition is usually performed in air, and in most cases, metal oxides or metal hydroxides are formed. (Formation of the first layer of the anode) (Coating step) The first layer 20 is a solution (first coating liquid) in which a salt of at least one metal among ruthenium, iridium, and titanium is dissolved, and is applied to an electrode base for electrolysis. It is obtained by thermal decomposition (baking) in the presence of oxygen. The contents of ruthenium, iridium, and titanium in the first coating liquid are approximately equal to those of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 100 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of the second layer) The second layer 30 is formed as necessary, for example, a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (a second coating solution) is applied to the first layer 20 It is obtained by thermal decomposition in the presence of oxygen. (Formation of the first layer of the cathode by thermal decomposition method) (Coating step) The first layer 20 is a solution (first coating solution) in which metal salts of various combinations are dissolved on the electrode substrate for electrolysis , Obtained by thermal decomposition (firing) in the presence of oxygen. The content ratio of the metal in the first coating liquid is substantially equal to that of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 10 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of Intermediate Layer) The intermediate layer is formed as necessary. For example, a solution (second coating solution) containing a palladium compound or a platinum compound is coated on a substrate, and then obtained by thermal decomposition in the presence of oxygen. Alternatively, instead of applying the solution, only the substrate is heated, thereby forming a nickel oxide intermediate layer on the surface of the substrate. (Formation of the first layer of the cathode using ion plating) The first layer 20 may also be formed by ion plating. As an example, the method of fixing a base material in a chamber and irradiating an electron beam with a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma environment is argon and oxygen. Ruthenium is deposited on the substrate in the form of ruthenium oxide. (Formation of the first layer using a plated cathode) The first layer 20 may also be formed by a plating method. As an example, if a substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed. (Formation of the first layer of the cathode using thermal spraying) The first layer 20 can also be formed by a thermal spraying method. As an example, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed by plasma-spraying nickel oxide particles onto a substrate. The electrode for electrolysis in this embodiment can be used by being integrated with a separator such as an ion exchange membrane or a microporous membrane. Therefore, the laminated body in this embodiment can be used as a membrane-integrated electrode, and the replacement and attachment of the cathode and the anode when the electrode is not required to be replaced, the operation efficiency is greatly improved. In addition, by using a bulk electrode such as an ion exchange membrane or a microporous membrane, the electrolytic performance can be the same as or improved in the new product. Hereinafter, the ion exchange membrane will be described in detail. [Ion exchange membrane] The ion exchange membrane is not particularly limited as long as it can be laminated with an electrode for electrolysis, and various ion exchange membranes can be applied. In this embodiment, an ion exchange membrane having a membrane body containing a hydrocarbon polymer or a fluorine-containing polymer having an ion exchange group and a coating layer provided on at least one side of the membrane body is preferably used. The coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is preferably 0.1 to 10 m.2 / g. The gas generated by the ion exchange membrane of this structure during electrolysis has less influence on the electrolytic performance, and tends to exhibit stable electrolytic performance. The above-mentioned membrane system of a perfluorocarbon polymer to which an ion exchange group is introduced is provided with an ion exchange group (as -SO3 - Sulfonic acid layer and sulfonic acid layer derived from a carboxyl group (with -CO2 - The group represented by this is any of the carboxylic acid layers (hereinafter also referred to as "carboxylic acid groups"). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforced core material. Hereinafter, the inorganic particles and the binder will be described in detail in the description of the coating layer. Fig. 69 is a schematic sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 includes a membrane body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and coating layers 11 a and 11 b formed on both sides of the membrane body 10. In the ion-exchange membrane 1, the membrane body 10 is provided with an ion-exchange group (as -SO3 - The sulfonic acid layer 3, which is also referred to as a "sulfonic acid group" hereinafter, and an ion-exchange group (with -CO2 - The carboxylic acid layer 2 shown below is also referred to as a "carboxylic acid group", and the strength and dimensional stability are strengthened by the reinforcing core material 4. Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it can be suitably used as a cation exchange membrane. The ion exchange membrane may include only one of a sulfonic acid layer and a carboxylic acid layer. The ion exchange membrane is not necessarily reinforced by a reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example shown in FIG. 69. (Membrane Body) First, the membrane body 10 constituting the ion exchange membrane 1 will be described. The membrane body 10 may be any one having a function of selectively transmitting cations and containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group. The structure or material is not particularly limited, and an appropriate one can be appropriately selected. The hydrocarbon-based polymer or fluorine-containing polymer having an ion-exchange group in the membrane body 10 can be obtained, for example, from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group precursor that can become an ion-exchange group by hydrolysis or the like. . Specifically, for example, a polymer containing a fluorinated hydrocarbon in the main chain, a group which can be converted into an ion-exchange group by hydrolysis, or the like (ion-exchange group precursor) as a pendant side chain and capable of being melt-processed (hereinafter referred to as a case may be referred to “Fluorine-containing polymer (a)”) After preparing the precursor of the membrane body 10, the precursor of the ion exchange group is converted into an ion exchange group, whereby the membrane body 10 can be obtained. The fluorine-containing polymer (a) can be copolymerized, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. Manufacturing. Moreover, it can also manufacture by homopolymerizing 1 type of monomer selected from any of the following 1st group, the following 2nd group, and the following 3rd group. Examples of the monomers of the first group include fluoroethylene compounds. Examples of the fluoroethylene compound include fluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether. Especially when an ion exchange membrane is used as a membrane for alkaline electrolysis, the fluoroethylene compound is preferably a perfluoro monomer, and is preferably selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Perfluoro monomer in the group. Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid-type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include CF.2 = CF (OCF2 CYF)s -O (CZF)t -COOR and other monomers (here, s represents an integer from 0 to 2, t represents an integer from 1 to 12, and Y and Z each independently represent F or CF3 R represents a lower alkyl group. Lower alkyl is, for example, an alkyl group having 1 to 3 carbon atoms. Of these, CF is preferred2 = CF (OCF2 CYF)n -O (CF2 )m -COOR. Here, n is an integer of 0 to 2, m is an integer of 1 to 4, and Y is F or CF.3 , R represents CH3 , C2 H5 , Or C3 H7 . When an ion-exchange membrane is used as a cation-exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. The alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms. As the monomer of the second group, among the above, the monomers described below are more preferred. CF2 = CFOCF2 -CF (CF3 OCF2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )2 COOCH3 , CF2 = CF [OCF2 -CF (CF3 )]2 O (CF2 )2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )3 COOCH3 , CF2 = CFO (CF2 )2 COOCH3 , CF2 = CFO (CF2 )3 COOCH3 . Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfonic acid-type ion exchange group (sulfonic acid group). As the vinyl compound having a functional group convertible to a sulfonic acid group, for example, CF is preferably used.2 = CFO-X-CF2 -SO2 A monomer represented by F (here, X represents perfluoroalkylene). Specific examples of these include the monomers shown below. CF2 = CFOCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, CF2 = CF (CF2 )2 SO2 F, CF2 = CFO [CF2 CF (CF3 ) O]2 CF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF2 OCF3 OCF2 CF2 SO2 F. Of these, CF is more preferred2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, and CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F. Copolymers obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of vinyl fluoride, especially a common polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, an inert solvent such as perfluorocarbon or chlorofluorocarbon can be used, in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, at a temperature of 0 to 200 ° C. Polymerization is carried out under a pressure of 0.1 to 20 MPa. In the above-mentioned copolymerization, the type and ratio of the combination of the above-mentioned monomers are not particularly limited, and are selected and determined according to the type and amount of functional groups to be imparted to the obtained fluorine-containing polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is produced, at least one monomer may be selected from the above-mentioned first group and the second group for copolymerization. When a fluorinated polymer containing only a sulfonic acid group is produced, at least one monomer may be selected from the monomers of the first group and the third group and copolymerized. Furthermore, when a fluorinated polymer having a carboxylic acid group and a sulfonic acid group is prepared, at least one monomer is selected from the monomers of the first group, the second group, and the third group and copolymerized. Just fine. In this case, the copolymer containing the first group and the second group and the copolymer containing the first group and the third group are separately polymerized, and then the target fluorine-containing polymerization can be obtained by mixing them. Thing. The mixing ratio of each monomer is not particularly limited. When the amount of functional groups per unit of polymer is increased, the ratio of the monomers selected from the second group and the third group may be increased. The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of the exchange group per unit weight of the dry resin, and can be measured by neutralization titration or the like. In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. The membrane body 10 having such a layer structure can further improve the selective permeability of cations such as sodium ions. When the ion exchange membrane 1 is arranged in the electrolytic cell, the sulfonic acid layer 3 is usually arranged on the anode side of the electrolytic cell and the carboxylic acid layer 2 is arranged on the cathode side of the electrolytic cell. The sulfonic acid layer 3 is preferably made of a material having a low electrical resistance, and from the viewpoint of film strength, it is preferable that its film thickness is thicker than that of the carboxylic acid layer 2. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, and more preferably 3 to 15 times. The carboxylic acid layer 2 is preferably one having high anion repellency even if the film thickness is thin. Here, the anion repellency refers to a property that prevents anion from penetrating into or passing through the ion exchange membrane 1. In order to improve anion repellency, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity in the sulfonic acid layer. As the fluorine-containing polymer used in the sulfonic acid layer 3, for example, CF is suitably used.2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 A polymer obtained by using F as a monomer of group 3. As the fluorine-containing polymer used in the carboxylic acid layer 2, for example, CF is suitably used.2 = CFOCF2 CF (CF2 ) O (CF2 )2 COOCH3 A polymer obtained as a monomer of Group 2. (Coating layer) The ion exchange membrane preferably has a coating layer on at least one side of the membrane body. As shown in FIG. 69, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively. The coating layer contains inorganic particles and a binder. The average particle diameter of the inorganic particles is more preferably 0.90 μm or more. When the average particle diameter of the inorganic particles is 0.90 μm or more, not only the durability against gas adhesion is greatly improved, but also the durability against impurities is greatly improved. That is, a particularly significant effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the value of the specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by pulverizing raw stones can be used. Inorganic particles obtained by pulverizing raw stones are preferably used suitably. The average particle diameter of the inorganic particles may be 2 μm or less. When the average particle diameter of the inorganic particles is 2 μm or less, the film can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm. Here, the average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation). The shape of the inorganic particles is preferably irregular. Resistance to impurities is further improved. The particle size distribution of the inorganic particles is preferably wide. The inorganic particles preferably contain at least one inorganic substance selected from the group consisting of an oxide of a Group IV element of the periodic table, a nitride of a group IV element of the periodic table, and a carbide of a group IV element of the periodic table. From the viewpoint of durability, zirconia particles are more preferred. The inorganic particles are preferably inorganic particles produced by pulverizing rough particles of the inorganic particles, or spherical particles having uniform particle diameters by melting and refining the rough particles of the inorganic particles as the inorganic particles. There are no particular restrictions on the method of crushing the rough stone, and examples thereof include a ball mill, a bead mill, a colloid mill, a cone mill, a disc mill, a roller mill, a powder mill, a hammer mill, a granulator, and a VSI mill Machines, Willy mills, roll mills, jet mills, etc. Moreover, it is preferable to wash it after crushing, and as a washing method at this time, acid treatment is preferred. This makes it possible to reduce impurities such as iron adhering to the surfaces of the inorganic particles. The coating layer preferably contains a binder. The binder is a component that holds inorganic particles on the surface of the ion exchange membrane and forms a coating layer. From the viewpoint of resistance to an electrolytic solution or an electrolytic product, the binder preferably contains a fluorine-containing polymer. As the binder, a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group is more preferred from the viewpoints of resistance to an electrolytic solution or a product of electrolysis and adhesion to the surface of an ion exchange membrane. When a coating layer is provided on a layer (sulfonic acid layer) containing a fluorinated polymer having a sulfonic acid group, it is more preferable to use a fluorine-containing type having a sulfonic acid group as a binding agent for the coating layer. polymer. When a coating layer is provided on a layer (carboxylic acid layer) containing a fluorinated polymer having a carboxylic acid group, it is more preferable to use a compound having a carboxylic acid group as a binder for the coating layer. Fluoropolymer. The content of the inorganic particles in the coating layer is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. The content of the binder is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass. The distribution density of the coating layer in the ion exchange membrane is preferably per 1 cm2 It is 0.05 ~ 2 mg. When the ion exchange membrane has a concave-convex shape on the surface, the distribution density of the coating layer is preferably 1 cm2 It is 0.5 to 2 mg. The method for forming the coating layer is not particularly limited, and a known method can be used. For example, a method of applying a coating liquid in which inorganic particles are dispersed in a solution containing a binder by spraying or the like can be cited. (Reinforced core material) The ion exchange membrane preferably has a reinforced core material disposed inside the membrane body. The reinforced core material is a member that strengthens the strength or dimensional stability of the ion exchange membrane. By disposing the reinforced core material inside the membrane body, the expansion and contraction of the ion exchange membrane can be controlled to a desired range, in particular. This ion-exchange membrane does not expand or contract more than necessary during electrolysis or the like, and can maintain excellent dimensional stability for a long period of time. The structure of the reinforcing core material is not particularly limited, and for example, a yarn called a reinforcing yarn may be formed by spinning. The so-called reinforcing yarn is a member constituting a reinforcing core material, and refers to a yarn capable of imparting required dimensional stability and mechanical strength to an ion exchange membrane and stably existing in the ion exchange membrane. By using a reinforced core material spun from this reinforcing yarn, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane. The material for reinforcing the core material and the reinforcing yarn used therefor is not particularly limited. It is preferably a material resistant to acids or alkalis. In terms of long-term heat resistance and chemical resistance, it is preferable to include Fiber of fluoropolymer. Examples of the fluorine-containing polymer used as the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). ), Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, from the viewpoint of heat resistance and chemical resistance, it is preferred to use a fiber containing polytetrafluoroethylene. The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The textile density (the number of weaves per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited. For example, a woven fabric, a non-woven fabric, a knitted fabric, or the like can be used, and a woven fabric form is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, and more preferably 30 to 150 μm. Woven or knitted fabrics can use monofilament, multifilament or any of these yarns, cut yarns, etc. The weaving method can use various weaving methods such as plain weaving, leno weaving, knitting, rib weaving, thin crepe weaving, etc. The spinning method and configuration of the reinforced core material in the membrane body are not particularly limited, and the appropriate size can be appropriately set in consideration of the size or shape of the ion exchange membrane, the physical properties required for the ion exchange membrane, and the use environment. For example, the reinforced core material may be arranged along a specific direction of the film body. From the viewpoint of dimensional stability, it is preferable to arrange the reinforced core material along a specific first direction, and along a second substantially perpendicular to the first direction. Orientation with other reinforced core materials. By arranging a plurality of reinforcing core materials in a substantially lined manner inside the longitudinal film body of the film body, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. For example, a configuration in which a reinforced core material (longitudinal yarn) arranged in the longitudinal direction and a reinforced core material (horizontal yarn) arranged in the horizontal direction is preferably woven into the surface of the film body. From the viewpoints of dimensional stability, mechanical strength, and ease of manufacture, it is more preferable to produce a plain weave fabric in which longitudinal and transverse yarns are alternately woven one by one, or twisted with two warp yarns and one side yarn. Interwoven leno weaves, twill weave woven by weaving the same number of cross yarns in every 2 or more parallel yarns. It is particularly preferable to arrange the reinforced core material in two directions of the MD direction (Machine Direction) and the TD direction (Transverse Direction) of the ion exchange membrane. That is, it is preferable to perform plain weaving in the MD direction and the TD direction. Here, the MD direction refers to a direction (traveling direction) in which the membrane body or various core materials (for example, a reinforced core material, a reinforced yarn, a sacrificial yarn described below, etc.) are transported in the manufacturing steps of the ion exchange membrane described below ), The TD direction refers to a direction substantially perpendicular to the MD direction. In addition, the yarn woven in the MD direction is referred to as an MD yarn, and the yarn woven in the TD direction is referred to as a TD yarn. Generally, the ion exchange membrane used in electrolysis is rectangular, and the length direction is MD direction and the width direction is TD direction. By weaving a reinforced core material as MD yarn and a reinforced core material as TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. The arrangement interval of the reinforced core material is not particularly limited, and an appropriate arrangement may be appropriately set in consideration of physical properties required for the ion exchange membrane and use environment. The opening ratio of the reinforced core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane. The so-called aperture ratio of the reinforced core material refers to the total area (B) of the surface through which any substance such as ions (the electrolyte and its cations (for example, sodium ions)) can pass through. Ratio (B / A). The total area (B) of the surface through which substances such as ions can pass may refer to the total area of areas in the ion exchange membrane that are not blocked by the reinforced core material or the like contained in the ion exchange membrane. FIG. 70 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 70 is an enlarged view of a part of the ion exchange membrane, and only the arrangement of the reinforced core materials 21 and 22 in the area is illustrated, and other components are omitted. The total area of the reinforced core material is subtracted from the area (A) of the area surrounded by the reinforced core material 21 arranged in the longitudinal direction and the reinforced core material 22 arranged in the horizontal direction, which also includes the area of the reinforced core material ( C). The total area (B) of the area (A) through which substances such as ions can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I). Opening ratio = (B) / (A) = ((A)-(C)) / (A)… (I) In the reinforced core material, it is particularly preferable from the viewpoint of chemical resistance and heat resistance The morphology is a tape-like yarn or high-alignment monofilament containing PTFE. Specifically, it is more preferable to use a reinforced core material which uses a band-shaped yarn obtained by cutting a high-strength porous sheet containing PTFE into a band shape, or 50 to 300 of a highly-oriented monofilament containing PTFE. Denim plain weave fabric with a textile density of 10 to 50 per inch, with a thickness in the range of 50 to 100 μm. The aperture ratio of the ion-exchange membrane containing the reinforced core material is more preferably 60% or more. Examples of the shape of the reinforcing yarn include round yarn and ribbon yarn. (Communication hole) The ion exchange membrane preferably has a communication hole inside the membrane body. The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, the so-called communication hole is a tubular hole formed inside the membrane body, and is formed by dissolving a sacrificial core material (or sacrificial yarn) described below. The shape or diameter of the communication hole can be controlled by selecting the shape or diameter of the sacrificial core material (sacrificial yarn). By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured during electrolysis. The shape of the communication hole is not particularly limited. According to the manufacturing method described below, the shape of the sacrificial core material used for forming the communication hole can be made. The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With this structure, in the portion where the communication hole is formed on the cathode side of the reinforced core material, ions (for example, sodium ions) transported through the electrolyte filled with the communication hole can also flow to the cathode side of the reinforced core material. As a result, since the flow of cations is not blocked, the resistance of the ion exchange membrane can be further reduced. The communication hole may be formed only in one specific direction of the membrane body constituting the ion exchange membrane. From the viewpoint of exhibiting more stable electrolytic performance, it is preferably formed in both the longitudinal direction and the lateral direction of the membrane body. [Manufacturing Method] As a suitable method for manufacturing the ion exchange membrane, a method having the following steps (1) to (6) can be mentioned. (1) Step: a step of producing a fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted to an ion-exchange group by hydrolysis. (2) Step: by weaving at least a plurality of reinforcing core materials and sacrificial yarns that have properties of dissolving in acid or alkali and forming communicating holes to obtain reinforcements of sacrificial yarns arranged between adjacent reinforcing core materials. Material steps. (3) Step: a step of membrane-forming the above-mentioned fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted into an ion-exchange group by hydrolysis. (4) Step: a step of burying the above-mentioned reinforcing material in the above-mentioned film to obtain a film body in which the above-mentioned reinforcing material is internally arranged as necessary. (5) Step: a step of hydrolyzing the membrane body obtained in step (4) (hydrolysis step). (6) Step: a step (coating step) of providing a coating layer on the film body obtained in step (5). Each step will be described in detail below. (1) Step: Step for producing fluoropolymer In step (1), a fluoropolymer is produced using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the monomers of the raw materials may be adjusted in the production of the fluorine-containing polymer forming each layer. (2) Step: Manufacturing steps of reinforcing material The so-called reinforcing material is a woven fabric of textile reinforcing yarn. A reinforcing core material is formed by embedding a reinforcing material in the film. When making an ion exchange membrane with communicating holes, sacrificial yarns are also woven into the reinforcing material together. In this case, the blending amount of the sacrificial yarn is preferably 10 to 80% by mass of the entire reinforcing material, and more preferably 30 to 70% by mass. By weaving the sacrificial yarn, the reinforcing core material can be prevented from being detached. Sacrificial yarns are soluble in the manufacturing steps of the film or in an electrolytic environment. Rhenium, polyethylene terephthalate (PET), cellulose, and polyamide can be used. In addition, polyvinyl alcohol having a thickness of 20 to 50 denier, monofilament or multifilament is also preferred. Furthermore, in step (2), the aperture ratio or the arrangement of the communication holes can be controlled by adjusting the configuration of the reinforced core material or the sacrificial yarn. (3) Step: Film formation step In the step (3), the fluorinated polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single-layer structure, as described above, a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or a multilayer structure of three or more layers. As a method of film formation, the following are mentioned, for example. A method of separately forming a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group into a membrane. A method for making a composite film from a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group by coextrusion. Moreover, the film may be plural. In addition, coextrusion of a heterogeneous film is preferred because it improves the bonding strength at the interface. (4) Step: the step of obtaining the film body In step (4), the reinforcing material obtained in step (2) is embedded in the inside of the film obtained in step (3) to obtain the reinforcing material inside. Membrane body. As a preferred method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) on the cathode side by a coextrusion method (hereinafter, The layer containing it is called the first layer) and a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonium fluoride functional group) (hereinafter, the layer containing it is referred to as a second layer). It is necessary to use a heating source and a vacuum source to separate the breathable and heat-resistant release paper, and sequentially laminate the reinforcing material and the second / first layer composite film on a flat plate or a drum with a large number of fine holes on the surface. At the melting temperature of each polymer, the method of integration is performed while removing the air between the layers by decompression; (ii) Different from the second / first layer composite film, the The fluorine-containing polymer (third layer) is separately formed into a film, and if necessary, a heating source and a vacuum source are used to separate the third layer film, the reinforced core material, Layer / first layer of composite film is sequentially laminated on a plate or drum with a large number of fine holes on the surface, Each of the polymer melt temperature, while removed under reduced pressure by the air between the layers while the integration method. Here, coextrusion of the first layer and the second layer helps to improve the bonding strength of the interface. In addition, the method of integrating under reduced pressure has a feature that the thickness of the third layer on the reinforcing material is larger than that of the pressure pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane body, it has a property capable of sufficiently maintaining the mechanical strength of the ion exchange membrane. In addition, the variation of the laminate described here is an example. The required layer structure or physical properties of the film body may be considered, and an appropriate laminate pattern (for example, a combination of layers) may be appropriately selected and then co-extruded. Furthermore, in order to further improve the electrical performance of the ion exchange membrane, a fluorine-containing polymer containing both a carboxylic acid group precursor and a sulfonic acid group precursor may be further interposed between the first layer and the second layer. Instead of the second layer, a fourth layer containing a fluorinated polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is used. The formation method of the fourth layer may be a method of separately manufacturing a fluorinated polymer having a carboxylic acid group precursor and a fluorinated polymer having a sulfonic acid group precursor and then mixing them. A method in which a monomer of a precursor is copolymerized with a monomer having a sulfonic acid group precursor. When the fourth layer is made into an ion-exchange membrane, the co-extruded film of the first layer and the fourth layer can be formed, and the third layer and the second layer can be separately formed into a membrane. The method described herein is laminated, and the three layers of the first layer / the fourth layer / the second layer can also be co-extruded to form a film. In this case, the direction of travel of the extruded film is the MD direction. As a result, a film body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material. Moreover, it is preferable that the ion exchange membrane has a protruding portion, that is, a protruding portion containing a fluorinated polymer having a sulfonic acid group on the surface side including the sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming a convex portion on the surface of a resin can be adopted. Specifically, the method of embossing the surface of a film main body is mentioned, for example. For example, when the composite film is integrated with a reinforcing material or the like, the convex portion can be formed by using a release paper that has been embossed in advance. When the convex portion is formed by embossing, the height of the convex portion or the arrangement density can be controlled by controlling the transferred embossed shape (shape of the release paper). (5) Hydrolysis step In step (5), a step of hydrolyzing the membrane body obtained in step (4) to convert an ion-exchange group precursor to an ion-exchange group (hydrolysis step) is performed. In step (5), a dissolution hole can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body by using an acid or an alkali. In addition, the sacrificial yarn may not be completely dissolved and removed, but may remain in the communication hole. In addition, the sacrificial yarn remaining in the communication hole can be removed by dissolving the electrolytic solution when the ion exchange membrane is supplied for electrolysis. Sacrificial yarns are those which are soluble in acids or alkalis in the manufacturing steps of ion exchange membranes or in an electrolytic environment. The sacrificial yarns are dissolved to form communication holes in this part. Step (5) can be carried out by immersing the film body obtained in step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (Dimethyl sulfoxide) can be used. The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35 mass% of DMSO. The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the thicker the apparent thickness. It is more preferably 75 to 100 ° C. The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes. Here, the step of forming the communication hole by dissolving the sacrificial yarn will be described in more detail. 71 (a) and (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane. In FIGS. 71 (a) and (b), only the reinforcing yarn 52, the sacrificial yarn 504a, and the communication hole 504 formed by the sacrificial yarn 504a are shown, and other members such as the film body are not shown. First, a knitting-reinforcing material is made from the reinforcing yarn 52 constituting the reinforcing core material in the ion-exchange membrane and the sacrificial yarn 504a used to form the communication hole 504 in the ion-exchange membrane. Then, in step (5), the communication hole 504 is formed by dissolving the sacrificial yarn 504a. According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a can be adjusted according to how the reinforcing core material and the communication hole are arranged in the membrane body of the ion exchange membrane, which is relatively simple. In FIG. 71 (a), the flat woven reinforcing material woven with the reinforcing yarn 52 and the sacrificial yarn 504a in the longitudinal and transverse directions on the paper surface is illustrated. The arrangement of the reinforcing yarn 52 and the sacrificial yarn 504a in the reinforcing material may be changed as required . (6) Coating step In step (6), a coating liquid containing inorganic particles obtained by pulverizing or melting the raw stone and a binder is prepared, and the coating liquid is applied to the ion exchange obtained in step (5). The surface of the film is dried to form a coating layer. As the binding agent, it is preferred that the fluorine-containing polymer having an ion-exchange group precursor is hydrolyzed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to ion-exchange. Substitute counter ion for H+ The resulting binding agent (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group). This makes it easy to dissolve in water or ethanol described below, and is therefore preferred. This binding agent was dissolved in a solution obtained by mixing water and ethanol. Furthermore, the preferred volume ratio of water to ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1 to 1: 2. The coating liquid was obtained by dispersing the inorganic particles in the dissolving liquid thus obtained by a ball mill. At this time, the average particle diameter of the particles and the like can also be adjusted by adjusting the time during dispersion and the rotation speed. Moreover, the preferable blending amount of the inorganic particles and the binder is as described above. The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, and it is preferable to make a thin coating liquid. Thereby, the surface of an ion exchange membrane can be apply | coated uniformly. When dispersing the inorganic particles, a surfactant may be added to the dispersion liquid. The surfactant is preferably a nonionic surfactant, and examples thereof include HS-210, NS-210, P-210, and E-212 manufactured by Nippon Oil Corporation. An ion exchange membrane can be obtained by applying the obtained coating solution to the surface of an ion exchange membrane by spray coating or roll coating. [Microporous membrane] The microporous membrane of this embodiment is not particularly limited as long as it can be laminated with an electrode for electrolysis as described above, and various microporous membranes can be applied. The porosity of the microporous membrane of this embodiment is not particularly limited, and it can be set to, for example, 20 to 90, and preferably 30 to 85. The porosity can be calculated by the following formula, for example. Porosity = (1-(film weight in dry state) / (weight calculated from the volume calculated from the thickness, width, and length of the film and the density of the film material)) × 100 average pore diameter of the microporous membrane of this embodiment It is not particularly limited, and may be, for example, 0.01 μm to 10 μ, and preferably 0.05 μm to 5 μm. The said average pore diameter cuts a film | membrane perpendicularly along a thickness direction, and observes a cut surface by FE-SEM, for example. The average pore diameter can be determined by measuring the diameter of the observed pores at about 100 points and obtaining an average value. The thickness of the microporous membrane in this embodiment is not particularly limited, and it can be set to, for example, 10 μm to 1,000 μm, and preferably 50 μm to 600 μm. The thickness can be measured, for example, using a micrometer (manufactured by Mitutoyo Co., Ltd.). As specific examples of the microporous membrane described above, there can be mentioned Zilfon Perl UTP 500 (also referred to as a Zilfon membrane in this embodiment) manufactured by Agfa, International Publication No. 2013-183584, and International Publication No. 2016-203701. No., etc. In this embodiment, the separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having an EW (ion exchange equivalent) different from the first ion exchange resin layer. The separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having a functional group different from the first ion exchange resin layer. The ion exchange equivalent can be adjusted by the introduced functional group, and the functional group that can be introduced is as described above. In this embodiment, the part of the laminated body 25 sandwiched between the anode gasket 12 and the cathode gasket 13 is preferably a non-conductive surface. Furthermore, the "current-carrying surface" corresponds to a portion designed to move the electrolyte between the anode chamber and the cathode chamber, and the "non-current-carrying surface" is a portion that does not belong to the current-carrying surface. Moreover, in this embodiment, the outermost peripheral edge of the laminated body may be located on the inner side of the current-carrying surface direction or on the outer side than the outermost peripheral edges of the anode-side gasket and the cathode-side gasket, and is preferably located on the outside. When configured in this manner, the outermost peripheral edge located on the outer side can be held, so there is a tendency that workability during assembly of the electrolytic cell is improved. Here, the outermost peripheral edge of the laminated body is the outermost peripheral edge in a state where a separator and an electrode for electrolysis are combined. That is, if the outermost peripheral edge of the electrode for electrolysis is outside the contact surface compared with the outermost peripheral edge of the separator, it means the outermost peripheral edge of the electrode for electrolysis, and if compared with the outermost peripheral edge of the separator, electrolysis If the outermost peripheral edge of the electrode is inside the contact surface, it means the outermost peripheral edge of the diaphragm. This positional relationship will be described with reference to FIGS. 72 and 73. FIGS. 72 and 73 show the positional relationship between the gasket and the laminated body in particular when two electrolytic cells are viewed from the α direction shown in FIG. 64B. In Figs. 72 and 73, a rectangular gasket A having an opening in the center is located closest to the front. A rectangular separator B is located on the back side, and a rectangular electrolytic electrode C is located on the back side. That is, the opening portion of the gasket A is a portion corresponding to the conductive surface of the laminated body. In FIG. 72, the outermost peripheral edge A1 of the gasket A is located on the inner side of the current-carrying surface than the outermost peripheral edge B1 of the separator B and the outermost peripheral edge C1 of the electrode C for electrolysis. Moreover, in FIG. 73, the outermost peripheral edge A1 of the gasket A is located more outward than the outermost peripheral edge C1 of the electrolytic electrode C, but the outermost peripheral edge B1 of the separator B and the outermost peripheral edge of the gasket A Compared to A1, it is located on the outer side of the current-carrying surface. In this embodiment, the laminated body may be sandwiched between the anode-side gasket and the cathode-side gasket, and the electrode for electrolysis itself may not be directly sandwiched by the anode-side gasket and the cathode-side gasket. That is, as long as the electrolytic electrode itself is fixed to the separator, only the separator may be directly sandwiched between the anode-side gasket and the cathode-side gasket. In this embodiment, from the viewpoint of more stably fixing the electrode for electrolysis in the electrolytic cell, it is preferable that both the electrode for electrolysis and the separator are sandwiched by the anode-side gasket and the cathode-side gasket. In this embodiment, the separator and the electrode for electrolysis are fixed at least by an anode gasket and a cathode gasket, and are in the form of a laminated body, but may have other fixing structures, for example, the fixing structures illustrated below may be adopted. Furthermore, each fixing structure may be used alone, or may be used in combination of two or more. In this embodiment, it is preferable that at least a part of the electrode for electrolysis passes through the separator and is fixed. This aspect will be described using FIG. 74A. In FIG. 74A, at least a part of the electrode 2 for electrolysis passes through the separator 3 and is fixed. An example in which the electrode 2 for electrolysis is a porous metal electrode is shown in FIG. 74A. That is, in FIG. 74A, the portions of the plurality of electrolysis electrodes 2 are shown independently, but the cross sections of the metal porous electrodes connected to each other and shown as a whole (the same applies to the following FIGS. 75 to 78). Under this kind of electrode structure, for example, if the diaphragm 3 at a specific position (which should be a fixed part) is pressed against the electrode 2 for electrolysis, a part of the diaphragm 3 enters into the uneven structure or hole on the surface of the electrode 2 for electrolysis. In the structure, the concave portion of the electrode surface or the convex portion around the hole penetrates the separator 3, and preferably penetrates to the outer surface 3b of the separator 3 as shown in FIG. 74A. As described above, the fixed structure of FIG. 74A can be manufactured by pressing the separator 3 against the electrode 2 for electrolysis. In this case, the pressure-bonding and heat suction are performed while the separator 3 is softened by heating. . Thereby, the electrode 2 for electrolysis penetrates the separator 3. Alternatively, it may be performed while the separator 3 is melted. In this case, it is preferable to suck the separator 3 from the outer surface 2b side (back surface side) of the electrode 2 for electrolysis in the state shown in FIG. 74B. The region where the separator 3 is pressed against the electrode 2 for electrolysis constitutes a "fixed portion". The fixed structure shown in FIG. 74A can be observed through a loupe, an optical microscope, or an electron microscope. In addition, by fixing the diaphragm 3 through the electrolytic electrode 2 and conducting inspection using a tester or the like between the outer surface 3b of the diaphragm 3 and the outer surface 2b of the electrolytic electrode 2, a fixed structure as shown in FIG. 74A can be inferred. In this embodiment, it is preferable that at least a part of the electrode for electrolysis in the fixing portion is located inside the separator and is fixed. This aspect will be described using FIG. 75A. As described above, the surface of the electrode 2 for electrolysis has a concave-convex structure or a hole structure. In the embodiment shown in FIG. 75A, a part of the electrode surface is inserted and fixed to the diaphragm 3 at a specific position (a position to be a fixed portion). The fixing structure shown in FIG. 75A can be manufactured by pressing the separator 3 against the electrode 2 for electrolysis. In this case, it is preferable to form the fixed structure shown in FIG. 75A by thermal compression bonding and thermal suction in a state where the diaphragm 3 is softened by heating. Alternatively, the diaphragm 3 may be melted to form the fixed structure shown in FIG. 75A. In this case, it is preferable to suck the separator 3 from the outer surface 2b side (back surface side) of the electrode 2 for electrolysis. The fixed structure shown in FIG. 75A can be observed by a loupe, an optical microscope, or an electron microscope. A method of making a section by a microtome and observing the sample is particularly preferred after the sample is embedded. Furthermore, in the fixed structure shown in FIG. 75A, since the electrolysis electrode 2 does not penetrate the separator 3, the continuity by the continuity check between the outer surface 3b of the separator 3 and the outer surface 2b of the electrolytic electrode 2 is not confirmed . In this embodiment, it is preferable that the laminated body further include a fixing member for fixing the separator and the electrode for electrolysis. This aspect will be described with reference to FIGS. 76A to 76C. The fixing structure shown in FIG. 76A is a structure in which a fixing member 7 different from the electrolytic electrode 2 and the separator 3 is used, and the fixing member 7 penetrates and fixes the electrolytic electrode 2 and the separator 3. The electrode 2 for electrolysis does not necessarily have to be penetrated by the fixing member 7 and may be fixed by the fixing member 7 so as not to be separated from the separator 2. The material of the fixing member 7 is not particularly limited. As the fixing member 7, for example, a metal or a resin can be used. In the case of a metal, nickel, nickel-chromium alloy, titanium, stainless steel (SUS), etc. can be mentioned. It may also be an oxide of these. As the resin, a fluororesin (for example, PTFE (polytetrafluoroethylene), PFA (copolymer of tetrafluoroethylene and perfluoroalkoxyethylene)), ETFE (copolymer of tetrafluoroethylene and ethylene), or the following Material of the diaphragm 3 described) or PVDF (polyvinylidene fluoride), EPDM (ethylene-propylene-diene rubber), PP (polyethylene), PE (polypropylene), nylon, aromatic polyamide, and the like. In this embodiment, for example, a yarn-shaped metal or resin is used, as shown in FIGS. 76B and 76C, at a specific position between the electrolytic electrode 2 and the outer surface 2b, 3b of the separator 3 (the position to be a fixed portion). It can also be fixed by sewing. Alternatively, the electrolysis electrode 2 and the separator 3 may be fixed using a fixing mechanism such as a fold-stitch sewing machine. The fixing structure shown in FIG. 77 is a structure in which an organic resin (adhesive layer) is fixed between the electrolytic electrode 2 and the separator 3. That is, in FIG. 77, the organic resin as the fixing member 7 is arranged at a specific position (a position to be a fixed portion) between the electrolytic electrode 2 and the separator 3, and is subsequently fixed. For example, an organic resin is applied to the inner surface 2a of the electrode 2 for electrolysis, the inner surface 3a of the separator 3, or both or one of the inner surfaces 2a, 3a of the electrode 2 for electrolysis and the separator 3. Then, the electrolytic electrode 2 and the separator 3 are bonded to each other, whereby a fixing structure shown in FIG. 77 can be formed. The material of the organic resin is not particularly limited. For example, a fluororesin (for example, PTFE, PFE (Polyfluoroethylene, Polyfluoroethylene), PFPE (Perfluoropolyether, perfluoropolyether)) can be used, or the same as the separator 3 described above. Resins of the same material. Also, commercially available fluorine-based adhesives, PTFE dispersions, and the like can be used as appropriate. Furthermore, general-purpose vinyl acetate-based adhesives, ethylene-vinyl acetate copolymerization-based adhesives, acrylic resin-based adhesives, α-olefin-based adhesives, styrene-butadiene rubber-based latex adhesives, Vinyl chloride resin adhesive, chloroprene adhesive, nitrile rubber adhesive, urethane rubber adhesive, epoxy adhesive, silicone resin adhesive, modified silicone Adhesives, epoxy-modified polysiloxane resin-based adhesives, silylated urethane resin-based adhesives, cyanoacrylate-based adhesives, and the like. In this embodiment, an organic resin that is soluble in the electrolytic solution or dissolved and decomposed in the electrolysis can be used. The organic resin dissolved in the electrolytic solution or dissolved and decomposed in the electrolysis is not limited to the following, and examples thereof include vinyl acetate-based adhesives, ethylene-vinyl acetate copolymerization-based adhesives, and acrylic resin-based adhesives. , Α-olefin-based adhesives, styrene butadiene rubber-based latex adhesives, vinyl chloride resin-based adhesives, chloroprene-based adhesives, nitrile rubber-based adhesives, urethane rubber-based adhesives, Epoxy-based adhesive, polysiloxane-based adhesive, modified polysiloxane-based adhesive, epoxy-modified polysiloxane-based adhesive, silylated urethane resin-based adhesive, cyano Acrylate-based adhesives and the like. The fixed structure shown in FIG. 77 can be observed with an optical microscope or an electron microscope. A method of making a section by a microtome and observing the sample is particularly preferred after the sample is embedded. In this embodiment, it is preferable that at least a part of the fixing member holds the separator and the electrode for electrolysis from the outside. This aspect will be described using FIG. 78A. The fixing structure shown in FIG. 78A is a structure that holds and fixes the electrolytic electrode 2 and the separator 3 from the outside. That is, the outer surface 2b of the electrode 2 for electrolysis and the outer surface 3b of the separator 3 are clamped and fixed by the holding member serving as the fixing member 7. The fixed structure shown in FIG. 78A also includes a state in which the holding member is sunk in the electrolytic electrode 2 or the separator 3. Examples of the holding member include an adhesive tape and a jig. In this embodiment, a holding member dissolved in an electrolytic solution may be used. Examples of the holding member dissolved in the electrolytic solution include PET tapes, jigs, PVA tapes, and jigs. The fixing structure shown in FIG. 78A is different from those in FIGS. 74 to 77, and is not a junction of the interface between the electrolytic electrode 2 and the separator 3, and the inner surfaces 2 a and 3 a of the electrolytic electrode 2 and the separator 3 are only in contact or facing each other. In the state, the fixed state of the electrolytic electrode 2 and the separator 3 can be released and separated by removing the holding member. Although not shown in FIG. 78A, the electrolytic electrode 2 and the separator 3 may be fixed to the electrolytic cell using a holding member. In the present embodiment, it is preferable that at least a part of the fixing member fixes the separator and the electrode for electrolysis by magnetic force. This aspect will be described using FIG. 78B. The fixing structure shown in FIG. 78B is a structure that holds and fixes the electrolytic electrode 2 and the separator 3 from the outside. The difference from FIG. 78A is that a pair of magnets is used as a holding member used as a fixing member. In the state of the fixed structure shown in FIG. 78B, after the laminated body 1 is installed in the electrolytic cell, the holding member can be left directly or removed from the laminated body 1 when the electrolytic cell is running. FIG. 78B is not shown, but the electrolytic electrode 2 and the separator 3 may be fixed to the electrolytic cell using a holding member. In addition, when a magnetic material adhering to a magnet is used as a part of the material of the electrolytic cell, one kind of holding material may be provided on the diaphragm surface side, and the electrolytic cell, the electrode for electrolysis 2 and the diaphragm 3 may be clamped and fixed. Furthermore, a plurality of series of fixed portions may be provided. In other words, 1, 2, 3,... N fixing portions may be arranged from the contour side of the laminated body 1 toward the inside. n is an integer of 1 or more. The m-th (m <n) fixing portion and the L-th (m <L ≦ n) fixing portion may be formed by different fixing patterns. The fixing portion formed on the current-carrying surface is preferably linearly symmetric. Thereby, there is a tendency that stress concentration can be suppressed. For example, if the two orthogonal directions are set to the X direction and the Y direction, one of the X direction and the Y direction may be arranged in each direction, or plural numbers may be arranged at equal intervals in the X direction and the Y direction. It forms a fixed part. The number of the fixed portions in the X direction and the Y direction is not limited, but it is preferable to set the number of the fixed portions in the X direction and the Y direction to 100 or less, respectively. From the viewpoint of ensuring the planarity of the current-carrying surface, the number of the fixed portions in the X direction and the Y direction is preferably 50 or less. In the fixing portion in this embodiment, when the fixing structure shown in FIG. 74A or FIG. 76 is provided, from the viewpoint of preventing a short circuit caused by the contact between the anode and the cathode, the film surface of the fixing portion is preferably Apply sealant. As the sealing material, for example, the materials described in the above adhesive can be used. The laminated body in this embodiment may have various fixing portions at various positions as described above, and it is preferable that such fixing portions exist on the non-conductive surface from the viewpoint of sufficiently ensuring the electrolytic performance. The laminated body in this embodiment may have various fixed portions at various positions as described above, but it is particularly preferable that the fixed electrode does not have a fixed portion (non-fixed portion), and the electrode for electrolysis satisfies the "bearing force" described above. That is, it is preferable that the force per unit mass and unit area in the non-fixed part of the electrode for electrolysis is less than 1.5 N / mg · cm.2 . In this embodiment, it is preferable that the separator is included in an ion exchange membrane containing an organic resin on the surface layer, and the electrode for electrolysis is fixed in the organic resin. As described above, the organic resin can be formed as a surface layer of an ion exchange membrane by various known methods. (Water Electrolysis) The electrolytic cell in the case of performing water electrolysis in this embodiment has a structure in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis described above is changed to a microporous membrane. In addition, the electrolyzer is different from the case where the salt electrolysis is performed in the point that the supplied raw material is water. Regarding other configurations, the electrolytic cell in the case of performing water electrolysis may also have the same configuration as the electrolytic cell in the case of performing salt electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. In the case of water electrolysis, only oxygen is generated in the anode chamber, so the same material as the cathode chamber can be used. Examples include nickel. The anode coating is preferably a catalyst coating for generating oxygen. Examples of the catalyst coating layer include metals, oxides, hydroxides, and the like of platinum group metals and transition metal groups. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used. (Manufacturing method of electrolytic cell and method of updating laminated body) The method of updating the laminated body in the electrolytic cell according to this embodiment includes: separating the laminated body from the anode-side gasket and the cathode-side gasket in this embodiment; A step of removing the laminated body from the electrolytic cell; and a step of clamping a new laminated body between the anode-side gasket and the cathode-side gasket. In addition, the "new laminated body" means a laminated body in this embodiment, and at least one of the electrode for electrolysis and the separator may be a new product. In the step of sandwiching the laminated body, from the viewpoint of more stably fixing the electrode for electrolysis in the electrolytic cell, it is preferable that both the electrode for electrolysis and the separator are clamped by the anode-side gasket and the cathode-side gasket. hold. In addition, the method for manufacturing an electrolytic cell according to this embodiment includes a step of sandwiching the laminated body in this embodiment between an anode-side gasket and a cathode-side gasket. Since the manufacturing method of the electrolytic cell and the method for updating the laminated body according to this embodiment are configured as described above, it is possible to improve the operation efficiency when the electrodes in the electrolytic cell are updated, and further, excellent electrolytic performance can be obtained after the update. In the step of sandwiching the laminated body, from the viewpoint of more stable fixing of the electrode for electrolysis in the electrolytic cell, it is also preferable that both the electrode for electrolysis and the separator are an anode-side gasket and a cathode-side gasket Holding. <Fifth Embodiment> Here, a fifth embodiment of the present invention will be described in detail with reference to FIGS. 91 to 102. [Manufacturing method of electrolytic cell] The manufacturing method of the electrolytic cell of the fifth embodiment (hereinafter referred to as "this embodiment" in the item of "Fifth Embodiment") is to provide an anode with A method for manufacturing a new electrolytic cell by arranging an electrolytic electrode or a laminated body of the electrolytic electrode and a new separator to an existing electrolytic cell facing a cathode and a separator disposed between the anode and the cathode, and using the electrode for electrolysis Or the wound body of the said laminated body. As described above, according to the manufacturing method of the electrolytic cell of this embodiment, since the electrode for electrolysis or a wound body of a laminated body of the electrolytic electrode and a new separator is used, it is possible to reduce the use of electrolysis when used as a component of an electrolytic cell. The size of the electrode or the laminated body can be transported after the size, which can improve the work efficiency when the electrode in the electrolytic cell is renewed. In this embodiment, an existing electrolytic cell includes an anode, a cathode facing the anode, and a separator disposed between the anode and the cathode as constituent members. In other words, it includes an electrolytic cell. The existing electrolytic cell is not particularly limited as long as it includes the aforementioned constituent members, and various known configurations can be applied. In this embodiment, the new electrolytic cell is a member that has an electrode or a laminate for electrolysis in addition to a member that already functions as an anode or a cathode in an existing electrolytic cell. That is, the "electrode for electrolysis" to be arranged when manufacturing a new electrolytic cell functions as an anode or a cathode, and is different from the cathode and the anode in the existing electrolytic cell. In this embodiment, even when the electrolytic performance of the anode and / or the cathode deteriorates with the operation of the existing electrolytic cell, the anode and / or the cathode can be renewed by disposing an electrode for electrolysis different from these. performance. In addition, in the case where a multilayer body is used in this embodiment, since a new ion exchange membrane is also provided, the performance of the ion exchange membrane accompanying the deterioration of the running performance can be updated at the same time. The "renewal performance" herein means a performance that is the same as or higher than the initial performance of an existing electrolytic cell before it is put into operation. In this embodiment, it is assumed that both the existing electrolytic cell is "an electrolytic cell already supplied for operation" and the new electrolytic cell is "an electrolytic cell that has not been supplied for operation". That is, if an electrolytic cell manufactured as a new electrolytic cell is supplied for one operation, it becomes "an existing electrolytic cell in this embodiment", and an electrode or a laminate formed by disposing the electrolytic cell in the existing electrolytic cell becomes " New electrolytic cell in this embodiment ". Hereinafter, an embodiment of an electrolytic cell will be described in detail using a case where salt electrolysis is performed using an ion exchange membrane as a separator. In addition, in the item of <5th Embodiment>, unless otherwise specified, the "electrolytic cell in this embodiment" includes "existing electrolytic cell in this embodiment" and "new electrolysis in this embodiment" Slot ". [Electrolytic cell] First, an electrolytic cell that can be used as a constituent unit of the electrolytic cell in this embodiment will be described. FIG. 91 is a sectional view of the electrolytic cell 1. FIG. The electrolytic cell 1 includes an anode chamber 10, a cathode chamber 20, a partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, an anode 11 provided in the anode chamber 10, and a cathode 21 provided in the cathode chamber 20. If necessary, a reverse current absorber 18 having a base material 18a and a reverse current absorbing layer 18b formed on the base material 18a and provided in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 provided in the cathode chamber 20, and a reverse current absorber 18 provided in the cathode chamber 20. The reverse current absorber 18 has a base material 18a and is formed on the cathode as shown in FIG. 95. The reverse current absorbing layer 18b on the substrate 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the current collector 23 and the cathode 21. The support 24 is provided between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via a metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be indirectly connected through a current collector, a support, a metal elastomer, or a partition wall. The entire surface of the cathode 21 is preferably covered with a catalyst layer for reduction reaction. In addition, the form of electrical connection may be to directly install the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22, and laminate the cathode 21 on the metal elastic body 22, respectively. The form. Examples of a method for directly mounting the respective constituent members to each other include welding and the like. The reverse current sink 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40. Fig. 92 is a sectional view of two adjacent electrolytic cells 1 in the electrolytic cell 4. FIG. 93 shows the electrolytic cell 4. Fig. 94 shows the steps for assembling the electrolytic cell 4. As shown in FIG. 92, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are sequentially arranged in series. An ion exchange membrane 2 is arranged between the anode chamber of one of the two electrolytic cells adjacent to the electrolytic cell and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are separated by the cation exchange membrane 2. As shown in FIG. 93, the electrolytic cell 4 includes a plurality of electrolytic cells 1 connected in series through a dielectric exchange membrane 2. That is, the electrolytic cell 4 is a bipolar electrolytic cell having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 94, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series through a dielectric exchange membrane 2 and connecting them with a press 5. The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. Among the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4, the anode 11 of the electrolytic cell 1 located at the extreme end is electrically connected to the anode terminal 7. The cathode 21 of the electrolytic cell at the end opposite to the anode terminal 7 of the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 to the cathode terminal 6 through the anode and cathode of each electrolytic cell 1. Furthermore, an electrolytic cell having only an anode chamber (anode terminal cell) and an electrolytic cell having only a cathode chamber (cathode terminal cell) may be disposed at both ends of the connected electrolytic cells 1. In this case, the anode terminal 7 is connected to an anode terminal cell disposed at one end thereof, and the cathode terminal 6 is connected to a cathode terminal cell disposed at the other end. When electrolysis of brine is performed, brine is supplied to each anode chamber 10 and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid system is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (omitted from the figure) through an electrolytic solution supply hose (omitted from the figure). In addition, the electrolytic solution and the products of electrolysis are recovered by an electrolytic solution recovery tube (omitted from the figure). During the electrolysis, the sodium ions in the brine start from the anode chamber 10 of an electrolytic cell 1 and pass through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Accordingly, the current in the electrolysis flows in a direction in which the electrolytic cells 1 are connected in series. That is, a current flows from the anode chamber 10 to the cathode chamber 20 through the cation exchange membrane 2. Along with the electrolysis of brine, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen are generated on the cathode 21 side. (Anode Chamber) The anode chamber 10 includes an anode 11 or an anode power source 11. The term “feeder” used herein refers to an electrode that is degraded (ie, an existing electrode) or an electrode that is not formed with a catalyst coating. When the electrode for electrolysis in this embodiment is inserted on the anode side, 11 functions as an anode power source. When the electrode for electrolysis in this embodiment is not inserted on the anode side, 11 functions as an anode. The anode chamber 10 preferably includes an anode-side electrolytic solution supply unit that supplies an electrolytic solution to the anode chamber 10, and a baffle plate that is disposed above the anode-side electrolytic solution supply unit and is disposed substantially parallel or inclined to the partition wall 30. And an anode-side gas-liquid separation portion disposed above the baffle and separating gas from an electrolyte mixed with the gas. (Anode) When the electrode for electrolysis in this embodiment is not inserted on the anode side, an anode 11 is provided in a frame (ie, an anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as a so-called DSA (registered trademark) can be used. The so-called DSA is an electrode with a titanium substrate covered with an oxide containing ruthenium, iridium, and titanium as components. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode Feeder) When the electrode for electrolysis in the present embodiment is inserted on the anode side, an anode feeder 11 is provided in the frame of the anode chamber 10. As the anode power source 11, a metal electrode such as a so-called DSA (registered trademark) may be used, or titanium without a catalyst coating layer may be used. Alternatively, a DSA having a thinner catalyst coating thickness may be used. Furthermore, a used anode can also be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode-side electrolytic solution supply unit) The anode-side electrolytic solution supply unit is a person that supplies an electrolytic solution to the anode chamber 10 and is connected to an electrolytic solution supply pipe. The anode-side electrolytic solution supply portion is preferably arranged below the anode chamber 10. As the anode-side electrolytic solution supply portion, for example, a tube (dispersion tube) having an opening formed on the surface can be used. The tube is more preferably arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies an electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is transported into the electrolytic cell 1 through the tube, and is supplied into the anode chamber 10 from an opening provided on the surface of the tube. Since the tube is arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell, the electrolyte can be uniformly supplied to the inside of the anode chamber 10, which is preferable. (Anode-side gas-liquid separation section) The anode-side gas-liquid separation section is preferably disposed above the baffle. In electrolysis, the anode-side gas-liquid separator has a function of separating a generated gas such as chlorine gas from the electrolytic solution. In addition, unless otherwise specified, the so-called upper means the upper direction in the electrolytic cell 1 of FIG. 91, and the lower means the lower direction of the electrolytic cell 1 in FIG. 91. During the electrolysis, if the generated gas generated in the electrolytic cell 1 and the electrolyte become mixed phase (gas-liquid mixed phase) and are discharged out of the system, there will be physical damage to the ion exchange membrane due to vibration caused by pressure fluctuations inside the electrolytic cell 1. Situation. In order to suppress this situation, it is preferable to provide an anode-side gas-liquid separation section in the electrolytic cell 1 in this embodiment to separate gas from liquid. It is preferable to provide a defoaming plate for eliminating bubbles in the anode-side gas-liquid separation section. The gas and liquid mixed phase flow can be separated into the electrolyte and the gas by breaking the bubbles when passing through the defoaming plate. As a result, vibration during electrolysis can be prevented. (Baffle) The baffle is preferably disposed above the anode-side electrolytic solution supply portion, and is disposed substantially parallel or inclined to the partition wall 30. The baffle is a partition that controls the flow of the electrolyte in the anode chamber 10. By providing the baffle, the electrolyte (brine, etc.) can be circulated inside the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle is preferably arranged to separate a space near the anode 11 from a space near the partition wall 30. From this viewpoint, the baffle is preferably provided so as to face the respective surfaces of the anode 11 and the partition wall 30. In the space near the anode separated by the baffle, by performing electrolysis, the concentration of the electrolyte (brine concentration) is reduced, and a gas such as chlorine gas is generated. As a result, a difference in gas-liquid specific gravity occurs between the space near the anode 11 separated by the baffle and the space near the partition wall 30. With this situation, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform. Although not shown in FIG. 91, a current collector may be separately provided inside the anode chamber 10. The current collector may be made of the same material or structure as the current collector of the cathode chamber described below. Moreover, in the anode chamber 10, the anode 11 itself can also be made to function as a current collector. (Partition Wall) The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes referred to as a spacer, and divides the anode chamber 10 and the cathode chamber 20. As the partition wall 30, those known as separators for electrolysis can be used, and examples thereof include partition walls in which a plate containing nickel is welded on the cathode side, and a plate containing titanium is welded on the anode side. (Cathode chamber) The cathode chamber 20 functions as a cathode power source when the electrode for electrolysis in this embodiment is inserted on the cathode side, and when the electrode for electrolysis in this embodiment is not inserted on the cathode side , 21 functions as a cathode. When there is a reverse current sink, the cathode or the cathode power source 21 is electrically connected to the reverse current sink system. The cathode chamber 20 preferably includes a cathode-side electrolytic solution supply unit and a cathode-side gas-liquid separation unit similarly to the anode chamber 10. It should be noted that, among the parts constituting the cathode chamber 20, the same descriptions as the parts constituting the anode chamber 10 are omitted. (Cathode) When the electrode for electrolysis in this embodiment is not inserted on the cathode side, a cathode 21 is provided in a frame (ie, a cathode frame) of the cathode chamber 20. The cathode 21 is preferably a catalyst layer having a nickel substrate and a coated nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include: Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. If necessary, a reduction treatment is performed on the cathode 21. In addition, as the base material of the cathode 21, nickel, a nickel alloy, or nickel-plated iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Cathode Feeder) When the electrode for electrolysis in this embodiment is inserted on the cathode side, a cathode feed member 21 is provided in the frame of the cathode chamber 20. The cathode feed body 21 may be covered with a catalyst component. This catalyst component can be used as a cathode and remain. Examples of the components of the catalyst layer include Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. In addition, nickel, a nickel alloy, and iron or stainless steel plated with nickel without a catalyst coating can be used. In addition, as a base material of the cathode power supply body 21, nickel, a nickel alloy, or nickel plating on iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Reverse current absorbing layer) As the material of the reverse current absorbing layer, a material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected. Examples include nickel and iron. (Current Collector) The cathode chamber 20 preferably includes a current collector 23. This improves the current collection effect. In this embodiment, the current collector 23 is preferably a porous plate, and is arranged so as to be substantially parallel to the surface of the cathode 21. The current collector 23 is preferably composed of a conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, an alloy, or a composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a mesh shape. (Metal Elastomer) By providing the metal elastomer 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, each anode 11 and each cathode The distance between 21 becomes shorter, and the voltage applied to the plurality of electrolytic cells 1 connected in series can be reduced. By reducing the voltage, power consumption can be reduced. In addition, when the metal elastic body 22 is provided, when the laminated body including the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the pressure of the metal elastic body 22 can stably maintain the electrode for electrolysis. At the starting position. As the metal elastic body 22, a spring member such as a coil spring or a coil, a cushioning pad, or the like can be used. As the metal elastic body 22, it is possible to use a suitable one in consideration of the stress against the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side or on the surface of the partition wall on the anode chamber 10 side. Generally, the two compartments are divided such that the cathode compartment 20 is smaller than the anode compartment 10. Therefore, in terms of the strength of the frame, it is preferable that the metal elastic body 22 is disposed between the current collector 23 and the cathode 21 of the cathode compartment 20. The metal elastic body 23 is preferably made of a conductive metal such as nickel, iron, copper, silver, or titanium. (Support) The cathode chamber 20 is preferably provided with a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently. The support 24 preferably contains a conductive metal such as nickel, iron, copper, silver, and titanium. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a mesh shape. The support 24 is, for example, a plate. The plurality of support bodies 24 are arranged between the partition wall 30 and the current collector 23. The plurality of support bodies 24 are arranged so that their respective faces are parallel to each other. The support 24 is disposed so as to be substantially perpendicular to the partition wall 30 and the current collector 23. (Anode-Side Gasket, Cathode-Side Gasket) The anode-side gasket is preferably arranged on the surface of the frame constituting the anode chamber 10. The cathode-side gasket is preferably disposed on a surface of a frame constituting the cathode chamber 20. The anode-side gasket provided in one electrolytic cell and the cathode-side gasket of an adjacent electrolytic cell are connected to each other by sandwiching the ion exchange membrane 2 (see FIG. 92). With these gaskets, when a plurality of electrolytic cells 1 are connected in series through the dielectric exchange membrane 2, airtightness can be imparted to the connection points. The so-called gasket is a seal between the ion exchange membrane and the electrolytic cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. The gasket is required to be resistant to corrosive electrolytes or generated gases, and can be used for a long time. Therefore, in terms of chemical resistance or hardness, generally, ethylene-propylene-diene rubber (EPDM rubber), ethylene-propylene rubber (EPM rubber) sulfide or peroxide crosslinked material can be used as a mat. sheet. In addition, if necessary, a gasket covering a region (liquid-contacting portion) in contact with the liquid may be coated with a fluorine resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). . These gaskets may have openings so as not to hinder the flow of the electrolytic solution, and their shapes are not particularly limited. For example, a frame-shaped gasket is attached to the periphery of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20 with an adhesive or the like. In addition, when, for example, two dielectric cells 1 are connected to the dielectric separator exchange membrane 2 (see FIG. 92), the dielectric separator exchange membrane 2 may fasten each electrolytic cell 1 to which a gasket is attached. This makes it possible to prevent the electrolytic solution, alkali metal hydroxide, chlorine gas, hydrogen gas, and the like from being leaked to the outside of the electrolytic cell 1. [Procedure for using wound body] The wound body in this embodiment may be a wound body of an electrode for electrolysis, or a wound body of a laminate of an electrode for electrolysis and a new separator. This rolled body is used in the manufacturing method of the electrolytic cell of this embodiment. As a specific example of the procedure of using the wound body, the method is not limited to the following, and the following methods can be cited. First, in an existing electrolytic cell, a fixed state of an adjacent electrolytic cell and an ion exchange membrane formed by a press is applied. After the release, a gap is formed between the electrolytic cell and the ion exchange membrane. Next, a person who releases the wound state of the wound body of the electrode for electrolysis is inserted into the gap, and the members are connected again by a press. Furthermore, when a wound body of a laminated body is used, for example, the following methods can be cited: after forming a gap between the electrolytic cell and the ion exchange membrane in the manner described above, removing the existing ion exchange membrane to be updated, Next, a person who has released the winding state of the wound body of the laminated body is inserted into the gap, and the members are connected again by a press. By this method, an electrode or a laminate for electrolysis can be arranged on the surface of an anode or a cathode in an existing electrolytic cell, and the performance of the ion exchange membrane, the anode, and / or the cathode can be updated. As described above, in the present embodiment, it is preferable that the step of using the wound body includes the step (B) of releasing the wound state of the wound body, and it is more preferable that the step of using the electrolysis after step (B) is performed. Step (C) of disposing an electrode or a laminate on the surface of at least one of an anode and a cathode. In the present embodiment, it is preferable that the step of using the wound body includes a step (A) of obtaining the wound body by maintaining the electrode for electrolysis or the laminated body in a wound state. In step (A), an electrode for electrolysis or a laminate can be wound to form a wound body, or an electrode for electrolysis or a laminate can be wound to a core to form a wound body. The core that can be used here is not particularly limited, and for example, a member having a substantially cylindrical shape and a size suitable for an electrode or a laminate for electrolysis can be used. [Electrode for Electrolysis] In this embodiment, the electrode for electrolysis is not particularly limited as long as it can be used as a wound body, that is, a person capable of being wound. The electrode for electrolysis may be one that functions as a cathode in an electrolytic cell, or one that functions as an anode. Regarding the material and shape of the electrode for electrolysis, the step of using the wound body or the configuration of the electrolytic cell in the present embodiment can be considered, and it is appropriately selected from the aspects of forming the wound body. Hereinafter, preferred aspects of the electrode for electrolysis in this embodiment will be described, but these are merely examples of preferred aspects for making a wound body, and other aspects than those described below may be appropriately adopted. Electrode for electrolysis. The electrode for electrolysis in this embodiment can obtain good operability, and has good adhesion to a separator such as an ion exchange membrane or a microporous membrane, and a power supply (a deteriorated electrode and an electrode without a catalyst coating layer). From the viewpoint of force, the force per unit mass and area is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ) Above, and more preferably 0.1 N / mg · cm2 Above, more preferably 0.14 N / (mg · cm2 )the above. From the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The above-mentioned bearing force can be set to the above range, for example, by appropriately adjusting a porosity, an electrode thickness, an arithmetic average surface roughness, and the like described below. More specifically, for example, if the opening ratio is increased, the bearing force tends to be small, and if the opening ratio is decreased, the bearing force tends to be large. In addition, from the viewpoint of obtaining good operability, it has good adhesion to separators such as ion-exchange membranes or microporous membranes, deteriorated electrodes, and feeders without a catalyst coating, and so on in terms of economy. From a viewpoint, the mass per unit area is preferably 48 mg / cm2 Below, more preferably 30 mg / cm2 Below, more preferably 20 mg / cm2 In the following, from the viewpoint of combining the operability, adhesiveness, and economy, 15 mg / cm is preferred.2 the following. The lower limit value is not particularly limited, for example, 1 mg / cm2 about. The above-mentioned mass per unit area can be set to the above range, for example, by appropriately adjusting the opening ratio and thickness of the electrode described below. More specifically, for example, if the thickness is the same, the mass per unit area tends to become smaller if the opening ratio is increased, and the mass per unit area tends to be larger if the opening ratio is decreased. . The withstand force can be measured by the following method (i) or (ii). Specifically, it is as described in the examples. As for the bearing capacity, the value obtained by the measurement of the method (i) (also referred to as "bearing capacity (1)") and the value obtained by the measurement of the method (ii) (also referred to as "bearing capacity (2) ) ") May be the same or different, but it is preferred that any value does not reach 1.5 N / mg · cm2 . [Method (i)] A nickel plate (thickness: 1.2 mm, 200 mm square) obtained by spraying with alumina of grain number 320 was laminated in order, and the perfluorocarbon polymer film with an ion exchange group was introduced. Ion-exchange membrane (170 mm square, details of the so-called ion-exchange membrane as described in the examples) and electrode samples (130 mm square) coated with inorganic particles and binders on both sides. After sufficient immersion, excess moisture adhering to the surface of the laminated body was removed to obtain a sample for measurement. In addition, the arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment is 0.5 to 0.8 μm. The specific calculation method of the arithmetic average surface roughness (Ra) is as described in the examples. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. This average value is divided by the area of the overlapped part of the electrode sample and the ion-exchange membrane and the mass of the electrode sample of the overlapped part of the ion-exchange membrane to calculate the force per unit mass and unit area (1) (N / mg · cm2 ). With the force (1) per unit mass and unit area obtained by method (i), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 ), More preferably 0.2 N / (mg ・ cm2 )the above. [Method (ii)] A nickel plate (thickness 1.2 mm, 200 mm square, the same nickel plate as in the above method (i)) and an electrode sample (130 mm square), and the laminated body is sufficiently immersed in pure water, and then excess water adhered to the surface of the laminated body is removed to obtain a sample for measurement. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate and the mass of the electrode sample in the overlapped portion of the nickel plate to calculate the adhesion force per unit mass and unit area (2) (N / mg · cm2 ). With the force (2) per unit mass and unit area obtained by method (ii), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. Furthermore, from the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 )the above. The electrode for electrolysis in this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, and good operability can be obtained. It can be used in contact with separators such as ion exchange membranes or microporous membranes, degraded electrodes (feeders), and non-formed The electrode (feeder) of the dielectric coating has good adhesion, can be wound into a roll shape and bent well, and it is easy to handle at a large size (for example, 1.5 m × 2.5 m). In particular, it is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and even more It is preferably 100 μm or less, and from the viewpoint of operability and economy, it is more preferably 50 μm or less. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and further, for a large size (for example, From the viewpoint of easy handling at a size of 1.5 m × 2.5 m), it is more preferably 95% or more. The upper limit is 100%. [Method (2)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 280 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesive force and being able to be wound into a roll shape and bent well, the ratio measured by the following method (3) is preferably 75% or more. It is preferably 80% or more, and from the viewpoint of ease of handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 90% or more. The upper limit is 100%. [Method (3)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 145 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesion and preventing gas retention during electrolysis, a porous structure is preferred, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80%, and more preferably 20 to 75%. The open porosity is the ratio of the perforated portion per unit volume. There are various calculation methods for the opening part according to the submicron order or only the openings that can be seen visually. In this embodiment, the volume V can be calculated from the values of the gauge thickness, width, and length of the electrode, and then the weight W can be measured to calculate the aperture ratio A using the following formula. A = (1- (W / (V × ρ)) × 100 ρ Density of electrode material (g / cm3 ). E.g. in the case of nickel 8.908 g / cm3 In the case of titanium is 4.506 g / cm3 . The adjustment of the opening rate can be appropriately adjusted by the following methods: if it is a punched metal, change the area of the punched metal per unit area; if it is a porous metal, change SW (short diameter), LW (long diameter), Feed value; if it is a wire mesh, change the wire diameter and mesh number of the metal fiber; if it is electroforming, change the pattern of the photoresist used; if it is a non-woven fabric, change the metal fiber diameter and fiber density; In the case of a foamed metal, a template or the like for forming a void is changed. Hereinafter, a more specific embodiment of the electrode for electrolysis in this embodiment will be described. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer is described below, and may include a plurality of layers or a single-layer structure. As shown in FIG. 96, the electrode 100 for electrolysis according to this embodiment includes an electrode base material 10 for electrolysis and a pair of first layers 20 covering one surface of the electrode base material 10 for electrolysis. The first layer 20 preferably covers the entire electrode base material 10 for electrolysis. As a result, the catalyst activity and durability of the electrode for electrolysis can be easily improved. Furthermore, the first layer 20 may be formed only on one surface area of the electrode base material 10 for electrolysis. As shown in FIG. 96, the surface of the first layer 20 may be covered by the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, the second layer 30 may be laminated on only one surface of the first layer 20. (Electrode base material for electrolysis) The electrode base material 10 for electrolysis is not particularly limited, and for example, nickel, nickel alloy, stainless steel, or a valve metal typified by titanium can be used, and it is preferably selected from nickel (Ni) And at least one element of titanium (Ti). When stainless steel is used in a high-concentration alkaline aqueous solution, considering the elution of iron and chromium, and the conductivity of stainless steel is about 1/10 of that of nickel, it is preferable to use a substrate containing nickel (Ni) as the base material. Electrode substrate for electrolysis. In addition, when the electrode base material 10 for electrolysis is used in a chlorine gas generating environment in a high-concentration saline solution, the material is preferably titanium with high corrosion resistance. The shape of the electrode substrate 10 for electrolysis is not particularly limited, and a suitable shape can be selected according to the purpose. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. Among them, punched metal or porous metal is preferred. In addition, the so-called electroforming is a technique for producing a precise patterned metal thin film by combining a photolithographic process and an electroplating method. It is a method for obtaining a metal thin film by forming a pattern on a substrate with a photoresist, and performing electroplating on a portion not protected by the photoresist. Regarding the shape of the electrode substrate for electrolysis, there are suitable specifications according to the distance between the anode and the cathode in the electrolytic cell. There is no particular limitation. When the anode and the cathode have a limited distance, porous metal and punched metal shapes can be used. In the case of a so-called zero-pitch electrolytic cell where the ion exchange membrane is connected to the electrode, a braided thin wire can be used. The finished woven mesh, metal mesh, foamed metal, metal non-woven fabric, porous metal, punched metal, metal porous foil, etc. Examples of the electrode base material 10 for electrolysis include a porous metal foil, a metal wire mesh, a metal nonwoven fabric, a punched metal, a porous metal, or a foamed metal. As a sheet material before being processed into a punched metal or a porous metal, a sheet material formed by rolling and an electrolytic foil are preferred. The electrolytic foil is preferably further subjected to a plating treatment using the same element as the base material as a post-treatment to form unevenness on one or both sides. As described above, the thickness of the electrode base material 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, even more preferably 155 μm or less, even more preferably 135 μm or less, and even more preferably 125. μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, and further more preferably 50 μm or less in terms of operability and economy. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the electrode base material for electrolysis, it is preferable to reduce the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing environment. In addition, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, it is preferable to use steel sand and alumina powder to form unevenness on the surface, and then increase the surface area by acid treatment. Alternatively, it is preferable to increase the surface area by applying a plating treatment to the same element as the substrate. In order to bring the first layer 20 into close contact with the surface of the electrode base material 10 for electrolysis, it is preferable that the surface area of the electrode base material 10 for electrolysis is increased. Examples of the treatment for increasing the surface area include blasting treatment using steel wire grain, steel sand, alumina sand, etc., acid treatment using sulfuric acid or hydrochloric acid, and plating treatment using the same element as the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm. Next, a case where the electrode for electrolysis in this embodiment is used as an anode for salt electrolysis will be described. (First layer) In FIG. 96, the first layer 20 as a catalyst layer contains at least one of ruthenium oxide, iridium oxide, and titanium oxide. Examples of the ruthenium oxide include RuO2 Wait. Examples of the iridium oxide include IrO2 Wait. Examples of the titanium oxide include TiO2 Wait. The first layer 20 is preferably two oxides containing ruthenium oxide and titanium oxide, or three oxides containing ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and further, the adhesion with the second layer 30 is further improved. In the case where the first layer 20 contains two oxides of ruthenium oxide and titanium oxide, the titanium oxide contained in the first layer 20 is better than 1 mol of the ruthenium oxide contained in the first layer 20 It is 1 to 9 moles, more preferably 1 to 4 moles. By setting the composition ratio of the two oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains three oxides of ruthenium oxide, iridium oxide, and titanium oxide, the iridium oxide contained in the first layer 20 is 1 mole relative to the ruthenium oxide contained in the first layer 20 The amount is preferably 0.2 to 3 moles, and more preferably 0.3 to 2.5 moles. In addition, the titanium oxide contained in the first layer 20 is preferably 0.3 to 8 moles, and more preferably 1 to 7 moles relative to 1 mole of the ruthenium oxide contained in the first layer 20. By setting the composition ratio of the three oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains at least two oxides selected from the group consisting of ruthenium oxide, iridium oxide, and titanium oxide, these oxides preferably form a solid solution. By forming an oxide solid solution, the electrode 100 for electrolysis exhibits excellent durability. In addition to the above composition, as long as it contains at least one of ruthenium oxide, iridium oxide, and titanium oxide, various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like called DSA (registered trademark) may be used as the first layer 20. The first layer 20 need not be a single layer, and may include a plurality of layers. For example, the first layer 20 may include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. (Second layer) The second layer 30 preferably contains ruthenium and titanium. This can further reduce the chlorine overvoltage immediately after electrolysis. The second layer 30 is preferably a palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. This can further reduce the chlorine overvoltage immediately after electrolysis. The thicker the second layer 30 is, the longer the time during which the electrolytic performance can be maintained. From the viewpoint of economy, the thickness is preferably 0.05 to 3 μm. Next, a case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis will be described. (First layer) The components of the first layer 20 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. In the case of containing at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal, a platinum group metal, a platinum group metal oxide, and a platinum group metal hydroxide are preferred. The alloy containing a platinum group metal contains at least one platinum group metal of platinum, palladium, rhodium, ruthenium, and iridium. The platinum group metal preferably contains platinum. The platinum group metal oxide is preferably a ruthenium oxide. The platinum group metal hydroxide is preferably a ruthenium hydroxide. The platinum group metal alloy is preferably an alloy containing platinum and nickel, iron, and cobalt. It is preferable to further contain an oxide or hydroxide of a lanthanoid as a second component as necessary. Accordingly, the electrode 100 for electrolysis exhibits excellent durability. The lanthanide oxide or hydroxide preferably contains at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, and praseodymium. It is preferable to further contain an oxide or hydroxide of a transition metal as a third component as necessary. By adding the third component, the electrode 100 for electrolysis can exhibit more excellent durability and reduce the electrolytic voltage. Examples of preferred combinations include ruthenium, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + osmium, ruthenium + rhenium + platinum, ruthenium + rhenium + Platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur , Ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + osmium, ruthenium + rhenium + manganese, ruthenium + 钐 + iron, ruthenium + rhenium + cobalt, ruthenium + 钐 + zinc, ruthenium + 钐+ Gallium, Ruthenium + 钐 + Sulfur, Ruthenium + 钐 + Lead, Ruthenium + 钐 + Ni, Pt + Ce, Pt + Pd + Ce, Pt + Pd + La + Ce, Pt + Ir, Pt + Pd, Pt + I + Palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, alloys of platinum and nickel, alloys of platinum and cobalt, alloys of platinum and iron, etc. When the platinum group metal, platinum group metal oxide, platinum group metal hydroxide, and platinum group metal-containing alloy are not contained, the main component of the catalyst is preferably nickel. Preferably, it contains at least one of nickel metal, oxide, and hydroxide. As a second component, a transition metal may be added. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon. Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, and the like. If necessary, an intermediate layer may be provided between the first layer 20 and the electrode base material 10 for electrolysis. By providing the intermediate layer, the durability of the electrode 100 for electrolysis can be improved. The intermediate layer is preferably one having an affinity for both the first layer 20 and the electrode base material 10 for electrolysis. The intermediate layer is preferably a nickel oxide, a platinum group metal, a platinum group metal oxide, or a platinum group metal hydroxide. The intermediate layer can be formed by coating and firing a solution containing the components forming the intermediate layer, or heat-treating the substrate at a temperature of 300 to 600 ° C in an air environment to form a surface oxide layer. . In addition, it can be formed by a known method such as a thermal spray method or an ion plating method. (Second layer) The components of the first layer 30 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. Examples of preferred combinations of the elements contained in the second layer include the combinations listed in the first layer. The combination of the first layer and the second layer may be a combination with the same composition but a different composition ratio, or a combination with a different composition. As the thickness of the catalyst layer, the thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 μm to 20 μm. When it is 0.01 μm or more, it can fully function as a catalyst. If it is 20 μm or less, it is less likely to fall off from the substrate, and a strong catalyst layer can be formed. More preferably, it is 0.05 μm to 15 μm. More preferably, it is 0.1 μm to 10 μm. It is more preferably 0.2 μm to 8 μm. The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer, is preferably 315 μm or less, more preferably 220 μm or less, and further preferably 170 μm in terms of the operability of the electrode. Below, still more preferably 150 μm or less, even more preferably 145 μm or less, even more preferably 140 μm or less, even more preferably 138 μm or less, and even more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. The thickness of the electrode can be determined by measuring with an electronic digital thickness gauge (Mitutoyo Co., Ltd., showing a minimum of 0.001 mm). The thickness of the electrode substrate for electrolysis was measured in the same manner as the electrode thickness. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness. In this embodiment, from the viewpoint of ensuring sufficient electrolytic performance, it is preferable that the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, and Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, At least one catalyst component in the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy. In this embodiment, if the electrode for electrolysis is an electrode with a wide elastic deformation area, better operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating is formed. From the viewpoint that the layered power supply has a better adhesion, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, still more preferably 170 μm or less, and even more preferably 150 μm. Hereinafter, it is particularly preferably 145 μm or less, more preferably 140 μm or less, even more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. In addition, in this embodiment, "the elastic deformation area is wide" means that the electrode for electrolysis is wound into a wound body, and warping caused by winding is unlikely to occur after the wound state is released. When the thickness of the electrode for electrolysis includes a catalyst layer described below, it means the thickness of the electrode substrate for electrolysis and the thickness of the catalyst layer. (Manufacturing method of the electrode for electrolysis) Next, one Embodiment of the manufacturing method of the electrode 100 for electrolysis is demonstrated in detail. In this embodiment, the first layer 20 is formed on the electrode substrate for electrolysis by using a method such as firing (thermal decomposition) of a coating film under an oxygen environment, or ion plating, plating, or thermal spraying. The second layer 30 is preferably used to produce the electrode 100 for electrolysis. Such a manufacturing method according to this embodiment can achieve high productivity of the electrode 100 for electrolysis. Specifically, a catalyst layer is formed on an electrode substrate for electrolysis by a coating step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. The term "thermal decomposition" means heating a metal salt that becomes a precursor to decompose it into a metal or a metal oxide and a gaseous substance. Decomposition products differ depending on the type of metal used, the type of salt, and the environment in which thermal decomposition is performed, but most metals tend to form oxides easily in an oxidizing environment. In the industrial manufacturing process of electrodes, thermal decomposition is usually performed in air, and in most cases, metal oxides or metal hydroxides are formed. (Formation of the first layer of the anode) (Coating step) The first layer 20 is a solution (first coating liquid) in which a salt of at least one metal among ruthenium, iridium, and titanium is dissolved, and is applied to an electrode base for electrolysis. It is obtained by thermal decomposition (baking) in the presence of oxygen. The contents of ruthenium, iridium, and titanium in the first coating liquid are approximately equal to those of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 100 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of the second layer) The second layer 30 is formed as necessary, for example, a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (a second coating solution) is applied to the first layer 20 It is obtained by thermal decomposition in the presence of oxygen. (Formation of the first layer of the cathode by thermal decomposition method) (Coating step) The first layer 20 is a solution (first coating solution) in which metal salts of various combinations are dissolved on the electrode substrate for electrolysis , Obtained by thermal decomposition (firing) in the presence of oxygen. The content ratio of the metal in the first coating liquid is substantially equal to that of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 10 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of Intermediate Layer) The intermediate layer is formed as necessary. For example, a solution (second coating solution) containing a palladium compound or a platinum compound is coated on a substrate, and then obtained by thermal decomposition in the presence of oxygen. Alternatively, instead of applying the solution, only the substrate is heated, thereby forming a nickel oxide intermediate layer on the surface of the substrate. (Formation of the first layer of the cathode using ion plating) The first layer 20 may also be formed by ion plating. As an example, the method of fixing a base material in a chamber and irradiating an electron beam with a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma environment is argon and oxygen. Ruthenium is deposited on the substrate in the form of ruthenium oxide. (Formation of the first layer using a plated cathode) The first layer 20 may also be formed by a plating method. As an example, if a substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed. (Formation of the first layer of the cathode using thermal spraying) The first layer 20 can also be formed by a thermal spraying method. As an example, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed by plasma-spraying nickel oxide particles onto a substrate. [Laminate] The electrode for electrolysis in this embodiment can be used as a laminate with a separator such as an ion exchange membrane or a microporous membrane. That is, the multilayer system in this embodiment includes an electrode for electrolysis and a new separator. The new separator is not particularly limited as long as it is different from the separator in the existing electrolytic cell, and various known separators can be applied. The new separator may be the same material, shape, and physical properties as the separator in the existing electrolytic cell. Hereinafter, an ion exchange membrane which is one aspect of the separator will be described in detail. [Ion exchange membrane] The ion exchange membrane is not particularly limited as long as it can be laminated with an electrode for electrolysis, and various ion exchange membranes can be applied. In this embodiment, an ion exchange membrane having a membrane body containing a hydrocarbon polymer or a fluorine-containing polymer having an ion exchange group and a coating layer provided on at least one side of the membrane body is preferably used. The coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is preferably 0.1 to 10 m.2 / g. The gas generated by the ion exchange membrane of this structure during electrolysis has less influence on the electrolytic performance, and tends to exhibit stable electrolytic performance. The above-mentioned membrane system of a perfluorocarbon polymer to which an ion exchange group is introduced is provided with an ion exchange group (as -SO3 - Sulfonic acid layer and sulfonic acid layer derived from a carboxyl group (with -CO2 - The group represented by this is any of the carboxylic acid layers (hereinafter also referred to as "carboxylic acid groups"). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforced core material. Hereinafter, the inorganic particles and the binder will be described in detail in the description of the coating layer. Fig. 97 is a schematic sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 includes a membrane body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and coating layers 11 a and 11 b formed on both sides of the membrane body 10. In the ion-exchange membrane 1, the membrane body 10 is provided with an ion-exchange group (as -SO3 - The sulfonic acid layer 3, which is also referred to as a "sulfonic acid group" hereinafter, and an ion-exchange group (with -CO2 - The carboxylic acid layer 2 shown below is also referred to as a "carboxylic acid group", and the strength and dimensional stability are strengthened by the reinforcing core material 4. Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it can be suitably used as a cation exchange membrane. The ion exchange membrane may include only one of a sulfonic acid layer and a carboxylic acid layer. The ion exchange membrane is not necessarily reinforced by a reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example shown in FIG. 97. (Membrane Body) First, the membrane body 10 constituting the ion exchange membrane 1 will be described. The membrane body 10 may be any one having a function of selectively transmitting cations and containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group. The structure or material is not particularly limited, and an appropriate one can be appropriately selected. The hydrocarbon-based polymer or fluorine-containing polymer having an ion-exchange group in the membrane body 10 can be obtained, for example, from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group precursor that can become an ion-exchange group by hydrolysis or the like. . Specifically, for example, a polymer containing a fluorinated hydrocarbon in the main chain, a group which can be converted into an ion-exchange group by hydrolysis, or the like (ion-exchange group precursor) as a pendant side chain and capable of being melt-processed (hereinafter referred to as a case may be referred to “Fluorine-containing polymer (a)”) After preparing the precursor of the membrane body 10, the precursor of the ion exchange group is converted into an ion exchange group, whereby the membrane body 10 can be obtained. The fluorine-containing polymer (a) can be copolymerized, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. Manufacturing. Moreover, it can also manufacture by homopolymerizing 1 type of monomer selected from any of the following 1st group, the following 2nd group, and the following 3rd group. Examples of the monomers of the first group include fluoroethylene compounds. Examples of the fluoroethylene compound include fluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether. Especially when an ion exchange membrane is used as a membrane for alkaline electrolysis, the fluoroethylene compound is preferably a perfluoro monomer, and is preferably selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Perfluoro monomer in the group. Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid-type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include CF.2 = CF (OCF2 CYF)s -O (CZF)t -COOR and other monomers (here, s represents an integer from 0 to 2, t represents an integer from 1 to 12, and Y and Z each independently represent F or CF3 R represents a lower alkyl group. Lower alkyl is, for example, an alkyl group having 1 to 3 carbon atoms. Of these, CF is preferred2 = CF (OCF2 CYF)n -O (CF2 )m -COOR. Here, n is an integer of 0 to 2, m is an integer of 1 to 4, and Y is F or CF.3 , R represents CH3 , C2 H5 , Or C3 H7 . When an ion-exchange membrane is used as a cation-exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. The alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms. As the monomer of the second group, among the above, the monomers described below are more preferred. CF2 = CFOCF2 -CF (CF3 OCF2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )2 COOCH3 , CF2 = CF [OCF2 -CF (CF3 )]2 O (CF2 )2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )3 COOCH3 , CF2 = CFO (CF2 )2 COOCH3 , CF2 = CFO (CF2 )3 COOCH3 . Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfonic acid-type ion exchange group (sulfonic acid group). As the vinyl compound having a functional group convertible to a sulfonic acid group, for example, CF is preferably used.2 = CFO-X-CF2 -SO2 A monomer represented by F (here, X represents perfluoroalkylene). Specific examples of these include the monomers shown below. CF2 = CFOCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, CF2 = CF (CF2 )2 SO2 F, CF2 = CFO [CF2 CF (CF3 ) O]2 CF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF2 OCF3 OCF2 CF2 SO2 F. Of these, CF is more preferred2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, and CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F. Copolymers obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of vinyl fluoride, especially a common polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, an inert solvent such as perfluorocarbon or chlorofluorocarbon can be used, in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, at a temperature of 0 to 200 ° C. Polymerization is carried out under a pressure of 0.1 to 20 MPa. In the above-mentioned copolymerization, the type and ratio of the combination of the above-mentioned monomers are not particularly limited, and are selected and determined according to the type and amount of functional groups to be imparted to the obtained fluorine-containing polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is produced, at least one monomer may be selected from the above-mentioned first group and the second group for copolymerization. When a fluorinated polymer containing only a sulfonic acid group is produced, at least one monomer may be selected from the monomers of the first group and the third group and copolymerized. Furthermore, when a fluorinated polymer having a carboxylic acid group and a sulfonic acid group is prepared, at least one monomer is selected from the monomers of the first group, the second group, and the third group and copolymerized. Just fine. In this case, the copolymer containing the first group and the second group and the copolymer containing the first group and the third group are separately polymerized, and then the target fluorine-containing polymerization can be obtained by mixing them. Thing. The mixing ratio of each monomer is not particularly limited. When the amount of functional groups per unit of polymer is increased, the ratio of the monomers selected from the second group and the third group may be increased. The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of the exchange group per unit weight of the dry resin, and can be measured by neutralization titration or the like. In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. The membrane body 10 having such a layer structure can further improve the selective permeability of cations such as sodium ions. When the ion exchange membrane 1 is arranged in the electrolytic cell, the sulfonic acid layer 3 is usually arranged on the anode side of the electrolytic cell and the carboxylic acid layer 2 is arranged on the cathode side of the electrolytic cell. The sulfonic acid layer 3 is preferably made of a material having a low electrical resistance, and from the viewpoint of film strength, it is preferable that its film thickness is thicker than that of the carboxylic acid layer 2. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, and more preferably 3 to 15 times. The carboxylic acid layer 2 is preferably one having high anion repellency even if the film thickness is thin. Here, the anion repellency refers to a property that prevents anion from penetrating into or passing through the ion exchange membrane 1. In order to improve anion repellency, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity in the sulfonic acid layer. As the fluorine-containing polymer used in the sulfonic acid layer 3, for example, CF is suitably used.2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 A polymer obtained by using F as a monomer of group 3. As the fluorine-containing polymer used in the carboxylic acid layer 2, for example, CF is suitably used.2 = CFOCF2 CF (CF2 ) O (CF2 )2 COOCH3 A polymer obtained as a monomer of Group 2. (Coating layer) The ion exchange membrane preferably has a coating layer on at least one side of the membrane body. As shown in FIG. 97, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively. The coating layer contains inorganic particles and a binder. The average particle diameter of the inorganic particles is more preferably 0.90 μm or more. When the average particle diameter of the inorganic particles is 0.90 μm or more, not only the durability against gas adhesion is greatly improved, but also the durability against impurities is greatly improved. That is, a particularly significant effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the value of the specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by pulverizing raw stones can be used. Inorganic particles obtained by pulverizing raw stones are preferably used suitably. The average particle diameter of the inorganic particles may be 2 μm or less. When the average particle diameter of the inorganic particles is 2 μm or less, the film can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm. Here, the average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation). The shape of the inorganic particles is preferably irregular. Resistance to impurities is further improved. The particle size distribution of the inorganic particles is preferably wide. The inorganic particles preferably contain at least one inorganic substance selected from the group consisting of an oxide of a Group IV element of the periodic table, a nitride of a group IV element of the periodic table, and a carbide of a group IV element of the periodic table. From the viewpoint of durability, zirconia particles are more preferred. The inorganic particles are preferably inorganic particles produced by pulverizing rough particles of the inorganic particles, or spherical particles having uniform particle diameters by melting and refining the rough particles of the inorganic particles as the inorganic particles. There are no particular restrictions on the method of crushing the rough stone, and examples thereof include a ball mill, a bead mill, a colloid mill, a cone mill, a disc mill, a roller mill, a powder mill, a hammer mill, a granulator, and a VSI mill Machines, Willy mills, roll mills, jet mills, etc. Moreover, it is preferable to wash it after crushing, and as a washing method at this time, acid treatment is preferred. This makes it possible to reduce impurities such as iron adhering to the surfaces of the inorganic particles. The coating layer preferably contains a binder. The binder is a component that holds inorganic particles on the surface of the ion exchange membrane and forms a coating layer. From the viewpoint of resistance to an electrolytic solution or an electrolytic product, the binder preferably contains a fluorine-containing polymer. As the binder, a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group is more preferred from the viewpoints of resistance to an electrolytic solution or a product of electrolysis and adhesion to the surface of an ion exchange membrane. When a coating layer is provided on a layer (sulfonic acid layer) containing a fluorinated polymer having a sulfonic acid group, it is more preferable to use a fluorine-containing type having a sulfonic acid group as a binding agent for the coating layer. polymer. When a coating layer is provided on a layer (carboxylic acid layer) containing a fluorinated polymer having a carboxylic acid group, it is more preferable to use a compound having a carboxylic acid group as a binder for the coating layer. Fluoropolymer. The content of the inorganic particles in the coating layer is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. The content of the binder is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass. The distribution density of the coating layer in the ion exchange membrane is preferably per 1 cm2 It is 0.05 ~ 2 mg. When the ion exchange membrane has a concave-convex shape on the surface, the distribution density of the coating layer is preferably 1 cm2 It is 0.5 to 2 mg. The method for forming the coating layer is not particularly limited, and a known method can be used. For example, a method of applying a coating liquid in which inorganic particles are dispersed in a solution containing a binder by spraying or the like can be cited. (Reinforced core material) The ion exchange membrane preferably has a reinforced core material disposed inside the membrane body. The reinforced core material is a member that strengthens the strength or dimensional stability of the ion exchange membrane. By disposing the reinforced core material inside the membrane body, the expansion and contraction of the ion exchange membrane can be controlled to a desired range, in particular. This ion-exchange membrane does not expand or contract more than necessary during electrolysis or the like, and can maintain excellent dimensional stability for a long period of time. The structure of the reinforcing core material is not particularly limited, and for example, a yarn called a reinforcing yarn may be formed by spinning. The so-called reinforcing yarn is a member constituting a reinforcing core material, and refers to a yarn capable of imparting required dimensional stability and mechanical strength to an ion exchange membrane and stably existing in the ion exchange membrane. By using a reinforced core material spun from this reinforcing yarn, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane. The material for reinforcing the core material and the reinforcing yarn used therefor is not particularly limited. It is preferably a material resistant to acids or alkalis. In terms of long-term heat resistance and chemical resistance, it is preferable to include Fiber of fluoropolymer. Examples of the fluorine-containing polymer used as the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). ), Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, from the viewpoint of heat resistance and chemical resistance, it is preferred to use a fiber containing polytetrafluoroethylene. The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The textile density (the number of weaves per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited. For example, a woven fabric, a non-woven fabric, a knitted fabric, or the like can be used, and a woven fabric form is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, and more preferably 30 to 150 μm. Woven or knitted fabrics can use monofilament, multifilament or any of these yarns, cut yarns, etc. The weaving method can use various weaving methods such as plain weaving, leno weaving, knitting, rib weaving, thin crepe weaving, etc. The spinning method and configuration of the reinforced core material in the membrane body are not particularly limited, and the appropriate size can be appropriately set in consideration of the size or shape of the ion exchange membrane, the physical properties required for the ion exchange membrane, and the use environment. For example, the reinforced core material may be arranged along a specific direction of the film body. From the viewpoint of dimensional stability, it is preferable to arrange the reinforced core material along a specific first direction, and along a second substantially perpendicular to the first direction. Orientation with other reinforced core materials. By arranging a plurality of reinforcing core materials in a substantially lined manner inside the longitudinal film body of the film body, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. For example, a configuration in which a reinforced core material (longitudinal yarn) arranged in the longitudinal direction and a reinforced core material (horizontal yarn) arranged in the horizontal direction is preferably woven into the surface of the film body. From the viewpoints of dimensional stability, mechanical strength, and ease of manufacture, it is more preferable to produce a plain weave fabric in which longitudinal and transverse yarns are alternately woven one by one, or twisted with two warp yarns and one side yarn. Interwoven leno weaves, twill weave woven by weaving the same number of cross yarns in every 2 or more parallel yarns. It is particularly preferable to arrange the reinforced core material in two directions of the MD direction (Machine Direction) and the TD direction (Transverse Direction) of the ion exchange membrane. That is, it is preferable to perform plain weaving in the MD direction and the TD direction. Here, the MD direction refers to a direction (traveling direction) in which the membrane body or various core materials (for example, a reinforced core material, a reinforced yarn, a sacrificial yarn described below, etc.) are transported in the manufacturing steps of the ion exchange membrane described below ), The TD direction refers to a direction substantially perpendicular to the MD direction. In addition, the yarn woven in the MD direction is referred to as an MD yarn, and the yarn woven in the TD direction is referred to as a TD yarn. Generally, the ion exchange membrane used in electrolysis is rectangular, and the length direction is MD direction and the width direction is TD direction. By weaving a reinforced core material as MD yarn and a reinforced core material as TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. The arrangement interval of the reinforced core material is not particularly limited, and an appropriate arrangement may be appropriately set in consideration of physical properties required for the ion exchange membrane and use environment. The opening ratio of the reinforced core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane. The so-called aperture ratio of the reinforced core material refers to the total area (B) of the surface through which any substance such as ions (the electrolyte and its cations (for example, sodium ions)) can pass through. Ratio (B / A). The total area (B) of the surface through which substances such as ions can pass may refer to the total area of areas in the ion exchange membrane that are not blocked by the reinforced core material or the like contained in the ion exchange membrane. Fig. 98 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 98 is an enlarged view of a part of the ion exchange membrane, and illustrates only the arrangement of the reinforced core materials 21 and 22 in the area, and other components are omitted. The total area of the reinforced core material is subtracted from the area (A) of the area surrounded by the reinforced core material 21 arranged in the longitudinal direction and the reinforced core material 22 arranged in the horizontal direction, which also includes the area of the reinforced core material ( C). The total area (B) of the area (A) through which substances such as ions can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I). Opening ratio = (B) / (A) = ((A)-(C)) / (A)… (I) In the reinforced core material, it is particularly preferable from the viewpoint of chemical resistance and heat resistance The morphology is a tape-like yarn or high-alignment monofilament containing PTFE. Specifically, it is more preferable to use a reinforced core material which uses a band-shaped yarn obtained by cutting a high-strength porous sheet containing PTFE into a band shape, or 50 to 300 of a highly-oriented monofilament containing PTFE. Denim plain weave fabric with a textile density of 10 to 50 per inch, with a thickness in the range of 50 to 100 μm. The aperture ratio of the ion-exchange membrane containing the reinforced core material is more preferably 60% or more. Examples of the shape of the reinforcing yarn include round yarn and ribbon yarn. (Communication hole) The ion exchange membrane preferably has a communication hole inside the membrane body. The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, the so-called communication hole is a tubular hole formed inside the membrane body, and is formed by dissolving a sacrificial core material (or sacrificial yarn) described below. The shape or diameter of the communication hole can be controlled by selecting the shape or diameter of the sacrificial core material (sacrificial yarn). By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured during electrolysis. The shape of the communication hole is not particularly limited. According to the manufacturing method described below, the shape of the sacrificial core material used for forming the communication hole can be made. The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With this structure, in the portion where the communication hole is formed on the cathode side of the reinforced core material, ions (for example, sodium ions) transported through the electrolyte filled with the communication hole can also flow to the cathode side of the reinforced core material. As a result, since the flow of cations is not blocked, the resistance of the ion exchange membrane can be further reduced. The communication hole may be formed only in one specific direction of the membrane body constituting the ion exchange membrane. From the viewpoint of exhibiting more stable electrolytic performance, it is preferably formed in both the longitudinal direction and the lateral direction of the membrane body. [Manufacturing Method] As a suitable method for manufacturing the ion exchange membrane, a method having the following steps (1) to (6) can be mentioned. (1) Step: a step of producing a fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted to an ion-exchange group by hydrolysis. (2) Step: by weaving at least a plurality of reinforcing core materials and sacrificial yarns that have properties of dissolving in acid or alkali and forming communicating holes to obtain reinforcements of sacrificial yarns arranged between adjacent reinforcing core materials. Material steps. (3) Step: a step of membrane-forming the above-mentioned fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted into an ion-exchange group by hydrolysis. (4) Step: a step of burying the above-mentioned reinforcing material in the above-mentioned film to obtain a film body in which the above-mentioned reinforcing material is internally arranged as necessary. (5) Step: a step of hydrolyzing the membrane body obtained in step (4) (hydrolysis step). (6) Step: a step (coating step) of providing a coating layer on the film body obtained in step (5). Each step will be described in detail below. (1) Step: Step for producing fluoropolymer In step (1), a fluoropolymer is produced using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the monomers of the raw materials may be adjusted in the production of the fluorine-containing polymer forming each layer. (2) Step: Manufacturing steps of reinforcing material The so-called reinforcing material is a woven fabric of textile reinforcing yarn. A reinforcing core material is formed by embedding a reinforcing material in the film. When making an ion exchange membrane with communicating holes, sacrificial yarns are also woven into the reinforcing material together. In this case, the blending amount of the sacrificial yarn is preferably 10 to 80% by mass of the entire reinforcing material, and more preferably 30 to 70% by mass. By weaving the sacrificial yarn, the reinforcing core material can be prevented from being detached. Sacrificial yarns are soluble in the manufacturing steps of the film or in an electrolytic environment. Rhenium, polyethylene terephthalate (PET), cellulose, and polyamide can be used. In addition, polyvinyl alcohol having a thickness of 20 to 50 denier, monofilament or multifilament is also preferred. Furthermore, in step (2), the aperture ratio or the arrangement of the communication holes can be controlled by adjusting the configuration of the reinforced core material or the sacrificial yarn. (3) Step: Film formation step In the step (3), the fluorinated polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single-layer structure, as described above, a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or a multilayer structure of three or more layers. As a method of film formation, the following are mentioned, for example. A method of separately forming a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group into a membrane. A method for making a composite film from a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group by coextrusion. Moreover, the film may be plural. In addition, coextrusion of a heterogeneous film is preferred because it improves the bonding strength at the interface. (4) Step: the step of obtaining the film body In step (4), the reinforcing material obtained in step (2) is embedded in the inside of the film obtained in step (3) to obtain the reinforcing material inside. Membrane body. As a preferred method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) on the cathode side by a coextrusion method (hereinafter, The layer containing it is called the first layer) and a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonium fluoride functional group) (hereinafter, the layer containing it is referred to as a second layer). It is necessary to use a heating source and a vacuum source to separate the breathable and heat-resistant release paper, and sequentially laminate the reinforcing material and the second / first layer composite film on a flat plate or a drum with a large number of fine holes on the surface. At the melting temperature of each polymer, the method of integration is performed while removing the air between the layers by decompression; (ii) Different from the second / first layer composite film, the The fluorine-containing polymer (third layer) is separately formed into a film, and if necessary, a heating source and a vacuum source are used to separate the third layer film, the reinforced core material, Layer / first layer of composite film is sequentially laminated on a plate or drum with a large number of fine holes on the surface, Each of the polymer melt temperature, while removed under reduced pressure by the air between the layers while the integration method. Here, coextrusion of the first layer and the second layer helps to improve the bonding strength of the interface. In addition, the method of integrating under reduced pressure has a feature that the thickness of the third layer on the reinforcing material is larger than that of the pressure pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane body, it has a property capable of sufficiently maintaining the mechanical strength of the ion exchange membrane. In addition, the variation of the laminate described here is an example. The required layer structure or physical properties of the film body may be considered, and an appropriate laminate pattern (for example, a combination of layers) may be appropriately selected and then co-extruded. Furthermore, in order to further improve the electrical performance of the ion exchange membrane, a fluorine-containing polymer containing both a carboxylic acid group precursor and a sulfonic acid group precursor may be further interposed between the first layer and the second layer. Instead of the second layer, a fourth layer containing a fluorinated polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is used. The formation method of the fourth layer may be a method of separately manufacturing a fluorinated polymer having a carboxylic acid group precursor and a fluorinated polymer having a sulfonic acid group precursor and then mixing them. A method in which a monomer of a precursor is copolymerized with a monomer having a sulfonic acid group precursor. When the fourth layer is made into an ion-exchange membrane, the co-extruded film of the first layer and the fourth layer can be formed, and the third layer and the second layer can be separately formed into a membrane. The method described herein is laminated, and the three layers of the first layer / the fourth layer / the second layer can also be co-extruded to form a film. In this case, the direction of travel of the extruded film is the MD direction. As a result, a film body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material. Moreover, it is preferable that the ion exchange membrane has a protruding portion, that is, a protruding portion containing a fluorinated polymer having a sulfonic acid group on the surface side including the sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming a convex portion on the surface of a resin can be adopted. Specifically, the method of embossing the surface of a film main body is mentioned, for example. For example, when the composite film is integrated with a reinforcing material or the like, the convex portion can be formed by using a release paper that has been embossed in advance. When the convex portion is formed by embossing, the height of the convex portion or the arrangement density can be controlled by controlling the transferred embossed shape (shape of the release paper). (5) Hydrolysis step In step (5), a step of hydrolyzing the membrane body obtained in step (4) to convert an ion-exchange group precursor to an ion-exchange group (hydrolysis step) is performed. In step (5), a dissolution hole can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body by using an acid or an alkali. In addition, the sacrificial yarn may not be completely dissolved and removed, but may remain in the communication hole. In addition, the sacrificial yarn remaining in the communication hole can be removed by dissolving the electrolytic solution when the ion exchange membrane is supplied for electrolysis. Sacrificial yarns are those which are soluble in acids or alkalis in the manufacturing steps of ion exchange membranes or in an electrolytic environment. The sacrificial yarns are dissolved to form communication holes in this part. Step (5) can be carried out by immersing the film body obtained in step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (Dimethyl sulfoxide) can be used. The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35 mass% of DMSO. The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the thicker the apparent thickness. It is more preferably 75 to 100 ° C. The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes. Here, the step of forming the communication hole by dissolving the sacrificial yarn will be described in more detail. Figs. 99 (a) and (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane. In FIGS. 99 (a) and (b), only the reinforcing yarn 52, the sacrificial yarn 504a, and the communication hole 504 formed by the sacrificial yarn 504a are shown, and other members such as the film body are not shown. First, a knitting-reinforcing material is made from the reinforcing yarn 52 constituting the reinforcing core material in the ion-exchange membrane and the sacrificial yarn 504a used to form the communication hole 504 in the ion-exchange membrane. Then, in step (5), the communication hole 504 is formed by dissolving the sacrificial yarn 504a. According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a can be adjusted according to how the reinforcing core material and the communication hole are arranged in the membrane body of the ion exchange membrane, which is relatively simple. In Fig. 99 (a), the plain woven reinforcing material woven with the reinforcing yarn 52 and the sacrificial yarn 504a in the longitudinal and transverse directions on the paper surface is exemplified. The configuration of the reinforcing yarn 52 and the sacrificial yarn 504a in the reinforcing material may be changed as necessary . (6) Coating step In step (6), a coating liquid containing inorganic particles obtained by pulverizing or melting the raw stone and a binder is prepared, and the coating liquid is applied to the ion exchange obtained in step (5). The surface of the film is dried to form a coating layer. As the binding agent, it is preferred that the fluorine-containing polymer having an ion-exchange group precursor is hydrolyzed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to ion-exchange. Substitute counter ion for H+ The resulting binding agent (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group). This makes it easy to dissolve in water or ethanol described below, and is therefore preferred. This binding agent was dissolved in a solution obtained by mixing water and ethanol. Furthermore, the preferred volume ratio of water to ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1 to 1: 2. The coating liquid was obtained by dispersing the inorganic particles in the dissolving liquid thus obtained by a ball mill. At this time, the average particle diameter of the particles and the like can also be adjusted by adjusting the time during dispersion and the rotation speed. Moreover, the preferable blending amount of the inorganic particles and the binder is as described above. The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, and it is preferable to make a thin coating liquid. Thereby, the surface of an ion exchange membrane can be apply | coated uniformly. When dispersing the inorganic particles, a surfactant may be added to the dispersion liquid. The surfactant is preferably a nonionic surfactant, and examples thereof include HS-210, NS-210, P-210, and E-212 manufactured by Nippon Oil Corporation. An ion exchange membrane can be obtained by applying the obtained coating solution to the surface of an ion exchange membrane by spray coating or roll coating. [Microporous membrane] The microporous membrane of this embodiment is not particularly limited as long as it can be laminated with an electrode for electrolysis as described above, and various microporous membranes can be applied. The porosity of the microporous membrane of this embodiment is not particularly limited, and it can be set to, for example, 20 to 90, and preferably 30 to 85. The porosity can be calculated by the following formula, for example. Porosity = (1-(film weight in dry state) / (weight calculated from the volume calculated from the thickness, width, and length of the film and the density of the film material)) × 100 average pore diameter of the microporous membrane of this embodiment It is not particularly limited, and may be, for example, 0.01 μm to 10 μ, and preferably 0.05 μm to 5 μm. The said average pore diameter cuts a film | membrane perpendicularly along a thickness direction, and observes a cut surface by FE-SEM, for example. The average pore diameter can be determined by measuring the diameter of the observed pores at about 100 points and obtaining an average value. The thickness of the microporous membrane in this embodiment is not particularly limited, and it can be set to, for example, 10 μm to 1,000 μm, and preferably 50 μm to 600 μm. The thickness can be measured, for example, using a micrometer (manufactured by Mitutoyo Co., Ltd.). As specific examples of the microporous membrane described above, there can be mentioned Zilfon Perl UTP 500 (also referred to as a Zilfon membrane in this embodiment) manufactured by Agfa, International Publication No. 2013-183584, and International Publication No. 2016-203701. No., etc. In this embodiment, the separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having an EW (ion exchange equivalent) different from the first ion exchange resin layer. The separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having a functional group different from the first ion exchange resin layer. The ion exchange equivalent can be adjusted by the introduced functional group, and the functional group that can be introduced is as described above. (Water Electrolysis) The electrolytic cell in the case of performing water electrolysis in this embodiment has a constitution in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis described above is changed to a microporous membrane. In addition, the electrolyzer is different from the case where the salt electrolysis is performed in the point that the supplied raw material is water. Regarding other configurations, the electrolytic cell in the case of performing water electrolysis may also have the same configuration as the electrolytic cell in the case of performing salt electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. In the case of water electrolysis, only oxygen is generated in the anode chamber, so the same material as the cathode chamber can be used. Examples include nickel. The anode coating is preferably a catalyst coating for generating oxygen. Examples of the catalyst coating layer include metals, oxides, hydroxides, and the like of platinum group metals and transition metal groups. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used. [Renewing method of electrode] The manufacturing method of the electrolytic cell of this embodiment can also be implemented as a method of updating the electrode (anode and / or cathode). That is, the method for updating an electrode of this embodiment is a method for updating an existing electrode by using an electrode for electrolysis, and using the wound body of the above electrode for electrolysis. As a specific example of the step of using the wound body, the method is not limited to the following, and a method of disposing the wound body of the wound body of the electrode for electrolysis on the surface of an existing electrode can be cited. By this method, the electrode for electrolysis can be arranged on the surface of an existing anode or cathode, and the performance of the anode and / or cathode can be updated. As described above, in the present embodiment, it is preferable that the step of using the wound body includes a step (B ') of releasing the wound state of the wound body, and it is more preferable that the step is after the step (B'). Step (C ') of disposing an electrode for electrolysis on the surface of an existing electrode. In the method for updating an electrode of this embodiment, it is preferable that the step of using the wound body includes a step (A ') of maintaining the electrode for electrolysis in a wound state to obtain the wound body. In step (A '), the electrode for electrolysis itself may be wound to form a wound body, or the electrode for electrolysis may be wound around a core to form a wound body. The core that can be used here is not particularly limited, and for example, a member having a substantially cylindrical shape and a size suitable for the electrode for electrolysis can be used. [Manufacturing method of rolled body] In the manufacturing method of the electrolytic cell of this embodiment and the method of updating the electrode of this embodiment, the step (A) or (A ') that can be implemented can also be used as the manufacturing method of the rolled body While implementing. That is, the manufacturing method of the rolled body of this embodiment is to manufacture a rolled body of an existing electrolytic cell including an anode, a cathode facing the anode, and a separator disposed between the anode and the cathode. The method further includes a step of winding the electrode for electrolysis or a laminate of the electrode for electrolysis and a new separator to obtain the wound body. In the step of obtaining the wound body, the electrode for electrolysis itself may be wound to form a wound body, or the electrode for electrolysis may be wound around a core to form a wound body. The core that can be used here is not particularly limited, and for example, a member having a substantially cylindrical shape and a size suitable for the electrode for electrolysis can be used. <Sixth Embodiment> Here, a sixth embodiment of the present invention will be described in detail with reference to FIGS. 103 to 111. [Manufacturing method of electrolytic cell] The manufacturing method of the electrolytic cell of the sixth embodiment (hereinafter referred to as "this embodiment" in the item of "Sixth Embodiment") is to provide an anode with A method for manufacturing a new electrolytic cell by disposing a laminate on an existing electrolytic cell facing a cathode and a separator disposed between the anode and the cathode, and having a method in which an electrode for electrolysis and a new separator are not melted in the separator. Step (A) of obtaining the above-mentioned laminated body by integrating at temperature; and step (B) of replacing the above-mentioned separator in the existing electrolytic cell with the above-mentioned laminated body after the above-mentioned step (A). As described above, according to the manufacturing method of the electrolytic cell of this embodiment, the electrode for electrolysis and the separator can be integrated without using an impractical method such as thermocompression bonding, so that the electrode refreshment in the electrolytic cell can be improved. Efficiency at the time. In this embodiment, an existing electrolytic cell includes an anode, a cathode facing the anode, and a separator disposed between the anode and the cathode as constituent members. In other words, it includes an electrolytic cell. The existing electrolytic cell is not particularly limited as long as it includes the aforementioned constituent members, and various known configurations can be applied. In this embodiment, the new electrolytic cell is a member that has an electrode or a laminate for electrolysis in addition to a member that already functions as an anode or a cathode in an existing electrolytic cell. That is, the "electrode for electrolysis" to be arranged when manufacturing a new electrolytic cell functions as an anode or a cathode, and is different from the cathode and the anode in the existing electrolytic cell. In this embodiment, even when the electrolytic performance of the anode and / or the cathode deteriorates with the operation of the existing electrolytic cell, the anode and / or the cathode can be renewed by disposing an electrode for electrolysis different from these. performance. Furthermore, since a new ion exchange membrane constituting the laminated body is also arranged together, the performance of the ion exchange membrane accompanying the deterioration of the running performance can also be updated at the same time. The "renewal performance" herein means a performance that is the same as or higher than the initial performance of an existing electrolytic cell before it is put into operation. In this embodiment, it is assumed that both the existing electrolytic cell is "an electrolytic cell already supplied for operation" and the new electrolytic cell is "an electrolytic cell that has not been supplied for operation". That is, if an electrolytic cell manufactured as a new electrolytic cell is supplied for one operation, it becomes "an existing electrolytic cell in this embodiment", and an electrode or a laminate formed by disposing the electrolytic cell in the existing electrolytic cell becomes " New electrolytic cell in this embodiment ". Hereinafter, an embodiment of an electrolytic cell will be described in detail using a case where salt electrolysis is performed using an ion exchange membrane as a separator. In addition, in the item of "Sixth Embodiment", unless otherwise specified, "the electrolytic cell in this embodiment" includes "existing electrolytic cell in this embodiment" and "new electrolysis in this embodiment" Slot ". [Electrolytic cell] First, an electrolytic cell that can be used as a constituent unit of the electrolytic cell in this embodiment will be described. Fig. 103 is a sectional view of the electrolytic cell 1. The electrolytic cell 1 includes an anode chamber 10, a cathode chamber 20, a partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, an anode 11 provided in the anode chamber 10, and a cathode 21 provided in the cathode chamber 20. If necessary, a reverse current absorber 18 having a base material 18a and a reverse current absorbing layer 18b formed on the base material 18a and provided in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 provided in the cathode chamber 20, and a reverse current absorber 18 provided in the cathode chamber 20. The reverse current absorber 18 has a base material 18a and is formed on the cathode as shown in FIG. 107. The reverse current absorbing layer 18b on the substrate 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the current collector 23 and the cathode 21. The support 24 is provided between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via a metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be indirectly connected through a current collector, a support, a metal elastomer, or a partition wall. The entire surface of the cathode 21 is preferably covered with a catalyst layer for reduction reaction. In addition, the form of electrical connection may be to directly install the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22, and laminate the cathode 21 on the metal elastic body 22, respectively. The form. Examples of a method for directly mounting the respective constituent members to each other include welding and the like. The reverse current sink 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40. FIG. 104 is a cross-sectional view of two adjacent electrolytic cells 1 in the electrolytic cell 4. FIG. 105 shows the electrolytic cell 4. Fig. 106 shows the steps for assembling the electrolytic cell 4. As shown in FIG. 104, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are sequentially arranged in series. An ion exchange membrane 2 is arranged between the anode chamber of one of the two electrolytic cells adjacent to the electrolytic cell and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are separated by the cation exchange membrane 2. As shown in FIG. 105, the electrolytic cell 4 includes a plurality of electrolytic cells 1 connected in series through a separator exchange membrane 2. That is, the electrolytic cell 4 is a bipolar electrolytic cell having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 106, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series through a separator exchange membrane 2 and connecting them with a press 5. The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. Among the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4, the anode 11 of the electrolytic cell 1 located at the extreme end is electrically connected to the anode terminal 7. The cathode 21 of the electrolytic cell at the end opposite to the anode terminal 7 of the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 to the cathode terminal 6 through the anode and cathode of each electrolytic cell 1. Furthermore, an electrolytic cell having only an anode chamber (anode terminal cell) and an electrolytic cell having only a cathode chamber (cathode terminal cell) may be disposed at both ends of the connected electrolytic cells 1. In this case, the anode terminal 7 is connected to an anode terminal cell disposed at one end thereof, and the cathode terminal 6 is connected to a cathode terminal cell disposed at the other end. When electrolysis of brine is performed, brine is supplied to each anode chamber 10 and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid system is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (omitted from the figure) through an electrolytic solution supply hose (omitted from the figure). In addition, the electrolytic solution and the products of electrolysis are recovered by an electrolytic solution recovery tube (omitted from the figure). During the electrolysis, the sodium ions in the brine start from the anode chamber 10 of an electrolytic cell 1 and pass through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Accordingly, the current in the electrolysis flows in a direction in which the electrolytic cells 1 are connected in series. That is, a current flows from the anode chamber 10 to the cathode chamber 20 through the cation exchange membrane 2. Along with the electrolysis of brine, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen are generated on the cathode 21 side. (Anode Chamber) The anode chamber 10 includes an anode 11 or an anode power source 11. The term “feeder” used herein refers to an electrode that is degraded (ie, an existing electrode) or an electrode that is not formed with a catalyst coating. When the electrode for electrolysis in this embodiment is inserted on the anode side, 11 functions as an anode power source. When the electrode for electrolysis in this embodiment is not inserted on the anode side, 11 functions as an anode. The anode chamber 10 preferably includes an anode-side electrolytic solution supply unit that supplies an electrolytic solution to the anode chamber 10, and a baffle plate that is disposed above the anode-side electrolytic solution supply unit and is disposed substantially parallel or inclined to the partition wall 30. And an anode-side gas-liquid separation portion disposed above the baffle and separating gas from an electrolyte mixed with the gas. (Anode) When the electrode for electrolysis in this embodiment is not inserted on the anode side, an anode 11 is provided in a frame (ie, an anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as a so-called DSA (registered trademark) can be used. The so-called DSA is an electrode with a titanium substrate covered with an oxide containing ruthenium, iridium, and titanium as components. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode Feeder) When the electrode for electrolysis in the present embodiment is inserted on the anode side, an anode feeder 11 is provided in the frame of the anode chamber 10. As the anode power source 11, a metal electrode such as a so-called DSA (registered trademark) may be used, or titanium without a catalyst coating layer may be used. Alternatively, a DSA having a thinner catalyst coating thickness may be used. Furthermore, a used anode can also be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode-side electrolytic solution supply unit) The anode-side electrolytic solution supply unit is a person that supplies an electrolytic solution to the anode chamber 10 and is connected to an electrolytic solution supply pipe. The anode-side electrolytic solution supply portion is preferably arranged below the anode chamber 10. As the anode-side electrolytic solution supply portion, for example, a tube (dispersion tube) having an opening formed on the surface can be used. The tube is more preferably arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies an electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is transported into the electrolytic cell 1 through the tube, and is supplied into the anode chamber 10 from an opening provided on the surface of the tube. Since the tube is arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell, the electrolyte can be uniformly supplied to the inside of the anode chamber 10, which is preferable. (Anode-side gas-liquid separation section) The anode-side gas-liquid separation section is preferably disposed above the baffle. In electrolysis, the anode-side gas-liquid separator has a function of separating a generated gas such as chlorine gas from the electrolytic solution. In addition, unless otherwise specified, the so-called upper means the upper direction in the electrolytic cell 1 of FIG. 103, and the lower means the lower direction of the electrolytic cell 1 in FIG. 103. During the electrolysis, if the generated gas generated in the electrolytic cell 1 and the electrolyte become mixed phase (gas-liquid mixed phase) and are discharged out of the system, there will be physical damage to the ion exchange membrane due to vibration caused by pressure fluctuations inside the electrolytic cell 1. Situation. In order to suppress this situation, it is preferable to provide an anode-side gas-liquid separation section in the electrolytic cell 1 in this embodiment to separate gas from liquid. It is preferable to provide a defoaming plate for eliminating bubbles in the anode-side gas-liquid separation section. The gas and liquid mixed phase flow can be separated into the electrolyte and the gas by breaking the bubbles when passing through the defoaming plate. As a result, vibration during electrolysis can be prevented. (Baffle) The baffle is preferably disposed above the anode-side electrolytic solution supply portion, and is disposed substantially parallel or inclined to the partition wall 30. The baffle is a partition that controls the flow of the electrolyte in the anode chamber 10. By providing the baffle, the electrolyte (brine, etc.) can be circulated inside the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle is preferably arranged to separate a space near the anode 11 from a space near the partition wall 30. From this viewpoint, the baffle is preferably provided so as to face the respective surfaces of the anode 11 and the partition wall 30. In the space near the anode separated by the baffle, by performing electrolysis, the concentration of the electrolyte (brine concentration) is reduced, and a gas such as chlorine gas is generated. As a result, a difference in gas-liquid specific gravity occurs between the space near the anode 11 separated by the baffle and the space near the partition wall 30. With this situation, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform. Although not shown in FIG. 103, a current collector may be separately provided inside the anode chamber 10. The current collector may be made of the same material or structure as the current collector of the cathode chamber described below. Moreover, in the anode chamber 10, the anode 11 itself can also be made to function as a current collector. (Partition Wall) The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes referred to as a spacer, and divides the anode chamber 10 and the cathode chamber 20. As the partition wall 30, those known as separators for electrolysis can be used, and examples thereof include partition walls in which a plate containing nickel is welded on the cathode side, and a plate containing titanium is welded on the anode side. (Cathode chamber) The cathode chamber 20 functions as a cathode power source when the electrode for electrolysis in this embodiment is inserted on the cathode side, and when the electrode for electrolysis in this embodiment is not inserted on the cathode side , 21 functions as a cathode. When there is a reverse current sink, the cathode or the cathode power source 21 is electrically connected to the reverse current sink system. The cathode chamber 20 preferably includes a cathode-side electrolytic solution supply unit and a cathode-side gas-liquid separation unit similarly to the anode chamber 10. It should be noted that, among the parts constituting the cathode chamber 20, the same descriptions as the parts constituting the anode chamber 10 are omitted. (Cathode) When the electrode for electrolysis in this embodiment is not inserted on the cathode side, a cathode 21 is provided in a frame (ie, a cathode frame) of the cathode chamber 20. The cathode 21 is preferably a catalyst layer having a nickel substrate and a coated nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include: Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. If necessary, a reduction treatment is performed on the cathode 21. In addition, as the base material of the cathode 21, nickel, a nickel alloy, or nickel-plated iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Cathode Feeder) When the electrode for electrolysis in this embodiment is inserted on the cathode side, a cathode feed member 21 is provided in the frame of the cathode chamber 20. The cathode feed body 21 may be covered with a catalyst component. This catalyst component can be used as a cathode and remain. Examples of the components of the catalyst layer include Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. In addition, nickel, a nickel alloy, and iron or stainless steel plated with nickel without a catalyst coating can be used. In addition, as a base material of the cathode power supply body 21, nickel, a nickel alloy, or nickel plating on iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Reverse current absorbing layer) As the material of the reverse current absorbing layer, a material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected. Examples include nickel and iron. (Current Collector) The cathode chamber 20 preferably includes a current collector 23. This improves the current collection effect. In this embodiment, the current collector 23 is preferably a porous plate, and is arranged so as to be substantially parallel to the surface of the cathode 21. The current collector 23 is preferably composed of a conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, an alloy, or a composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a mesh shape. (Metal Elastomer) By providing the metal elastomer 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, each anode 11 and each cathode The distance between 21 becomes shorter, and the voltage applied to the plurality of electrolytic cells 1 connected in series can be reduced. By reducing the voltage, power consumption can be reduced. In addition, when the metal elastic body 22 is provided, when the laminated body including the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the pressure of the metal elastic body 22 can stably maintain the electrode for electrolysis. At the starting position. As the metal elastic body 22, a spring member such as a coil spring or a coil, a cushioning pad, or the like can be used. As the metal elastic body 22, it is possible to use a suitable one in consideration of the stress against the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side or on the surface of the partition wall on the anode chamber 10 side. Generally, the two compartments are divided such that the cathode compartment 20 is smaller than the anode compartment 10. Therefore, in terms of the strength of the frame, it is preferable that the metal elastic body 22 is disposed between the current collector 23 and the cathode 21 of the cathode compartment 20. The metal elastic body 23 is preferably made of a conductive metal such as nickel, iron, copper, silver, or titanium. (Support) The cathode chamber 20 is preferably provided with a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently. The support 24 preferably contains a conductive metal such as nickel, iron, copper, silver, and titanium. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a mesh shape. The support 24 is, for example, a plate. The plurality of support bodies 24 are arranged between the partition wall 30 and the current collector 23. The plurality of support bodies 24 are arranged so that their respective faces are parallel to each other. The support 24 is disposed so as to be substantially perpendicular to the partition wall 30 and the current collector 23. (Anode-Side Gasket, Cathode-Side Gasket) The anode-side gasket is preferably arranged on the surface of the frame constituting the anode chamber 10. The cathode-side gasket is preferably disposed on a surface of a frame constituting the cathode chamber 20. The anode-side gasket provided in one electrolytic cell and the cathode-side gasket of an adjacent electrolytic cell are connected to each other by sandwiching the ion exchange membrane 2 (see FIG. 104). With these gaskets, when a plurality of electrolytic cells 1 are connected in series through the dielectric exchange membrane 2, airtightness can be imparted to the connection points. The so-called gasket is a seal between the ion exchange membrane and the electrolytic cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. The gasket is required to be resistant to corrosive electrolytes or generated gases, and can be used for a long time. Therefore, in terms of chemical resistance or hardness, generally, ethylene-propylene-diene rubber (EPDM rubber), ethylene-propylene rubber (EPM rubber) sulfide or peroxide crosslinked material can be used as a mat. sheet. In addition, if necessary, a gasket covering a region (liquid-contacting portion) in contact with the liquid may be coated with a fluorine resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). . These gaskets may have openings so as not to hinder the flow of the electrolytic solution, and their shapes are not particularly limited. For example, a frame-shaped gasket is attached to the periphery of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20 with an adhesive or the like. In addition, for example, when two dielectric cells 1 are connected to the dielectric separator exchange membrane 2 (see FIG. 104), the dielectric separator exchange membrane 2 may fasten each electrolytic cell 1 to which a gasket is attached. This makes it possible to prevent the electrolytic solution, alkali metal hydroxide, chlorine gas, hydrogen gas, and the like from being leaked to the outside of the electrolytic cell 1. [Laminate] The electrode for electrolysis in this embodiment is used as a laminate with a separator such as an ion exchange membrane or a microporous membrane. That is, the multilayer system in this embodiment includes an electrode for electrolysis and a new separator. The new separator is not particularly limited as long as it is different from the separator in the existing electrolytic cell, and various known separators can be applied. The new separator may be the same material, shape, and physical properties as the separator in the existing electrolytic cell. Specific examples of the electrode and the separator for electrolysis will be described in detail. (Step (A)) In step (A) in this embodiment, a laminate is obtained by integrating an electrode for electrolysis and a new separator at a temperature at which the separator does not melt. "The temperature at which the diaphragm does not melt" can be specified as the softening point of the new diaphragm. This temperature may vary depending on the material constituting the separator, and is preferably 0 to 100 ° C, more preferably 5 to 80 ° C, and even more preferably 10 to 50 ° C. The above integration is preferably performed under normal pressure. As a specific method of the integration, all methods other than a typical method of melting a separator such as thermocompression bonding can be used, and it is not particularly limited. As a preferred example, a method of integrating a liquid between an electrode for electrolysis and a separator and integrating the surface tension of the liquid described below can be cited. [Step (B)] In step (B) in this embodiment, after step (A), the separator in the existing electrolytic cell is exchanged with the laminate. The method of exchange is not particularly limited, and examples include the following methods. First, the fixed state of an adjacent electrolytic cell and an ion exchange membrane formed by a press in an existing electrolytic cell is released. A gap is formed between the ion exchange membrane and the existing ion exchange membrane, which is the object of the update. Then, the laminated body is inserted into the gap, and the members are connected again by a press. By this method, the laminated body can be arranged on the surface of the anode or the cathode in the existing electrolytic cell, and the performance of the ion exchange membrane, the anode, and / or the cathode can be updated. [Electrolysis Electrode] In this embodiment, the electrode for electrolysis is not particularly limited as long as it can be integrated with a new separator as described above, that is, it can be integrated. The electrode for electrolysis may be one that functions as a cathode in an electrolytic cell, or one that functions as an anode. Regarding the material, shape, and the like of the electrode for electrolysis, an appropriate one can be appropriately selected in consideration of the steps (A), (B), and the configuration of the electrolytic cell in the present embodiment. In the following, preferred aspects of the electrode for electrolysis in this embodiment will be described, but these are merely examples of preferred aspects for integration with the new diaphragm, and the aspects described below can also be appropriately adopted Electrolysis electrodes other than. The electrode for electrolysis in this embodiment can obtain good operability, and has good adhesion to a separator such as an ion exchange membrane or a microporous membrane, and a power supply (a deteriorated electrode and an electrode without a catalyst coating layer). From the viewpoint of force, the force per unit mass and area is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ) Above, and more preferably 0.1 N / mg · cm2 Above, more preferably 0.14 N / (mg · cm2 )the above. From the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The above-mentioned bearing force can be set to the above range, for example, by appropriately adjusting a porosity, an electrode thickness, an arithmetic average surface roughness, and the like described below. More specifically, for example, if the opening ratio is increased, the bearing force tends to be small, and if the opening ratio is decreased, the bearing force tends to be large. In addition, from the viewpoint of obtaining good operability, it has good adhesion to separators such as ion-exchange membranes or microporous membranes, deteriorated electrodes, and feeders without a catalyst coating, and so on in terms of economy. From a viewpoint, the mass per unit area is preferably 48 mg / cm2 Below, more preferably 30 mg / cm2 Below, more preferably 20 mg / cm2 In the following, from the viewpoint of combining the operability, adhesiveness, and economy, 15 mg / cm is preferred.2 the following. The lower limit value is not particularly limited, for example, 1 mg / cm2 about. The above-mentioned mass per unit area can be set to the above range, for example, by appropriately adjusting the opening ratio and thickness of the electrode described below. More specifically, for example, if the thickness is the same, the mass per unit area tends to become smaller if the opening ratio is increased, and the mass per unit area tends to be larger if the opening ratio is decreased. . The withstand force can be measured by the following method (i) or (ii). Specifically, it is as described in the examples. As for the bearing capacity, the value obtained by the measurement of the method (i) (also referred to as "bearing capacity (1)") and the value obtained by the measurement of the method (ii) (also referred to as "bearing capacity (2) ) ") May be the same or different, but it is preferred that any value does not reach 1.5 N / mg · cm2 . [Method (i)] A nickel plate (thickness: 1.2 mm, 200 mm square) obtained by spraying with alumina of grain number 320 was laminated in order, and the perfluorocarbon polymer film with an ion exchange group was introduced. Ion-exchange membrane (170 mm square, details of the so-called ion-exchange membrane as described in the examples) and electrode samples (130 mm square) coated with inorganic particles and binders on both sides. After sufficient immersion, excess moisture adhering to the surface of the laminated body was removed to obtain a sample for measurement. In addition, the arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment is 0.5 to 0.8 μm. The specific calculation method of the arithmetic average surface roughness (Ra) is as described in the examples. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. This average value is divided by the area of the overlapped part of the electrode sample and the ion-exchange membrane and the mass of the electrode sample of the overlapped part of the ion-exchange membrane to calculate the force per unit mass and unit area (1) (N / mg · cm2 ). With the force (1) per unit mass and unit area obtained by method (i), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 ), More preferably 0.2 N / (mg ・ cm2 )the above. [Method (ii)] A nickel plate (thickness 1.2 mm, 200 mm square, the same nickel plate as in the above method (i)) and an electrode sample (130 mm square), and the laminated body is sufficiently immersed in pure water, and then excess water adhered to the surface of the laminated body is removed to obtain a sample for measurement. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate and the mass of the electrode sample in the overlapped portion of the nickel plate to calculate the adhesion force per unit mass and unit area (2) (N / mg · cm2 ). With the force (2) per unit mass and unit area obtained by method (ii), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. Furthermore, from the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 )the above. The electrode for electrolysis in this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, and good operability can be obtained. It can be used in contact with separators such as ion exchange membranes or microporous membranes, degraded electrodes (feeders), and non-formed The electrode (feeder) of the dielectric coating has good adhesion, can be wound into a roll shape and bent well, and it is easy to handle at a large size (for example, 1.5 m × 2.5 m). In particular, it is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and even more It is preferably 100 μm or less, and from the viewpoint of operability and economy, it is more preferably 50 μm or less. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In this embodiment, it is preferable that a new separator is integrated with an electrode for electrolysis, and then a liquid is interposed therebetween. Any liquid can be used as long as the liquid has surface tension such as water or an organic solvent. The greater the surface tension of the liquid, the greater the force it will bear between the new separator and the electrode for electrolysis. Therefore, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the values in parentheses are the surface tension of the liquid at 20 ° C). Hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m), water (72.76 mN / m), if In the case of a liquid having a large surface tension, the new separator is integrated with the electrode for electrolysis (into a laminated body), and electrode replacement tends to become easier. The amount of liquid between the new diaphragm and the electrode for electrolysis is sufficient to be adhered to each other by surface tension. As a result, the amount of liquid is small. Therefore, even if the laminated body is installed in the electrolytic cell, it is mixed into the electrolytic solution. In the meantime, it will not affect the electrolysis itself. From a practical point of view, as the liquid, a liquid having a surface tension of 24 mN / m to 80 mN / m such as ethanol, ethylene glycol, and water is preferably used. Particularly preferred is water or a caustic soda, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, etc. dissolved in water to make an alkaline aqueous solution. Moreover, you may adjust surface tension by making these liquids contain a surfactant. By including a surfactant, the adhesion between the new separator and the electrode for electrolysis changes, and the operability can be adjusted. The surfactant is not particularly limited, and any of an ionic surfactant and a nonionic surfactant can be used. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and further, for a large size (for example, From the viewpoint of easy handling at a size of 1.5 m × 2.5 m), it is more preferably 95% or more. The upper limit is 100%. [Method (2)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 280 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesive force and being able to be wound into a roll shape and bent well, the ratio measured by the following method (3) is preferably 75% or more. It is preferably 80% or more, and from the viewpoint of ease of handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 90% or more. The upper limit is 100%. [Method (3)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 145 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesion and preventing gas retention during electrolysis, a porous structure is preferred, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80%, and more preferably 20 to 75%. The open porosity is the ratio of the perforated portion per unit volume. There are various calculation methods for the opening part according to the submicron order or only the openings that can be seen visually. In this embodiment, the volume V can be calculated from the values of the gauge thickness, width, and length of the electrode, and then the weight W can be measured to calculate the aperture ratio A using the following formula. A = (1- (W / (V × ρ)) × 100 ρ Density of electrode material (g / cm3 ). E.g. in the case of nickel 8.908 g / cm3 In the case of titanium is 4.506 g / cm3 . The adjustment of the opening rate can be appropriately adjusted by the following methods: if it is a punched metal, change the area of the punched metal per unit area; if it is a porous metal, change SW (short diameter), LW (long diameter), Feed value; if it is a wire mesh, change the wire diameter and mesh number of the metal fiber; if it is electroforming, change the pattern of the photoresist used; if it is a non-woven fabric, change the metal fiber diameter and fiber density; In the case of a foamed metal, a template or the like for forming a void is changed. Hereinafter, a more specific embodiment of the electrode for electrolysis in this embodiment will be described. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer is described below, and may include a plurality of layers or a single-layer structure. As shown in FIG. 108, the electrode 100 for electrolysis according to this embodiment includes an electrode base material 10 for electrolysis, and a first layer 20 covering one of both surfaces of the electrode base material 10 for electrolysis. The first layer 20 preferably covers the entire electrode base material 10 for electrolysis. As a result, the catalyst activity and durability of the electrode for electrolysis can be easily improved. Furthermore, the first layer 20 may be formed only on one surface area of the electrode base material 10 for electrolysis. As shown in FIG. 108, the surface of the first layer 20 may be covered by the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, the second layer 30 may be laminated on only one surface of the first layer 20. (Electrode base material for electrolysis) The electrode base material 10 for electrolysis is not particularly limited, and for example, nickel, nickel alloy, stainless steel, or a valve metal typified by titanium can be used, and it is preferably selected from nickel (Ni) And at least one element of titanium (Ti). When stainless steel is used in a high-concentration alkaline aqueous solution, considering the elution of iron and chromium, and the conductivity of stainless steel is about 1/10 of that of nickel, it is preferable to use a substrate containing nickel (Ni) as the base material. Electrode substrate for electrolysis. In addition, when the electrode base material 10 for electrolysis is used in a chlorine gas generating environment in a high-concentration saline solution, the material is preferably titanium with high corrosion resistance. The shape of the electrode substrate 10 for electrolysis is not particularly limited, and a suitable shape can be selected according to the purpose. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. Among them, punched metal or porous metal is preferred. In addition, the so-called electroforming is a technique for producing a precise patterned metal thin film by combining a photolithographic process and an electroplating method. It is a method for obtaining a metal thin film by forming a pattern on a substrate with a photoresist, and performing electroplating on a portion not protected by the photoresist. Regarding the shape of the electrode substrate for electrolysis, there are suitable specifications according to the distance between the anode and the cathode in the electrolytic cell. There is no particular limitation. When the anode and the cathode have a limited distance, porous metal and punched metal shapes can be used. In the case of a so-called zero-pitch electrolytic cell where the ion exchange membrane is connected to the electrode, a braided thin wire can be used. The finished woven mesh, metal mesh, foamed metal, metal non-woven fabric, porous metal, punched metal, metal porous foil, etc. Examples of the electrode base material 10 for electrolysis include a porous metal foil, a metal wire mesh, a metal nonwoven fabric, a punched metal, a porous metal, or a foamed metal. As a sheet material before being processed into a punched metal or a porous metal, a sheet material formed by rolling and an electrolytic foil are preferred. The electrolytic foil is preferably further subjected to a plating treatment using the same element as the base material as a post-treatment to form unevenness on one or both sides. As described above, the thickness of the electrode base material 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, even more preferably 155 μm or less, even more preferably 135 μm or less, and even more preferably 125. μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, and further more preferably 50 μm or less in terms of operability and economy. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the electrode base material for electrolysis, it is preferable to reduce the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing environment. In addition, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, it is preferable to use steel sand and alumina powder to form unevenness on the surface, and then increase the surface area by acid treatment. Alternatively, it is preferable to increase the surface area by applying a plating treatment to the same element as the substrate. In order to bring the first layer 20 into close contact with the surface of the electrode base material 10 for electrolysis, it is preferable that the surface area of the electrode base material 10 for electrolysis is increased. Examples of the treatment for increasing the surface area include blasting treatment using steel wire grain, steel sand, alumina sand, etc., acid treatment using sulfuric acid or hydrochloric acid, and plating treatment using the same element as the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm. Next, a case where the electrode for electrolysis in this embodiment is used as an anode for salt electrolysis will be described. (First layer) In FIG. 108, the first layer 20 as a catalyst layer contains at least one of ruthenium oxide, iridium oxide, and titanium oxide. Examples of the ruthenium oxide include RuO2 Wait. Examples of the iridium oxide include IrO2 Wait. Examples of the titanium oxide include TiO2 Wait. The first layer 20 is preferably two oxides containing ruthenium oxide and titanium oxide, or three oxides containing ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and further, the adhesion with the second layer 30 is further improved. In the case where the first layer 20 contains two oxides of ruthenium oxide and titanium oxide, the titanium oxide contained in the first layer 20 is better than 1 mol of the ruthenium oxide contained in the first layer 20 It is 1 to 9 moles, more preferably 1 to 4 moles. By setting the composition ratio of the two oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains three oxides of ruthenium oxide, iridium oxide, and titanium oxide, the iridium oxide contained in the first layer 20 is 1 mole relative to the ruthenium oxide contained in the first layer 20 The amount is preferably 0.2 to 3 moles, and more preferably 0.3 to 2.5 moles. In addition, the titanium oxide contained in the first layer 20 is preferably 0.3 to 8 moles, and more preferably 1 to 7 moles relative to 1 mole of the ruthenium oxide contained in the first layer 20. By setting the composition ratio of the three oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains at least two oxides selected from the group consisting of ruthenium oxide, iridium oxide, and titanium oxide, these oxides preferably form a solid solution. By forming an oxide solid solution, the electrode 100 for electrolysis exhibits excellent durability. In addition to the above composition, as long as it contains at least one of ruthenium oxide, iridium oxide, and titanium oxide, various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like called DSA (registered trademark) may be used as the first layer 20. The first layer 20 need not be a single layer, and may include a plurality of layers. For example, the first layer 20 may include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. (Second layer) The second layer 30 preferably contains ruthenium and titanium. This can further reduce the chlorine overvoltage immediately after electrolysis. The second layer 30 is preferably a palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. This can further reduce the chlorine overvoltage immediately after electrolysis. The thicker the second layer 30 is, the longer the time during which the electrolytic performance can be maintained. From the viewpoint of economy, the thickness is preferably 0.05 to 3 μm. Next, a case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis will be described. (First layer) The components of the first layer 20 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. In the case of containing at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal, a platinum group metal, a platinum group metal oxide, and a platinum group metal hydroxide are preferred. The alloy containing a platinum group metal contains at least one platinum group metal of platinum, palladium, rhodium, ruthenium, and iridium. The platinum group metal preferably contains platinum. The platinum group metal oxide is preferably a ruthenium oxide. The platinum group metal hydroxide is preferably a ruthenium hydroxide. The platinum group metal alloy is preferably an alloy containing platinum and nickel, iron, and cobalt. It is preferable to further contain an oxide or hydroxide of a lanthanoid as a second component as necessary. Accordingly, the electrode 100 for electrolysis exhibits excellent durability. The lanthanide oxide or hydroxide preferably contains at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, and praseodymium. It is preferable to further contain an oxide or hydroxide of a transition metal as a third component as necessary. By adding the third component, the electrode 100 for electrolysis can exhibit more excellent durability and reduce the electrolytic voltage. Examples of preferred combinations include ruthenium, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + osmium, ruthenium + rhenium + platinum, ruthenium + rhenium + Platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur , Ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + osmium, ruthenium + rhenium + manganese, ruthenium + 钐 + iron, ruthenium + rhenium + cobalt, ruthenium + 钐 + zinc, ruthenium + 钐+ Gallium, Ruthenium + 钐 + Sulfur, Ruthenium + 钐 + Lead, Ruthenium + 钐 + Ni, Pt + Ce, Pt + Pd + Ce, Pt + Pd + La + Ce, Pt + Ir, Pt + Pd, Pt + I + Palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, alloys of platinum and nickel, alloys of platinum and cobalt, alloys of platinum and iron, etc. When the platinum group metal, platinum group metal oxide, platinum group metal hydroxide, and platinum group metal-containing alloy are not contained, the main component of the catalyst is preferably nickel. Preferably, it contains at least one of nickel metal, oxide, and hydroxide. As a second component, a transition metal may be added. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon. Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, and the like. If necessary, an intermediate layer may be provided between the first layer 20 and the electrode base material 10 for electrolysis. By providing the intermediate layer, the durability of the electrode 100 for electrolysis can be improved. The intermediate layer is preferably one having an affinity for both the first layer 20 and the electrode base material 10 for electrolysis. The intermediate layer is preferably a nickel oxide, a platinum group metal, a platinum group metal oxide, or a platinum group metal hydroxide. The intermediate layer can be formed by coating and firing a solution containing the components forming the intermediate layer, or heat-treating the substrate at a temperature of 300 to 600 ° C in an air environment to form a surface oxide layer. . In addition, it can be formed by a known method such as a thermal spray method or an ion plating method. (Second layer) The components of the first layer 30 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. Examples of preferred combinations of the elements contained in the second layer include the combinations listed in the first layer. The combination of the first layer and the second layer may be a combination with the same composition but a different composition ratio, or a combination with a different composition. As the thickness of the catalyst layer, the thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 μm to 20 μm. When it is 0.01 μm or more, it can fully function as a catalyst. If it is 20 μm or less, it is less likely to fall off from the substrate, and a strong catalyst layer can be formed. More preferably, it is 0.05 μm to 15 μm. More preferably, it is 0.1 μm to 10 μm. It is more preferably 0.2 μm to 8 μm. The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer, is preferably 315 μm or less, more preferably 220 μm or less, and further preferably 170 μm in terms of the operability of the electrode. Below, still more preferably 150 μm or less, even more preferably 145 μm or less, even more preferably 140 μm or less, even more preferably 138 μm or less, and even more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. The thickness of the electrode can be determined by measuring with an electronic digital thickness gauge (Mitutoyo Co., Ltd., showing a minimum of 0.001 mm). The thickness of the electrode substrate for electrolysis was measured in the same manner as the electrode thickness. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness. In this embodiment, from the viewpoint of ensuring sufficient electrolytic performance, it is preferable that the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, and Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, At least one catalyst component in the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy. In this embodiment, if the electrode for electrolysis is an electrode with a wide elastic deformation area, better operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating is formed. From the viewpoint that the layered power supply has a better adhesion, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, still more preferably 170 μm or less, and even more preferably 150 μm. Hereinafter, it is particularly preferably 145 μm or less, more preferably 140 μm or less, even more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. In addition, in this embodiment, "the elastic deformation area is wide" means that the electrode for electrolysis is wound into a wound body, and warping caused by winding is unlikely to occur after the wound state is released. When the thickness of the electrode for electrolysis includes a catalyst layer described below, it means the thickness of the electrode substrate for electrolysis and the thickness of the catalyst layer. (Manufacturing method of the electrode for electrolysis) Next, one Embodiment of the manufacturing method of the electrode 100 for electrolysis is demonstrated in detail. In this embodiment, the first layer 20 is formed on the electrode substrate for electrolysis by using a method such as firing (thermal decomposition) of a coating film under an oxygen environment, or ion plating, plating, or thermal spraying. The second layer 30 is preferably used to produce the electrode 100 for electrolysis. Such a manufacturing method according to this embodiment can achieve high productivity of the electrode 100 for electrolysis. Specifically, a catalyst layer is formed on an electrode substrate for electrolysis by a coating step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. The term "thermal decomposition" means heating a metal salt that becomes a precursor to decompose it into a metal or a metal oxide and a gaseous substance. Decomposition products differ depending on the type of metal used, the type of salt, and the environment in which thermal decomposition is performed, but most metals tend to form oxides easily in an oxidizing environment. In the industrial manufacturing process of electrodes, thermal decomposition is usually performed in air, and in most cases, metal oxides or metal hydroxides are formed. (Formation of the first layer of the anode) (Coating step) The first layer 20 is a solution (first coating liquid) in which a salt of at least one metal among ruthenium, iridium, and titanium is dissolved, and is applied to an electrode base for electrolysis. It is obtained by thermal decomposition (baking) in the presence of oxygen. The contents of ruthenium, iridium, and titanium in the first coating liquid are approximately equal to those of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 100 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of the second layer) The second layer 30 is formed as necessary, for example, a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (a second coating solution) is applied to the first layer 20 It is obtained by thermal decomposition in the presence of oxygen. (Formation of the first layer of the cathode by thermal decomposition method) (Coating step) The first layer 20 is a solution (first coating solution) in which metal salts of various combinations are dissolved on the electrode substrate for electrolysis , Obtained by thermal decomposition (firing) in the presence of oxygen. The content ratio of the metal in the first coating liquid is substantially equal to that of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 10 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of Intermediate Layer) The intermediate layer is formed as necessary. For example, a solution (second coating solution) containing a palladium compound or a platinum compound is coated on a substrate, and then obtained by thermal decomposition in the presence of oxygen. Alternatively, instead of applying the solution, only the substrate is heated, thereby forming a nickel oxide intermediate layer on the surface of the substrate. (Formation of the first layer of the cathode using ion plating) The first layer 20 may also be formed by ion plating. As an example, the method of fixing a base material in a chamber and irradiating an electron beam with a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma environment is argon and oxygen. Ruthenium is deposited on the substrate in the form of ruthenium oxide. (Formation of the first layer using a plated cathode) The first layer 20 may also be formed by a plating method. As an example, if a substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed. (Formation of the first layer of the cathode using thermal spraying) The first layer 20 can also be formed by a thermal spraying method. As an example, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed by plasma-spraying nickel oxide particles onto a substrate. Hereinafter, an ion exchange membrane which is one aspect of the separator will be described in detail. [Ion exchange membrane] The ion exchange membrane is not particularly limited as long as it can be laminated with an electrode for electrolysis, and various ion exchange membranes can be applied. In this embodiment, an ion exchange membrane having a membrane body containing a hydrocarbon polymer or a fluorine-containing polymer having an ion exchange group and a coating layer provided on at least one side of the membrane body is preferably used. The coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is preferably 0.1 to 10 m.2 / g. The gas generated by the ion exchange membrane of this structure during electrolysis has less influence on the electrolytic performance, and tends to exhibit stable electrolytic performance. The above-mentioned membrane system of a perfluorocarbon polymer to which an ion exchange group is introduced is provided with an ion exchange group (as -SO3 - Sulfonic acid layer and sulfonic acid layer derived from a carboxyl group (with -CO2 - The group represented by this is any of the carboxylic acid layers (hereinafter also referred to as "carboxylic acid groups"). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforced core material. Hereinafter, the inorganic particles and the binder will be described in detail in the description of the coating layer. Fig. 109 is a schematic sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 includes a membrane body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and coating layers 11 a and 11 b formed on both sides of the membrane body 10. In the ion-exchange membrane 1, the membrane body 10 is provided with an ion-exchange group (as -SO3 - The sulfonic acid layer 3, which is also referred to as a "sulfonic acid group" hereinafter, and an ion-exchange group (with -CO2 - The carboxylic acid layer 2 shown below is also referred to as a "carboxylic acid group", and the strength and dimensional stability are strengthened by the reinforcing core material 4. Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it can be suitably used as a cation exchange membrane. The ion exchange membrane may include only one of a sulfonic acid layer and a carboxylic acid layer. The ion exchange membrane is not necessarily reinforced by a reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example shown in FIG. 109. (Membrane Body) First, the membrane body 10 constituting the ion exchange membrane 1 will be described. The membrane body 10 may be any one having a function of selectively transmitting cations and containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group. The structure or material is not particularly limited, and an appropriate one can be appropriately selected. The hydrocarbon-based polymer or fluorine-containing polymer having an ion-exchange group in the membrane body 10 can be obtained, for example, from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group precursor that can become an ion-exchange group by hydrolysis or the like. . Specifically, for example, a polymer containing a fluorinated hydrocarbon in the main chain, a group which can be converted into an ion-exchange group by hydrolysis, or the like (ion-exchange group precursor) as a pendant side chain and capable of being melt-processed (hereinafter referred to as a case may be referred to “Fluorine-containing polymer (a)”) After preparing the precursor of the membrane body 10, the precursor of the ion exchange group is converted into an ion exchange group, whereby the membrane body 10 can be obtained. The fluorine-containing polymer (a) can be copolymerized, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. Manufacturing. Moreover, it can also manufacture by homopolymerizing 1 type of monomer selected from any of the following 1st group, the following 2nd group, and the following 3rd group. Examples of the monomers of the first group include fluoroethylene compounds. Examples of the fluoroethylene compound include fluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether. Especially when an ion exchange membrane is used as a membrane for alkaline electrolysis, the fluoroethylene compound is preferably a perfluoro monomer, and is preferably selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Perfluoro monomer in the group. Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid-type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include CF.2 = CF (OCF2 CYF)s -O (CZF)t -COOR and other monomers (here, s represents an integer from 0 to 2, t represents an integer from 1 to 12, and Y and Z each independently represent F or CF3 R represents a lower alkyl group. Lower alkyl is, for example, an alkyl group having 1 to 3 carbon atoms. Of these, CF is preferred2 = CF (OCF2 CYF)n -O (CF2 )m -COOR. Here, n is an integer of 0 to 2, m is an integer of 1 to 4, and Y is F or CF.3 , R represents CH3 , C2 H5 , Or C3 H7 . When an ion-exchange membrane is used as a cation-exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. The alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms. As the monomer of the second group, among the above, the monomers described below are more preferred. CF2 = CFOCF2 -CF (CF3 OCF2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )2 COOCH3 , CF2 = CF [OCF2 -CF (CF3 )]2 O (CF2 )2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )3 COOCH3 , CF2 = CFO (CF2 )2 COOCH3 , CF2 = CFO (CF2 )3 COOCH3 . Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfonic acid-type ion exchange group (sulfonic acid group). As the vinyl compound having a functional group convertible to a sulfonic acid group, for example, CF is preferably used.2 = CFO-X-CF2 -SO2 A monomer represented by F (here, X represents perfluoroalkylene). Specific examples of these include the monomers shown below. CF2 = CFOCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, CF2 = CF (CF2 )2 SO2 F, CF2 = CFO [CF2 CF (CF3 ) O]2 CF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF2 OCF3 OCF2 CF2 SO2 F. Of these, CF is more preferred2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, and CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F. Copolymers obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of vinyl fluoride, especially a common polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, an inert solvent such as perfluorocarbon or chlorofluorocarbon can be used, in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, at a temperature of 0 to 200 ° C. Polymerization is carried out under a pressure of 0.1 to 20 MPa. In the above-mentioned copolymerization, the type and ratio of the combination of the above-mentioned monomers are not particularly limited, and are selected and determined according to the type and amount of functional groups to be imparted to the obtained fluorine-containing polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is produced, at least one monomer may be selected from the above-mentioned first group and the second group for copolymerization. When a fluorinated polymer containing only a sulfonic acid group is produced, at least one monomer may be selected from the monomers of the first group and the third group and copolymerized. Furthermore, when a fluorinated polymer having a carboxylic acid group and a sulfonic acid group is prepared, at least one monomer is selected from the monomers of the first group, the second group, and the third group and copolymerized. Just fine. In this case, the copolymer containing the first group and the second group and the copolymer containing the first group and the third group are separately polymerized, and then the target fluorine-containing polymerization can be obtained by mixing them. Thing. The mixing ratio of each monomer is not particularly limited. When the amount of functional groups per unit of polymer is increased, the ratio of the monomers selected from the second group and the third group may be increased. The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of the exchange group per unit weight of the dry resin, and can be measured by neutralization titration or the like. In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. The membrane body 10 having such a layer structure can further improve the selective permeability of cations such as sodium ions. When the ion exchange membrane 1 is arranged in the electrolytic cell, the sulfonic acid layer 3 is usually arranged on the anode side of the electrolytic cell and the carboxylic acid layer 2 is arranged on the cathode side of the electrolytic cell. The sulfonic acid layer 3 is preferably made of a material having a low electrical resistance, and from the viewpoint of film strength, it is preferable that its film thickness is thicker than that of the carboxylic acid layer 2. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, and more preferably 3 to 15 times. The carboxylic acid layer 2 is preferably one having high anion repellency even if the film thickness is thin. Here, the anion repellency refers to a property that prevents anion from penetrating into or passing through the ion exchange membrane 1. In order to improve anion repellency, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity in the sulfonic acid layer. As the fluorine-containing polymer used in the sulfonic acid layer 3, for example, CF is suitably used.2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 A polymer obtained by using F as a monomer of group 3. As the fluorine-containing polymer used in the carboxylic acid layer 2, for example, CF is suitably used.2 = CFOCF2 CF (CF2 ) O (CF2 )2 COOCH3 A polymer obtained as a monomer of Group 2. (Coating layer) The ion exchange membrane preferably has a coating layer on at least one side of the membrane body. As shown in FIG. 109, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively. The coating layer contains inorganic particles and a binder. The average particle diameter of the inorganic particles is more preferably 0.90 μm or more. When the average particle diameter of the inorganic particles is 0.90 μm or more, not only the durability against gas adhesion is greatly improved, but also the durability against impurities is greatly improved. That is, a particularly significant effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the value of the specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by pulverizing raw stones can be used. Inorganic particles obtained by pulverizing raw stones are preferably used suitably. The average particle diameter of the inorganic particles may be 2 μm or less. When the average particle diameter of the inorganic particles is 2 μm or less, the film can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm. Here, the average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation). The shape of the inorganic particles is preferably irregular. Resistance to impurities is further improved. The particle size distribution of the inorganic particles is preferably wide. The inorganic particles preferably contain at least one inorganic substance selected from the group consisting of an oxide of a Group IV element of the periodic table, a nitride of a group IV element of the periodic table, and a carbide of a group IV element of the periodic table. From the viewpoint of durability, zirconia particles are more preferred. The inorganic particles are preferably inorganic particles produced by pulverizing rough particles of the inorganic particles, or spherical particles having uniform particle diameters by melting and refining the rough particles of the inorganic particles as the inorganic particles. There are no particular restrictions on the method of crushing the rough stone, and examples thereof include a ball mill, a bead mill, a colloid mill, a cone mill, a disc mill, a roller mill, a powder mill, a hammer mill, a granulator, and a VSI mill Machines, Willy mills, roll mills, jet mills, etc. Moreover, it is preferable to wash it after crushing, and as a washing method at this time, acid treatment is preferred. This makes it possible to reduce impurities such as iron adhering to the surfaces of the inorganic particles. The coating layer preferably contains a binder. The binder is a component that holds inorganic particles on the surface of the ion exchange membrane and forms a coating layer. From the viewpoint of resistance to an electrolytic solution or an electrolytic product, the binder preferably contains a fluorine-containing polymer. As the binder, a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group is more preferred from the viewpoints of resistance to an electrolytic solution or a product of electrolysis and adhesion to the surface of an ion exchange membrane. When a coating layer is provided on a layer (sulfonic acid layer) containing a fluorinated polymer having a sulfonic acid group, it is more preferable to use a fluorine-containing type having a sulfonic acid group as a binding agent for the coating layer. polymer. When a coating layer is provided on a layer (carboxylic acid layer) containing a fluorinated polymer having a carboxylic acid group, it is more preferable to use a compound having a carboxylic acid group as a binder for the coating layer. Fluoropolymer. The content of the inorganic particles in the coating layer is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. The content of the binder is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass. The distribution density of the coating layer in the ion exchange membrane is preferably per 1 cm2 It is 0.05 ~ 2 mg. When the ion exchange membrane has a concave-convex shape on the surface, the distribution density of the coating layer is preferably 1 cm2 It is 0.5 to 2 mg. The method for forming the coating layer is not particularly limited, and a known method can be used. For example, a method of applying a coating liquid in which inorganic particles are dispersed in a solution containing a binder by spraying or the like can be cited. (Reinforced core material) The ion exchange membrane preferably has a reinforced core material disposed inside the membrane body. The reinforced core material is a member that strengthens the strength or dimensional stability of the ion exchange membrane. By disposing the reinforced core material inside the membrane body, the expansion and contraction of the ion exchange membrane can be controlled to a desired range, in particular. This ion-exchange membrane does not expand or contract more than necessary during electrolysis or the like, and can maintain excellent dimensional stability for a long period of time. The structure of the reinforcing core material is not particularly limited, and for example, a yarn called a reinforcing yarn may be formed by spinning. The so-called reinforcing yarn is a member constituting a reinforcing core material, and refers to a yarn capable of imparting required dimensional stability and mechanical strength to an ion exchange membrane and stably existing in the ion exchange membrane. By using a reinforced core material spun from this reinforcing yarn, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane. The material for reinforcing the core material and the reinforcing yarn used therefor is not particularly limited. It is preferably a material resistant to acids or alkalis. In terms of long-term heat resistance and chemical resistance, it is preferable to include Fiber of fluoropolymer. Examples of the fluorine-containing polymer used as the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). ), Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, from the viewpoint of heat resistance and chemical resistance, it is preferred to use a fiber containing polytetrafluoroethylene. The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The textile density (the number of weaves per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited. For example, a woven fabric, a non-woven fabric, a knitted fabric, or the like can be used, and a woven fabric form is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, and more preferably 30 to 150 μm. Woven or knitted fabrics can use monofilament, multifilament or any of these yarns, cut yarns, etc. The weaving method can use various weaving methods such as plain weaving, leno weaving, knitting, rib weaving, thin crepe weaving, etc. The spinning method and configuration of the reinforced core material in the membrane body are not particularly limited, and the appropriate size can be appropriately set in consideration of the size or shape of the ion exchange membrane, the physical properties required for the ion exchange membrane, and the use environment. For example, the reinforced core material may be arranged along a specific direction of the film body. From the viewpoint of dimensional stability, it is preferable to arrange the reinforced core material along a specific first direction, and along a second substantially perpendicular to the first direction. Orientation with other reinforced core materials. By arranging a plurality of reinforcing core materials in a substantially lined manner inside the longitudinal film body of the film body, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. For example, a configuration in which a reinforced core material (longitudinal yarn) arranged in the longitudinal direction and a reinforced core material (horizontal yarn) arranged in the horizontal direction is preferably woven into the surface of the film body. From the viewpoints of dimensional stability, mechanical strength, and ease of manufacture, it is more preferable to produce a plain weave fabric in which longitudinal and transverse yarns are alternately woven one by one, or twisted with two warp yarns and one side yarn. Interwoven leno weaves, twill weave woven by weaving the same number of cross yarns in every 2 or more parallel yarns. It is particularly preferable to arrange the reinforced core material in two directions of the MD direction (Machine Direction) and the TD direction (Transverse Direction) of the ion exchange membrane. That is, it is preferable to perform plain weaving in the MD direction and the TD direction. Here, the MD direction refers to a direction (traveling direction) in which the membrane body or various core materials (for example, a reinforced core material, a reinforced yarn, a sacrificial yarn described below, etc.) are transported in the manufacturing steps of the ion exchange membrane described below ), The TD direction refers to a direction substantially perpendicular to the MD direction. In addition, the yarn woven in the MD direction is referred to as an MD yarn, and the yarn woven in the TD direction is referred to as a TD yarn. Generally, the ion exchange membrane used in electrolysis is rectangular, and the length direction is MD direction and the width direction is TD direction. By weaving a reinforced core material as MD yarn and a reinforced core material as TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. The arrangement interval of the reinforced core material is not particularly limited, and an appropriate arrangement may be appropriately set in consideration of physical properties required for the ion exchange membrane and use environment. The opening ratio of the reinforced core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane. The so-called aperture ratio of the reinforced core material refers to the total area (B) of the surface through which any substance such as ions (the electrolyte and its cations (for example, sodium ions)) can pass through. Ratio (B / A). The total area (B) of the surface through which substances such as ions can pass may refer to the total area of areas in the ion exchange membrane that are not blocked by the reinforced core material or the like contained in the ion exchange membrane. FIG. 110 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 110 is an enlarged view of a part of the ion exchange membrane, and illustrates only the arrangement of the reinforced core materials 21 and 22 in the area, and other components are omitted. The total area of the reinforced core material is subtracted from the area (A) of the area surrounded by the reinforced core material 21 arranged in the longitudinal direction and the reinforced core material 22 arranged in the horizontal direction, which also includes the area of the reinforced core material ( C). The total area (B) of the area (A) through which substances such as ions can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I). Opening ratio = (B) / (A) = ((A)-(C)) / (A)… (I) In the reinforced core material, it is particularly preferable from the viewpoint of chemical resistance and heat resistance The morphology is a tape-like yarn or high-alignment monofilament containing PTFE. Specifically, it is more preferable to use a reinforced core material which uses a band-shaped yarn obtained by cutting a high-strength porous sheet containing PTFE into a band shape, or 50 to 300 of a highly-oriented monofilament containing PTFE. Denim plain weave fabric with a textile density of 10 to 50 per inch, with a thickness in the range of 50 to 100 μm. The aperture ratio of the ion-exchange membrane containing the reinforced core material is more preferably 60% or more. Examples of the shape of the reinforcing yarn include round yarn and ribbon yarn. (Communication hole) The ion exchange membrane preferably has a communication hole inside the membrane body. The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, the so-called communication hole is a tubular hole formed inside the membrane body, and is formed by dissolving a sacrificial core material (or sacrificial yarn) described below. The shape or diameter of the communication hole can be controlled by selecting the shape or diameter of the sacrificial core material (sacrificial yarn). By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured during electrolysis. The shape of the communication hole is not particularly limited. According to the manufacturing method described below, the shape of the sacrificial core material used for forming the communication hole can be made. The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With this structure, in the portion where the communication hole is formed on the cathode side of the reinforced core material, ions (for example, sodium ions) transported through the electrolyte filled with the communication hole can also flow to the cathode side of the reinforced core material. As a result, since the flow of cations is not blocked, the resistance of the ion exchange membrane can be further reduced. The communication hole may be formed only in one specific direction of the membrane body constituting the ion exchange membrane. From the viewpoint of exhibiting more stable electrolytic performance, it is preferably formed in both the longitudinal direction and the lateral direction of the membrane body. [Manufacturing Method] As a suitable method for manufacturing the ion exchange membrane, a method having the following steps (1) to (6) can be mentioned. (1) Step: a step of producing a fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted to an ion-exchange group by hydrolysis. (2) Step: by weaving at least a plurality of reinforcing core materials and sacrificial yarns that have properties of dissolving in acid or alkali and forming communicating holes to obtain reinforcements of sacrificial yarns arranged between adjacent reinforcing core materials. Material steps. (3) Step: a step of membrane-forming the above-mentioned fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted into an ion-exchange group by hydrolysis. (4) Step: a step of burying the above-mentioned reinforcing material in the above-mentioned film to obtain a film body in which the above-mentioned reinforcing material is internally arranged as necessary. (5) Step: a step of hydrolyzing the membrane body obtained in step (4) (hydrolysis step). (6) Step: a step (coating step) of providing a coating layer on the film body obtained in step (5). Each step will be described in detail below. (1) Step: Step for producing fluoropolymer In step (1), a fluoropolymer is produced using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the monomers of the raw materials may be adjusted in the production of the fluorine-containing polymer forming each layer. (2) Step: Manufacturing steps of reinforcing material The so-called reinforcing material is a woven fabric of textile reinforcing yarn. A reinforcing core material is formed by embedding a reinforcing material in the film. When making an ion exchange membrane with communicating holes, sacrificial yarns are also woven into the reinforcing material together. In this case, the blending amount of the sacrificial yarn is preferably 10 to 80% by mass of the entire reinforcing material, and more preferably 30 to 70% by mass. By weaving the sacrificial yarn, the reinforcing core material can be prevented from being detached. Sacrificial yarns are soluble in the manufacturing steps of the film or in an electrolytic environment. Rhenium, polyethylene terephthalate (PET), cellulose, and polyamide can be used. In addition, polyvinyl alcohol having a thickness of 20 to 50 denier, monofilament or multifilament is also preferred. Furthermore, in step (2), the aperture ratio or the arrangement of the communication holes can be controlled by adjusting the configuration of the reinforced core material or the sacrificial yarn. (3) Step: Film formation step In the step (3), the fluorinated polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single-layer structure, as described above, a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or a multilayer structure of three or more layers. As a method of film formation, the following are mentioned, for example. A method of separately forming a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group into a membrane. A method for making a composite film from a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group by coextrusion. Moreover, the film may be plural. In addition, coextrusion of a heterogeneous film is preferred because it improves the bonding strength at the interface. (4) Step: the step of obtaining the film body In step (4), the reinforcing material obtained in step (2) is embedded in the inside of the film obtained in step (3) to obtain the reinforcing material inside. Membrane body. As a preferred method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) on the cathode side by a coextrusion method (hereinafter, The layer containing it is called the first layer) and a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonium fluoride functional group) (hereinafter, the layer containing it is referred to as a second layer). It is necessary to use a heating source and a vacuum source to separate the breathable and heat-resistant release paper, and sequentially laminate the reinforcing material and the second / first layer composite film on a flat plate or a drum with a large number of fine holes on the surface. At the melting temperature of each polymer, the method of integration is performed while removing the air between the layers by decompression; (ii) Different from the second / first layer composite film, the The fluorine-containing polymer (third layer) is separately formed into a film, and if necessary, a heating source and a vacuum source are used to separate the third layer film, the reinforced core material, Layer / first layer of composite film is sequentially laminated on a plate or drum with a large number of fine holes on the surface, Each of the polymer melt temperature, while removed under reduced pressure by the air between the layers while the integration method. Here, coextrusion of the first layer and the second layer helps to improve the bonding strength of the interface. In addition, the method of integrating under reduced pressure has a feature that the thickness of the third layer on the reinforcing material is larger than that of the pressure pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane body, it has a property capable of sufficiently maintaining the mechanical strength of the ion exchange membrane. In addition, the variation of the laminate described here is an example. The required layer structure or physical properties of the film body may be considered, and an appropriate laminate pattern (for example, a combination of layers) may be appropriately selected and then co-extruded. Furthermore, in order to further improve the electrical performance of the ion exchange membrane, a fluorine-containing polymer containing both a carboxylic acid group precursor and a sulfonic acid group precursor may be further interposed between the first layer and the second layer. Instead of the second layer, a fourth layer containing a fluorinated polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is used. The formation method of the fourth layer may be a method of separately manufacturing a fluorinated polymer having a carboxylic acid group precursor and a fluorinated polymer having a sulfonic acid group precursor and then mixing them. A method in which a monomer of a precursor is copolymerized with a monomer having a sulfonic acid group precursor. When the fourth layer is made into an ion-exchange membrane, the co-extruded film of the first layer and the fourth layer can be formed, and the third layer and the second layer can be separately formed into a membrane. The method described herein is laminated, and the three layers of the first layer / the fourth layer / the second layer can also be co-extruded to form a film. In this case, the direction of travel of the extruded film is the MD direction. As a result, a film body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material. Moreover, it is preferable that the ion exchange membrane has a protruding portion, that is, a protruding portion containing a fluorinated polymer having a sulfonic acid group on the surface side including the sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming a convex portion on the surface of a resin can be adopted. Specifically, the method of embossing the surface of a film main body is mentioned, for example. For example, when the composite film is integrated with a reinforcing material or the like, the convex portion can be formed by using a release paper that has been embossed in advance. When the convex portion is formed by embossing, the height of the convex portion or the arrangement density can be controlled by controlling the transferred embossed shape (shape of the release paper). (5) Hydrolysis step In step (5), a step of hydrolyzing the membrane body obtained in step (4) to convert an ion-exchange group precursor to an ion-exchange group (hydrolysis step) is performed. In step (5), a dissolution hole can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body by using an acid or an alkali. In addition, the sacrificial yarn may not be completely dissolved and removed, but may remain in the communication hole. In addition, the sacrificial yarn remaining in the communication hole can be removed by dissolving the electrolytic solution when the ion exchange membrane is supplied for electrolysis. Sacrificial yarns are those which are soluble in acids or alkalis in the manufacturing steps of ion exchange membranes or in an electrolytic environment. The sacrificial yarns are dissolved to form communication holes in this part. Step (5) can be carried out by immersing the film body obtained in step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (Dimethyl sulfoxide) can be used. The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35 mass% of DMSO. The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the thicker the apparent thickness. It is more preferably 75 to 100 ° C. The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes. Here, the step of forming the communication hole by dissolving the sacrificial yarn will be described in more detail. 111 (a) and (b) are schematic diagrams for describing a method for forming a communication hole of an ion exchange membrane. In FIGS. 111 (a) and (b), only the reinforcing yarn 52, the sacrificial yarn 504a, and the communication hole 504 formed by the sacrificial yarn 504a are shown, and other members such as the film body are not shown. First, a knitting-reinforcing material is made from the reinforcing yarn 52 constituting the reinforcing core material in the ion-exchange membrane and the sacrificial yarn 504a used to form the communication hole 504 in the ion-exchange membrane. Then, in step (5), the communication hole 504 is formed by dissolving the sacrificial yarn 504a. According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a can be adjusted according to how the reinforcing core material and the communication hole are arranged in the membrane body of the ion exchange membrane, which is relatively simple. In FIG. 111 (a), the plain woven reinforcing material woven with the reinforcing yarn 52 and the sacrificial yarn 504a in the longitudinal direction and the transverse direction of the paper surface is exemplified. The configuration of the reinforcing yarn 52 and the sacrificial yarn 504a in the reinforcing material may be changed as necessary . (6) Coating step In step (6), a coating liquid containing inorganic particles obtained by pulverizing or melting the raw stone and a binder is prepared, and the coating liquid is applied to the ion exchange obtained in step (5). The surface of the film is dried to form a coating layer. As the binding agent, it is preferred that the fluorine-containing polymer having an ion-exchange group precursor is hydrolyzed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to ion-exchange. Substitute counter ion for H+ The resulting binding agent (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group). This makes it easy to dissolve in water or ethanol described below, and is therefore preferred. This binding agent was dissolved in a solution obtained by mixing water and ethanol. Furthermore, the preferred volume ratio of water to ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1 to 1: 2. The coating liquid was obtained by dispersing the inorganic particles in the dissolving liquid thus obtained by a ball mill. At this time, the average particle diameter of the particles and the like can also be adjusted by adjusting the time during dispersion and the rotation speed. Moreover, the preferable blending amount of the inorganic particles and the binder is as described above. The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, and it is preferable to make a thin coating liquid. Thereby, the surface of an ion exchange membrane can be apply | coated uniformly. When dispersing the inorganic particles, a surfactant may be added to the dispersion liquid. The surfactant is preferably a nonionic surfactant, and examples thereof include HS-210, NS-210, P-210, and E-212 manufactured by Nippon Oil Corporation. An ion exchange membrane can be obtained by applying the obtained coating solution to the surface of an ion exchange membrane by spray coating or roll coating. [Microporous membrane] The microporous membrane of this embodiment is not particularly limited as long as it can be laminated with an electrode for electrolysis as described above, and various microporous membranes can be applied. The porosity of the microporous membrane of this embodiment is not particularly limited, and it can be set to, for example, 20 to 90, and preferably 30 to 85. The porosity can be calculated by the following formula, for example. Porosity = (1-(film weight in dry state) / (weight calculated from the volume calculated from the thickness, width, and length of the film and the density of the film material)) × 100 average pore diameter of the microporous membrane of this embodiment It is not particularly limited, and may be, for example, 0.01 μm to 10 μ, and preferably 0.05 μm to 5 μm. The said average pore diameter cuts a film | membrane perpendicularly along a thickness direction, and observes a cut surface by FE-SEM, for example. The average pore diameter can be determined by measuring the diameter of the observed pores at about 100 points and obtaining an average value. The thickness of the microporous membrane in this embodiment is not particularly limited, and it can be set to, for example, 10 μm to 1,000 μm, and preferably 50 μm to 600 μm. The thickness can be measured, for example, using a micrometer (manufactured by Mitutoyo Co., Ltd.). As specific examples of the microporous membrane described above, there can be mentioned Zilfon Perl UTP 500 (also referred to as a Zilfon membrane in this embodiment) manufactured by Agfa, International Publication No. 2013-183584, and International Publication No. 2016-203701. No., etc. In this embodiment, the separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having an EW (ion exchange equivalent) different from the first ion exchange resin layer. The separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having a functional group different from the first ion exchange resin layer. The ion exchange equivalent can be adjusted by the introduced functional group, and the functional group that can be introduced is as described above. (Water Electrolysis) The electrolytic cell in the case of performing water electrolysis in this embodiment has a constitution in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis described above is changed to a microporous membrane. In addition, the electrolyzer is different from the case where the salt electrolysis is performed in the point that the supplied raw material is water. Regarding other configurations, the electrolytic cell in the case of performing water electrolysis may also have the same configuration as the electrolytic cell in the case of performing salt electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. In the case of water electrolysis, only oxygen is generated in the anode chamber, so the same material as the cathode chamber can be used. Examples include nickel. The anode coating is preferably a catalyst coating for generating oxygen. Examples of the catalyst coating layer include metals, oxides, hydroxides, and the like of platinum group metals and transition metal groups. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used. <Seventh Embodiment> Here, a seventh embodiment of the present invention will be described in detail with reference to FIGS. 112 to 122. [Manufacturing method of electrolytic cell] Electrolysis of the first aspect (hereinafter also referred to as "the first aspect") of the seventh embodiment (hereinafter referred to as "this embodiment" in the item of "the seventh embodiment") The manufacturing method of the tank is to use an existing electrolytic cell rack including an anode, a cathode facing the anode, a separator fixed between the anode and the cathode, and an electrolytic cell rack supporting the anode, the cathode, and the separator. The electrolytic cell is provided with a method of manufacturing a new electrolytic cell by disposing a laminated body of an electrode for electrolysis and a new separator, and has a step (A) of releasing the fixation of the separator in the electrolytic cell rack, and after the step (A), Step (B) of exchanging the diaphragm with the laminated body. As described above, according to the manufacturing method of the electrolytic cell of the first aspect, the electrodes can be updated without taking out each component to the outside of the electrolytic cell rack, and the working efficiency when the electrodes in the electrolytic cell are updated can be improved. In addition, the manufacturing method of the electrolytic cell of the second aspect (hereinafter also referred to as the "second aspect") of this embodiment is to fix the anode provided with the anode, the cathode opposite to the anode, and the anode and the anode. A method for manufacturing a new electrolytic cell by arranging electrodes for electrolysis in an existing electrolytic cell supporting the anode, the cathode, and the electrolytic cell rack of the electrolytic cell rack, and a method for manufacturing a new electrolytic cell in the electrolytic cell rack. The fixed step (A), and the step (B ') of disposing the electrode for electrolysis between the separator and the anode or the cathode after the step (A). As described above, according to the manufacturing method of the electrolytic cell of the second aspect, the electrodes can be updated without taking out each component to the outside of the electrolytic cell rack, and the working efficiency when the electrodes in the electrolytic cell are updated can be improved. Hereinafter, when referred to as "the manufacturing method of the electrolytic cell of this embodiment", it includes the manufacturing method of the electrolytic cell of the first aspect and the manufacturing method of the electrolytic cell of the second aspect. In the manufacturing method of the electrolytic cell of this embodiment, the electrolytic cell includes an anode, a cathode opposite to the anode, a separator disposed between the anode and the cathode, and a support for the anode, the cathode, and the separator. The electrolytic cell rack serves as a constituent member. In other words, the existing electrolytic cell includes a diaphragm, an electrolytic cell, and an electrolytic cell rack supporting these. The existing electrolytic cell is not particularly limited as long as it includes the aforementioned constituent members, and various known configurations can be applied. In the manufacturing method of the electrolytic cell of the present embodiment, the new electrolytic cell is a member that has an electrode or a laminate for electrolysis in addition to a member that already functions as an anode or a cathode in an existing electrolytic cell. That is, in the first aspect and the second aspect, the "electrode for electrolysis" disposed when manufacturing a new electrolytic cell functions as an anode or a cathode, and is different from the cathode and the anode in the existing electrolytic cell. . In the manufacturing method of the electrolytic cell of this embodiment, even when the electrolytic performance of the anode and / or the cathode deteriorates due to the operation of the existing electrolytic cell, it can be updated by disposing an electrode for electrolysis different from these. Anode and / or cathode performance. In addition, in the first aspect using the laminated body, since a new ion exchange membrane is also provided, the performance of the ion exchange membrane accompanying the deterioration of the running performance can be updated at the same time. The "renewal performance" herein means a performance that is the same as or higher than the initial performance of an existing electrolytic cell before it is put into operation. In the manufacturing method of the electrolytic cell of this embodiment, it is assumed that both the existing electrolytic cell is "an electrolytic cell already supplied for operation" and the new electrolytic cell is "an electrolytic cell not yet supplied for operation". That is, if an electrolytic cell manufactured as a new electrolytic cell is supplied for one operation, it becomes "an existing electrolytic cell in this embodiment", and an electrode or a laminate formed by disposing the electrolytic cell in the existing electrolytic cell becomes " New electrolytic cell in this embodiment ". Hereinafter, an embodiment of an electrolytic cell will be described in detail using a case where salt electrolysis is performed using an ion exchange membrane as a separator. In addition, in the item of "Seventh Embodiment", unless otherwise specified, "the electrolytic cell in this embodiment" includes "existing electrolytic cell in this embodiment" and "new electrolysis in this embodiment" Slot ". [Electrolytic cell] First, an electrolytic cell that can be used as a constituent unit of the electrolytic cell in this embodiment will be described. FIG. 112 is a sectional view of the electrolytic cell 1. FIG. The electrolytic cell 1 includes an anode chamber 10, a cathode chamber 20, a partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, an anode 11 provided in the anode chamber 10, and a cathode 21 provided in the cathode chamber 20. If necessary, a reverse current absorber 18 having a base material 18a and a reverse current absorbing layer 18b formed on the base material 18a and provided in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 provided in the cathode chamber 20, and a reverse current absorber 18 provided in the cathode chamber 20. The reverse current absorber 18 has a base material 18a as shown in FIG. The reverse current absorbing layer 18b on the substrate 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the current collector 23 and the cathode 21. The support 24 is provided between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via a metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be indirectly connected through a current collector, a support, a metal elastomer, or a partition wall. The entire surface of the cathode 21 is preferably covered with a catalyst layer for reduction reaction. In addition, the form of electrical connection may be to directly install the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22, and laminate the cathode 21 on the metal elastic body 22, respectively. The form. Examples of a method for directly mounting the respective constituent members to each other include welding and the like. The reverse current sink 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40. FIG. 113 is a cross-sectional view of two adjacent electrolytic cells 1 in the electrolytic cell 4. Fig. 114 shows the electrolytic cell 4 as an existing electrolytic cell. FIG. 115 shows the steps of assembling the electrolytic cell 4 (different from steps (A) to (B) and steps (A ') to (B')). As shown in FIG. 113, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are sequentially arranged in series. An ion exchange membrane 2 is arranged between the anode chamber of one of the two electrolytic cells adjacent to the electrolytic cell and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are separated by the cation exchange membrane 2. As shown in FIG. 114, the electrolytic cell 4 is constituted by a plurality of electrolytic cells 1 connected in series by an electrolytic cell frame 8 supporting a dielectric spacer exchange membrane 2. That is, the electrolytic cell 4 includes a plurality of electrolytic cells 1 arranged in series, an ion exchange membrane 2 disposed between adjacent electrolytic cells 1, and a bipolar electrolytic cell supporting the electrolytic cell rack 8. As shown in FIG. 115, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via a dielectric exchange membrane 2 and connecting them with a press 5 in an electrolytic cell rack 8. The electrolytic cell rack is not particularly limited as long as it can support and connect various members, and various known forms can be applied. There is no particular limitation as a mechanism provided in the electrolytic cell rack to connect the various members, and examples thereof include a pressing mechanism using hydraulic pressure or a mechanism having a connecting rod as a mechanism. The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. Among the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4, the anode 11 of the electrolytic cell 1 located at the extreme end is electrically connected to the anode terminal 7. The cathode 21 of the electrolytic cell at the end opposite to the anode terminal 7 of the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 to the cathode terminal 6 through the anode and cathode of each electrolytic cell 1. Furthermore, an electrolytic cell having only an anode chamber (anode terminal cell) and an electrolytic cell having only a cathode chamber (cathode terminal cell) may be disposed at both ends of the connected electrolytic cells 1. In this case, the anode terminal 7 is connected to an anode terminal cell disposed at one end thereof, and the cathode terminal 6 is connected to a cathode terminal cell disposed at the other end. When electrolysis of brine is performed, brine is supplied to each anode chamber 10 and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid system is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (omitted from the figure) through an electrolytic solution supply hose (omitted from the figure). In addition, the electrolytic solution and the products of electrolysis are recovered by an electrolytic solution recovery tube (omitted from the figure). During the electrolysis, the sodium ions in the brine start from the anode chamber 10 of an electrolytic cell 1 and pass through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Accordingly, the current in the electrolysis flows in a direction in which the electrolytic cells 1 are connected in series. That is, a current flows from the anode chamber 10 to the cathode chamber 20 through the cation exchange membrane 2. Along with the electrolysis of brine, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen are generated on the cathode 21 side. (Anode Chamber) The anode chamber 10 includes an anode 11 or an anode power source 11. The term “feeder” used herein refers to an electrode that is degraded (ie, an existing electrode) or an electrode that is not formed with a catalyst coating. When the electrode for electrolysis in this embodiment is inserted on the anode side, 11 functions as an anode power source. When the electrode for electrolysis in this embodiment is not inserted on the anode side, 11 functions as an anode. The anode chamber 10 preferably includes an anode-side electrolytic solution supply unit that supplies an electrolytic solution to the anode chamber 10, and a baffle plate that is disposed above the anode-side electrolytic solution supply unit and is disposed substantially parallel or inclined to the partition wall 30. And an anode-side gas-liquid separation portion disposed above the baffle and separating gas from an electrolyte mixed with the gas. (Anode) When the electrode for electrolysis in this embodiment is not inserted on the anode side, an anode 11 is provided in a frame (ie, an anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as a so-called DSA (registered trademark) can be used. The so-called DSA is an electrode with a titanium substrate covered with an oxide containing ruthenium, iridium, and titanium as components. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode Feeder) When the electrode for electrolysis in the present embodiment is inserted on the anode side, an anode feeder 11 is provided in the frame of the anode chamber 10. As the anode power source 11, a metal electrode such as a so-called DSA (registered trademark) may be used, or titanium without a catalyst coating layer may be used. Alternatively, a DSA having a thinner catalyst coating thickness may be used. Furthermore, a used anode can also be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Anode-side electrolytic solution supply unit) The anode-side electrolytic solution supply unit is a person that supplies an electrolytic solution to the anode chamber 10 and is connected to an electrolytic solution supply pipe. The anode-side electrolytic solution supply portion is preferably arranged below the anode chamber 10. As the anode-side electrolytic solution supply portion, for example, a tube (dispersion tube) having an opening formed on the surface can be used. The tube is more preferably arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies an electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is transported into the electrolytic cell 1 through the tube, and is supplied into the anode chamber 10 from an opening provided on the surface of the tube. Since the tube is arranged along the surface of the anode 11 parallel to the bottom 19 of the electrolytic cell, the electrolyte can be uniformly supplied to the inside of the anode chamber 10, which is preferable. (Anode-side gas-liquid separation section) The anode-side gas-liquid separation section is preferably disposed above the baffle. In electrolysis, the anode-side gas-liquid separator has a function of separating a generated gas such as chlorine gas from the electrolytic solution. Furthermore, unless otherwise specified, the so-called upper means the upper direction in the electrolytic cell 1 of FIG. 112, and the so-called lower means the lower direction in the electrolytic cell 1 of FIG. 112. During the electrolysis, if the generated gas generated in the electrolytic cell 1 and the electrolyte become mixed phase (gas-liquid mixed phase) and are discharged out of the system, there will be physical damage to the ion exchange membrane due to vibration caused by pressure fluctuations inside the electrolytic cell 1. Situation. In order to suppress this situation, it is preferable to provide an anode-side gas-liquid separation section in the electrolytic cell 1 in this embodiment to separate gas from liquid. It is preferable to provide a defoaming plate for eliminating bubbles in the anode-side gas-liquid separation section. The gas and liquid mixed phase flow can be separated into the electrolyte and the gas by breaking the bubbles when passing through the defoaming plate. As a result, vibration during electrolysis can be prevented. (Baffle) The baffle is preferably disposed above the anode-side electrolytic solution supply portion, and is disposed substantially parallel or inclined to the partition wall 30. The baffle is a partition that controls the flow of the electrolyte in the anode chamber 10. By providing the baffle, the electrolyte (brine, etc.) can be circulated inside the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle is preferably arranged to separate a space near the anode 11 from a space near the partition wall 30. From this viewpoint, the baffle is preferably provided so as to face the respective surfaces of the anode 11 and the partition wall 30. In the space near the anode separated by the baffle, by performing electrolysis, the concentration of the electrolyte (brine concentration) is reduced, and a gas such as chlorine gas is generated. As a result, a difference in gas-liquid specific gravity occurs between the space near the anode 11 separated by the baffle and the space near the partition wall 30. With this situation, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform. Although not shown in FIG. 112, a current collector may be separately provided inside the anode chamber 10. The current collector may be made of the same material or structure as the current collector of the cathode chamber described below. Moreover, in the anode chamber 10, the anode 11 itself can also be made to function as a current collector. (Partition Wall) The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes referred to as a spacer, and divides the anode chamber 10 and the cathode chamber 20. As the partition wall 30, those known as separators for electrolysis can be used, and examples thereof include partition walls in which a plate containing nickel is welded on the cathode side, and a plate containing titanium is welded on the anode side. (Cathode chamber) The cathode chamber 20 functions as a cathode power source when the electrode for electrolysis in this embodiment is inserted on the cathode side, and when the electrode for electrolysis in this embodiment is not inserted on the cathode side , 21 functions as a cathode. When there is a reverse current sink, the cathode or the cathode power source 21 is electrically connected to the reverse current sink system. The cathode chamber 20 preferably includes a cathode-side electrolytic solution supply unit and a cathode-side gas-liquid separation unit similarly to the anode chamber 10. It should be noted that, among the parts constituting the cathode chamber 20, the same descriptions as the parts constituting the anode chamber 10 are omitted. (Cathode) When the electrode for electrolysis in this embodiment is not inserted on the cathode side, a cathode 21 is provided in a frame (ie, a cathode frame) of the cathode chamber 20. The cathode 21 is preferably a catalyst layer having a nickel substrate and a coated nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include: Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. If necessary, a reduction treatment is performed on the cathode 21. In addition, as the base material of the cathode 21, nickel, a nickel alloy, or nickel-plated iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Cathode Feeder) When the electrode for electrolysis in this embodiment is inserted on the cathode side, a cathode feed member 21 is provided in the frame of the cathode chamber 20. The cathode feed body 21 may be covered with a catalyst component. This catalyst component can be used as a cathode and remain. Examples of the components of the catalyst layer include Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and spraying. These methods can also be combined. The catalyst layer may have a plurality of layers and a plurality of elements as required. In addition, nickel, a nickel alloy, and iron or stainless steel plated with nickel without a catalyst coating can be used. In addition, as a base material of the cathode power supply body 21, nickel, a nickel alloy, or nickel plating on iron or stainless steel can be used. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. (Reverse current absorbing layer) As the material of the reverse current absorbing layer, a material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected. Examples include nickel and iron. (Current Collector) The cathode chamber 20 preferably includes a current collector 23. This improves the current collection effect. In this embodiment, the current collector 23 is preferably a porous plate, and is arranged so as to be substantially parallel to the surface of the cathode 21. The current collector 23 is preferably composed of a conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, an alloy, or a composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a mesh shape. (Metal Elastomer) By providing the metal elastomer 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, each anode 11 and each cathode The distance between 21 becomes shorter, and the voltage applied to the plurality of electrolytic cells 1 connected in series can be reduced. By reducing the voltage, power consumption can be reduced. In addition, when the metal elastic body 22 is provided, when the laminated body including the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the pressure of the metal elastic body 22 can stably maintain the electrode for electrolysis. At the starting position. As the metal elastic body 22, a spring member such as a coil spring or a coil, a cushioning pad, or the like can be used. As the metal elastic body 22, it is possible to use a suitable one in consideration of the stress against the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side or on the surface of the partition wall on the anode chamber 10 side. Generally, the two compartments are divided such that the cathode compartment 20 is smaller than the anode compartment 10. Therefore, in terms of the strength of the frame, it is preferable that the metal elastic body 22 is disposed between the current collector 23 and the cathode 21 of the cathode compartment 20. The metal elastic body 23 is preferably made of a conductive metal such as nickel, iron, copper, silver, or titanium. (Support) The cathode chamber 20 is preferably provided with a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently. The support 24 preferably contains a conductive metal such as nickel, iron, copper, silver, and titanium. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a mesh shape. The support 24 is, for example, a plate. The plurality of support bodies 24 are arranged between the partition wall 30 and the current collector 23. The plurality of support bodies 24 are arranged so that their respective faces are parallel to each other. The support 24 is disposed so as to be substantially perpendicular to the partition wall 30 and the current collector 23. (Anode-Side Gasket, Cathode-Side Gasket) The anode-side gasket is preferably arranged on the surface of the frame constituting the anode chamber 10. The cathode-side gasket is preferably disposed on a surface of a frame constituting the cathode chamber 20. The anode-side gasket provided in one electrolytic cell and the cathode-side gasket of an adjacent electrolytic cell are connected to each other by sandwiching the ion exchange membrane 2 (see FIG. 113). With these gaskets, when a plurality of electrolytic cells 1 are connected in series through the dielectric exchange membrane 2, airtightness can be imparted to the connection points. The so-called gasket is a seal between the ion exchange membrane and the electrolytic cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. The gasket is required to be resistant to corrosive electrolytes or generated gases, and can be used for a long time. Therefore, in terms of chemical resistance or hardness, generally, ethylene-propylene-diene rubber (EPDM rubber), ethylene-propylene rubber (EPM rubber) sulfide or peroxide crosslinked material can be used as a mat. sheet. In addition, if necessary, a gasket covering a region (liquid-contacting portion) in contact with the liquid may be coated with a fluorine resin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA). . These gaskets may have openings so as not to hinder the flow of the electrolytic solution, and their shapes are not particularly limited. For example, a frame-shaped gasket is attached to the periphery of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20 with an adhesive or the like. In addition, when, for example, two electrolytic cells 1 are connected to the dielectric separator exchange membrane 2 (see FIG. 113), the dielectric separator exchange membrane 2 may fasten each electrolytic cell 1 to which a gasket is attached. This makes it possible to prevent the electrolytic solution, alkali metal hydroxide, chlorine gas, hydrogen gas, and the like from being leaked to the outside of the electrolytic cell 1. [Laminate] In the method for manufacturing an electrolytic cell according to this embodiment, the electrode for electrolysis can be used as a laminate with a separator such as an ion exchange membrane or a microporous membrane. That is, the multilayer system in this embodiment includes an electrode for electrolysis and a new separator. The new separator is not particularly limited as long as it is different from the separator in the existing electrolytic cell, and various known separators can be applied. The new separator may be the same material, shape, and physical properties as the separator in the existing electrolytic cell. Specific examples of the electrode and the separator for electrolysis will be described in detail. (Step (A)) In step (A) of the first aspect, the diaphragm is unfixed in the electrolytic cell rack. The so-called "in the electrolytic cell rack" means that step (A) is performed while the electrolytic cell (that is, a member including an anode and a cathode) and the diaphragm are supported by the electrolytic cell rack while the electrolytic cell is removed from the electrolytic cell rack. Except appearance. The method for releasing the fixing of the diaphragm is not particularly limited. For example, the method of releasing the pressing of the pressing device in the electrolytic cell rack to form a gap between the electrolytic cell and the diaphragm is set to take the diaphragm out of the electrolytic cell rack. State methods, etc. In step (A), it is preferable to release the fixation of the diaphragm in the electrolytic cell rack by sliding the anode and the cathode in the arrangement directions, respectively. With this operation, a state in which the separator can be taken out of the electrolytic cell rack without taking the electrolytic cell out of the electrolytic cell rack can be set. [Step (B)] In step (B) in the first aspect, after step (A), the diaphragm in the existing electrolytic cell is exchanged with the laminate. The method of exchange is not particularly limited, and examples thereof include a method of removing an existing diaphragm that is a target of renewal after forming a gap between the electrolytic cell and the ion exchange membrane, and then inserting the laminated body into the gap. By this method, the laminated body can be arranged on the surface of the anode or the cathode in the existing electrolytic cell, and the performance of the ion exchange membrane, the anode, and / or the cathode can be updated. After performing step (B), it is preferable to fix the laminated body in the electrolytic cell rack by pressing from the anode and the cathode. Specifically, after exchanging the diaphragm and the laminated body in the existing electrolytic cell, the members of the existing electrolytic cell such as the laminated body and the electrolytic cell can be pressed and connected again by a press. By this method, the laminated body can be fixed on the surface of an anode or a cathode in an existing electrolytic cell. A specific example of steps (A) to (B) in the first aspect will be described based on Figs. 117 (A) and (B). First, the pressing by the pressing device 5 is released, and the plurality of electrolytic cells 1 and the ion exchange membranes 2 are slid along the arrangement direction α. Thereby, a gap S can be formed between the electrolytic cell 1 and the ion exchange membrane 2 without taking the electrolytic cell 1 out of the electrolytic cell rack 8, and the ion exchange membrane 2 can be taken out of the electrolytic cell rack 8 Of the state. Next, the ion exchange membrane 2 of the existing electrolytic cell to be exchanged is taken out of the electrolytic cell rack 8 and, instead, the laminated body 9 of the new ion exchange membrane 2a and the electrode 100 for electrolysis is inserted between the adjacent electrolytic cells 1 ( That is, the gap S). Thereby, the laminated body 9 is arrange | positioned between the adjacent electrolytic cells 1, and these are in the state supported by the electrolytic cell rack 8. Then, the plurality of electrolytic cells 1 and the laminated body 9 are connected by pressing the pressing device 5 in the arrangement direction α. (Step (A ')) In step (A') in the second aspect, the diaphragm is unfixed in the electrolytic cell rack in the same manner as in the first aspect. In step (A '), it is also preferable to release the fixation of the diaphragm in the electrolytic cell rack by sliding the anode and the cathode along the arrangement directions, respectively. With this operation, a state in which the separator can be taken out of the electrolytic cell rack without taking the electrolytic cell out of the electrolytic cell rack can be set. [Step (B ')] In step (B') in the second aspect, after step (A '), an electrode for electrolysis is disposed between the separator and the anode or cathode. The method for disposing the electrode for electrolysis is not particularly limited, and examples thereof include a method of forming a gap between the electrolytic cell and the ion exchange membrane, and then inserting the electrode for electrolysis into the gap. By this method, the electrode for electrolysis can be arranged on the surface of the anode or the cathode in the existing electrolytic cell, and the performance of the anode or the cathode can be updated. After step (B ') is performed, it is preferable to fix the electrode for electrolysis in the electrolytic cell rack by pressing from the anode and the cathode. Specifically, after placing the electrode for electrolysis on the surface of an anode or a cathode in an existing electrolytic cell, the components of the existing electrolytic cell, such as the electrode for electrolytic use and the electrolytic cell, are pressed again by a press, and then link. By this method, the laminated body can be fixed on the surface of an anode or a cathode in an existing electrolytic cell. A specific example of steps (A ') to (B') in the second aspect will be described based on Figs. 118 (A) and (B). First, the pressing by the pressing device 5 is released, and the plurality of electrolytic cells 1 and the ion exchange membranes 2 are slid along the arrangement direction α. Thereby, it is possible to form a gap S between the electrolytic cell 1 and the ion exchange membrane 2 without taking the electrolytic cell 1 out of the electrolytic cell rack 8. Then, the electrode 100 for electrolysis is inserted between the adjacent electrolytic cells 1 (that is, the gap S). As a result, the electrodes 100 for electrolysis are arranged between the adjacent electrolytic cells 1, and these are in a state supported by the electrolytic cell rack 8. Then, the plurality of electrolytic cells 1 and the electrode 100 for electrolysis are connected by pressing the pressing device 5 in the arrangement direction α. Furthermore, in step (B) in the first aspect, it is preferable that the laminated body is fixed to the surface of at least one of the anode and the cathode at a temperature at which the laminated body does not melt. "The temperature at which the laminate does not melt" can be specified as the softening point of the new separator. This temperature may vary depending on the material constituting the separator, and is preferably 0 to 100 ° C, more preferably 5 to 80 ° C, and even more preferably 10 to 50 ° C. The above-mentioned fixing is preferably performed under normal pressure. Preferably, the electrode for electrolysis and the new separator are integrated at a temperature at which the separator does not melt, and a laminated body is obtained and then used in step (B). As a specific method of the integration, all methods other than a typical method of melting a separator such as thermocompression bonding can be used, and it is not particularly limited. As a preferred example, a method of integrating a liquid between an electrode for electrolysis and a separator and integrating the surface tension of the liquid described below can be cited. [Electrolysis Electrode] In the method for manufacturing an electrolytic cell according to this embodiment, the electrode for electrolysis is not particularly limited as long as it can be used for electrolysis. The electrode for electrolysis may be one that functions as a cathode in an electrolytic cell, or one that functions as an anode. Regarding the material, shape, and the like of the electrode for electrolysis, an appropriate one may be appropriately selected in consideration of the configuration of the electrolytic cell and the like. Hereinafter, the preferred aspect of the electrode for electrolysis in this embodiment will be described, but these are only examples of the preferred aspect in the case where a laminated body is integrated with a new separator in the first aspect. It is also possible to use electrodes for electrolysis other than those described below. The electrode for electrolysis in this embodiment can obtain good operability, and has good adhesion to a separator such as an ion exchange membrane or a microporous membrane, and a power supply (a deteriorated electrode and an electrode without a catalyst coating layer). From the viewpoint of force, the force per unit mass and area is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ) Above, and more preferably 0.1 N / mg · cm2 Above, more preferably 0.14 N / (mg · cm2 )the above. From the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.2 N / (mg · cm2 )the above. The above-mentioned bearing force can be set to the above range, for example, by appropriately adjusting a porosity, an electrode thickness, an arithmetic average surface roughness, and the like described below. More specifically, for example, if the opening ratio is increased, the bearing force tends to be small, and if the opening ratio is decreased, the bearing force tends to be large. In addition, from the viewpoint of obtaining good operability, it has good adhesion to separators such as ion-exchange membranes or microporous membranes, deteriorated electrodes, and feeders without a catalyst coating, and so on in terms of economy. From a viewpoint, the mass per unit area is preferably 48 mg / cm2 Below, more preferably 30 mg / cm2 Below, more preferably 20 mg / cm2 In the following, from the viewpoint of combining the operability, adhesiveness, and economy, 15 mg / cm is preferred.2 the following. The lower limit value is not particularly limited, for example, 1 mg / cm2 about. The above-mentioned mass per unit area can be set to the above range, for example, by appropriately adjusting the opening ratio and thickness of the electrode described below. More specifically, for example, if the thickness is the same, the mass per unit area tends to become smaller if the opening ratio is increased, and the mass per unit area tends to be larger if the opening ratio is decreased. . The withstand force can be measured by the following method (i) or (ii). Specifically, it is as described in the examples. As for the bearing capacity, the value obtained by the measurement of the method (i) (also referred to as "bearing capacity (1)") and the value obtained by the measurement of the method (ii) (also referred to as "bearing capacity (2) ) ") May be the same or different, but it is preferred that any value does not reach 1.5 N / mg · cm2 . [Method (i)] A nickel plate (thickness: 1.2 mm, 200 mm square) obtained by spraying with alumina of grain number 320 was laminated in order, and the perfluorocarbon polymer film with an ion exchange group was introduced. Ion-exchange membrane (170 mm square, details of the so-called ion-exchange membrane as described in the examples) and electrode samples (130 mm square) coated with inorganic particles and binders on both sides. After sufficient immersion, excess moisture adhering to the surface of the laminated body was removed to obtain a sample for measurement. In addition, the arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment is 0.5 to 0.8 μm. The specific calculation method of the arithmetic average surface roughness (Ra) is as described in the examples. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. This average value is divided by the area of the overlapped part of the electrode sample and the ion-exchange membrane and the mass of the electrode sample of the overlapped part of the ion-exchange membrane to calculate the force per unit mass and unit area (1) (N / mg · cm2 ). With the force (1) per unit mass and unit area obtained by method (i), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. From the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 ), More preferably 0.2 N / (mg ・ cm2 )the above. [Method (ii)] A nickel plate (thickness 1.2 mm, 200 mm square, the same nickel plate as in the above method (i)) and an electrode sample (130 mm square), and the laminated body is sufficiently immersed in pure water, and then excess water adhered to the surface of the laminated body is removed to obtain a sample for measurement. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, using a tensile compression tester, only the electrode sample in the measurement sample was raised in a vertical direction at 10 mm / min, and the measurement electrode sample was in a vertical direction. Load when rising 10 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate and the mass of the electrode sample in the overlapped portion of the nickel plate to calculate the adhesion force per unit mass and unit area (2) (N / mg · cm2 ). With the force (2) per unit mass and unit area obtained by method (ii), good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, degraded electrodes, and no catalyst coating. From the viewpoint that the layer power supply has good adhesion, it is preferably 1.6 N / (mg · cm2 ) Or less, preferably less than 1.6 N / (mg · cm2 ), More preferably less than 1.5 N / (mg · cm2 ), More preferably 1.2 N / mg · cm2 Below, more preferably 1.20 N / mg · cm2 the following. Further more preferably 1.1 N / mg ・ cm2 In the following, even more preferably 1.10 N / mg · cm2 Below, particularly preferably 1.0 N / mg · cm2 Below, particularly preferred is 1.00 N / mg · cm2 the following. Furthermore, from the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm2 ), More preferably 0.08 N / (mg ・ cm2 ), More preferably 0.1 N / (mg · cm2 ), And from the viewpoint of easy handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 0.14 N / (mg · cm2 )the above. The electrode for electrolysis in this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, and good operability can be obtained. It can be used in contact with separators such as ion exchange membranes or microporous membranes, degraded electrodes (feeders), and non-formed The electrode (feeder) of the dielectric coating has good adhesion, can be wound into a roll shape and bent well, and it is easy to handle at a large size (for example, 1.5 m × 2.5 m). In particular, it is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and even more It is preferably 100 μm or less, and from the viewpoint of operability and economy, it is more preferably 50 μm or less. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the manufacturing method of the electrolytic cell of this embodiment, it is preferable that a new separator is integrated with an electrode for electrolysis, and then a liquid is interposed therebetween. Any liquid can be used as long as the liquid has surface tension such as water or an organic solvent. The greater the surface tension of the liquid, the greater the force it will bear between the new separator and the electrode for electrolysis. Therefore, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the values in parentheses are the surface tension of the liquid at 20 ° C). Hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m), water (72.76 mN / m), if In the case of a liquid having a large surface tension, the new separator is integrated with the electrode for electrolysis (into a laminated body), and electrode replacement tends to become easier. The amount of liquid between the new diaphragm and the electrode for electrolysis is sufficient to be adhered to each other by surface tension. As a result, the amount of liquid is small. Therefore, even if the laminated body is installed in the electrolytic cell, it is mixed into the electrolytic solution. In the meantime, it will not affect the electrolysis itself. From a practical point of view, as the liquid, a liquid having a surface tension of 24 mN / m to 80 mN / m such as ethanol, ethylene glycol, and water is preferably used. Particularly preferred is water or a caustic soda, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, etc. dissolved in water to make an alkaline aqueous solution. Moreover, you may adjust surface tension by making these liquids contain a surfactant. By including a surfactant, the adhesion between the new separator and the electrode for electrolysis changes, and the operability can be adjusted. The surfactant is not particularly limited, and any of an ionic surfactant and a nonionic surfactant can be used. The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and further, for a large size (for example, From the viewpoint of easy handling at a size of 1.5 m × 2.5 m), it is more preferably 95% or more. The upper limit is 100%. [Method (2)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 280 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesive force and being able to be wound into a roll shape and bent well, the ratio measured by the following method (3) is preferably 75% or more. It is preferably 80% or more, and from the viewpoint of ease of handling at a large size (for example, a size of 1.5 m × 2.5 m), it is more preferably 90% or more. The upper limit is 100%. [Method (3)] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) were sequentially laminated. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the laminated body was placed on the curved surface of a polyethylene tube (outer diameter of 145 mm) in such a manner that the electrode sample in the laminated body became the outer side. Water fully impregnates the laminate and the tube, removes excess water adhering to the surface of the laminate and the tube, and after 1 minute, the ratio of the area of the ion exchange membrane (170 mm square) to the area of the electrode sample in close contact ( %). The electrode for electrolysis in this embodiment is not particularly limited, and good operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes (feeders), and electrodes without a catalyst coating. (Feeder) From the viewpoint of having a good adhesion and preventing gas retention during electrolysis, a porous structure is preferred, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80%, and more preferably 20 to 75%. The open porosity is the ratio of the perforated portion per unit volume. There are various calculation methods for the opening part according to the submicron order or only the openings that can be seen visually. In this embodiment, the volume V can be calculated from the values of the gauge thickness, width, and length of the electrode, and then the weight W can be measured to calculate the aperture ratio A using the following formula. A = (1- (W / (V × ρ)) × 100 ρ Density of electrode material (g / cm3 ). E.g. in the case of nickel 8.908 g / cm3 In the case of titanium is 4.506 g / cm3 . The adjustment of the opening rate can be appropriately adjusted by the following methods: if it is a punched metal, change the area of the punched metal per unit area; if it is a porous metal, change SW (short diameter), LW (long diameter), Feed value; if it is a wire mesh, change the wire diameter and mesh number of the metal fiber; if it is electroforming, change the pattern of the photoresist used; if it is a non-woven fabric, change the metal fiber diameter and fiber density; In the case of a foamed metal, a template or the like for forming a void is changed. Hereinafter, a more specific embodiment of the electrode for electrolysis in this embodiment will be described. The electrode for electrolysis of this embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer is described below, and may include a plurality of layers or a single-layer structure. As shown in FIG. 119, the electrode 100 for electrolysis according to this embodiment includes an electrode base material 10 for electrolysis and a pair of first layers 20 covering one surface of the electrode base material 10 for electrolysis. The first layer 20 preferably covers the entire electrode base material 10 for electrolysis. As a result, the catalyst activity and durability of the electrode for electrolysis can be easily improved. Furthermore, the first layer 20 may be formed only on one surface area of the electrode base material 10 for electrolysis. As shown in FIG. 119, the surface of the first layer 20 may be covered by the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, the second layer 30 may be laminated on only one surface of the first layer 20. (Electrode base material for electrolysis) The electrode base material 10 for electrolysis is not particularly limited, and for example, nickel, nickel alloy, stainless steel, or a valve metal typified by titanium can be used, and it is preferably selected from nickel (Ni) And at least one element of titanium (Ti). When stainless steel is used in a high-concentration alkaline aqueous solution, considering the elution of iron and chromium, and the conductivity of stainless steel is about 1/10 of that of nickel, it is preferable to use a substrate containing nickel (Ni) as the base material. Electrode substrate for electrolysis. In addition, when the electrode base material 10 for electrolysis is used in a chlorine gas generating environment in a high-concentration saline solution, the material is preferably titanium with high corrosion resistance. The shape of the electrode substrate 10 for electrolysis is not particularly limited, and a suitable shape can be selected according to the purpose. As the shape, any of a punched metal, a non-woven fabric, a foamed metal, a porous metal, a porous metal foil formed by electroforming, and a so-called woven mesh made of a braided metal wire can be used. Among them, punched metal or porous metal is preferred. In addition, the so-called electroforming is a technique for producing a precise patterned metal thin film by combining a photolithographic process and an electroplating method. It is a method for obtaining a metal thin film by forming a pattern on a substrate with a photoresist, and performing electroplating on a portion not protected by the photoresist. Regarding the shape of the electrode substrate for electrolysis, there are suitable specifications according to the distance between the anode and the cathode in the electrolytic cell. There is no particular limitation. When the anode and the cathode have a limited distance, porous metal and punched metal shapes can be used. In the case of a so-called zero-pitch electrolytic cell where the ion exchange membrane is connected to the electrode, a braided thin wire can be used. The finished woven mesh, metal mesh, foamed metal, metal non-woven fabric, porous metal, punched metal, metal porous foil, etc. Examples of the electrode base material 10 for electrolysis include a porous metal foil, a metal wire mesh, a metal nonwoven fabric, a punched metal, a porous metal, or a foamed metal. As a sheet material before being processed into a punched metal or a porous metal, a sheet material formed by rolling and an electrolytic foil are preferred. The electrolytic foil is preferably further subjected to a plating treatment using the same element as the base material as a post-treatment to form unevenness on one or both sides. As described above, the thickness of the electrode base material 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, even more preferably 155 μm or less, even more preferably 135 μm or less, and even more preferably 125. μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, and further more preferably 50 μm or less in terms of operability and economy. The lower limit value is not particularly limited, and is, for example, 1 μm, preferably 5 μm, and more preferably 15 μm. In the electrode base material for electrolysis, it is preferable to reduce the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing environment. In addition, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, it is preferable to use steel sand and alumina powder to form unevenness on the surface, and then increase the surface area by acid treatment. Alternatively, it is preferable to increase the surface area by applying a plating treatment to the same element as the substrate. In order to bring the first layer 20 into close contact with the surface of the electrode base material 10 for electrolysis, it is preferable that the surface area of the electrode base material 10 for electrolysis is increased. Examples of the treatment for increasing the surface area include blasting treatment using steel wire grain, steel sand, alumina sand, etc., acid treatment using sulfuric acid or hydrochloric acid, and plating treatment using the same element as the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 μm to 50 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm. Next, a case where the electrode for electrolysis in this embodiment is used as an anode for salt electrolysis will be described. (First layer) In FIG. 119, the first layer 20 as a catalyst layer contains at least one of ruthenium oxide, iridium oxide, and titanium oxide. Examples of the ruthenium oxide include RuO2 Wait. Examples of the iridium oxide include IrO2 Wait. Examples of the titanium oxide include TiO2 Wait. The first layer 20 is preferably two oxides containing ruthenium oxide and titanium oxide, or three oxides containing ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and further, the adhesion with the second layer 30 is further improved. In the case where the first layer 20 contains two oxides of ruthenium oxide and titanium oxide, the titanium oxide contained in the first layer 20 is better than 1 mol of the ruthenium oxide contained in the first layer 20 It is 1 to 9 moles, more preferably 1 to 4 moles. By setting the composition ratio of the two oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains three oxides of ruthenium oxide, iridium oxide, and titanium oxide, the iridium oxide contained in the first layer 20 is 1 mole relative to the ruthenium oxide contained in the first layer 20 The amount is preferably 0.2 to 3 moles, and more preferably 0.3 to 2.5 moles. In addition, the titanium oxide contained in the first layer 20 is preferably 0.3 to 8 moles, and more preferably 1 to 7 moles relative to 1 mole of the ruthenium oxide contained in the first layer 20. By setting the composition ratio of the three oxides within this range, the electrode 100 for electrolysis exhibits excellent durability. In the case where the first layer 20 contains at least two oxides selected from the group consisting of ruthenium oxide, iridium oxide, and titanium oxide, these oxides preferably form a solid solution. By forming an oxide solid solution, the electrode 100 for electrolysis exhibits excellent durability. In addition to the above composition, as long as it contains at least one of ruthenium oxide, iridium oxide, and titanium oxide, various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like called DSA (registered trademark) may be used as the first layer 20. The first layer 20 need not be a single layer, and may include a plurality of layers. For example, the first layer 20 may include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. (Second layer) The second layer 30 preferably contains ruthenium and titanium. This can further reduce the chlorine overvoltage immediately after electrolysis. The second layer 30 is preferably a palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. This can further reduce the chlorine overvoltage immediately after electrolysis. The thicker the second layer 30 is, the longer the time during which the electrolytic performance can be maintained. From the viewpoint of economy, the thickness is preferably 0.05 to 3 μm. Next, a case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis will be described. (First layer) The components of the first layer 20 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. In the case of containing at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal, a platinum group metal, a platinum group metal oxide, and a platinum group metal hydroxide are preferred. The alloy containing a platinum group metal contains at least one platinum group metal of platinum, palladium, rhodium, ruthenium, and iridium. The platinum group metal preferably contains platinum. The platinum group metal oxide is preferably a ruthenium oxide. The platinum group metal hydroxide is preferably a ruthenium hydroxide. The platinum group metal alloy is preferably an alloy containing platinum and nickel, iron, and cobalt. It is preferable to further contain an oxide or hydroxide of a lanthanoid as a second component as necessary. Accordingly, the electrode 100 for electrolysis exhibits excellent durability. The lanthanide oxide or hydroxide preferably contains at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, and praseodymium. It is preferable to further contain an oxide or hydroxide of a transition metal as a third component as necessary. By adding the third component, the electrode 100 for electrolysis can exhibit more excellent durability and reduce the electrolytic voltage. Examples of preferred combinations include ruthenium, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + osmium, ruthenium + rhenium + platinum, ruthenium + rhenium + Platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur , Ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + osmium, ruthenium + rhenium + manganese, ruthenium + 钐 + iron, ruthenium + rhenium + cobalt, ruthenium + 钐 + zinc, ruthenium + 钐+ Gallium, Ruthenium + 钐 + Sulfur, Ruthenium + 钐 + Lead, Ruthenium + 钐 + Ni, Pt + Ce, Pt + Pd + Ce, Pt + Pd + La + Ce, Pt + Ir, Pt + Pd, Pt + I + Palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, alloys of platinum and nickel, alloys of platinum and cobalt, alloys of platinum and iron, etc. When the platinum group metal, platinum group metal oxide, platinum group metal hydroxide, and platinum group metal-containing alloy are not contained, the main component of the catalyst is preferably nickel. Preferably, it contains at least one of nickel metal, oxide, and hydroxide. As a second component, a transition metal may be added. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon. Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, and the like. If necessary, an intermediate layer may be provided between the first layer 20 and the electrode base material 10 for electrolysis. By providing the intermediate layer, the durability of the electrode 100 for electrolysis can be improved. The intermediate layer is preferably one having an affinity for both the first layer 20 and the electrode base material 10 for electrolysis. The intermediate layer is preferably a nickel oxide, a platinum group metal, a platinum group metal oxide, or a platinum group metal hydroxide. The intermediate layer can be formed by coating and firing a solution containing the components forming the intermediate layer, or heat-treating the substrate at a temperature of 300 to 600 ° C in an air environment to form a surface oxide layer. . In addition, it can be formed by a known method such as a thermal spray method or an ion plating method. (Second layer) The components of the first layer 30 as the catalyst layer include: C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr , Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and other metals and oxides or hydroxides of these metals. It may contain at least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal-containing alloy, and may not contain it. Examples of preferred combinations of the elements contained in the second layer include the combinations listed in the first layer. The combination of the first layer and the second layer may be a combination with the same composition but a different composition ratio, or a combination with a different composition. As the thickness of the catalyst layer, the thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 μm to 20 μm. When it is 0.01 μm or more, it can fully function as a catalyst. If it is 20 μm or less, it is less likely to fall off from the substrate, and a strong catalyst layer can be formed. More preferably, it is 0.05 μm to 15 μm. More preferably, it is 0.1 μm to 10 μm. It is more preferably 0.2 μm to 8 μm. The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer, is preferably 315 μm or less, more preferably 220 μm or less, and further preferably 170 μm in terms of the operability of the electrode. Below, still more preferably 150 μm or less, even more preferably 145 μm or less, even more preferably 140 μm or less, even more preferably 138 μm or less, and even more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. The thickness of the electrode can be determined by measuring with an electronic digital thickness gauge (Mitutoyo Co., Ltd., showing a minimum of 0.001 mm). The thickness of the electrode substrate for electrolysis was measured in the same manner as the electrode thickness. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness. In the manufacturing method of the electrolytic cell of this embodiment, from the viewpoint of ensuring sufficient electrolytic performance, it is preferable that the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, At least one catalyst component in the group consisting of Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy. In this embodiment, if the electrode for electrolysis is an electrode with a wide elastic deformation area, better operability can be obtained. It can be used with separators such as ion exchange membranes or microporous membranes, deteriorated electrodes, and no catalyst coating is formed. From the viewpoint that the layered power supply has a better adhesion, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, still more preferably 170 μm or less, and even more preferably 150 μm. Hereinafter, it is particularly preferably 145 μm or less, more preferably 140 μm or less, even more preferably 138 μm or less, and still more preferably 135 μm or less. If it is 135 μm or less, good operability can be obtained. Furthermore, from the same viewpoint as above, it is preferably 130 μm or less, more preferably 130 μm or less, still more preferably 115 μm or less, and still more preferably 65 μm or less. The lower limit value is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more in practical terms. In addition, in this embodiment, "the elastic deformation area is wide" means that the electrode for electrolysis is wound into a wound body, and warping caused by winding is unlikely to occur after the wound state is released. When the thickness of the electrode for electrolysis includes a catalyst layer described below, it means the thickness of the electrode substrate for electrolysis and the thickness of the catalyst layer. (Manufacturing method of the electrode for electrolysis) Next, one Embodiment of the manufacturing method of the electrode 100 for electrolysis is demonstrated in detail. In this embodiment, the first layer 20 is formed on the electrode substrate for electrolysis by using a method such as firing (thermal decomposition) of a coating film under an oxygen environment, or ion plating, plating, or thermal spraying. The second layer 30 is preferably used to produce the electrode 100 for electrolysis. Such a manufacturing method according to this embodiment can achieve high productivity of the electrode 100 for electrolysis. Specifically, a catalyst layer is formed on an electrode substrate for electrolysis by a coating step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. The term "thermal decomposition" means heating a metal salt that becomes a precursor to decompose it into a metal or a metal oxide and a gaseous substance. Decomposition products differ depending on the type of metal used, the type of salt, and the environment in which thermal decomposition is performed, but most metals tend to form oxides easily in an oxidizing environment. In the industrial manufacturing process of electrodes, thermal decomposition is usually performed in air, and in most cases, metal oxides or metal hydroxides are formed. (Formation of the first layer of the anode) (Coating step) The first layer 20 is a solution (first coating liquid) in which a salt of at least one metal among ruthenium, iridium, and titanium is dissolved, and is applied to an electrode base for electrolysis. It is obtained by thermal decomposition (baking) in the presence of oxygen. The contents of ruthenium, iridium, and titanium in the first coating liquid are approximately equal to those of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 100 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of the second layer) The second layer 30 is formed as necessary, for example, a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (a second coating solution) is applied to the first layer 20 It is obtained by thermal decomposition in the presence of oxygen. (Formation of the first layer of the cathode by thermal decomposition method) (Coating step) The first layer 20 is a solution (first coating solution) in which metal salts of various combinations are dissolved on the electrode substrate for electrolysis , Obtained by thermal decomposition (firing) in the presence of oxygen. The content ratio of the metal in the first coating liquid is substantially equal to that of the first layer 20. The metal salt may be a chloride salt, a nitrate salt, a sulfate salt, a metal alkoxide, or any other form. The solvent of the first coating liquid can be selected according to the type of the metal salt, and alcohols such as water and butanol can be used. The solvent is preferably water or a mixed solvent of water and an alcohol. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, and it is preferably 10 to 150 g / L in terms of considering the thickness of the coating film formed by one coating. range. As a method for applying the first coating solution to the electrode substrate 10 for electrolysis, an immersion method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution can be used to coat the first coating with a brush. The liquid coating method, the roller method using a sponge-shaped roller impregnated with the first coating liquid, the electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid have opposite charges and are sprayed and sprayed. Among them, a drum method or an electrostatic coating method which is excellent in industrial productivity is preferred. (Drying step, thermal decomposition step) After the first coating solution is applied to the electrode base material 10 for electrolysis, it is dried at a temperature of 10 to 90 ° C, and heated in a firing furnace heated to 350 to 650 ° C. break down. If necessary, pre-baking may be performed at 100 to 350 ° C between drying and thermal decomposition. The drying, pre-baking and thermal decomposition temperatures can be appropriately selected according to the composition of the first coating liquid or the type of the solvent. The time for each thermal decomposition is preferably longer, and from the viewpoint of the productivity of the electrode, it is preferably 3 to 60 minutes, more preferably 5 to 20 minutes. The above-mentioned cycle of coating, drying and thermal decomposition is repeated to form the coating (first layer 20) to a specific thickness. After the first layer 20 is formed, if further heating for a long period of time after the firing is required, the stability of the first layer 20 can be further improved. (Formation of Intermediate Layer) The intermediate layer is formed as necessary. For example, a solution (second coating solution) containing a palladium compound or a platinum compound is coated on a substrate, and then obtained by thermal decomposition in the presence of oxygen. Alternatively, instead of applying the solution, only the substrate is heated, thereby forming a nickel oxide intermediate layer on the surface of the substrate. (Formation of the first layer of the cathode using ion plating) The first layer 20 may also be formed by ion plating. As an example, the method of fixing a base material in a chamber and irradiating an electron beam with a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma environment is argon and oxygen. Ruthenium is deposited on the substrate in the form of ruthenium oxide. (Formation of the first layer using a plated cathode) The first layer 20 may also be formed by a plating method. As an example, if a substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed. (Formation of the first layer of the cathode using thermal spraying) The first layer 20 can also be formed by a thermal spraying method. As an example, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed by plasma-spraying nickel oxide particles onto a substrate. Hereinafter, an ion exchange membrane which is one aspect of the separator will be described in detail. [Ion exchange membrane] The ion exchange membrane is not particularly limited as long as it can be laminated with an electrode for electrolysis, and various ion exchange membranes can be applied. In the manufacturing method of the electrolytic cell of this embodiment, it is preferable to use a film body having a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and a coating provided on at least one side of the film body Layer of ion exchange membrane. The coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is preferably 0.1 to 10 m.2 / g. The gas generated by the ion exchange membrane of this structure during electrolysis has less influence on the electrolytic performance, and tends to exhibit stable electrolytic performance. The above-mentioned membrane system of a perfluorocarbon polymer to which an ion exchange group is introduced is provided with an ion exchange group (as -SO3 - Sulfonic acid layer and sulfonic acid layer derived from a carboxyl group (with -CO2 - The group represented by this is any of the carboxylic acid layers (hereinafter also referred to as "carboxylic acid groups"). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforced core material. Hereinafter, the inorganic particles and the binder will be described in detail in the description of the coating layer. Fig. 120 is a schematic sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 includes a membrane body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group, and coating layers 11 a and 11 b formed on both sides of the membrane body 10. In the ion-exchange membrane 1, the membrane body 10 is provided with an ion-exchange group (as -SO3 - The sulfonic acid layer 3, which is also referred to as a "sulfonic acid group" hereinafter, and an ion-exchange group (with -CO2 - The carboxylic acid layer 2 shown below is also referred to as a "carboxylic acid group", and the strength and dimensional stability are strengthened by the reinforcing core material 4. Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it can be suitably used as a cation exchange membrane. The ion exchange membrane may include only one of a sulfonic acid layer and a carboxylic acid layer. The ion-exchange membrane is not necessarily reinforced by a reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example shown in FIG. 120. (Membrane Body) First, the membrane body 10 constituting the ion exchange membrane 1 will be described. The membrane body 10 may be any one having a function of selectively transmitting cations and containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group. The structure or material is not particularly limited, and an appropriate one can be appropriately selected. The hydrocarbon-based polymer or fluorine-containing polymer having an ion-exchange group in the membrane body 10 can be obtained, for example, from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange group precursor that can become an ion-exchange group by hydrolysis or the like. . Specifically, for example, a polymer containing a fluorinated hydrocarbon in the main chain, a group which can be converted into an ion-exchange group by hydrolysis, or the like (ion-exchange group precursor) as a pendant side chain and capable of being melt-processed (hereinafter referred to as a case may be referred to “Fluorine-containing polymer (a)”) After preparing the precursor of the membrane body 10, the precursor of the ion exchange group is converted into an ion exchange group, whereby the membrane body 10 can be obtained. The fluorine-containing polymer (a) can be copolymerized, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. Manufacturing. Moreover, it can also manufacture by homopolymerizing 1 type of monomer selected from any of the following 1st group, the following 2nd group, and the following 3rd group. Examples of the monomers of the first group include fluoroethylene compounds. Examples of the fluoroethylene compound include fluoroethylene, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether. Especially when an ion exchange membrane is used as a membrane for alkaline electrolysis, the fluoroethylene compound is preferably a perfluoro monomer, and is preferably selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Perfluoro monomer in the group. Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid-type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include CF.2 = CF (OCF2 CYF)s -O (CZF)t -COOR and other monomers (here, s represents an integer from 0 to 2, t represents an integer from 1 to 12, and Y and Z each independently represent F or CF3 R represents a lower alkyl group. Lower alkyl is, for example, an alkyl group having 1 to 3 carbon atoms. Of these, CF is preferred2 = CF (OCF2 CYF)n -O (CF2 )m -COOR. Here, n is an integer of 0 to 2, m is an integer of 1 to 4, and Y is F or CF.3 , R represents CH3 , C2 H5 , Or C3 H7 . When an ion-exchange membrane is used as a cation-exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. The alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms. As the monomer of the second group, among the above, the monomers described below are more preferred. CF2 = CFOCF2 -CF (CF3 OCF2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )2 COOCH3 , CF2 = CF [OCF2 -CF (CF3 )]2 O (CF2 )2 COOCH3 , CF2 = CFOCF2 CF (CF3 ) O (CF2 )3 COOCH3 , CF2 = CFO (CF2 )2 COOCH3 , CF2 = CFO (CF2 )3 COOCH3 . Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfonic acid-type ion exchange group (sulfonic acid group). As the vinyl compound having a functional group convertible to a sulfonic acid group, for example, CF is preferably used.2 = CFO-X-CF2 -SO2 A monomer represented by F (here, X represents perfluoroalkylene). Specific examples of these include the monomers shown below. CF2 = CFOCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, CF2 = CF (CF2 )2 SO2 F, CF2 = CFO [CF2 CF (CF3 ) O]2 CF2 CF2 SO2 F, CF2 = CFOCF2 CF (CF2 OCF3 OCF2 CF2 SO2 F. Of these, CF is more preferred2 = CFOCF2 CF (CF3 OCF2 CF2 CF2 SO2 F, and CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 F. Copolymers obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of vinyl fluoride, especially a common polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, an inert solvent such as perfluorocarbon or chlorofluorocarbon can be used, in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, at a temperature of 0 to 200 ° C. Polymerization is carried out under a pressure of 0.1 to 20 MPa. In the above-mentioned copolymerization, the type and ratio of the combination of the above-mentioned monomers are not particularly limited, and are selected and determined according to the type and amount of functional groups to be imparted to the obtained fluorine-containing polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is produced, at least one monomer may be selected from the above-mentioned first group and the second group for copolymerization. When a fluorinated polymer containing only a sulfonic acid group is produced, at least one monomer may be selected from the monomers of the first group and the third group and copolymerized. Furthermore, when a fluorinated polymer having a carboxylic acid group and a sulfonic acid group is prepared, at least one monomer is selected from the monomers of the first group, the second group, and the third group and copolymerized. Just fine. In this case, the copolymer containing the first group and the second group and the copolymer containing the first group and the third group are separately polymerized, and then the target fluorine-containing polymerization can be obtained by mixing them. Thing. The mixing ratio of each monomer is not particularly limited. When the amount of functional groups per unit of polymer is increased, the ratio of the monomers selected from the second group and the third group may be increased. The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of the exchange group per unit weight of the dry resin, and can be measured by neutralization titration or the like. In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. The membrane body 10 having such a layer structure can further improve the selective permeability of cations such as sodium ions. When the ion exchange membrane 1 is arranged in the electrolytic cell, the sulfonic acid layer 3 is usually arranged on the anode side of the electrolytic cell and the carboxylic acid layer 2 is arranged on the cathode side of the electrolytic cell. The sulfonic acid layer 3 is preferably made of a material having a low electrical resistance, and from the viewpoint of film strength, it is preferable that its film thickness is thicker than that of the carboxylic acid layer 2. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, and more preferably 3 to 15 times. The carboxylic acid layer 2 is preferably one having high anion repellency even if the film thickness is thin. Here, the anion repellency refers to a property that prevents anion from penetrating into or passing through the ion exchange membrane 1. In order to improve anion repellency, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity in the sulfonic acid layer. As the fluorine-containing polymer used in the sulfonic acid layer 3, for example, CF is suitably used.2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 A polymer obtained by using F as a monomer of group 3. As the fluorine-containing polymer used in the carboxylic acid layer 2, for example, CF is suitably used.2 = CFOCF2 CF (CF2 ) O (CF2 )2 COOCH3 A polymer obtained as a monomer of Group 2. (Coating layer) The ion exchange membrane preferably has a coating layer on at least one side of the membrane body. As shown in FIG. 120, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively. The coating layer contains inorganic particles and a binder. The average particle diameter of the inorganic particles is more preferably 0.90 μm or more. When the average particle diameter of the inorganic particles is 0.90 μm or more, not only the durability against gas adhesion is greatly improved, but also the durability against impurities is greatly improved. That is, a particularly significant effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the value of the specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by pulverizing raw stones can be used. Inorganic particles obtained by pulverizing raw stones are preferably used suitably. The average particle diameter of the inorganic particles may be 2 μm or less. When the average particle diameter of the inorganic particles is 2 μm or less, the film can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm. Here, the average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation). The shape of the inorganic particles is preferably irregular. Resistance to impurities is further improved. The particle size distribution of the inorganic particles is preferably wide. The inorganic particles preferably contain at least one inorganic substance selected from the group consisting of an oxide of a Group IV element of the periodic table, a nitride of a group IV element of the periodic table, and a carbide of a group IV element of the periodic table. From the viewpoint of durability, zirconia particles are more preferred. The inorganic particles are preferably inorganic particles produced by pulverizing rough particles of the inorganic particles, or spherical particles having uniform particle diameters by melting and refining the rough particles of the inorganic particles as the inorganic particles. There are no particular restrictions on the method of crushing the rough stone, and examples thereof include a ball mill, a bead mill, a colloid mill, a cone mill, a disc mill, a roller mill, a powder mill, a hammer mill, a granulator, and a VSI mill Machines, Willy mills, roll mills, jet mills, etc. Moreover, it is preferable to wash it after crushing, and as a washing method at this time, acid treatment is preferred. This makes it possible to reduce impurities such as iron adhering to the surfaces of the inorganic particles. The coating layer preferably contains a binder. The binder is a component that holds inorganic particles on the surface of the ion exchange membrane and forms a coating layer. From the viewpoint of resistance to an electrolytic solution or an electrolytic product, the binder preferably contains a fluorine-containing polymer. As the binder, a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group is more preferred from the viewpoints of resistance to an electrolytic solution or a product of electrolysis and adhesion to the surface of an ion exchange membrane. When a coating layer is provided on a layer (sulfonic acid layer) containing a fluorinated polymer having a sulfonic acid group, it is more preferable to use a fluorine-containing type having a sulfonic acid group as a binding agent for the coating layer. polymer. When a coating layer is provided on a layer (carboxylic acid layer) containing a fluorinated polymer having a carboxylic acid group, it is more preferable to use a compound having a carboxylic acid group as a binder for the coating layer. Fluoropolymer. The content of the inorganic particles in the coating layer is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. The content of the binder is preferably 10 to 60% by mass, and more preferably 10 to 50% by mass. The distribution density of the coating layer in the ion exchange membrane is preferably per 1 cm2 It is 0.05 ~ 2 mg. When the ion exchange membrane has a concave-convex shape on the surface, the distribution density of the coating layer is preferably 1 cm2 It is 0.5 to 2 mg. The method for forming the coating layer is not particularly limited, and a known method can be used. For example, a method of applying a coating liquid in which inorganic particles are dispersed in a solution containing a binder by spraying or the like can be cited. (Reinforced core material) The ion exchange membrane preferably has a reinforced core material disposed inside the membrane body. The reinforced core material is a member that strengthens the strength or dimensional stability of the ion exchange membrane. By disposing the reinforced core material inside the membrane body, the expansion and contraction of the ion exchange membrane can be controlled to a desired range, in particular. This ion-exchange membrane does not expand or contract more than necessary during electrolysis or the like, and can maintain excellent dimensional stability for a long period of time. The structure of the reinforcing core material is not particularly limited, and for example, a yarn called a reinforcing yarn may be formed by spinning. The so-called reinforcing yarn is a member constituting a reinforcing core material, and refers to a yarn capable of imparting required dimensional stability and mechanical strength to an ion exchange membrane and stably existing in the ion exchange membrane. By using a reinforced core material spun from this reinforcing yarn, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane. The material for reinforcing the core material and the reinforcing yarn used therefor is not particularly limited. It is preferably a material resistant to acids or alkalis. In terms of long-term heat resistance and chemical resistance, it is preferable to include Fiber of fluoropolymer. Examples of the fluorine-containing polymer used as the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). ), Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, from the viewpoint of heat resistance and chemical resistance, it is preferred to use a fiber containing polytetrafluoroethylene. The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The textile density (the number of weaves per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited. For example, a woven fabric, a non-woven fabric, a knitted fabric, or the like can be used, and a woven fabric form is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, and more preferably 30 to 150 μm. Woven or knitted fabrics can use monofilament, multifilament or any of these yarns, cut yarns, etc. The weaving method can use various weaving methods such as plain weaving, leno weaving, knitting, rib weaving, thin crepe weaving, etc. The spinning method and configuration of the reinforced core material in the membrane body are not particularly limited, and the appropriate size can be appropriately set in consideration of the size or shape of the ion exchange membrane, the physical properties required for the ion exchange membrane, and the use environment. For example, the reinforced core material may be arranged along a specific direction of the film body. From the viewpoint of dimensional stability, it is preferable to arrange the reinforced core material along a specific first direction, and along a second substantially perpendicular to the first direction. Orientation with other reinforced core materials. By arranging a plurality of reinforcing core materials in a substantially lined manner inside the longitudinal film body of the film body, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. For example, a configuration in which a reinforced core material (longitudinal yarn) arranged in the longitudinal direction and a reinforced core material (horizontal yarn) arranged in the horizontal direction is preferably woven into the surface of the film body. From the viewpoints of dimensional stability, mechanical strength, and ease of manufacture, it is more preferable to produce a plain weave fabric in which longitudinal and transverse yarns are alternately woven one by one, or twisted with two warp yarns and one side yarn. Interwoven leno weaves, twill weave woven by weaving the same number of cross yarns in every 2 or more parallel yarns. It is particularly preferable to arrange the reinforced core material in two directions of the MD direction (Machine Direction) and the TD direction (Transverse Direction) of the ion exchange membrane. That is, it is preferable to perform plain weaving in the MD direction and the TD direction. Here, the MD direction refers to a direction (traveling direction) in which the membrane body or various core materials (for example, a reinforced core material, a reinforced yarn, a sacrificial yarn described below, etc.) are transported in the manufacturing steps of the ion exchange membrane described below ), The TD direction refers to a direction substantially perpendicular to the MD direction. In addition, the yarn woven in the MD direction is referred to as an MD yarn, and the yarn woven in the TD direction is referred to as a TD yarn. Generally, the ion exchange membrane used in electrolysis is rectangular, and the length direction is MD direction and the width direction is TD direction. By weaving a reinforced core material as MD yarn and a reinforced core material as TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions. The arrangement interval of the reinforced core material is not particularly limited, and an appropriate arrangement may be appropriately set in consideration of physical properties required for the ion exchange membrane and use environment. The opening ratio of the reinforced core material is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane. The so-called aperture ratio of the reinforced core material refers to the total area (B) of the surface through which any substance such as ions (the electrolyte and its cations (for example, sodium ions)) can pass through. Ratio (B / A). The total area (B) of the surface through which substances such as ions can pass may refer to the total area of areas in the ion exchange membrane that are not blocked by the reinforced core material or the like contained in the ion exchange membrane. FIG. 121 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 121 is an enlarged view of a part of the ion exchange membrane, and only the arrangement of the reinforced core materials 21 and 22 in the area is illustrated, and other components are omitted. The total area of the reinforced core material is subtracted from the area (A) of the area surrounded by the reinforced core material 21 arranged in the longitudinal direction and the reinforced core material 22 arranged in the horizontal direction, which also includes the area of the reinforced core material ( C). The total area (B) of the area (A) through which substances such as ions can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I). Opening ratio = (B) / (A) = ((A)-(C)) / (A)… (I) In the reinforced core material, it is particularly preferable from the viewpoint of chemical resistance and heat resistance The morphology is a tape-like yarn or high-alignment monofilament containing PTFE. Specifically, it is more preferable to use a reinforced core material which uses a band-shaped yarn obtained by cutting a high-strength porous sheet containing PTFE into a band shape, or 50 to 300 of a highly-oriented monofilament containing PTFE. Denim plain weave fabric with a textile density of 10 to 50 per inch, with a thickness in the range of 50 to 100 μm. The aperture ratio of the ion-exchange membrane containing the reinforced core material is more preferably 60% or more. Examples of the shape of the reinforcing yarn include round yarn and ribbon yarn. (Communication hole) The ion exchange membrane preferably has a communication hole inside the membrane body. The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, the so-called communication hole is a tubular hole formed inside the membrane body, and is formed by dissolving a sacrificial core material (or sacrificial yarn) described below. The shape or diameter of the communication hole can be controlled by selecting the shape or diameter of the sacrificial core material (sacrificial yarn). By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured during electrolysis. The shape of the communication hole is not particularly limited. According to the manufacturing method described below, the shape of the sacrificial core material used for forming the communication hole can be made. The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With this structure, in the portion where the communication hole is formed on the cathode side of the reinforced core material, ions (for example, sodium ions) transported through the electrolyte filled with the communication hole can also flow to the cathode side of the reinforced core material. As a result, since the flow of cations is not blocked, the resistance of the ion exchange membrane can be further reduced. The communication hole may be formed only in one specific direction of the membrane body constituting the ion exchange membrane. From the viewpoint of exhibiting more stable electrolytic performance, it is preferably formed in both the longitudinal direction and the lateral direction of the membrane body. [Manufacturing Method] As a suitable method for manufacturing the ion exchange membrane, a method having the following steps (1) to (6) can be mentioned. (1) Step: a step of producing a fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted to an ion-exchange group by hydrolysis. (2) Step: by weaving at least a plurality of reinforcing core materials and sacrificial yarns that have properties of dissolving in acid or alkali and forming communicating holes to obtain reinforcements of sacrificial yarns arranged between adjacent reinforcing core materials. Material steps. (3) Step: a step of membrane-forming the above-mentioned fluorine-containing polymer having an ion-exchange group or an ion-exchange group precursor that can be converted into an ion-exchange group by hydrolysis. (4) Step: a step of burying the above-mentioned reinforcing material in the above-mentioned film to obtain a film body in which the above-mentioned reinforcing material is internally arranged as necessary. (5) Step: a step of hydrolyzing the membrane body obtained in step (4) (hydrolysis step). (6) Step: a step (coating step) of providing a coating layer on the film body obtained in step (5). Each step will be described in detail below. (1) Step: Step for producing fluoropolymer In step (1), a fluoropolymer is produced using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the monomers of the raw materials may be adjusted in the production of the fluorine-containing polymer forming each layer. (2) Step: Manufacturing steps of reinforcing material The so-called reinforcing material is a woven fabric of textile reinforcing yarn. A reinforcing core material is formed by embedding a reinforcing material in the film. When making an ion exchange membrane with communicating holes, sacrificial yarns are also woven into the reinforcing material together. In this case, the blending amount of the sacrificial yarn is preferably 10 to 80% by mass of the entire reinforcing material, and more preferably 30 to 70% by mass. By weaving the sacrificial yarn, the reinforcing core material can be prevented from being detached. Sacrificial yarns are soluble in the manufacturing steps of the film or in an electrolytic environment. Rhenium, polyethylene terephthalate (PET), cellulose, and polyamide can be used. In addition, polyvinyl alcohol having a thickness of 20 to 50 denier, monofilament or multifilament is also preferred. Furthermore, in step (2), the aperture ratio or the arrangement of the communication holes can be controlled by adjusting the configuration of the reinforced core material or the sacrificial yarn. (3) Step: Film formation step In the step (3), the fluorinated polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single-layer structure, as described above, a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or a multilayer structure of three or more layers. As a method of film formation, the following are mentioned, for example. A method of separately forming a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group into a membrane. A method for making a composite film from a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group by coextrusion. Moreover, the film may be plural. In addition, coextrusion of a heterogeneous film is preferred because it improves the bonding strength at the interface. (4) Step: the step of obtaining the film body In step (4), the reinforcing material obtained in step (2) is embedded in the inside of the film obtained in step (3) to obtain the reinforcing material inside. Membrane body. As a preferred method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) on the cathode side by a coextrusion method (hereinafter, The layer containing it is called the first layer) and a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonium fluoride functional group) (hereinafter, the layer containing it is referred to as a second layer). It is necessary to use a heating source and a vacuum source to separate the breathable and heat-resistant release paper, and sequentially laminate the reinforcing material and the second / first layer composite film on a flat plate or a drum with a large number of fine holes on the surface. At the melting temperature of each polymer, the method of integration is performed while removing the air between the layers by decompression; (ii) Different from the second / first layer composite film, the The fluorine-containing polymer (third layer) is separately formed into a film, and if necessary, a heating source and a vacuum source are used to separate the third layer film, the reinforced core material, Layer / first layer of composite film is sequentially laminated on a plate or drum with a large number of fine holes on the surface, Each of the polymer melt temperature, while removed under reduced pressure by the air between the layers while the integration method. Here, coextrusion of the first layer and the second layer helps to improve the bonding strength of the interface. In addition, the method of integrating under reduced pressure has a feature that the thickness of the third layer on the reinforcing material is larger than that of the pressure pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane body, it has a property capable of sufficiently maintaining the mechanical strength of the ion exchange membrane. In addition, the variation of the laminate described here is an example. The required layer structure or physical properties of the film body may be considered, and an appropriate laminate pattern (for example, a combination of layers) may be appropriately selected and then co-extruded. Furthermore, in order to further improve the electrical performance of the ion exchange membrane, a fluorine-containing polymer containing both a carboxylic acid group precursor and a sulfonic acid group precursor may be further interposed between the first layer and the second layer. Instead of the second layer, a fourth layer containing a fluorinated polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is used. The formation method of the fourth layer may be a method of separately manufacturing a fluorinated polymer having a carboxylic acid group precursor and a fluorinated polymer having a sulfonic acid group precursor and then mixing them. A method in which a monomer of a precursor is copolymerized with a monomer having a sulfonic acid group precursor. When the fourth layer is made into an ion-exchange membrane, the co-extruded film of the first layer and the fourth layer can be formed, and the third layer and the second layer can be separately formed into a membrane. The method described herein is laminated, and the three layers of the first layer / the fourth layer / the second layer can also be co-extruded to form a film. In this case, the direction of travel of the extruded film is the MD direction. As a result, a film body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material. Moreover, it is preferable that the ion exchange membrane has a protruding portion, that is, a protruding portion containing a fluorinated polymer having a sulfonic acid group on the surface side including the sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming a convex portion on the surface of a resin can be adopted. Specifically, the method of embossing the surface of a film main body is mentioned, for example. For example, when the composite film is integrated with a reinforcing material or the like, the convex portion can be formed by using a release paper that has been embossed in advance. When the convex portion is formed by embossing, the height of the convex portion or the arrangement density can be controlled by controlling the transferred embossed shape (shape of the release paper). (5) Hydrolysis step In step (5), a step of hydrolyzing the membrane body obtained in step (4) to convert an ion-exchange group precursor to an ion-exchange group (hydrolysis step) is performed. In step (5), a dissolution hole can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body by using an acid or an alkali. In addition, the sacrificial yarn may not be completely dissolved and removed, but may remain in the communication hole. In addition, the sacrificial yarn remaining in the communication hole can be removed by dissolving the electrolytic solution when the ion exchange membrane is supplied for electrolysis. Sacrificial yarns are those which are soluble in acids or alkalis in the manufacturing steps of ion exchange membranes or in an electrolytic environment. The sacrificial yarns are dissolved to form communication holes in this part. Step (5) can be carried out by immersing the film body obtained in step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (Dimethyl sulfoxide) can be used. The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35 mass% of DMSO. The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the thicker the apparent thickness. It is more preferably 75 to 100 ° C. The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes. Here, the step of forming the communication hole by dissolving the sacrificial yarn will be described in more detail. Figures 122 (a) and (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane. In Figs. 122 (a) and (b), only the reinforcing yarn 52, the sacrificial yarn 504a, and the communication hole 504 formed by the sacrificial yarn 504a are shown, and other members such as the film body are not shown. First, a knitting-reinforcing material is made from the reinforcing yarn 52 constituting the reinforcing core material in the ion-exchange membrane and the sacrificial yarn 504a used to form the communication hole 504 in the ion-exchange membrane. Then, in step (5), the communication hole 504 is formed by dissolving the sacrificial yarn 504a. According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a can be adjusted according to how the reinforcing core material and the communication hole are arranged in the membrane body of the ion exchange membrane, which is relatively simple. In FIG. 122 (a), the plain weaving reinforcing material woven with the reinforcing yarn 52 and the sacrificial yarn 504a in the longitudinal and transverse directions on the paper surface is illustrated. The configuration of the reinforcing yarn 52 and the sacrificial yarn 504a in the reinforcing material may be changed as necessary . (6) Coating step In step (6), a coating liquid containing inorganic particles obtained by pulverizing or melting the raw stone and a binder is prepared, and the coating liquid is applied to the ion exchange obtained in step (5). The surface of the film is dried to form a coating layer. As the binding agent, it is preferred that the fluorine-containing polymer having an ion-exchange group precursor is hydrolyzed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to ion-exchange. Substitute counter ion for H+ The resulting binding agent (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group). This makes it easy to dissolve in water or ethanol described below, and is therefore preferred. This binding agent was dissolved in a solution obtained by mixing water and ethanol. Furthermore, the preferred volume ratio of water to ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and even more preferably 2: 1 to 1: 2. The coating liquid was obtained by dispersing the inorganic particles in the dissolving liquid thus obtained by a ball mill. At this time, the average particle diameter of the particles and the like can also be adjusted by adjusting the time during dispersion and the rotation speed. Moreover, the preferable blending amount of the inorganic particles and the binder is as described above. The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, and it is preferable to make a thin coating liquid. Thereby, the surface of an ion exchange membrane can be apply | coated uniformly. When dispersing the inorganic particles, a surfactant may be added to the dispersion liquid. The surfactant is preferably a nonionic surfactant, and examples thereof include HS-210, NS-210, P-210, and E-212 manufactured by Nippon Oil Corporation. An ion exchange membrane can be obtained by applying the obtained coating solution to the surface of an ion exchange membrane by spray coating or roll coating. [Microporous membrane] The microporous membrane of this embodiment is not particularly limited as long as it can be laminated with an electrode for electrolysis as described above, and various microporous membranes can be applied. The porosity of the microporous membrane of this embodiment is not particularly limited, and it can be set to, for example, 20 to 90, and preferably 30 to 85. The porosity can be calculated by the following formula, for example. Porosity = (1-(film weight in dry state) / (weight calculated from the volume calculated from the thickness, width, and length of the film and the density of the film material)) × 100 average pore diameter of the microporous membrane of this embodiment It is not particularly limited, and may be, for example, 0.01 μm to 10 μ, and preferably 0.05 μm to 5 μm. The said average pore diameter cuts a film | membrane perpendicularly along a thickness direction, and observes a cut surface by FE-SEM, for example. The average pore diameter can be determined by measuring the diameter of the observed pores at about 100 points and obtaining an average value. The thickness of the microporous membrane in this embodiment is not particularly limited, and it can be set to, for example, 10 μm to 1,000 μm, and preferably 50 μm to 600 μm. The thickness can be measured, for example, using a micrometer (manufactured by Mitutoyo Co., Ltd.). Specific examples of the microporous membrane described above include those described in Zilfon Perl UTP 500 manufactured by Agfa Corporation, International Publication No. 2013-183584, International Publication No. 2016-203701, and the like. In the manufacturing method of the electrolytic cell of this embodiment, the separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having an EW (ion exchange equivalent) different from the first ion exchange resin layer. The separator preferably includes a first ion exchange resin layer and a second ion exchange resin layer having a functional group different from the first ion exchange resin layer. The ion exchange equivalent can be adjusted by the introduced functional group, and the functional group that can be introduced is as described above. (Water Electrolysis) The electrolytic cell in the case of performing water electrolysis in this embodiment has a constitution in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis described above is changed to a microporous membrane. In addition, the electrolyzer is different from the case where the salt electrolysis is performed in the point that the supplied raw material is water. Regarding other configurations, the electrolytic cell in the case of performing water electrolysis may also have the same configuration as the electrolytic cell in the case of performing salt electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. In the case of water electrolysis, only oxygen is generated in the anode chamber, so the same material as the cathode chamber can be used. Examples include nickel. The anode coating is preferably a catalyst coating for generating oxygen. Examples of the catalyst coating layer include metals, oxides, hydroxides, and the like of platinum group metals and transition metal groups. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used. [Examples] The present invention will be described in more detail by the following examples and comparative examples, but the present invention is not limited at all by the following examples. <Verification of the First Embodiment> An experimental example corresponding to the first embodiment (hereinafter referred to as "exemplary" in the following "Verification of the First Embodiment") is prepared as follows, and does not correspond to the first embodiment. The experimental example corresponding to the embodiment (hereinafter referred to as "comparative example" in the item of "Verification of the First Embodiment") was evaluated by the following method. The details will be described with reference to FIGS. 10 to 21 as appropriate. [Evaluation method] (1) Porosity The electrode was cut into a size of 130 mm x 100 mm. An electronic digital thickness gauge (manufactured by Mitutoyo Co., Ltd., showing a minimum of 0.001 mm) was used to uniformly measure 10 points in the plane and calculate the average value. The volume was calculated using this as the electrode thickness (gauge thickness). Thereafter, the mass was measured using an electronic balance, and the weight was determined based on the specific gravity of the metal (the specific gravity of nickel = 8.908 g / cm3 , Specific gravity of titanium = 4.506 g / cm3 ) Calculate the porosity or porosity. Porosity (void ratio) (%) = (1-(electrode mass) / (electrode volume × metal specific gravity)) × 100 (2) mass per unit area (mg / cm2 ) Cut the electrode to a size of 130 mm × 100 mm and measure the mass with an electronic balance. Divide this value by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force per unit mass / area (1) (Adhesive force) (N / mg ・ cm2 )) [Method (i)] The measurement system used a tensile compression tester (Imada Manufacturing Co., Ltd., the tester body: SDT-52NA type tensile compression tester, load meter: SL-6001 load meter). A nickel plate having a thickness of 1.2 mm and a thickness of 200 mm was sprayed with alumina with a grain number of 320. The arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment was 0.7 μm. Here, the surface roughness measurement uses a stylus-type surface roughness measuring machine SJ-310 (Mitutoyo Co., Ltd.). The measurement sample was set on a platform parallel to the ground, and the arithmetic average roughness Ra was measured under the following measurement conditions. When the measurement is performed 6 times, the average value is described. <Shape of Stylus> Conical, Taper Angle = 60 °, Tip Radius = 2 μm, Static Measuring Force = 0.75 mN <Roughness Standard> JIS2001 <Evaluation Curve> R <Filter> GAUSS <Critical Value λc> 0.8 mm <Critical The value λs> 2.5 μm <the number of intervals> 5 <forward sweep, backward sweep> There is a chuck for fixing the nickel plate to the lower side of the tensile compression tester so as to be vertical. The following ion exchange membrane A was used as a separator. As the reinforcing core material, a 90-denier monofilament (hereinafter referred to as PTFE yarn) made of polytetrafluoroethylene (PTFE) was used. As the sacrificial yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 6 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. First, a woven fabric is obtained by plain weaving with 24 PTFE yarns arranged in each of the two directions of TD and MD and two sacrificial yarns arranged between adjacent PTFE yarns. The obtained woven fabric was crimped by a roller to obtain a woven fabric having a thickness of 70 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.85 mg equivalent / g of dry resin, resin A, and CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer B had a resin B having an ion exchange capacity of 1.03 mg equivalent / g of the dry resin. Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 μm and a thickness of the resin B layer of 104 μm was obtained by a co-extrusion T-die method. Then, on a heating plate having a heating source and a vacuum source inside, and micropores on its surface, a release paper (cone-shaped embossing processing with a height of 50 μm), a reinforcing material, and a film X were sequentially laminated on the heating plate surface temperature. After heating and decompressing under the conditions of 223 ° C and a degree of reduced pressure of 0.067 MPa for 2 minutes, the release paper was removed to obtain a composite film. Saponification was performed by immersing the obtained composite film in an aqueous solution at 80 ° C. containing 30% by mass of dimethylsulfinium (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. After that, it was immersed in a 50 ° C aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour to replace the counter ion of the ion-exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC. Furthermore, 20% by mass of zirconia having a particle size of 1 μm was added to a 5% by mass ethanol solution of the acid type resin of the resin B to disperse it to prepare a suspension, and both sides of the composite film were prepared by a suspension spray method. Spraying was performed to form a coating of zirconia on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconia was measured by fluorescent X-ray measurement, and the result was 0.5 mg / cm2 . The average particle diameter is measured using a particle size distribution meter ("SALD (registered trademark) 2200" manufactured by Shimadzu Corporation). The ion exchange membrane (separator) obtained above was immersed in pure water for more than 12 hours and used in the test. It was made to contact the said nickel plate fully wetted with pure water, and it adhere | attached by the tension | tensile_strength of water. At this time, the nickel plate and the upper end of the ion-exchange membrane are aligned. The electrode sample (electrode) used for the measurement was cut into a 130 mm square. The ion exchange membrane A was cut into 170 mm squares. Two stainless steel plates (1 mm in thickness, 9 mm in length, and 170 mm in width) were sandwiched on one side of the electrode, aligned with the center of the stainless steel plate and the electrode, and uniformly fixed by 4 clamps. The center of the stainless steel plate was clamped by a clamp on the upper side of the tensile compression tester, and the electrode was suspended. At this time, the load to the testing machine was set to 0 N. Remove the stainless steel plate, electrode, and clamp assembly from the tensile compression tester temporarily. In order to fully wet the electrode with pure water, immerse it in a tank filled with pure water. Thereafter, the center of the stainless steel plate was clamped again to the chuck on the upper side of the tensile compression tester, and the electrode was suspended. The upper chuck of the tensile compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the ion exchange membrane using the surface tension of pure water. At this time, the bonding surface is 130 mm in width and 110 mm in length. The pure water filled in the washing bottle is blown to the electrode and the ion exchange membrane as a whole, and the diaphragm and the electrode are fully wetted again. After that, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (38 mm outer diameter) was gently pressed from above the electrode, and rolled from top to bottom to remove excess Remove pure water. The roller is applied only once. The electrode was raised at a speed of 10 mm / minute, and the load measurement was started. The overlapping portion of the electrode and the diaphragm was recorded as a load at a width of 130 mm and a length of 100 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area where the electrode overlaps with the ion exchange membrane and the electrode mass in the area where it overlaps with the ion exchange membrane to calculate the force per unit mass and area (1). The mass of the electrode overlapping the ion exchange membrane is based on the mass per unit area (mg / cm) of (2) above.2 The value obtained in) is calculated by ratio calculation. The environment of the measuring room is 23 ± 2 ℃ and relative humidity 30 ± 5%. In addition, the electrodes used in the examples and comparative examples can be attached independently without sagging or peeling when they are adhered to the ion exchange membrane of a nickel plate fixed vertically by surface tension. In addition, the model of the evaluation method of bearing capacity (1) is shown in FIG. The measurement lower limit of the tensile tester is 0.01 (N). (4) Force per unit mass and unit area (2) (Adhesive force) (N / mg ・ cm2 )) [Method (ii)] The measurement system used a tensile compression tester (Imada Manufacturing Co., Ltd., the tester body: SDT-52NA type tensile compression tester, load meter: SL-6001 load meter). The nickel plate similar to the method (i) was fixed vertically to a chuck on the lower side of the tensile compression tester. The electrode sample (electrode) used for the measurement was cut into a 130 mm square. The ion exchange membrane A was cut into 170 mm squares. Two stainless steel plates (1 mm in thickness, 9 mm in length, and 170 mm in width) were sandwiched on one side of the electrode, aligned with the center of the stainless steel plate and the electrode, and uniformly fixed by 4 clamps. The center of the stainless steel plate was clamped by a clamp on the upper side of the tensile compression tester, and the electrode was suspended. At this time, the load to the testing machine was set to 0 N. Remove the stainless steel plate, electrode, and clamp assembly from the tensile compression tester temporarily. In order to fully wet the electrode with pure water, immerse it in a tank filled with pure water. Thereafter, the center of the stainless steel plate was clamped again to the chuck on the upper side of the tensile compression tester, and the electrode was suspended. The upper chuck of the tensile compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the nickel plate by the surface tension of the solution. At this time, the bonding surface is 130 mm in width and 110 mm in length. The pure water filled in the washing bottle is blown to the entire electrode and the nickel plate, and the nickel plate and the electrode are fully wetted again. After that, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (38 mm outer diameter) was gently pressed from above the electrode, and rolled from top to bottom to remove excess The solution was removed. The roller is applied only once. The electrode was raised at a speed of 10 mm / minute, and the load measurement was started. The load at the time when the longitudinal overlap between the electrode and the nickel plate became 100 mm was recorded. This measurement was performed three times and the average value was calculated. The average value is divided by the area where the electrode overlaps with the nickel plate and the mass of the electrode with the area overlapping with the nickel plate to calculate the force per unit mass and unit area (2). The mass of the electrode overlapping the diaphragm is based on the mass per unit area (mg / cm) of (2) above.2 The value obtained in) is calculated by ratio calculation. The environment of the measurement room was 23 ± 2 ° C and 30 ± 5% relative humidity. In addition, the electrodes used in the examples and comparative examples can be attached independently without sagging or peeling when they are adhered to a nickel plate that is fixed vertically by surface tension. The measurement lower limit of the tensile tester is 0.01 (N). (5) Evaluation method of cylindrical winding with a diameter of 280 mm (1) (%) (film and cylinder) Evaluation method (1) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In Comparative Examples 10 and 11, the electrode was integrated with the ion-exchange membrane by hot pressing. Therefore, one body of the ion-exchange membrane and the electrode (130 mm square electrode system) was prepared. The ion exchange membrane was fully immersed in pure water, and then placed on the curved surface of a plastic (polyethylene) tube made of 280 mm outside diameter. Thereafter, the excess solution was removed by a roller formed by winding an independent foaming type EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outer diameter of 38 mm). The roller system rolls on the ion exchange membrane from the left side to the right side of the pattern diagram shown in FIG. 11. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the plastic tube electrode with an outer diameter of 280 mm was measured. (6) Evaluation method of cylindrical winding with a diameter of 280 mm (2) (%) (film and electrode) Evaluation method (2) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into a 130 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. The ion exchange membrane and the electrode were fully immersed in pure water, and then laminated. The laminated body was placed on a curved surface of a plastic (polyethylene) tube having an outer diameter of 280 mm so that the electrodes became outside. Thereafter, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (outer diameter of 38 mm) was gently pressed from above the electrode, and from the left side of the pattern diagram shown in FIG. 12 Scroll to the right to remove excess solution. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the electrode was measured. (7) 145 mm diameter cylindrical winding evaluation method (3) (%) (film and electrode) Evaluation method (3) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into a 130 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. The ion exchange membrane and the electrode were fully immersed in pure water, and then laminated. The laminated body was placed on a curved surface of a plastic (polyethylene) tube having an outer diameter of 145 mm so that the electrodes became outside. Thereafter, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wound around a vinyl chloride tube (outer diameter of 38 mm) was gently pressed from above the electrode, and from the left side of the pattern diagram shown in FIG. 13 Scroll to the right to remove excess solution. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the electrode was measured. (8) Operability (induction evaluation) (A) The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into 95 × 110 mm. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In each example, the ion exchange membrane and the electrode were fully immersed in three solutions of sodium bicarbonate aqueous solution, 0.1 N aqueous NaOH solution, and pure water, and then laminated, and then placed on a Teflon plate. The distance between the anode cell and the cathode cell used in the electrolytic evaluation was set to about 3 cm, and the stacked body that was left standing was lifted up to be inserted and sandwiched therebetween. When performing this operation, check whether the electrode is deviated or dropped while operating. (B) The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut to a size of 170 mm square, and the electrode was cut to 95 × 110 mm. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In each example, the ion exchange membrane and the electrode were fully immersed in three solutions of sodium bicarbonate aqueous solution, 0.1 N aqueous NaOH solution, and pure water, and then laminated, and then placed on a Teflon plate. Hold the corners of the two adjacent parts of the laminate, and lift up the laminate so that it is vertical. From this state, the two corners of the hand held are moved so that the film becomes convex or concave. This operation was repeated once more to confirm the followability of the electrode to the film. Based on the following indicators, the results were evaluated on four levels of 1-4. 1: Good operation 2: Can operate 3: Difficult operation 4: Generally inoperable Here, for the sample of Comparative Example 5, a large size of 1.3 m × 2.5 m with an electrode and 1.5 m × 2.8 m with an ion exchange membrane The electrolytic cells are operated in the same size. The evaluation result of Comparative Example 5 (hereinafter referred to as "3") serves as an index for evaluating the differences between the above-mentioned evaluations (A) and (B) and when the large size is made. That is, in the case where the results obtained by evaluating a small laminated body are "1" and "2", it is evaluated that there is no problem in operability even in the case of making a large size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common salt concentration in caustic soda (ppm, 50% conversion)) The electrolytic performance was evaluated by the following electrolytic experiment. A titanium anode cell (anode termination cell) having an anode chamber provided with an anode was opposed to a cathode cell having a cathode chamber (cathode termination cell) made of nickel provided with a cathode. A pair of spacers are arranged between the cells, and a laminate (a laminate of the ion exchange membrane A and the electrode for electrolysis) is sandwiched between the pair of spacers. Then, the anode cell, the gasket, the laminate, the gasket, and the cathode are closely contacted to obtain an electrolytic cell, and an electrolytic cell including the electrolytic cell is prepared. As the anode, a mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride was applied to a titanium substrate that had been subjected to spraying and acid etching treatment as a pretreatment, and was then dried and fired. The anode is fixed to the anode chamber by welding. As the cathode, those described in Examples and Comparative Examples were used. As the current collector of the cathode chamber, a porous metal made of nickel was used. The size of the current collector is 95 mm in length × 110 mm in width. As the metal elastic body, a pad woven with fine nickel wires is used. A metal elastomer was placed on the current collector. A nickel net made of a nickel wire with a diameter of 150 μm and a plain mesh with a 40-mesh mesh was covered thereon, and the four corners of the Ni net were fixed to the current collector by a rope made of Teflon (registered trademark). This Ni mesh was used as a power source. In this electrolytic cell, a zero-pitch structure is formed by utilizing the repulsive force of a pad of a metal elastomer. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As the separator, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used. Electrolysis of common salt is performed using the above electrolytic cell. The brine concentration (sodium chloride concentration) of the anode compartment was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode compartment was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell became 90 ° C. At current density of 6 kA / m2 Next, salt electrolysis was performed to measure voltage, current efficiency, and salt concentration in caustic soda. Here, the so-called current efficiency is the ratio of the amount of caustic soda generated to the flowing current. If the flowing current causes impurity ions or hydroxide ions instead of sodium ions to move in the ion exchange membrane, the current efficiency reduce. The current efficiency is obtained by dividing the Mohr number of caustic soda generated by a certain time by the Mohr number of electrons flowing in the meantime. The molar number of caustic soda is obtained by measuring the mass of caustic soda produced by electrolysis in a polymer tank. The salt concentration in caustic soda is a value obtained by converting the caustic soda concentration to 50%. In addition, Table 1 shows the specifications of the electrodes and power feeders used in the examples and comparative examples. (11) Measurement of the thickness of the catalyst layer, electrode substrate for electrolysis, and electrode thickness The thickness of the electrode substrate for electrolysis was measured uniformly on the surface using an electronic digital thickness gauge (manufactured by Mitutoyo Co., Ltd., showing at least 0.001 mm) Ten points were measured and the average value was calculated. This was used as the thickness (gauge thickness) of the electrode substrate for electrolysis. The thickness of the electrode is the same as that of the electrode substrate, and 10 points are uniformly measured in the plane by an electronic digital thickness meter, and the average value is calculated. This is used as the electrode thickness (gauge thickness). The thickness of the catalyst layer is determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. (12) Elastic deformation test of the electrode The ion exchange membrane A (diaphragm) produced in [Method (i)] and the electrode were cut into a size of 110 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the ion-exchange membrane was laminated with the electrode to make a laminated body, as shown in FIG. 14, and wound to an outer diameter of f32 mm without gaps. 20 cm PVC tube. In order to prevent the wound laminate from peeling or loosening from the PVC pipe, a polyethylene strap is used for fixing. Hold in this state for 6 hours. After that, the straps were removed, and the laminated body was unrolled from the PVC pipe. Place the electrode only on the platform, and measure the height L of the part that protrudes from the platform1 , L2 And find the average. This value is used as an index of electrode deformation. That is, a smaller value means that it is difficult to deform. When a porous metal is used, there are two types of the SW direction and the LW direction during winding. In this test, it was wound in the SW direction. Moreover, about the electrode which deform | transformed (the electrode which did not return to the original flat state), the softness after plastic deformation was evaluated by the method shown in FIG. That is, the deformed electrode is placed on a diaphragm that is fully immersed in pure water, one end is fixed, the opposite end of the floating is pressed against the diaphragm, the force is released, and the deformation electrode is evaluated to follow the diaphragm . (13) Evaluation of membrane damage The following ion exchange membrane B was used as a separator. As the reinforcing core material, polytetrafluoroethylene (PTFE) and a yarn of 100 denier twisted at 900 times / m into a yarn shape (hereinafter referred to as PTFE yarn) were used. As the sacrificial yarn of the warp yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 8 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. As the sacrificial yarn of the weft yarn, a yarn obtained by twisting polyethylene terephthalate (PET) with 35 deniers and 8 filaments at 200 times / m was used. First, plain weaving was performed by arranging 24 PTFE yarns per 24 inches and placing two sacrificial yarns between adjacent PTFE yarns to obtain a woven fabric with a thickness of 100 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.92 mg equivalent / g of dry resin polymer (A1),2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer (F1) had a polymer (B1) with an ion exchange capacity of 1.10 mg equivalent / g of dry resin. Using these polymers (A1) and (B1), a two-layer film with a thickness of 25 μm of a polymer (A1) layer and a thickness of 89 μm of a polymer (B1) layer was obtained by co-extrusion T-die method X . The ion exchange capacity of each polymer represents the ion exchange capacity when the ion exchange group precursor of each polymer is hydrolyzed and converted into an ion exchange group. Also, prepare separately with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer (F2) had a polymer (B2) with an ion exchange capacity of 1.10 mg equivalent / g of dry resin. This polymer single layer was extruded to obtain a film Y of 20 μm. Then, on a heating plate with a heating source and a vacuum source inside and micropores on the surface, the release paper, the film Y, the reinforcing material and the film X are sequentially laminated, and the conditions of the heating plate temperature 225 ° C and the decompression degree 0.022 MPa After depressurizing under heating for 2 minutes, the release paper was removed to obtain a composite film. The obtained composite membrane was immersed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH) for 1 hour to perform saponification, and then immersed in 0.5 N NaOH for 1 hour to ion-exchange The attached ions were replaced with Na and then washed with water. Furthermore, it dried at 60 degreeC. Also, will start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The polymer (B3) of the copolymer (F) having an ion exchange capacity of 1.05 mg equivalent / g of the dried resin was hydrolyzed and then made into an acid form by hydrochloric acid. In a solution prepared by dissolving the acid polymer (B3 ') in a 50/50 (mass ratio) mixed solution of water and ethanol at a ratio of 5% by mass, the polymer (B3') and zirconia Zirconium oxide particles having an average particle diameter of 0.02 μm were added so that the mass ratio of the particles was 20/80. Thereafter, it was dispersed in a suspension of zirconia particles by a ball mill to obtain a suspension. This suspension was coated on both surfaces of the ion exchange membrane by a spray method and dried to obtain an ion exchange membrane B having a coating layer containing a polymer (B3 ′) and zirconia particles. The coating density of zirconia was measured by fluorescent X-ray measurement, and it was 0.35 mg / cm2 . For the anode system, the same one as in (9) electrolytic evaluation was used. For the cathode system, those described in Examples and Comparative Examples were used. The collector, pad and feed system of the cathode chamber are the same as those used in (9) Electrolytic Evaluation. In other words, the Ni mesh is used as a power feeder, and a zero-pitch structure is formed by using the repulsive force of a pad of a metal elastic body. The gasket was the same as that used in (9) Electrolytic Evaluation. As the separator, the ion exchange membrane B produced by the above method was used. That is, the same electrolytic cell as in (9) was prepared, except that the laminated body of the ion exchange membrane B and the electrode for electrolysis was sandwiched between a pair of spacers. Electrolysis of common salt is performed using the above electrolytic cell. The brine concentration (sodium chloride concentration) of the anode compartment was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode compartment was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell became 70 ° C. At current density of 8 kA / m2 Next, salt electrolysis was performed. After 12 hours from the start of the electrolysis, the electrolysis was stopped, the ion exchange membrane B was taken out, and the damage state was observed. "0" means no damage. "1 to 3" means there is damage, the larger the number, the greater the degree of damage. (14) Ventilation resistance of the electrode The ventilation resistance of the electrode was measured using a permeability testing machine KES-F8 (trade name, Kato Tech Co., Ltd.). The unit of ventilation resistance value is kPa · s / m. The measurement was performed 5 times, and the average value is shown in Table 2. The measurement was performed under the following two conditions. The temperature in the measurement chamber was set to 24 ° C, and the relative humidity was set to 32%.・ Measurement condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Ventilation volume: 0.4 cc / cm2 / s Measurement range: SENSE L (low) Sample size: 50 mm × 50 mm • Measurement condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / cm2 / s Measurement range: SENSE M (medium) or H (high) Sample size: 50 mm × 50 mm [Example 1] As an electrode substrate for cathode electrolysis, an electrolytic nickel foil with a gauge thickness of 16 μm was prepared. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The nickel foil is punched to form a circular hole to form a porous foil. The opening ratio is 49%. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the electrode produced in Example 1 was 24 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The coating is also formed on the surface without roughening. It is the total thickness of ruthenium oxide and cerium oxide. Table 2 shows the measurement results of the adhesion force of the electrodes produced by the above methods. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. In order to use the electrode produced by the above method for electrolytic evaluation, it was cut into a size of 95 mm in length and 110 mm in width. Approximately the center of the carboxylic acid layer side of the ion-exchange membrane A (160 mm × 160 mm in size) of the ion exchange membrane A (160 mm × 160 mm) prepared in [Method (i)] with the roughened surface of the electrode equilibrated with a 0.1 N NaOH aqueous solution. The positions are opposite, and the surface tension of the aqueous solution makes them in close contact. Even if the four corners of the membrane part of the membrane-integrated electrode are grasped so that the electrode becomes the ground side and the membrane-integrated electrode is suspended parallel to the ground, there is no case of electrode peeling or deviation. In addition, even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not peel off or deviate. The membrane-integrated electrode is sandwiched between the anode cell and the cathode cell so that the electrode-attached surface becomes the cathode chamber side. The cross-sectional structure is a zero-pitch structure in which current collectors, pads, nickel grid feeders, electrodes, films, and anodes are sequentially arranged from the cathode chamber side. The obtained electrodes were subjected to electrolytic evaluation. The results are shown in Table 2. Shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF (fluorescence X-ray analysis), approximately 100% of the coating remained on the roughened surface, and the coating on the non-roughened surface decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 2] In Example 2, an electrolytic nickel foil having a gauge thickness of 22 μm was used as an electrode substrate for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.96 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening rate is 44%. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 29 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 7 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0033 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 3] In Example 3, an electrolytic nickel foil with a gauge thickness of 30 μm was used as an electrode substrate for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 1.38 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening rate is 44%. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 38 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 4] In Example 4, an electrolytic nickel foil with a gauge thickness of 16 μm was used as an electrode substrate for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The porosity is 75%. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 24 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The measurement of the air flow resistance of the electrode was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 5] In Example 5, an electrolytic nickel foil having a gauge thickness of 20 μm was prepared as an electrode substrate for cathode electrolysis. Both sides of the nickel foil are subjected to a roughening treatment by electrolytic nickel plating. The roughened surface has an arithmetic average roughness Ra of 0.96 μm. Both sides have the same roughness. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening ratio is 49%. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 30 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The measurement of the air flow resistance of the electrode was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on both sides. If Comparative Examples 1 to 4 are considered, it will be shown that even if there is little or no coating on the opposite side of the film, good electrolytic performance can be exhibited. [Example 6] Example 6 was evaluated in the same manner as in Example 1 except that the electrode substrate for cathode electrolysis was applied by ion plating, and the results are shown in Table 2. In addition, ion plating uses a Ru metal target at a heating temperature of 200 ° C, and a film formation pressure of 7 × 10 under an argon / oxygen environment.-2 Pa was formed into a film. The coating formed is ruthenium oxide. The thickness of the electrode is 26 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 7] Example 7 is an electrode base material for cathode electrolysis produced by an electroforming method. The shape of the photomask is a shape in which squares of 0.485 mm × 0.485 mm are arranged vertically and horizontally at intervals of 0.15 mm. By sequentially exposing, developing, and electroplating, a nickel porous foil having a gauge thickness of 20 μm and an opening ratio of 56% was obtained. The arithmetic average roughness Ra of the surface was 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 37 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis and is 17 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 8] The electrode base material for cathode electrolysis in Example 8 was produced by an electroforming method, the gauge thickness was 50 μm, and the open porosity was 56%. The arithmetic average roughness Ra of the surface was 0.73 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 60 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 9] In Example 9, a nickel non-woven fabric (manufactured by NIKKO TECHNO Co., Ltd.) having a gauge thickness of 150 μm and a porosity of 76% was used as an electrode base material for cathode electrolysis. Non-woven nickel fiber with a diameter of about 40 μm and a basis weight of 300 g / m2 . Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 165 μm. The thickness of the catalyst layer is 15 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 29 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0612 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 10] In Example 10, a nickel nonwoven fabric (manufactured by NIKKO TECHNO Co., Ltd.) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode base material for cathode electrolysis. Non-woven nickel fiber with a diameter of about 40 μm and a basis weight of 500 g / m2 . Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 215 μm. The thickness of the catalyst layer is 15 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 40 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0164 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 11] In Example 11, foamed nickel (manufactured by Mitsubishi Materials Co., Ltd.) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode base material for cathode electrolysis. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode was 210 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 17 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0402 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 12] In Example 12, a nickel mesh having a wire diameter of 50 μm, a 200 mesh, a gauge thickness of 100 μm, and an opening ratio of 37% was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. Even if the blasting treatment is performed, the aperture ratio does not change. Because it is difficult to measure the surface roughness of the metal mesh, in Example 12, a nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. . The arithmetic average roughness Ra of one metal wire mesh was 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 110 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 0.5 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0154 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 13] In Example 13, a nickel mesh having a wire diameter of 65 μm, a 150 mesh, a gauge thickness of 130 μm, and an opening ratio of 38% was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. Even if the blasting treatment is performed, the aperture ratio does not change. Because it is difficult to measure the surface roughness of the wire mesh, in Example 13, a nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface roughness of the wire mesh . The arithmetic average roughness Ra is 0.66 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 133 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 3 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 6.5 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0124 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The evaluation of membrane damage was also "0", which was good. [Example 14] In Example 14, the same base material (gauge thickness: 30 μm, open porosity: 44%) as that of Example 3 was used as the electrode base material for cathode electrolysis. An electrolytic evaluation was performed with the same configuration as in Example 1 except that no nickel mesh power feeder was provided. That is, the cross-sectional structure of the electrolytic cell is a zero-pitch structure in which a current collector, a pad, a membrane-integrated electrode, and an anode are sequentially arranged from the cathode chamber side, and the pad functions as a power feeder. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 15] Example 15 uses the same substrate (gauge thickness: 30 μm, open porosity: 44%) as that of Example 3 as the electrode substrate for cathode electrolysis. In place of the nickel grid feeder, a deteriorated cathode used in Reference Example 1 and an increased electrolytic voltage were provided. Other than that, electrolytic evaluation was performed with the same configuration as in Example 1. That is, the cross-sectional structure of the electrolytic cell is formed by sequentially arranging a current collector, a pad, a deteriorated cathode (functioning as a power feeder), an electrode for electrolysis (cathode), a separator, and an anode in order from a cathode chamber side. Zero-pitch structure, the cathode that is degraded and the electrolytic voltage becomes high functions as a feeder. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 16] As an electrode substrate for anode electrolysis, a titanium foil having a gauge thickness of 20 μm was prepared. Both sides of the titanium foil are roughened. This titanium foil was punched, and round holes were made to form a porous foil. The diameter of the holes was 1 mm, and the opening ratio was 14%. The arithmetic average roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L and a iridium concentration of 100 g / L so that the molar ratios of ruthenium, iridium and titanium are 0.25: 0.25: 0.5 Iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed. This mixed solution was sufficiently stirred and used as an anode coating solution. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). After applying the coating solution to a titanium porous foil, drying was performed at 60 ° C for 10 minutes, and firing was performed at 475 ° C for 10 minutes. After repeating the series of operations of coating, drying, pre-firing, and firing, firing was performed at 520 ° C for 1 hour. In order to use the electrode produced by the above method for electrolytic evaluation, it was cut into a size of 95 mm in length and 110 mm in width. By the surface tension of the aqueous solution, it was brought into close contact with the approximate center of the sulfonic acid layer side of the ion-exchange membrane A (size: 160 mm × 160 mm) produced in [Method (i)] equilibrated with a 0.1 N NaOH aqueous solution. . The cathode was prepared in the following procedure. First, a nickel wire mesh having a wire diameter of 150 μm and 40 mesh was prepared as a base material. After performing a spray treatment with alumina as a pretreatment, it was immersed in 6 N hydrochloric acid for 5 minutes, and thoroughly washed and dried with pure water. Then, a ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) and cerium chloride (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L so that the molar ratio of the ruthenium element to the cerium element is 1: 0.25 To mix. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 300 ° C for 3 minutes, and firing was performed at 550 ° C for 10 minutes. Thereafter, firing was performed at 550 ° C for 1 hour. The series of operations of coating, drying, pre-firing and firing are repeated. As the current collector of the cathode chamber, a porous metal made of nickel was used. The size of the current collector is 95 mm in length × 110 mm in width. As the metal elastic body, a pad woven with fine nickel wires is used. A metal elastomer was placed on the current collector. The cathode produced by the above method was covered thereon, and the four corners of the net were fixed to the current collector by using a rope made of Teflon (registered trademark). Even if the four corners of the membrane part of the membrane-integrated electrode which is integrated with the membrane and the anode are grasped, the electrode becomes the ground side and the membrane-integrated electrode is suspended in a manner parallel to the ground, there is no peeling or deviation of the electrode. In addition, even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not peel off or deviate. The anode used in Reference Example 3, which has been deteriorated and has an increased electrolytic voltage, is fixed to the anode cell by welding, and the membrane-integrated electrode is sandwiched between the anode cell and the cathode cell such that the electrode-attached surface becomes the anode chamber side. That is, the cross-sectional structure of the electrolytic cell is a zero-pitch structure in which a current collector, a pad, a cathode, a separator, an electrode for electrolysis (a titanium porous foil anode) are sequentially arranged from the cathode chamber side, and an anode that is deteriorated and has an increased electrolytic voltage. The anode that has deteriorated and has an increased electrolytic voltage functions as a power feeder. Furthermore, the anode of the titanium porous foil and the anode that has deteriorated and the electrolytic voltage becomes high are only in physical contact, and are not fixed by welding. With this configuration, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 26 μm. The thickness of the catalyst layer is 6 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 4 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0060 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 17] In Example 17, a titanium foil with a gauge thickness of 20 μm and an open porosity of 30% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode is 30 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 5 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0030 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 18] In Example 18, a titanium foil with a gauge thickness of 20 μm and an open porosity of 42% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.38 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode is 32 μm. The thickness of the catalyst layer is 12 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 2.5 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0022 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 19] In Example 19, a titanium foil having a gauge thickness of 50 μm and a porosity of 47% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.40 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode is 69 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis and is 19 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 8 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0024 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 20] Example 20 uses a gauge with a thickness of 100 μm, a titanium fiber diameter of about 20 μm, and a basis weight of 100 g / m2 The titanium non-woven fabric with a porosity of 78% is used as the electrode substrate for anode electrolysis. Other than that, evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode is 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 2 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 21] In Example 21, a titanium mesh with a thickness of 120 μm, a diameter of titanium fibers of about 60 μm, and a 150-mesh titanium mesh was used as the electrode substrate for anode electrolysis. The porosity is 42%. Spray treatment was performed with alumina of grain number 320. Because it is difficult to measure the surface roughness of the metal wire mesh, in Example 21, a titanium plate having a thickness of 1 mm was sprayed at the same time during the spraying. . The arithmetic average roughness Ra is 0.60 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode is 140 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 20 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 10 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0132 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 22] In Example 22, as in Example 16, an anode that was deteriorated and the electrolytic voltage became high was used as an anode power source, and the same titanium nonwoven fabric as in Example 20 was used as an anode. In the same manner as in Example 15, a cathode deteriorated and the electrolytic voltage became high was used as a cathode power source, and the same nickel foil electrode as in Example 3 was used as a cathode. The cross-sectional structure of the electrolytic cell is formed from the cathode chamber side in order to form a current collector, a pad, a deteriorated cathode with a higher voltage, a nickel porous foil cathode, a separator, a titanium non-woven anode, and a deteriorated anode with a higher electrolytic voltage. Pitch structure, the cathode and anode that are degraded and the electrolytic voltage becomes high function as a power feeder. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode (anode) is 114 μm, and the thickness of the catalyst layer is the thickness of the electrode (anode) minus the thickness of the electrode substrate for electrolysis to be 14 μm. The thickness of the electrode (cathode) is 38 μm, and the thickness of the catalyst layer is the thickness of the electrode (cathode) minus the thickness of the electrode base material for electrolysis to be 8 μm. Adequate adhesion was observed on both the anode and the cathode. Deformation test of electrode (anode), result L1 , L2 The average is 2 mm. Deformation test of electrode (cathode), result L1 , L2 The average is 0 mm. When the ventilation resistance of the electrode (anode) was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. When the ventilation resistance of the electrode (cathode) was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of the anode and cathode membrane damage was also "0", which was good. Furthermore, in Example 22, the cathode was attached to one side of the separator, and the anode was attached to the opposite side. The cathode and the anode were combined to perform film damage evaluation. [Example 23] In Example 23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa was used. Zirfon membranes were immersed in pure water for more than 12 hours for testing. Except for the above, the evaluation was performed in the same manner as in Example 3, and the results are shown in Table 2. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. Similar to the case of using an ion-exchange membrane as a separator, sufficient adhesion was observed, and the microporous membrane and the electrode were in close contact by surface tension, and the operability was "1", which was good. [Example 24] As an electrode substrate for cathode electrolysis, a carbon cloth made of woven carbon fiber with a gauge thickness of 566 μm was prepared. A coating solution for forming an electrode catalyst on the carbon cloth was prepared in the following order. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with a closed cell type wound around a cylinder made of PVC (polyvinyl chloride). The formed coating roller is arranged so that the coating liquid is always in contact with each other. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the fabricated electrode was 570 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 4 μm. The thickness of the catalyst layer is the total thickness of ruthenium oxide and cerium oxide. The obtained electrodes were subjected to electrolytic evaluation. The results are shown in Table 2. Deformation test of electrode, result L1 , L2 The average is 0 mm. The air flow resistance of the electrode was measured. As a result, it was 0.19 (kPa · s / m) under measurement condition 1 and 0.176 (kPa · s / m) under measurement condition 2. Moreover, the operability is "2", and it can be judged that it can be operated as a large laminated body. The voltage was high, and the film damage evaluation was "1", and the film damage was confirmed. The reason is considered to be that the electrode of Example 24 had a large ventilation resistance, and therefore, the NaOH generated in the electrode stayed at the interface between the electrode and the separator and became a high concentration. [Reference Example 1] In Reference Example 1, the cathode used in a large-scale electrolytic cell for 8 years as a cathode was deteriorated and the electrolytic voltage became high. The cathode was replaced by a nickel grid feeder on a pad of a cathode chamber, and electrolytic evaluation was performed through the ion exchange membrane A produced in [Method (i)]. In Reference Example 1, a membrane-integrated electrode is not used. The cross-sectional structure of the electrolytic cell is from the cathode chamber side, and the current collector, the pad, the deteriorated cathode, the ion exchange membrane A, and the anode are sequentially arranged to form a zero pitch. structure. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.04 V, the current efficiency was 97.0%, and the common salt concentration (50% conversion value) in caustic soda was 20 ppm. As a result of the deterioration of the cathode, the result was a higher voltage. [Reference Example 2] In Reference Example 2, a nickel grid feeder was used as the cathode. That is, electrolysis was performed using a nickel mesh without a catalyst coating. The nickel mesh cathode was placed on a pad of a cathode chamber, and electrolytic evaluation was performed through the ion exchange membrane A produced in [Method (i)]. The cross-sectional structure of the battery of Reference Example 2 is a zero-pitch structure in which a current collector, a pad, a nickel mesh, an ion exchange membrane A, and an anode are sequentially arranged from the cathode chamber side. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.38 V, the current efficiency was 97.7%, and the common salt concentration (50% conversion value) in caustic soda was 24 ppm. Since the cathode catalyst was not applied, the result was a higher voltage. [Reference Example 3] In Reference Example 3, the anode used in the large-scale electrolytic cell for about 8 years as the anode was deteriorated and the electrolytic voltage became high. The cross-sectional structure of the electrolytic cell in Reference Example 3 is formed from the cathode chamber side, in which the current collector, the pad, the cathode, the ion exchange membrane A produced in [Method (i)], and the anode that is degraded and has an increased electrolytic voltage are formed Zero-pitch structure. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.18 V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 22 ppm. As the anode deteriorates, the result is a higher voltage. [Comparative Example 1] In Comparative Example 1, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 33% after full-roll processing was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Since it is difficult to measure the surface roughness of the porous metal, in Comparative Example 1, a nickel plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the wire mesh. The arithmetic average roughness Ra is 0.68 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. The mass per unit area is 67.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.05 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 64%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 22%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 13 mm. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2. [Comparative Example 2] In Comparative Example 2, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 16% after full-roll processing was used as an electrode base material for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of the porous metal, in Comparative Example 2, a nickel plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the wire mesh. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 107 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 7 μm. Mass per unit area is 78.1 (mg / cm2 ). The force per unit mass and unit area (1) is 0.04 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 37%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 25%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 18.5 mm. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0176 (kPa · s / m) under measurement condition 2. [Comparative Example 3] In Comparative Example 3, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 40% after full-roll processing was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of the porous metal, in Comparative Example 3, a nickel plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the wire mesh. The arithmetic average roughness Ra is 0.70 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The electrode substrate for electrolysis was applied by the same ion plating as in Example 6. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 110 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. The force per unit mass and unit area (1) is 0.07 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 80%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 32%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "3", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 11 mm. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0030 (kPa · s / m) under measurement condition 2. [Comparative Example 4] Comparative Example 4 uses a nickel porous metal with a gauge thickness of 100 μm and a porosity of 58% after full-roll processing as the electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Since it is difficult to measure the surface roughness of the porous metal, in Comparative Example 4, a nickel plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the wire mesh. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 109 μm. The thickness of the catalyst layer is 9 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. The force per unit mass and unit area (1) is 0.06 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 69%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 39%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "3", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 11.5 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. [Comparative Example 5] Comparative Example 5 uses a nickel wire mesh having a gauge thickness of 300 μm and an opening ratio of 56% as an electrode substrate for cathode electrolysis. Since it is difficult to measure the surface roughness of the metal mesh, in Comparative Example 5, a nickel plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. . Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2. The thickness of the electrode is 308 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Mass per unit area is 49.2 (mg / cm2 ). Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 88%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 42%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and during operation, the electrode is peeled off from the film, etc. The operability is "3" and there are problems. It can be evaluated as "3" when it is actually operated in a large size. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 23 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2. [Comparative Example 6] In Comparative Example 6, a nickel wire mesh with a gauge thickness of 200 μm and an opening ratio of 37% was used as an electrode base material for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of the metal wire mesh, in Comparative Example 6, a nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying. The surface roughness of the nickel plate was used as the surface roughness of the metal wire mesh . The arithmetic average roughness Ra is 0.65 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the electrode electrolytic evaluation, the measurement result of the adhesion force, and the adhesion were performed in the same manner as in Example 1. The results are shown in Table 2. The thickness of the electrode is 210 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Mass per unit area is 56.4 mg / cm2 . Therefore, the result of the 145 mm diameter cylindrical winding evaluation method (3) was 63%, and the adhesion between the electrode and the separator was poor. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and during operation, the electrode is peeled off from the film, etc. The operability is "3" and there are problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 19 mm. When the airflow resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0096 (kPa · s / m) under measurement condition 2. [Comparative Example 7] In Comparative Example 7, a titanium porous metal having a gauge thickness of 500 μm and a porosity of 17% after full-roll processing was used as the electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Since it is difficult to measure the surface roughness of the porous metal, in Comparative Example 7, a titanium plate having a thickness of 1 mm was simultaneously sprayed during the spraying, and the surface roughness of the titanium plate was used as the surface roughness of the metal mesh. The arithmetic average roughness Ra is 0.60 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode was 508 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The mass per unit area is 152.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. When the air flow resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0072 (kPa · s / m) under measurement condition 2. [Comparative Example 8] In Comparative Example 8, a titanium porous metal having a gauge thickness of 800 μm and a porosity of 8% after full-roll processing was used as an electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Since it is difficult to measure the surface roughness of the porous metal, in Comparative Example 8, a titanium plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface roughness of the wire mesh. The arithmetic average roughness Ra is 0.61 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode is 808 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The mass per unit area is 251.3 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0172 (kPa · s / m) under measurement condition 2. [Comparative Example 9] In Comparative Example 9, a titanium porous metal having a gauge thickness of 1000 μm and a porosity of 46% after full-roll processing was used as an electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of the porous metal, in Comparative Example 9, a titanium plate having a thickness of 1 mm was simultaneously sprayed during the spraying, and the surface roughness of the titanium plate was used as the surface roughness of the wire mesh. The arithmetic average roughness Ra is 0.59 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2. The thickness of the electrode was 1011 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 11 μm. The mass per unit area is 245.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. [Comparative Example 10] In Comparative Example 10, a film-electrode assembly obtained by thermocompression-bonding an electrode to a separator was prepared with reference to a previous document (Example of Japanese Patent Laid-Open No. Sho 58-48686). Electrode coating was performed in the same manner as in Example 1 using a nickel porous metal having a gauge thickness of 100 μm and an open porosity of 33% as an electrode substrate for cathode electrolysis. Thereafter, an inertization treatment was performed on one side of the electrode in the following order. A polyimide adhesive tape (Zhongxing Chemical Co., Ltd.) was attached to one side of the electrode, and a PTFE dispersion (DuPont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was coated on the opposite side at 120 ° C. Dry in a muffle furnace for 10 minutes. The polyimide tape was peeled off, and sintered in a muffle furnace set at 380 ° C for 10 minutes. This operation was repeated twice to inertize one side of the electrode. Made from terminal functional group "-COOCH3 "Perfluorocarbon polymer (C polymer) and end group is" -SO2 F "is a film formed of two layers of perfluorocarbon polymer (S polymer). The thickness of the C polymer layer is 3 mils, and the thickness of the S polymer layer is 4 mils. This two-layer membrane is subjected to a saponification treatment, and an ion exchange group is introduced into the end of the polymer by hydrolysis. The C polymer end is hydrolyzed to a carboxylic acid group, and the S polymer end is hydrolyzed to a sulfo group. The ion exchange capacity based on the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity based on the carboxylic acid group was 0.9 meq / g. The surface having a carboxylic acid group as an ion-exchange group is opposed to the inertized electrode surface, and hot pressing is performed to integrate the ion-exchange membrane with the electrode. One side of the electrode is also exposed after thermocompression bonding, and there is no part of the electrode penetration film. Thereafter, in order to suppress the adhesion of bubbles generated in the electrolysis to the film, a perfluorocarbon polymer mixture into which zirconia and a sulfo group were introduced was applied on both sides. Thus, a membrane-electrode assembly of Comparative Example 10 was produced. Using this membrane electrode assembly, the force per unit mass and unit area (1) was measured. As a result, the electrode was strongly bonded to the membrane by thermocompression bonding, so the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed without moving the electrode, and the electrode was pulled upward by a stronger force. As a result, the electrode was able to withstand 1.50 (N / mg · cm2 ), A part of the film was broken. The force (1) per unit mass and unit area of the membrane electrode assembly of Comparative Example 10 is at least 1.50 (N / mg · cm2 ), Being strongly engaged. A cylindrical winding evaluation (1) with a diameter of 280 mm was carried out. As a result, the contact area with the plastic pipe was less than 5%. On the other hand, a cylindrical winding evaluation (280) with a diameter of 280 mm was performed. As a result, although the electrode and the membrane were 100% bonded, the separator was not initially wound around the cylinder. The results of the cylindrical winding evaluation (3) with a diameter of 145 mm are the same. This result means that the operability of the film is impaired by the integrated electrode, and it is difficult to roll it into a roll or bend it. The operability is "3" and there are problems. The film damage was evaluated as "0". When electrolytic evaluation was performed, the voltage became higher, the current efficiency became lower, the salt concentration (50% conversion value) in caustic soda increased, and the electrolytic performance deteriorated. The thickness of the electrode was 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. Deformation test of electrode, result L1 , L2 The average is 13 mm. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2. [Comparative Example 11] Comparative Example 11 uses a nickel mesh with a wire diameter of 150 μm, a 40 mesh size, a gauge thickness of 300 μm, and an opening ratio of 58% as an electrode substrate for cathode electrolysis. Other than that, it carried out similarly to the comparative example 10, and produced the membrane electrode assembly. Using this membrane electrode assembly, the force per unit mass and unit area (1) was measured. As a result, the electrode was strongly bonded to the membrane by thermocompression bonding, so the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed without moving the electrode, and the electrode was pulled upwards with a stronger force. As a result, the bearing capacity was 1.60 (N / mg · cm2 ), A part of the film was broken. The force (1) per unit mass and unit area of the membrane electrode assembly of Comparative Example 11 was at least 1.60 (N / mg · cm2 ), Being strongly engaged. Using this membrane electrode assembly, a cylindrical winding evaluation of 280 mm in diameter was performed (1). As a result, the contact area with the plastic pipe was less than 5%. On the other hand, a cylindrical winding evaluation (280) with a diameter of 280 mm was performed. As a result, although the electrode and the membrane were 100% bonded, the separator was not initially wound around the cylinder. The results of the cylindrical winding evaluation (3) with a diameter of 145 mm are the same. This result means that the operability of the film is impaired by the integrated electrode, and it is difficult to roll it into a roll or bend it. The operability is "3" and there are problems. When electrolytic evaluation was performed, the voltage became higher, the current efficiency became lower, the salt concentration in caustic soda increased, and the electrolytic performance deteriorated. The thickness of the electrode was 308 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Deformation test of electrode, result L1 , L2 The average is 23 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2. [Comparative Example 12] (Preparation of catalyst) 0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) were added to 150 ml of pure water to prepare a metal salt. Aqueous solution. 240 g of pure water was added to 100 g of a 15% tetramethylammonium hydroxide aqueous solution (Wako Pure Chemical Industries, Ltd.) to prepare an alkaline solution. While stirring the alkaline solution with a magnetic stirrer, the above-mentioned metal salt aqueous solution was added dropwise at 5 ml / min using a burette. The suspension containing the generated metal hydroxide fine particles was subjected to suction filtration, and then washed with water to remove alkaline components. Thereafter, the filtrate was transferred to 200 ml of 2-propanol (Kishida Chemical Co., Ltd.), and dispersed by an ultrasonic disperser (US-600T, Nippon Seiki Seisakusho Co., Ltd.) for another 10 minutes to obtain uniformity. Of suspension. A hydrophobic carbon black (DENKA BLACK (registered trademark) AB-7 (trade name), Denki Chemical Industry Co., Ltd.) 0.36 g, a hydrophilic carbon black (Ketjen Black (registered trademark) EC-600JD (trade name), Mitsubishi Chemical Co., Ltd.) was dispersed in 0.84 g of 100 ml of 2-propanol, and dispersed in an ultrasonic disperser for 10 minutes to obtain a suspension of carbon black. The suspension of the metal hydroxide precursor and the suspension of carbon black were mixed and dispersed by an ultrasonic disperser for 10 minutes. The suspension was subjected to suction filtration and dried at room temperature for half a day to obtain carbon black in which a metal hydroxide precursor was dispersed and fixed. Next, using an inert gas firing furnace (VMF165, Yamada Denki Co., Ltd.), firing was performed at 400 ° C for 1 hour in a nitrogen atmosphere to obtain carbon black A in which the electrode catalyst was dispersed and fixed. (Powder for reaction layer) To 1.6 g of carbon black A in which electrode catalyst was dispersed and immobilized, a surfactant Triton (registered trademark) X-100 (trade name, ICN Biomedical) diluted to 20% by weight with pure water was added. Co., Ltd.) 0.84 ml, pure water 15 ml, disperse by ultrasonic disperser for 10 minutes. To this dispersion was added 0.664 g of a PTFE (polytetrafluoroethylene) dispersion (PTFE30J (trade name), DuPont-Mitsui Fluorochemicals Co., Ltd.), and after stirring for 5 minutes, suction filtration was performed. Furthermore, it dried in the dryer at 80 degreeC for 1 hour, and grind | pulverized with the grinder, and obtained the powder A for reaction tanks. (Production of powder for gas diffusion layer) 20 g of hydrophobic carbon black (DENKA BLACK (registered trademark) AB-7 (trade name)) was diluted with pure water to 20% by weight of a surfactant using an ultrasonic disperser. 50 ml of Triton (registered trademark) X-100 (trade name) and 360 ml of pure water were dispersed for 10 minutes. 22.32 g of a PTFE dispersion was added to the obtained dispersion, and after stirring for 5 minutes, filtration was performed. Furthermore, it dried in the dryer at 80 degreeC for 1 hour, and grind | pulverized by the grinder, and obtained the powder A for gas diffusion layers. (Production of Gas Diffusion Electrode) 8.7 ml of ethanol was added to 4 g of powder A for gas diffusion layer, and the mixture was kneaded to form a maggot shape. The powder of the gas diffusion layer formed into a maggot shape was formed into a sheet shape by a roll forming machine, and a silver mesh (SW = 1, LW = 2, thickness = 0.3 mm) was embedded as a current collector, and the final shape was 1.8 mm Flakes. 2.2 ml of ethanol was added to 1 g of the powder A for the reaction layer, and the mixture was kneaded to obtain a maggot shape. The powder for the reaction layer formed into a maggot shape was formed into a sheet shape having a thickness of 0.2 mm by a roll forming machine. Further, the produced sheet obtained using the powder A for the gas diffusion layer and the two sheets obtained using the powder A for the reaction layer were laminated, and formed into a sheet shape of 1.8 mm by a roll forming machine. . The laminated sheet was dried at room temperature for one day and night, and ethanol was removed. Furthermore, in order to remove the remaining surfactant, a thermal decomposition treatment was performed in the air at 300 ° C for 1 hour. Wrapped in aluminum foil by a hot press (SA303 (trade name), TESTER SANGYO Co., Ltd.) at 50 kgf / cm at 360 ° C2 Hot pressing was performed for 1 minute to obtain a gas diffusion electrode. The thickness of the gas diffusion electrode is 412 μm. Using the obtained electrodes, electrolytic evaluation was performed. The cross-sectional structure of the electrolytic cell is a zero-pitch structure in which current collectors, pads, nickel grid feeders, electrodes, membranes, and anodes are sequentially arranged from the cathode chamber side. The results are shown in Table 2. Deformation test of electrode, result L1 , L2 The average value is 19 mm. The ventilation resistance of the electrode was measured. As a result, it was 25.88 (kPa · s / m) under measurement condition 1. In addition, the operability is "3" and there are problems. When electrolytic evaluation was performed, the current efficiency was lowered, the salt concentration in caustic soda was increased, and the electrolytic performance was significantly deteriorated. Membrane damage was evaluated as "3", which also had problems. From these results, it was found that if the gas diffusion electrode obtained in Comparative Example 12 was used, the electrolytic performance was significantly inferior. In addition, damage was observed on substantially the entire surface of the ion exchange membrane. The reason for this is considered to be that the gas resistance of the gas diffusion electrode of Comparative Example 12 was significantly large, and therefore, the NaOH generated in the electrode remained at the interface between the electrode and the separator and became a high concentration. [Comparative Example 13] A nickel wire having a gauge thickness of 150 μm was prepared as an electrode base material for cathode electrolysis. A roughening process using this nickel wire is performed. Since it is difficult to measure the surface roughness of the nickel wire, in Comparative Example 13, a nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface roughness of the nickel wire. Spray treatment was performed with alumina of grain number 320. The arithmetic average roughness Ra is 0.64 μm. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with a closed cell type wound around a cylinder made of PVC (polyvinyl chloride). The formed coating roller is arranged so that the coating liquid is always in contact with each other. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of one nickel wire produced in Comparative Example 13 was 158 μm. The nickel wire produced by the above method was cut into lengths of 110 mm and 95 mm. As shown in FIG. 16, the 110 mm nickel wire and the 95 mm nickel wire are vertically overlapped at the center of each nickel wire, and are placed by an instant adhesive (Aron Alpha (registered trademark), East Asia Synthesis Co., Ltd.) The intersection part is then used to make electrodes. The electrodes were evaluated, and the results are shown in Table 2. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The opening rate is 99.7%. The mass per unit area of the electrode is 0.5 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 15 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measuring device was set to H (high), and the ventilation resistance value was 0.0002 (kPa · s / m). For the electrode, a structure shown in FIG. 17 was used, and the electrode (cathode) was placed on a Ni grid power supply, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage became 3.16 V, which was high. [Comparative Example 14] In Comparative Example 14, the electrode prepared in Comparative Example 13 was used, and as shown in FIG. 18, the nickel wire of 110 mm and the nickel wire of 95 mm were vertically overlapped at the center of each nickel wire. An electrode was produced by using an instant adhesive (Aron Alpha (registered trademark), East Asia Synthesis Co., Ltd.) to intersect the intersection. The electrodes were evaluated, and the results are shown in Table 2. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The porosity is 99.4%. The mass per unit area of the electrode is 0.9 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 16 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measurement device was set to H (high), and the ventilation resistance was 0.0004 (kPa · s / m). For the electrode, a structure shown in FIG. 19 was used, and the electrode (cathode) was placed on a Ni grid power supply, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage was 3.18 V, which was high. [Comparative Example 15] In Comparative Example 15, the electrode prepared in Comparative Example 13 was used, and as shown in FIG. 20, a nickel wire of 110 mm and a nickel wire of 95 mm were vertically overlapped at the center of each nickel wire. An electrode was produced by using an instant adhesive (Aron Alpha (registered trademark), East Asia Synthesis Co., Ltd.) to intersect the intersection. The electrodes were evaluated, and the results are shown in Table 2. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The porosity is 98.8%. The mass per unit area of the electrode is 1.9 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 14 mm. In addition, the ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measurement device was set to H (high), and the ventilation resistance was 0.0005 (kPa · s / m). For the electrode, a structure shown in FIG. 21 was used, and the electrode (cathode) was set on a Ni grid power supply, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage was 3.18 V, which was high. [Table 1] [Table 2] In Table 2, all samples can be self-supported by surface tension before the measurement of "force per unit mass and unit area (1)" and "force per unit mass and unit area (2)" ( That is, there is no case of sagging). In Comparative Examples 1, 2, 7 to 9, the mass per unit area was large, and the force (1) per unit mass and unit area was small, so the adhesion with the separator was poor. Therefore, for the size of a large electrolytic cell (for example, 1.5 m in length and 3 m in width), there must be slack when handling a separator that is a polymer film. At this time, the electrode is peeled off and cannot withstand practical use. In Comparative Examples 3 and 4, since the force (1) per unit mass and unit area was small, the adhesion with the separator was poor. Therefore, when the size of a large-scale electrolytic cell (for example, 1.5 m in length and 3 m in width) is handled as a membrane of a polymer film, there must be slackness. At this time, the electrode is peeled off and cannot withstand practical use. Comparative Examples 5 and 6 had a large mass per unit area and had poor adhesion with the separator. Therefore, when the size of a large-scale electrolytic cell (for example, 1.5 m in length and 3 m in width) is handled as a membrane of a polymer film, there must be slackness. At this time, the electrode is peeled off and cannot withstand practical use. In Comparative Examples 10 and 11, since the film and the electrode were strongly joined by hot pressing, there was no case where peeling occurred from the film during the operation as in Comparative Examples 1, 2, 7 to 9. However, since it is strongly bonded to the electrode, it loses the flexibility of the polymer film, and it is difficult to roll it into a roll or bend it, and the workability is poor and it cannot withstand practical use. Furthermore, in Comparative Examples 10 and 11, the electrolytic performance was significantly deteriorated. It is thought that the reason for the large increase in voltage is that the flow of ions is blocked because the electrode is buried in the ion exchange membrane. It is considered that the reason for the decrease in current efficiency and the deterioration of the common salt concentration in caustic soda lies in the following reasons: the electrode was buried in a carboxylic acid layer that exhibited high current efficiency and ion selectivity, leading to the generation of a carboxylic acid layer The thickness is uneven, and the electrode embedded in a part of the carboxylic acid layer is penetrated. Furthermore, in Comparative Examples 10 and 11, when either the separator or the electrode had a problem and it was necessary to replace it, it was strongly bonded, so that it was not possible to replace only one of them, resulting in high cost. In Comparative Example 12, the electrolytic performance was significantly deteriorated. It is thought that the reason for the large increase in voltage is that the product stays at the interface between the separator and the electrode. In Comparative Examples 13 to 15, since the forces (1) and (2) per unit mass and unit area were small (below the lower limit of measurement), the adhesion with the separator was poor. Therefore, when the size of a large-scale electrolytic cell (for example, 1.5 m in length and 3 m in width) is handled as a membrane of a polymer film, there must be slackness. At this time, the electrode is peeled off and cannot withstand practical use. In this embodiment, the membrane and the electrode are closely adhered to the surface by a moderate force, so there is no problem such as electrode peeling during operation, and there is no case that the ion flow in the membrane is hindered, so it exhibits good electrolytic performance. <Verification of the Second Embodiment> An experimental example corresponding to the second embodiment (hereinafter referred to as "exemplary" in the following "Verification of the Second Embodiment") is prepared as follows, and does not correspond to the second embodiment. The experimental example corresponding to the embodiment (hereinafter referred to as "comparative example" in the item of "Verification of the Second Embodiment") was evaluated by the following method. The details will be described with reference to FIGS. 31 to 42 as appropriate. [Evaluation method] (1) Porosity The electrode was cut into a size of 130 mm x 100 mm. An electronic digital thickness gauge (manufactured by Mitutoyo Co., Ltd., showing a minimum of 0.001 mm) was used to uniformly measure 10 points in the plane and calculate the average value. The volume was calculated using this as the electrode thickness (gauge thickness). Thereafter, the mass was measured using an electronic balance, and the weight was determined based on the specific gravity of the metal (the specific gravity of nickel = 8.908 g / cm3 , Specific gravity of titanium = 4.506 g / cm3 ) Calculate the porosity or porosity. Porosity (void ratio) (%) = (1-(electrode mass) / (electrode volume × metal specific gravity)) × 100 (2) mass per unit area (mg / cm2 ) Cut the electrode to a size of 130 mm × 100 mm and measure the mass with an electronic balance. Divide this value by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force per unit mass / area (1) (Adhesive force) (N / mg ・ cm2 )) [Method (i)] The measurement system used a tensile compression tester (Imada Manufacturing Co., Ltd., the tester body: SDT-52NA type tensile compression tester, load meter: SL-6001 load meter). Using alumina with a grain number of 320, a nickel plate having a thickness of 1.2 mm and a square of 200 mm was spray-processed. The arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment was 0.7 μm. Here, the surface roughness measurement uses a stylus-type surface roughness measuring machine SJ-310 (Mitutoyo Co., Ltd.). The measurement sample was set on a platform parallel to the ground, and the arithmetic average roughness Ra was measured under the following measurement conditions. When the measurement is performed 6 times, the average value is described. <Shape of Stylus> Conical, Taper Angle = 60 °, Tip Radius = 2 μm, Static Measuring Force = 0.75 mN <Roughness Standard> JIS2001 <Evaluation Curve> R <Filter> GAUSS <Critical Value λc> 0.8 mm <Critical The value λs> 2.5 μm <the number of intervals> 5 <forward sweep, backward sweep> There is a chuck for fixing the nickel plate to the lower side of the tensile compression tester so as to be vertical. The following ion exchange membrane A was used as a separator. As the reinforcing core material, a 90-denier monofilament (hereinafter referred to as PTFE yarn) made of polytetrafluoroethylene (PTFE) was used. As the sacrificial yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 6 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. First, a woven fabric is obtained by plain weaving with 24 PTFE yarns arranged in each of the two directions of TD and MD and two sacrificial yarns arranged between adjacent PTFE yarns. The obtained woven fabric was crimped by a roller to obtain a woven fabric having a thickness of 70 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.85 mg equivalent / g of dry resin, resin A, and CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer B had a resin B having an ion exchange capacity of 1.03 mg equivalent / g of the dry resin. Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 μm and a thickness of the resin B layer of 104 μm was obtained by a co-extrusion T-die method. Then, on a heating plate having a heating source and a vacuum source inside, and micropores on its surface, a release paper (cone-shaped embossing processing with a height of 50 μm), a reinforcing material, and a film X were sequentially laminated on the heating plate surface temperature. After heating and decompressing under the conditions of 223 ° C and a degree of reduced pressure of 0.067 MPa for 2 minutes, the release paper was removed to obtain a composite film. Saponification was performed by immersing the obtained composite film in an aqueous solution at 80 ° C. containing 30% by mass of dimethylsulfinium (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. After that, it was immersed in a 50 ° C aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour to replace the counter ion of the ion-exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC. Furthermore, 20% by mass of zirconia having a particle size of 1 μm was added to a 5% by mass ethanol solution of the acid type resin of the resin B to disperse it to prepare a suspension, and both sides of the composite film were prepared by a suspension spray method. Spraying was performed to form a coating of zirconia on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconia was measured by fluorescent X-ray measurement, and the result was 0.5 mg / cm2 . The average particle diameter is measured using a particle size distribution meter ("SALD (registered trademark) 2200" manufactured by Shimadzu Corporation). The ion exchange membrane (separator) obtained above was immersed in pure water for more than 12 hours and used in the test. It was made to contact the said nickel plate fully wetted with pure water, and it adhere | attached by the tension | tensile_strength of water. At this time, the nickel plate and the upper end of the ion-exchange membrane are aligned. The electrode sample (electrode) used for the measurement was cut into a 130 mm square. The ion exchange membrane A was cut into 170 mm squares. Two stainless steel plates (1 mm in thickness, 9 mm in length, and 170 mm in width) were sandwiched on one side of the electrode, aligned with the center of the stainless steel plate and the electrode, and uniformly fixed by 4 clamps. The center of the stainless steel plate was clamped by a clamp on the upper side of the tensile compression tester, and the electrode was suspended. At this time, the load to the testing machine was set to 0 N. Remove the stainless steel plate, electrode, and clamp assembly from the tensile compression tester temporarily. In order to fully wet the electrode with pure water, immerse it in a tank filled with pure water. Thereafter, the center of the stainless steel plate was clamped again to the chuck on the upper side of the tensile compression tester, and the electrode was suspended. The upper chuck of the tensile compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the ion exchange membrane using the surface tension of pure water. At this time, the bonding surface is 130 mm in width and 110 mm in length. The pure water filled in the washing bottle is blown to the electrode and the ion exchange membrane as a whole, and the diaphragm and the electrode are fully wetted again. After that, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (38 mm outer diameter) was gently pressed from above the electrode, and rolled from top to bottom to remove excess Remove pure water. The roller is applied only once. The electrode was raised at a speed of 10 mm / minute, and the load measurement was started. The overlapping portion of the electrode and the diaphragm was recorded as a load at a width of 130 mm and a length of 100 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area where the electrode overlaps with the ion exchange membrane and the electrode mass in the area where it overlaps with the ion exchange membrane to calculate the force per unit mass and area (1). The mass of the electrode overlapping the ion exchange membrane is based on the mass per unit area (mg / cm) of (2) above.2 The value obtained in) is calculated by ratio calculation. The environment of the measuring room is 23 ± 2 ℃ and relative humidity 30 ± 5%. In addition, the electrodes used in the examples and comparative examples can be attached independently without sagging or peeling when they are adhered to the ion exchange membrane of a nickel plate fixed vertically by surface tension. In addition, the model of the evaluation method of bearing capacity (1) is shown in FIG. 31. The measurement lower limit of the tensile tester is 0.01 (N). (4) Force per unit mass and unit area (2) (Adhesive force) (N / mg ・ cm2 )) [Method (ii)] The measurement system used a tensile compression tester (Imada Manufacturing Co., Ltd., the tester body: SDT-52NA type tensile compression tester, load meter: SL-6001 load meter). The nickel plate similar to the method (i) was fixed vertically to a chuck on the lower side of the tensile compression tester. The electrode sample (electrode) used for the measurement was cut into a 130 mm square. The ion exchange membrane A was cut into 170 mm squares. Two stainless steel plates (1 mm in thickness, 9 mm in length, and 170 mm in width) were sandwiched on one side of the electrode, aligned with the center of the stainless steel plate and the electrode, and uniformly fixed by 4 clamps. The center of the stainless steel plate was clamped by a clamp on the upper side of the tensile compression tester, and the electrode was suspended. At this time, the load to the testing machine was set to 0 N. Remove the stainless steel plate, electrode, and clamp assembly from the tensile compression tester temporarily. In order to fully wet the electrode with pure water, immerse it in a tank filled with pure water. Thereafter, the center of the stainless steel plate was clamped again to the chuck on the upper side of the tensile compression tester, and the electrode was suspended. The upper chuck of the tensile compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the nickel plate by the surface tension of the solution. At this time, the bonding surface is 130 mm in width and 110 mm in length. The pure water filled in the washing bottle is blown to the entire electrode and the nickel plate, and the nickel plate and the electrode are fully wetted again. After that, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (38 mm outer diameter) was gently pressed from above the electrode, and rolled from top to bottom to remove excess The solution was removed. The roller is applied only once. The electrode was raised at a speed of 10 mm / minute, and the load measurement was started. The load at the time when the longitudinal overlap between the electrode and the nickel plate became 100 mm was recorded. This measurement was performed three times and the average value was calculated. The average value is divided by the area where the electrode overlaps with the nickel plate and the mass of the electrode with the area overlapping with the nickel plate to calculate the force per unit mass and unit area (2). The mass of the electrode overlapping the diaphragm is based on the mass per unit area (mg / cm) of (2) above.2 The value obtained in) is calculated by ratio calculation. The environment of the measurement room was 23 ± 2 ° C and 30 ± 5% relative humidity. In addition, the electrodes used in the examples and comparative examples can be attached independently without sagging or peeling when they are adhered to a nickel plate that is fixed vertically by surface tension. The measurement lower limit of the tensile tester is 0.01 (N). (5) Evaluation method of cylindrical winding with a diameter of 280 mm (1) (%) (film and cylinder) Evaluation method (1) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In Comparative Examples 1 and 2, the electrode was integrated with the ion-exchange membrane by hot pressing. Therefore, one body of the ion-exchange membrane and the electrode was prepared (the electrode system was 130 mm square). The ion exchange membrane was fully immersed in pure water, and then placed on the curved surface of a plastic (polyethylene) tube made of 280 mm outside diameter. Thereafter, the excess solution was removed by a roller formed by winding an independent foaming type EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outer diameter of 38 mm). The roller system rolls on the ion exchange membrane from the left side to the right side of the pattern diagram shown in FIG. 32. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the plastic tube electrode with an outer diameter of 280 mm was measured. (6) Evaluation method of cylindrical winding with a diameter of 280 mm (2) (%) (film and electrode) Evaluation method (2) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into a 130 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. The ion exchange membrane and the electrode were fully immersed in pure water, and then laminated. The laminated body was placed on a curved surface of a plastic (polyethylene) tube having an outer diameter of 280 mm so that the electrodes became outside. Thereafter, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (outer diameter of 38 mm) was gently pressed from above the electrode, and from the left side of the pattern diagram shown in FIG. 33 Scroll to the right to remove excess solution. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the electrode was measured. (7) 145 mm diameter cylindrical winding evaluation method (3) (%) (film and electrode) Evaluation method (3) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into a 130 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. The ion exchange membrane and the electrode were fully immersed in pure water, and then laminated. The laminated body was placed on a curved surface of a plastic (polyethylene) tube having an outer diameter of 145 mm so that the electrodes became outside. Thereafter, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (outer diameter of 38 mm) was gently pressed from above the electrode, and from the left side of the pattern diagram shown in FIG. 34 Scroll to the right to remove excess solution. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the electrode was measured. (8) Operability (induction evaluation) (A) The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into 95 × 110 mm. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In each example, the ion exchange membrane and the electrode were fully immersed in three solutions of sodium bicarbonate aqueous solution, 0.1 N aqueous NaOH solution, and pure water, and then laminated, and then placed on a Teflon plate. The distance between the anode cell and the cathode cell used in the electrolytic evaluation was set to about 3 cm, and the stacked body that was left standing was lifted up to be inserted and sandwiched therebetween. When performing this operation, check whether the electrode is deviated or dropped while operating. (B) The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut to a size of 170 mm square, and the electrode was cut to 95 × 110 mm. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In each example, the ion exchange membrane and the electrode were fully immersed in three solutions of sodium bicarbonate aqueous solution, 0.1 N aqueous NaOH solution, and pure water, and then laminated, and then placed on a Teflon plate. Hold the corners of the two adjacent parts of the laminate, and lift up the laminate so that it is vertical. From this state, the two corners of the hand held are moved so that the film becomes convex or concave. This operation was repeated once more to confirm the followability of the electrode to the film. Based on the following indicators, the results were evaluated on four levels of 1-4. 1: Good operation 2: Can operate 3: Difficult to operate 4: Generally inoperable Here, for the samples of Comparative Examples 2-5, dimensions of 1.3 m × 2.5 m with electrodes and 1.5 m × 2.8 m with ion exchange membrane The large electrolytic cell is operated in the same size. The evaluation result of Comparative Example 5 (hereinafter referred to as "3") serves as an index for evaluating the differences between the above-mentioned evaluations (A) and (B) and when the large size is made. That is, in the case where the results obtained by evaluating a small laminated body are "1" and "2", it is evaluated that there is no problem in operability even in the case of making a large size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common salt concentration in caustic soda (ppm, 50% conversion)) The electrolytic performance was evaluated by the following electrolytic experiment. A titanium anode cell (anode termination cell) having an anode chamber provided with an anode was opposed to a cathode cell having a cathode chamber (cathode termination cell) made of nickel provided with a cathode. A pair of spacers are arranged between the cells, and a laminate (a laminate of the ion exchange membrane A and the electrode for electrolysis) is sandwiched between the pair of spacers. Then, the anode cell, the gasket, the laminate, the gasket, and the cathode are closely contacted to obtain an electrolytic cell, and an electrolytic cell including the electrolytic cell is prepared. As the anode, a mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride was applied to a titanium substrate that had been subjected to spraying and acid etching treatment as a pretreatment, and was then dried and fired. The anode is fixed to the anode chamber by welding. As the cathode, those described in Examples and Comparative Examples were used. As the current collector of the cathode chamber, a porous metal made of nickel was used. The size of the current collector is 95 mm in length × 110 mm in width. As the metal elastic body, a pad woven with fine nickel wires is used. A metal elastomer was placed on the current collector. A nickel net made of a nickel wire with a diameter of 150 μm and a plain mesh with a 40-mesh mesh was covered thereon, and the four corners of the Ni net were fixed to the current collector by a rope made of Teflon (registered trademark). This Ni mesh was used as a power source. In this electrolytic cell, a zero-pitch structure is formed by utilizing the repulsive force of a pad of a metal elastomer. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As the separator, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used. Electrolysis of common salt is performed using the above electrolytic cell. The brine concentration (sodium chloride concentration) of the anode compartment was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode compartment was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell became 90 ° C. At current density of 6 kA / m2 Next, salt electrolysis was performed to measure voltage, current efficiency, and salt concentration in caustic soda. Here, the so-called current efficiency is the ratio of the amount of caustic soda generated to the flowing current. If the flowing current causes impurity ions or hydroxide ions instead of sodium ions to move in the ion exchange membrane, the current efficiency reduce. The current efficiency is obtained by dividing the Mohr number of caustic soda generated by a certain time by the Mohr number of electrons flowing in the meantime. The molar number of caustic soda is obtained by measuring the mass of caustic soda produced by electrolysis in a polymer tank. The salt concentration in caustic soda is a value obtained by converting the caustic soda concentration to 50%. In addition, Table 3 shows the specifications of the electrodes and power feeders used in the examples and comparative examples. (11) Measurement of the thickness of the catalyst layer, electrode substrate for electrolysis, and electrode thickness The thickness of the electrode substrate for electrolysis was measured uniformly on the surface using an electronic digital thickness gauge (manufactured by Mitutoyo Co., Ltd., showing at least 0.001 mm) Ten points were measured and the average value was calculated. This was used as the thickness (gauge thickness) of the electrode substrate for electrolysis. The thickness of the electrode is the same as that of the electrode substrate, and 10 points are uniformly measured in the plane by an electronic digital thickness meter, and the average value is calculated. This is used as the electrode thickness (gauge thickness). The thickness of the catalyst layer is determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. (12) Elastic deformation test of the electrode The ion exchange membrane A (diaphragm) produced in [Method (i)] and the electrode were cut into a size of 110 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the ion-exchange membrane and the electrode were stacked to form a laminated body, as shown in FIG. 35, and wound to an outer diameter of f32 mm without gaps. 20 cm PVC tube. In order to prevent the wound laminate from peeling or loosening from the PVC pipe, a polyethylene strap is used for fixing. Hold in this state for 6 hours. After that, the straps were removed, and the laminated body was unrolled from the PVC pipe. Place the electrode only on the platform, and measure the height L of the part that protrudes from the platform1 , L2 And find the average. This value is used as an index of electrode deformation. That is, a smaller value means that it is difficult to deform. When a porous metal is used, there are two types of the SW direction and the LW direction during winding. In this test, it was wound in the SW direction. Moreover, about the electrode which deform | transformed (the electrode which did not return to the original flat state), the softness after plastic deformation was evaluated by the method shown in FIG. That is, the deformed electrode is placed on a diaphragm that is fully immersed in pure water, one end is fixed, the opposite end of the floating is pressed against the diaphragm, the force is released, and the deformation electrode is evaluated to follow the diaphragm . (13) Evaluation of membrane damage The following ion exchange membrane B was used as a separator. As the reinforcing core material, polytetrafluoroethylene (PTFE) and a yarn of 100 denier twisted at 900 times / m into a yarn shape (hereinafter referred to as PTFE yarn) were used. As the sacrificial yarn of the warp yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 8 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. As the sacrificial yarn of the weft yarn, a yarn obtained by twisting polyethylene terephthalate (PET) with 35 deniers and 8 filaments at 200 times / m was used. First, plain weaving was performed by arranging 24 PTFE yarns per 24 inches and placing two sacrificial yarns between adjacent PTFE yarns to obtain a woven fabric with a thickness of 100 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.92 mg equivalent / g of dry resin polymer (A1),2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer (F1) had a polymer (B1) with an ion exchange capacity of 1.10 mg equivalent / g of dry resin. Using these polymers (A1) and (B1), a two-layer film with a thickness of 25 μm of a polymer (A1) layer and a thickness of 89 μm of a polymer (B1) layer was obtained by co-extrusion T-die method X . The ion exchange capacity of each polymer represents the ion exchange capacity when the ion exchange group precursor of each polymer is hydrolyzed and converted into an ion exchange group. Also, prepare separately with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer (F2) had a polymer (B2) with an ion exchange capacity of 1.10 mg equivalent / g of dry resin. This polymer single layer was extruded to obtain a film Y of 20 μm. Then, on a heating plate with a heating source and a vacuum source inside and micropores on the surface, the release paper, the film Y, the reinforcing material and the film X are sequentially laminated, and the conditions of the heating plate temperature 225 ° C and the decompression degree 0.022 MPa After depressurizing under heating for 2 minutes, the release paper was removed to obtain a composite film. The obtained composite membrane was immersed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH) for 1 hour to perform saponification, and then immersed in 0.5 N NaOH for 1 hour to ion-exchange The attached ions were replaced with Na and then washed with water. Furthermore, it dried at 60 degreeC. Also, will start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The polymer (B3) of the copolymer (F) having an ion exchange capacity of 1.05 mg equivalent / g of the dried resin was hydrolyzed and then made into an acid form by hydrochloric acid. In a solution prepared by dissolving the acid polymer (B3 ') in a 50/50 (mass ratio) mixed solution of water and ethanol at a ratio of 5% by mass, the polymer (B3') and zirconia Zirconium oxide particles having an average particle diameter of 0.02 μm were added so that the mass ratio of the particles was 20/80. Thereafter, it was dispersed in a suspension of zirconia particles by a ball mill to obtain a suspension. This suspension was coated on both surfaces of the ion exchange membrane by a spray method and dried to obtain an ion exchange membrane B having a coating layer containing a polymer (B3 ′) and zirconia particles. The coating density of zirconia was measured by fluorescent X-ray measurement, and it was 0.35 mg / cm2 . For the anode system, the same one as in (9) electrolytic evaluation was used. For the cathode system, those described in Examples and Comparative Examples were used. The collector, pad and feed system of the cathode chamber are the same as those used in (9) Electrolytic Evaluation. In other words, the Ni mesh is used as a power feeder, and a zero-pitch structure is formed by using the repulsive force of a pad of a metal elastic body. The gasket was the same as that used in (9) Electrolytic Evaluation. As the separator, the ion exchange membrane B produced by the above method was used. That is, the same electrolytic cell as in (9) was prepared, except that the laminated body of the ion exchange membrane B and the electrode for electrolysis was sandwiched between a pair of spacers. Electrolysis of common salt is performed using the above electrolytic cell. The brine concentration (sodium chloride concentration) of the anode compartment was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode compartment was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell became 70 ° C. At current density of 8 kA / m2 Next, salt electrolysis was performed. After 12 hours from the start of the electrolysis, the electrolysis was stopped, the ion exchange membrane B was taken out, and the damage state was observed. "0" means no damage. "1 to 3" means there is damage, the larger the number, the greater the degree of damage. (14) Ventilation resistance of the electrode The ventilation resistance of the electrode was measured using a permeability testing machine KES-F8 (trade name, Kato Tech Co., Ltd.). The unit of ventilation resistance value is kPa · s / m. The measurement was performed 5 times, and the average value is shown in Table 4. The measurement was performed under the following two conditions. The temperature in the measurement chamber was set to 24 ° C, and the relative humidity was set to 32%.・ Measurement condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Ventilation volume: 0.4 cc / cm2 / s Measurement range: SENSE L (low) Sample size: 50 mm × 50 mm • Measurement condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / cm2 / s Measurement range: SENSE M (medium) or H (high) Sample size: 50 mm × 50 mm [Example 2-1] As an electrode substrate for cathode electrolysis, an electrolytic nickel foil with a gauge thickness of 16 μm was prepared. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The nickel foil is punched to form a circular hole to form a porous foil. The opening ratio is 49%. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the electrode produced in Example 2-1 was 24 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The coating is also formed on the surface without roughening. It is the total thickness of ruthenium oxide and cerium oxide. Table 4 shows the measurement results of the adhesion force of the electrodes produced by the above methods. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. In order to use the electrode produced by the above method for electrolytic evaluation, it was cut into a size of 95 mm in length and 110 mm in width. Approximately the center of the carboxylic acid layer side of the ion-exchange membrane A (160 mm × 160 mm in size) of the ion exchange membrane A (160 mm × 160 mm) prepared in [Method (i)] with the roughened surface of the electrode equilibrated with a 0.1 N NaOH aqueous solution. The positions are opposite, and the surface tension of the aqueous solution makes them in close contact. Even if the four corners of the membrane part of the membrane-integrated electrode are grasped so that the electrode becomes the ground side and the membrane-integrated electrode is suspended parallel to the ground, there is no case of electrode peeling or deviation. In addition, even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not peel off or deviate. The membrane-integrated electrode is sandwiched between the anode cell and the cathode cell so that the electrode-attached surface becomes the cathode chamber side. The cross-sectional structure is a zero-pitch structure in which current collectors, pads, nickel grid feeders, electrodes, films, and anodes are sequentially arranged from the cathode chamber side. The obtained electrodes were subjected to electrolytic evaluation. The results are shown in Table 4. Shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF (fluorescence X-ray analysis), approximately 100% of the coating remained on the roughened surface, and the coating on the non-roughened surface decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 2-2] Example 2-2 uses an electrolytic nickel foil with a gauge thickness of 22 μm as the electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.96 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening rate is 44%. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 29 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 7 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0033 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 2-3] In Example 2-3, an electrolytic nickel foil with a gauge thickness of 30 μm was used as an electrode substrate for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 1.38 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening rate is 44%. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 38 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 2-4] In Example 2-4, an electrolytic nickel foil with a gauge thickness of 16 μm was used as an electrode substrate for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The porosity is 75%. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 24 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The measurement of the air flow resistance of the electrode was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 2-5] In Example 2-5, an electrolytic nickel foil with a gauge thickness of 20 μm was prepared as an electrode substrate for cathode electrolysis. Both sides of the nickel foil are subjected to a roughening treatment by electrolytic nickel plating. The roughened surface has an arithmetic average roughness Ra of 0.96 μm. Both sides have the same roughness. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening ratio is 49%. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 30 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The measurement of the air flow resistance of the electrode was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on both sides. In consideration of Comparative Examples 2-1 to 2-4, it is shown that even if there is little or no coating on the opposite side of the film, it can exhibit good electrolytic performance. [Example 2-6] Example 2-6 was performed in the same manner as in Example 2-1 except that the electrode substrate for cathode electrolysis was applied by ion plating, and the results are shown in Table 4. In addition, ion plating uses a Ru metal target at a heating temperature of 200 ° C, and a film formation pressure of 7 × 10 under an argon / oxygen environment.-2 Pa was formed into a film. The coating formed is ruthenium oxide. The thickness of the electrode is 26 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-7] Example 2-7 was an electrode base material for cathode electrolysis produced by an electroforming method. The shape of the photomask is a shape in which squares of 0.485 mm × 0.485 mm are arranged vertically and horizontally at intervals of 0.15 mm. By sequentially exposing, developing, and electroplating, a nickel porous foil having a gauge thickness of 20 μm and an opening ratio of 56% was obtained. The arithmetic average roughness Ra of the surface was 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 37 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis and is 17 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-8] The electrode base material for cathode electrolysis in Example 2-8 was produced by an electroforming method, the gauge thickness was 50 μm, and the opening ratio was 56%. The arithmetic average roughness Ra of the surface was 0.73 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 60 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-9] In Example 2-9, a nickel nonwoven fabric (manufactured by NIKKO TECHNO Co., Ltd.) having a gauge thickness of 150 μm and a porosity of 76% was used as an electrode substrate for cathode electrolysis. Non-woven nickel fiber with a diameter of about 40 μm and a basis weight of 300 g / m2 . Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 165 μm. The thickness of the catalyst layer is 15 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 29 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0612 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 2-10] In Example 2-10, a nickel non-woven fabric (manufactured by NIKKO TECHNO Co., Ltd.) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode substrate for cathode electrolysis. Non-woven nickel fiber with a diameter of about 40 μm and a basis weight of 500 g / m2 . Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 215 μm. The thickness of the catalyst layer is 15 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 40 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0164 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 2-11] In Example 2-11, a foamed nickel (manufactured by Mitsubishi Materials Co., Ltd.) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode base material for cathode electrolysis. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode was 210 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 17 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0402 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 2-12] In Example 2-12, a nickel mesh having a wire diameter of 50 μm, a 200 mesh, a gauge thickness of 100 μm, and an opening ratio of 37% was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. Even if the blasting treatment is performed, the aperture ratio does not change. Because it is difficult to measure the surface roughness of the metal wire mesh, the nickel plate with a thickness of 1 mm was sprayed at the same time in Example 2-12. The surface roughness of the nickel plate was used as the surface of the metal wire mesh. Roughness. The arithmetic average roughness Ra of one metal wire mesh was 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 110 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 0.5 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0154 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-13] In Example 2-13, a nickel mesh having a wire diameter of 65 μm, a 150 mesh, a gauge thickness of 130 μm, and an opening ratio of 38% was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. Even if the blasting treatment is performed, the aperture ratio does not change. Because it is difficult to measure the surface roughness of the metal mesh, in Example 2-13, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface of the metal mesh. Roughness. The arithmetic average roughness Ra is 0.66 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 133 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 3 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 6.5 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0124 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The evaluation of membrane damage was also "0", which was good. [Example 2-14] In Example 2-14, the same substrate (gauge thickness: 30 μm, open porosity: 44%) as that of Example 2-3 was used as the electrode substrate for cathode electrolysis. An electrolytic evaluation was performed with the same configuration as in Example 2-1, except that no nickel mesh power feeder was provided. That is, the cross-sectional structure of the electrolytic cell is a zero-pitch structure in which a current collector, a pad, a membrane-integrated electrode, and an anode are sequentially arranged from the cathode chamber side, and the pad functions as a power feeder. Other than that, evaluation was performed similarly to Example 2-1, and the result is shown in Table 4. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-15] In Example 2-15, the same substrate (gauge thickness: 30 μm, open porosity: 44%) as that of Example 2-3 was used as the electrode substrate for cathode electrolysis. In place of the nickel grid feeder, a deteriorated cathode used in Reference Example 1 and an increased electrolytic voltage were provided. Other than that, electrolytic evaluation was performed with the same configuration as in Example 2-1. That is, the cross-sectional structure of the electrolytic cell is formed by sequentially arranging a current collector, a pad, a deteriorated cathode (functioning as a power feeder), an electrode for electrolysis (cathode), a separator, and an anode in order from a cathode chamber side. Zero-pitch structure, the cathode that is degraded and the electrolytic voltage becomes high functions as a feeder. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-16] As an electrode substrate for anode electrolysis, a titanium foil having a gauge thickness of 20 μm was prepared. Both sides of the titanium foil are roughened. This titanium foil was punched, and round holes were made to form a porous foil. The diameter of the holes was 1 mm, and the opening ratio was 14%. The arithmetic average roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L and a iridium concentration of 100 g / L so that the molar ratios of ruthenium, iridium and titanium are 0.25: 0.25: 0.5 Iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed. This mixed solution was sufficiently stirred and used as an anode coating solution. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). After applying the coating solution to a titanium porous foil, drying was performed at 60 ° C for 10 minutes, and firing was performed at 475 ° C for 10 minutes. After repeating the series of operations of coating, drying, pre-firing, and firing, firing was performed at 520 ° C for 1 hour. In order to use the electrode produced by the above method for electrolytic evaluation, it was cut into a size of 95 mm in length and 110 mm in width. By the surface tension of the aqueous solution, it was brought into close contact with the approximate center of the sulfonic acid layer side of the ion-exchange membrane A (size: 160 mm × 160 mm) produced in [Method (i)] equilibrated with a 0.1 N NaOH aqueous solution. . The cathode was prepared in the following procedure. First, a nickel wire mesh having a wire diameter of 150 μm and 40 mesh was prepared as a base material. After performing a spray treatment with alumina as a pretreatment, it was immersed in 6 N hydrochloric acid for 5 minutes, and thoroughly washed and dried with pure water. Then, a ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) and cerium chloride (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L so that the molar ratio of the ruthenium element to the cerium element is 1: 0.25 To mix. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 300 ° C for 3 minutes, and firing was performed at 550 ° C for 10 minutes. Thereafter, firing was performed at 550 ° C for 1 hour. The series of operations of coating, drying, pre-firing and firing are repeated. As the current collector of the cathode chamber, a porous metal made of nickel was used. The size of the current collector is 95 mm in length × 110 mm in width. As the metal elastic body, a pad woven with fine nickel wires is used. A metal elastomer was placed on the current collector. The cathode produced by the above method was covered thereon, and the four corners of the net were fixed to the current collector by using a rope made of Teflon (registered trademark). Even if the four corners of the membrane part of the membrane-integrated electrode which is integrated with the membrane and the anode are grasped, the electrode becomes the ground side and the membrane-integrated electrode is suspended in a manner parallel to the ground, there is no peeling or deviation of the electrode. In addition, even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not peel off or deviate. The anode used in Reference Example 3, which has been deteriorated and has an increased electrolytic voltage, is fixed to the anode cell by welding, and the membrane-integrated electrode is sandwiched between the anode cell and the cathode cell such that the electrode-attached surface becomes the anode chamber side. That is, the cross-sectional structure of the electrolytic cell is a zero-pitch structure in which a current collector, a pad, a cathode, a separator, an electrode for electrolysis (a titanium porous foil anode) are sequentially arranged from the cathode chamber side, and an anode that is deteriorated and has an increased electrolytic voltage. The anode that has deteriorated and has an increased electrolytic voltage functions as a power feeder. Furthermore, the anode of the titanium porous foil and the anode that has deteriorated and the electrolytic voltage becomes high are only in physical contact, and are not fixed by welding. With this configuration, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 26 μm. The thickness of the catalyst layer is 6 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 4 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0060 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-17] In Example 2-17, a titanium foil with a gauge thickness of 20 μm and a porosity of 30% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 2-16, and the result is shown in Table 4. The thickness of the electrode is 30 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 5 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0030 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-18] In Example 2-18, a titanium foil with a gauge thickness of 20 μm and an open porosity of 42% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.38 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 2-16, and the result is shown in Table 4. The thickness of the electrode is 32 μm. The thickness of the catalyst layer is 12 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 2.5 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0022 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-19] In Example 2-19, a titanium foil with a gauge thickness of 50 μm and a porosity of 47% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.40 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 2-16, and the result is shown in Table 4. The thickness of the electrode is 69 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis and is 19 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 8 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0024 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-20] Example 2-20 uses a gauge with a thickness of 100 μm, a diameter of titanium fiber of about 20 μm, and a basis weight of 100 g / m2 The titanium non-woven fabric with a porosity of 78% is used as the electrode substrate for anode electrolysis. Other than that, evaluation was performed similarly to Example 2-16, and the result is shown in Table 4. The thickness of the electrode is 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 2 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-21] In Example 2-21, a titanium mesh with a thickness of 120 μm, a diameter of titanium fibers of about 60 μm, and a 150 mesh titanium wire mesh was used as the electrode substrate for anode electrolysis. The porosity is 42%. Spray treatment was performed with alumina of grain number 320. Because it is difficult to measure the surface roughness of the metal wire mesh, in Example 2-21, a titanium plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface of the metal wire mesh. Roughness. The arithmetic average roughness Ra is 0.60 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 2-16, and the result is shown in Table 4. The thickness of the electrode is 140 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 20 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 10 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0132 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 2-22] Example 2-22 uses an anode that is deteriorated and has an increased electrolytic voltage as an anode power source in the same manner as in Example 2-16, and uses the same titanium nonwoven fabric as that of Example 2-20 as an anode. In the same manner as in Example 2-15, a cathode that was deteriorated and the electrolytic voltage became high was used as a cathode power source, and the same nickel foil electrode as in Example 2-3 was used as a cathode. The cross-sectional structure of the electrolytic cell is formed from the cathode chamber side in order to form a current collector, a pad, a deteriorated cathode with a higher voltage, a nickel porous foil cathode, a separator, a titanium non-woven anode, and a deteriorated anode with a higher electrolytic voltage. Pitch structure, the cathode and anode that are degraded and the electrolytic voltage becomes high function as a power feeder. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode (anode) is 114 μm, and the thickness of the catalyst layer is the thickness of the electrode (anode) minus the thickness of the electrode substrate for electrolysis to be 14 μm. The thickness of the electrode (cathode) is 38 μm, and the thickness of the catalyst layer is the thickness of the electrode (cathode) minus the thickness of the electrode base material for electrolysis to be 8 μm. Adequate adhesion was observed on both the anode and the cathode. Deformation test of electrode (anode), result L1 , L2 The average is 2 mm. Deformation test of electrode (cathode), result L1 , L2 The average is 0 mm. When the ventilation resistance of the electrode (anode) was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. When the ventilation resistance of the electrode (cathode) was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of the anode and cathode membrane damage was also "0", which was good. Furthermore, in Example 2-22, the cathode was attached to one side of the separator, and the anode was attached to the opposite side. The cathode and the anode were combined to perform film damage evaluation. [Example 2-23] In Example 2-23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa was used. Zirfon membranes were immersed in pure water for more than 12 hours for testing. Except for the above, the evaluation was performed in the same manner as in Example 2-3, and the results are shown in Table 4. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. Similar to the case of using an ion-exchange membrane as a separator, sufficient adhesion was observed, and the microporous membrane and the electrode were in close contact by surface tension, and the operability was "1", which was good. [Example 2-24] As an electrode base material for cathode electrolysis, a carbon cloth made of woven carbon fiber with a gauge thickness of 566 μm was prepared. A coating solution for forming an electrode catalyst on the carbon cloth was prepared in the following order. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with a closed cell type wound around a cylinder made of PVC (polyvinyl chloride). The formed coating roller is arranged so that the coating liquid is always in contact with each other. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the fabricated electrode was 570 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 4 μm. The thickness of the catalyst layer is the total thickness of ruthenium oxide and cerium oxide. The obtained electrodes were subjected to electrolytic evaluation. The results are shown in Table 4. Deformation test of electrode, result L1 , L2 The average is 0 mm. The air flow resistance of the electrode was measured. As a result, it was 0.19 (kPa · s / m) under measurement condition 1 and 0.176 (kPa · s / m) under measurement condition 2. Moreover, the operability is "2", and it can be judged that it can be operated as a large laminated body. The voltage was high, and the film damage evaluation was "1", and the film damage was confirmed. The reason for this is considered to be that the electrode of Example 2-24 has a large ventilation resistance, so the NaOH generated in the electrode stays at the interface between the electrode and the separator and becomes a high concentration. [Reference Example 1] In Reference Example 1, the cathode used in a large-scale electrolytic cell for 8 years as a cathode was deteriorated and the electrolytic voltage became high. The cathode was replaced by a nickel grid feeder on a pad of a cathode chamber, and electrolytic evaluation was performed through the ion exchange membrane A produced in [Method (i)]. In Reference Example 1, a membrane-integrated electrode is not used. The cross-sectional structure of the electrolytic cell is from the cathode chamber side, and the current collector, the pad, the deteriorated cathode, the ion exchange membrane A, and the anode are sequentially arranged to form a zero pitch. structure. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.04 V, the current efficiency was 97.0%, and the common salt concentration (50% conversion value) in caustic soda was 20 ppm. As a result of the deterioration of the cathode, the result was a higher voltage. [Reference Example 2] In Reference Example 2, a nickel grid feeder was used as the cathode. That is, electrolysis was performed using a nickel mesh without a catalyst coating. The nickel mesh cathode was placed on a pad of a cathode chamber, and electrolytic evaluation was performed through the ion exchange membrane A produced in [Method (i)]. The cross-sectional structure of the battery of Reference Example 2 is a zero-pitch structure in which a current collector, a pad, a nickel mesh, an ion exchange membrane A, and an anode are sequentially arranged from the cathode chamber side. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.38 V, the current efficiency was 97.7%, and the common salt concentration (50% conversion value) in caustic soda was 24 ppm. Since the cathode catalyst was not applied, the result was a higher voltage. [Reference Example 3] In Reference Example 3, the anode used in the large-scale electrolytic cell for about 8 years as the anode was deteriorated and the electrolytic voltage became high. The cross-sectional structure of the electrolytic cell in Reference Example 3 is formed from the cathode chamber side, in which the current collector, the pad, the cathode, the ion exchange membrane A produced in [Method (i)], and the anode that is degraded and has an increased electrolytic voltage are formed Zero-pitch structure. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.18 V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 22 ppm. As the anode deteriorates, the result is a higher voltage. [Example 2-25] In Example 2-25, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 33% after full-roll processing was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 2-25, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.68 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. The mass per unit area is 67.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.05 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 64%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 22%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 13 mm. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2. [Example 2-26] In Example 2-26, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 16% after full-roll processing was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 2-26, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 107 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 7 μm. Mass per unit area is 78.1 (mg / cm2 ). The force per unit mass and unit area (1) is 0.04 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 37%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 25%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 18.5 mm. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0176 (kPa · s / m) under measurement condition 2. [Example 2-27] In Example 2-27, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 40% after full-roll processing was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 2-27, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.70 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The electrode substrate for electrolysis was applied by the same ion plating as in Example 2-6. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 110 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. The force per unit mass and unit area (1) is 0.07 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 80%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 32%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "3", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 11 mm. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0030 (kPa · s / m) under measurement condition 2. [Example 2-28] In Example 2-28, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 58% after full-roll processing was used as the electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 2-28, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 109 μm. The thickness of the catalyst layer is 9 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. The force per unit mass and unit area (1) is 0.06 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 69%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 39%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "3", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 11.5 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. [Example 2-29] In Example 2-29, a nickel wire mesh with a gauge thickness of 300 μm and an opening ratio of 56% was used as an electrode substrate for cathode electrolysis. Because it is difficult to measure the surface roughness of the metal mesh, in Example 2-29, the nickel plate with a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface of the metal mesh. Roughness. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 2-1, and the results are shown in Table 4. The thickness of the electrode is 308 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Mass per unit area is 49.2 (mg / cm2 ). Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 88%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 42%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and during operation, the electrode is peeled off from the film, etc. The operability is "3" and there are problems. It can be evaluated as "3" when it is actually operated in a large size. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 23 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2. [Example 2-30] In Example 2-30, a nickel wire mesh with a gauge thickness of 200 μm and an opening ratio of 37% was used as the electrode base material for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Since it is difficult to measure the surface roughness of the metal mesh, in Example 2-30, the nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface of the metal mesh. Roughness. The arithmetic average roughness Ra is 0.65 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, the electrode electrolytic evaluation, the measurement result of the adhesion force, and the adhesiveness were performed in the same manner as in Example 2-1. The results are shown in Table 4. The thickness of the electrode is 210 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Mass per unit area is 56.4 mg / cm2 . Therefore, the result of the 145 mm diameter cylindrical winding evaluation method (3) was 63%, and the adhesion between the electrode and the separator was poor. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and during operation, the electrode is peeled off from the film, etc. The operability is "3" and there are problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 19 mm. When the airflow resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0096 (kPa · s / m) under measurement condition 2. [Example 2-31] In Example 2-31, a titanium porous metal with a gauge thickness of 500 μm and a porosity of 17% after full-roll processing was used as the electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 2-31, a titanium plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.60 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 2-16, and the result is shown in Table 4. The thickness of the electrode was 508 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The mass per unit area is 152.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. When the air flow resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0072 (kPa · s / m) under measurement condition 2. [Example 2-32] In Example 2-32, a titanium porous metal with a gauge thickness of 800 μm and a porosity of 8% after full-roll processing was used as the electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 2-32, the titanium plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.61 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Example 2-16, and the results are shown in Table 4. The thickness of the electrode is 808 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The mass per unit area is 251.3 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0172 (kPa · s / m) under measurement condition 2. [Example 2-33] In Example 2-33, a titanium porous metal having a gauge thickness of 1000 μm and a porosity of 46% after full-roll processing was used as the electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 2-33, a titanium plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.59 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Example 2-16, and the results are shown in Table 4. The thickness of the electrode was 1011 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 11 μm. The mass per unit area is 245.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. [Example 2-34] A nickel wire having a gauge thickness of 150 μm was prepared as an electrode substrate for cathode electrolysis. A roughening process using this nickel wire is performed. Because it is difficult to measure the surface roughness of the nickel wire, in Example 2-34, the nickel plate having a thickness of 1 mm was sprayed at the same time when spraying, and the surface roughness of the nickel plate was used as the surface roughness of the nickel wire. . Spray treatment was performed with alumina of grain number 320. The arithmetic average roughness Ra is 0.64 μm. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with a closed cell type wound around a cylinder made of PVC (polyvinyl chloride). The formed coating roller is arranged so that the coating liquid is always in contact with each other. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of one nickel wire produced in Example 2-34 was 158 μm. The nickel wire produced by the above method was cut into lengths of 110 mm and 95 mm. As shown in FIG. 37, the 110 mm nickel wire and the 95 mm nickel wire are vertically overlapped at the center of each nickel wire, and are placed by an instant adhesive (Aron Alpha (registered trademark), East Asia Synthesis Co., Ltd.) The intersection part is then used to make electrodes. The electrodes were evaluated, and the results are shown in Table 4. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The opening rate is 99.7%. The mass per unit area of the electrode is 0.5 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 15 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measuring device was set to H (high), and the ventilation resistance value was 0.0002 (kPa · s / m). In addition, for the electrode, a structure shown in FIG. 38 was used, and the electrode (cathode) was set on a Ni grid feeder, and electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage became 3.16 V, which was high. [Example 2-35] In Example 2-35, the electrode produced in Example 2-34 was used. As shown in FIG. 39, a 110 mm nickel wire and a 95 mm nickel wire were used for each of the nickel wires. The centers were placed vertically overlapping, and the intersections were connected by an instant adhesive (Aron Alpha (registered trademark), Toa Synthetic Co., Ltd.) to make electrodes. The electrodes were evaluated, and the results are shown in Table 4. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The porosity is 99.4%. The mass per unit area of the electrode is 0.9 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 16 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measurement device was set to H (high), and the ventilation resistance was 0.0004 (kPa · s / m). For the electrode, a structure shown in FIG. 40 was used, and the electrode (cathode) was placed on a Ni grid power supply, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage was 3.18 V, which was high. [Example 2-36] In Example 2-36, the electrode produced in Example 2-34 was used. As shown in FIG. 41, a 110 mm nickel wire and a 95 mm nickel wire were used for each of the nickel wires. The centers were placed vertically overlapping, and the intersections were connected by an instant adhesive (Aron Alpha (registered trademark), Toa Synthetic Co., Ltd.) to make electrodes. The electrodes were evaluated, and the results are shown in Table 4. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The porosity is 98.8%. The mass per unit area of the electrode is 1.9 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 14 mm. In addition, the ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measurement device was set to H (high), and the ventilation resistance was 0.0005 (kPa · s / m). For the electrode, a structure shown in FIG. 42 was used, and the electrode (cathode) was placed on a Ni grid power supply, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage was 3.18 V, which was high. [Comparative Example 2-1] In Comparative Example 2-1, a thermocompression bonded body in which an electrode was thermocompression-bonded to a separator was prepared by referring to a previous document (an example of Japanese Patent Laid-Open No. Sho 58-48686). Electrode coating was performed in the same manner as in Example 2-1, using a nickel porous metal having a gauge thickness of 100 μm and an open porosity of 33% as an electrode substrate for cathode electrolysis. Thereafter, an inertization treatment was performed on one side of the electrode in the following order. A polyimide adhesive tape (Zhongxing Chemical Co., Ltd.) was attached to one side of the electrode, and a PTFE dispersion (DuPont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was coated on the opposite side at 120 ° C. Dry in a muffle furnace for 10 minutes. The polyimide tape was peeled off, and sintered in a muffle furnace set at 380 ° C for 10 minutes. This operation was repeated twice to inertize one side of the electrode. Made from terminal functional group "-COOCH3 "Perfluorocarbon polymer (C polymer) and end group is" -SO2 F "is a film formed of two layers of perfluorocarbon polymer (S polymer). The thickness of the C polymer layer is 3 mils, and the thickness of the S polymer layer is 4 mils. This two-layer membrane is subjected to a saponification treatment, and an ion exchange group is introduced into the end of the polymer by hydrolysis. The C polymer end is hydrolyzed to a carboxylic acid group, and the S polymer end is hydrolyzed to a sulfo group. The ion exchange capacity based on the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity based on the carboxylic acid group was 0.9 meq / g. The surface having a carboxylic acid group as an ion-exchange group is opposed to the inertized electrode surface, and hot pressing is performed to integrate the ion-exchange membrane with the electrode. One side of the electrode is also exposed after thermocompression bonding, and there is no part of the electrode penetration film. Thereafter, in order to suppress the adhesion of bubbles generated in the electrolysis to the film, a perfluorocarbon polymer mixture into which zirconia and a sulfo group were introduced was applied on both sides. Thus, a thermocompression bonded body of Comparative Example 2-1 was produced. Using this thermocompression bonded body, the force per unit mass and unit area (1) was measured. As a result, the electrode was strongly bonded to the film by thermocompression bonding, so the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed without moving the electrode, and the electrode was pulled upward by a stronger force. As a result, the electrode was able to withstand 1.50 (N / mg · cm2 ), A part of the film was broken. The force (1) per unit mass and unit area of the thermocompression bonded body of Comparative Example 2-1 was at least 1.50 (N / mg · cm2 ), Being strongly engaged. A cylindrical winding evaluation (1) with a diameter of 280 mm was carried out. As a result, the contact area with the plastic pipe was less than 5%. On the other hand, a cylindrical winding evaluation (280) with a diameter of 280 mm was performed. As a result, although the electrode and the membrane were 100% bonded, the separator was not initially wound around the cylinder. The results of the cylindrical winding evaluation (3) with a diameter of 145 mm are the same. This result means that the operability of the film is impaired by the integrated electrode, and it is difficult to roll it into a roll or bend it. The operability is "3" and there are problems. The film damage was evaluated as "0". When electrolytic evaluation was performed, the voltage became higher, the current efficiency became lower, the salt concentration (50% conversion value) in caustic soda increased, and the electrolytic performance deteriorated. The thickness of the electrode was 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. Deformation test of electrode, result L1 , L2 The average is 13 mm. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2. [Comparative Example 2-2] Comparative Example 2-2 uses a nickel mesh with a wire diameter of 150 μm, a 40 mesh, a gauge thickness of 300 μm, and an opening ratio of 58% as the electrode base material for cathode electrolysis. Other than that, a thermocompression bonded body was produced in the same manner as in Comparative Example 2-1. Using this thermocompression bonded body, the force per unit mass and unit area (1) was measured. As a result, the electrode was strongly bonded to the film by thermocompression bonding, so the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed without moving the electrode, and the electrode was pulled upwards with a stronger force. As a result, the bearing capacity was 1.60 (N / mg · cm2 ), A part of the film was broken. The force (1) per unit mass and unit area of the thermocompression bonded body of Comparative Example 2-2 was at least 1.60 (N / mg · cm2 ), Being strongly engaged. A cylindrical winding evaluation (1) of 280 mm diameter was performed using this thermocompression bonded joint. As a result, the contact area with the plastic pipe was less than 5%. On the other hand, a cylindrical winding evaluation (280) with a diameter of 280 mm was performed. As a result, although the electrode and the membrane were 100% bonded, the separator was not initially wound around the cylinder. The results of the cylindrical winding evaluation (3) with a diameter of 145 mm are the same. This result means that the operability of the film is impaired by the integrated electrode, and it is difficult to roll it into a roll or bend it. The operability is "3" and there are problems. When electrolytic evaluation was performed, the voltage became higher, the current efficiency became lower, the salt concentration in caustic soda increased, and the electrolytic performance deteriorated. The thickness of the electrode was 308 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Deformation test of electrode, result L1 , L2 The average is 23 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2. [table 3] [Table 4] In Table 4, all samples can be self-supported by surface tension before the measurement of "force per unit mass and unit area (1)" and "force per unit mass and unit area (2)" ( That is, there is no case of sagging). <Verification of the Third Embodiment> An experimental example corresponding to the third embodiment (hereinafter referred to as "exemplary" in the following "Verification of the Third Embodiment") is prepared as follows, and does not correspond to the third embodiment. The experimental example corresponding to the embodiment (hereinafter referred to as "comparative example" in the item of "Verification of the Third Embodiment") was evaluated by the following method. The details will be described with reference to FIGS. 57 to 62 as appropriate. (1) Electrolytic evaluation (voltage (V), current efficiency (%)) The electrolytic performance was evaluated by the following electrolytic experiment. A titanium anode cell (anode termination cell) having an anode chamber provided with an anode was opposed to a cathode cell having a cathode chamber (cathode termination cell) made of nickel provided with a cathode. A pair of gaskets are arranged between the cells, and the ion exchange membrane is sandwiched between the pair of gaskets. Then, the anode cell, the gasket, the ion-exchange membrane, the gasket, and the cathode were brought into close contact to obtain an electrolytic cell. As the anode, a mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride was applied to a titanium substrate that had been subjected to spraying and acid etching treatment as a pretreatment, and was then dried and fired. The anode is fixed to the anode chamber by welding. As the cathode, those described in Examples and Comparative Examples were used. As the current collector of the cathode chamber, a porous metal made of nickel was used. The size of the current collector is 95 mm in length × 110 mm in width. As the metal elastic body, a pad woven with fine nickel wires is used. A metal elastomer was placed on the current collector. A nickel net made of a nickel wire with a diameter of 150 μm and a plain mesh with a 40-mesh mesh was covered thereon, and the four corners of the Ni net were fixed to the current collector by a rope made of Teflon (registered trademark). This Ni mesh was used as a power source. In this electrolytic cell, a zero-pitch structure is set by utilizing the repulsive force of a pad made of a metal elastomer. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As the separator, the following ion exchange membrane was used. As the reinforcing core material, a 90-denier monofilament (hereinafter referred to as PTFE yarn) made of polytetrafluoroethylene (PTFE) was used. As the sacrificial yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 6 filaments twisted at 200 times / m was used. First, a woven fabric is obtained by plain weaving with 24 PTFE yarns arranged in each of the two directions of TD and MD and two sacrificial yarns arranged between adjacent PTFE yarns. The obtained woven fabric was crimped by a roller to obtain a woven fabric having a thickness of 70 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.85 mg equivalent / g of dry resin, resin A, and CF2 = CF2 With CF2 = CFOCF2 CF (CF2 OCF2 CF2 SO2 The copolymer B had a resin B having an ion exchange capacity of 1.03 mg equivalent / g of the dry resin. Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 μm and a thickness of the resin B layer of 104 μm was obtained by a co-extrusion T-die method. Then, on a heating plate having a heating source and a vacuum source inside, and micropores on its surface, a release paper (cone-shaped embossing processing with a height of 50 μm), a reinforcing material, and a film X were sequentially laminated on the heating plate surface temperature. After heating and decompressing under the conditions of 223 ° C and a degree of reduced pressure of 0.067 MPa for 2 minutes, the release paper was removed to obtain a composite film. Saponification was performed by immersing the obtained composite film in an aqueous solution at 80 ° C. containing 30% by mass of dimethylsulfinium (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. After that, it was immersed in a 50 ° C aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour to replace the counter ion of the ion-exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC. Furthermore, 20% by mass of zirconia having an average particle diameter (primary particle diameter) of 1 μm was added to a 5% by mass ethanol solution of the acid-type resin of the resin B, and a suspension was prepared by dispersing the suspension. The two surfaces of the composite membrane are sprayed to form a coating of zirconia on the surface of the composite membrane to obtain an ion exchange membrane. The coating density of zirconia was measured by fluorescent X-ray measurement, and the result was 0.5 mg / cm2 . The average particle diameter is measured using a particle size distribution meter (for example, "SALD (registered trademark) 2200" manufactured by Shimadzu Corporation). Electrolysis of common salt is performed using the above electrolytic cell. The brine concentration (sodium chloride concentration) of the anode compartment was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode compartment was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell became 90 ° C. At current density of 6 kA / m2 Next, salt electrolysis was performed to measure voltage and current efficiency. Here, the so-called current efficiency is the ratio of the amount of caustic soda generated to the flowing current. If the flowing current causes impurity ions or hydroxide ions instead of sodium ions to move in the ion exchange membrane, the current efficiency reduce. The current efficiency is obtained by dividing the Mohr number of caustic soda generated by a certain time by the Mohr number of electrons flowing in the meantime. The molar number of caustic soda is obtained by measuring the mass of caustic soda produced by electrolysis in a polymer tank. (2) Operability (induction evaluation) (A) The ion exchange membrane (diaphragm) described above was cut into a size of 170 mm square, and the electrodes obtained in the examples and comparative examples described below were cut into 95 × 110 mm. The ion exchange membrane and the electrode were laminated and placed on a Teflon plate. The distance between the anode cell and the cathode cell used in the electrolytic evaluation was set to about 3 cm, and the stacked body that was left standing was lifted up to be inserted and sandwiched therebetween. When performing this operation, check whether the electrode is deviated or dropped while operating. (B) In the same manner as in the above (A), the laminated body is placed on a Teflon plate. Hold the corners of the two adjacent parts of the laminate, and lift up the laminate so that it is vertical. From this state, the two corners of the hand held are moved so that the film becomes convex or concave. This operation was repeated once more to confirm the followability of the electrode to the film. Based on the following indicators, the results were evaluated on four levels of 1-4. 1: good operation 2: able to operate 3: difficult to operate 4: generally inoperable Here, for the samples of Examples 3-4, 3-6, as described below, the operation is correct even for the same size as the large electrolytic cell Evaluation. The evaluation results of Examples 3-4 and 3-6 are indicators for evaluating the differences between the above-mentioned evaluations (A) and (B) and when the large-size measurements are made. That is, in the case where the results obtained by evaluating the small-sized laminated body are "1" and "2", it is evaluated that the operability is good even in the case of making it into a large size. (3) Ratio of fixed area The area S1 is calculated as the area of the surface of the ion exchange membrane opposite to the electrode for electrolysis (the total of the portion corresponding to the current-carrying surface and the portion corresponding to the non-current-carrying surface). Then, the area of the electrode for electrolysis was calculated as the area S2 of the current-carrying surface. The areas S1 and S2 are specified by the areas when the laminated body of the ion exchange membrane and the electrode for electrolysis is viewed from the side of the electrode for electrolysis (see FIG. 57). In addition, since the shape of the electrode for electrolysis does not reach 90% even if it has holes, the electrode for electrolysis is regarded as a flat plate (the area of the hole is also included in the area). The area S3 of the fixed area is also specified as the area when the laminated body is viewed in plan as shown in FIG. 57 (the same is true of the area S3 ′ of only the portion corresponding to the current-carrying surface). When the PTFE tape described below is used as a fixing member, the overlapping portion of the tape is not included in the area. When the PTFE yarn or the adhesive described below is fixed as a fixing member, the area existing on the back surface side of the electrode and the separator is also included in the area. As described above, 100 × (S3 / S1) is calculated as the ratio α (%) of the area of the fixed area in the ion exchange membrane to the area of the surface opposite to the electrode for electrolysis. Furthermore, as a ratio β of the area of the fixed area corresponding to only the current-carrying surface to the area of the current-carrying surface, 100 × S3 ′ / S2 was calculated. [Example 3-1] An electrolytic nickel foil having a gauge thickness of 22 μm was prepared as an electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.96 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The nickel foil is punched to form a circular hole to form a porous foil. The opening rate is 44%. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the electrode produced in Example 3-1 was 24 μm. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide is 8 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. The coating is also formed on the surface without roughening. In order to use the electrode produced by the above method for electrolytic evaluation, it was cut into a size of 95 mm in length and 110 mm in width. The roughened surface of the electrode is arranged to face the approximate center of the carboxylic acid layer side of an ion exchange membrane (size: 160 mm × 160 mm) balanced with a 0.1 N NaOH aqueous solution. Use PTFE tape (manufactured by Nitto Denko) as shown in Figure 57 (however, Figure 57 is only a schematic diagram for explanation, and the dimensions may not be accurate. The same applies to the following diagrams). 4 sides fixed. In Example 3-1, the PTFE tape is a fixing member, and the ratio α is 60% and the ratio β is 1.0%. Even if the four corners of the membrane part of the membrane-integrated electrode are grasped so that the electrode becomes the ground side and the membrane-integrated electrode is suspended parallel to the ground, there is no case of electrode peeling or deviation. In addition, even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not peel off or deviate. The membrane-integrated electrode is sandwiched between the anode cell and the cathode cell so that the electrode-attached surface becomes the cathode chamber side. The cross-sectional structure is a zero-pitch structure in which current collectors, pads, nickel grid feeders, electrodes, films, and anodes are sequentially arranged from the cathode chamber side. The obtained electrodes were evaluated. The results are shown in Table 5. Shows lower voltage and higher current efficiency. The operability is also relatively good. [Example 3-2] As shown in FIG. 58, the evaluation was performed in the same manner as in Example 3-1 except that the area where the PTFE tape overlaps the electrolytic surface was increased. That is, in Example 3-2, since the area of the PTFE tape increases in the in-plane direction of the electrode for electrolysis, the area of the electrolytic surface in the electrode for electrolysis is reduced compared with Example 3-1. In Example 3-2, the ratio α was 69%, and the ratio β was 23%. The evaluation results are shown in Table 5. Shows lower voltage and higher current efficiency. The operability is also "1", which is good. [Example 3-3] As shown in FIG. 59, the evaluation was performed in the same manner as in Example 3-1 except that the area where the PTFE tape overlaps the electrolytic surface was increased. That is, in Example 3-3, since the area of the PTFE tape increases in the in-plane direction of the electrode for electrolysis, the area of the electrolytic surface in the electrode for electrolysis is reduced compared with Example 3-1. In Example 3-3, the ratio α was 87%, and the ratio β was 67%. The evaluation results are shown in Table 5. Shows lower voltage and higher current efficiency. The operability is also "1", which is good. [Example 3-4] The same electrode as in Example 3-1 was prepared, and cut to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode is arranged to face the approximate center of the carboxylic acid layer side of an ion exchange membrane (size: 160 mm × 160 mm) balanced with a 0.1 N NaOH aqueous solution. As shown in FIG. 60, a yarn made of PTFE was used to sew the ion exchange membrane and the electrode so that the left side of the electrode was extended longitudinally. The PTFE yarn is penetrated from the back side of the paper surface to the front side from the portion of the electrode 10 mm in the longitudinal direction and 10 mm in the transverse direction, and 35 mm in the longitudinal direction and 10 mm in the transverse direction from the front side of the paper surface to the back side. The yarn is penetrated again from the back side of the paper surface to the front side at a length of 60 mm in the longitudinal direction and 10 mm in the transverse direction, and penetrates from the front side of the paper surface to the back side at the longitudinal direction of 85 mm and a transverse 10 mm. The coating on the yarn through ion exchange membrane will be CF2 = CF2 With CF2 = CFOCF2 CF (CF2 OCF2 CF2 SO2 The acid type resin S of the resin having an ion exchange capacity of 1.03 mg equivalent / g based on the copolymer of F was dispersed in ethanol so as to be 5% by mass. As described above, in Example 3-4, the ratio α is 0.35%, and the ratio β is 0.86%. Even if the four corners of the membrane portion of the membrane-integrated electrode are held by the membrane and the electrode as one, the electrode becomes the ground side and the membrane-integrated electrode is suspended in a manner parallel to the ground, the electrode does not fall. Even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not fall off. The obtained electrodes were evaluated. The results are shown in Table 5. Shows lower voltage and higher current efficiency. The operability is also relatively good. Furthermore, in Example 3-4, the ion-exchange membrane and electrode which were changed to a large size were prepared. Four ion exchange membranes with a length of 1.5 m and a width of 2.5 m and a cathode with a length of 0.3 m and a width of 2.4 m were prepared. The cathode is arranged on the carboxylic acid layer side of the ion-exchange membrane in a gap-free manner, and the cathode and the ion-exchange membrane are bonded by PTFE yarn to produce a laminated body. In this example, the ratio α is 0.013%, and the ratio β is 0.017%. A membrane-integrated electrode in which a membrane and an electrode are integrated into a large electrolytic cell can be smoothly mounted. [Example 3-5] The same electrode as in Example 3-1 was prepared and cut into a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode is arranged to face the approximate center of the carboxylic acid layer side of an ion exchange membrane (size: 160 mm × 160 mm) balanced with a 0.1 N NaOH aqueous solution. An ion exchange membrane and an electrode were fixed using a polypropylene fixing resin shown in FIG. 61. That is, it is provided at a total of 2 locations in a portion of 20 mm from the corner of the electrode in the longitudinal direction and 20 mm in the transverse direction, and at a location of 20 mm in the longitudinal and 20 mm from the corner portion below the electrode. The same solution as in Example 3-4 was applied to a portion of the fixing resin penetrating the ion exchange membrane. As described above, in Examples 3-5, the fixing resin and the resin S become fixing members, and the ratio α is 0.47% and the ratio β is 1.1%. Even if the four corners of the membrane portion of the membrane-integrated electrode are held by the membrane and the electrode as one, the electrode becomes the ground side and the membrane-integrated electrode is suspended in a manner parallel to the ground, the electrode does not fall. Even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not fall off. The obtained electrodes were evaluated. The results are shown in Table 5. Shows lower voltage and higher current efficiency. The operability is also relatively good. [Example 3-6] The same electrode as in Example 3-1 was prepared, and cut to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode is arranged to face the approximate center of the carboxylic acid layer side of an ion exchange membrane (size: 160 mm × 160 mm) balanced with a 0.1 N NaOH aqueous solution. As shown in FIG. 62, a cyanoacrylate-based adhesive (trade name: Aron Alpha, Toa Synthesis Co., Ltd.) was used to fix the ion exchange membrane and the electrode. That is, the adhesive is fixed at five places (all at regular intervals) on one side of the electrode in the longitudinal direction and eight places (all at regular intervals) in one side of the electrode in the lateral direction. As described above, in Example 3-6, the adhesive becomes a fixing member, and the ratio α is 0.78% and the ratio β is 1.9%. Even if the four corners of the membrane portion of the membrane-integrated electrode are held by the membrane and the electrode as one, the electrode becomes the ground side and the membrane-integrated electrode is suspended in a manner parallel to the ground, the electrode does not fall. Even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not fall off. The obtained electrodes were evaluated. The results are shown in Table 5. Shows lower voltage and higher current efficiency. The operability is "1", which is also relatively good. Furthermore, in Example 3-6, the ion-exchange membrane and electrode which were changed to a large size were prepared. Four ion exchange membranes with a length of 1.5 m and a width of 2.5 m and a cathode with a length of 0.3 m and a width of 2.4 m were prepared. One edge of the four cathodes in the lateral direction was connected to each other with the above-mentioned adhesive to form one large cathode (1.2 m in length and 2.4 m in width). This large cathode was attached to the central portion of the carboxylic acid layer side of the ion exchange membrane by Aron Alpha to produce a laminate. That is, as in FIG. 62, the adhesive is fixed at five places (all at regular intervals) on one side of the electrode in the longitudinal direction and eight places (all at regular intervals) on one side of the electrode in the lateral direction. In this example, the ratio α is 0.019%, and the ratio β is 0.024%. A membrane-integrated electrode in which a membrane and an electrode are integrated into a large electrolytic cell can be smoothly mounted. [Example 3-7] The same electrode as in Example 3-1 was prepared and cut into a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode is arranged to face the approximate center of the carboxylic acid layer side of an ion exchange membrane (size: 160 mm × 160 mm) balanced with a 0.1 N NaOH aqueous solution. The same solution as in Example 3-4 was applied, and the ion exchange membrane and the electrode were fixed. That is, it is provided at a total of 2 places at a distance of 20 mm in the longitudinal direction and a width of 20 mm from a corner of the electrode, and at a distance of 20 mm in a longitudinal direction and a distance of 20 mm from a corner below the electrode (see FIG. 61). . As described above, in Example 3-7, the resin S is a fixing member, and the ratio α is 2.0% and the ratio β is 4.8%. Even if the four corners of the membrane portion of the membrane-integrated electrode are held by the membrane and the electrode as one, the electrode becomes the ground side and the membrane-integrated electrode is suspended in a manner parallel to the ground, the electrode does not fall. Even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not fall off. The obtained electrodes were evaluated. The results are shown in Table 5. Shows lower voltage and higher current efficiency. The operability is also relatively good. [Comparative Example 3-1] Evaluation was performed in the same manner as in Example 3-1, except that the area where the PTFE tape overlaps the electrolytic surface was increased. That is, in Comparative Example 3-1, since the area of the PTFE tape was increased in the in-plane direction of the electrode for electrolysis, the area of the electrolytic surface in the electrode for electrolysis was reduced compared to Example 3-1. In Comparative Example 3-1, the ratio α was 93%, and the ratio β was 83%. The evaluation results are shown in Table 5. The higher the voltage, the lower the current efficiency. The operability is "1", which is good. [Comparative Example 3-2] Evaluation was performed in the same manner as in Example 3-1, except that the area where the PTFE tape overlaps the electrolytic surface was increased. The evaluation results are shown in Table 5. That is, in Comparative Example 3-2, the area of the PTFE tape was increased in the in-plane direction of the electrode for electrolysis. In Comparative Example 3-2, the ratio α and the ratio β were 100%, and the entire electrolytic surface was a fixed area covered with PTFE. Therefore, the electrolytic solution could not be supplied and electrolysis could not be performed. The operability is "1", which is good. [Comparative Example 3-3] Evaluation was performed in the same manner as in Example 3-1, except that a PTFE tape was not used, that is, the ratio α and the ratio β were 0%. The evaluation results are shown in Table 5. Shows lower voltage and higher current efficiency. On the other hand, since there is no fixed region between the separator and the electrode, the separator and the electrode cannot be treated as a laminated body (integral body), and the operability is "4". The evaluation results of Examples 3-1 to 7 and Comparative Examples 3-1 to 3 are combined and shown in Table 5 below. [table 5] <Verification of the Fourth Embodiment> An experimental example corresponding to the fourth embodiment (hereinafter referred to as "exemplary" in the following "Verification of the Fourth Embodiment") is prepared as follows, and does not correspond to the fourth embodiment. The experimental example corresponding to the embodiment (hereinafter referred to as "comparative example" in the item of "Verification of the Fourth Embodiment") was evaluated by the following method. The details will be described with reference to FIGS. 79 to 90 as appropriate. [Evaluation method] (1) Porosity The electrode was cut into a size of 130 mm x 100 mm. An electronic digital thickness gauge (manufactured by Mitutoyo Co., Ltd., showing a minimum of 0.001 mm) was used to uniformly measure 10 points in the plane and calculate the average value. The volume was calculated using this as the electrode thickness (gauge thickness). Thereafter, the mass was measured using an electronic balance, and the weight was determined based on the specific gravity of the metal (the specific gravity of nickel = 8.908 g / cm3 , Specific gravity of titanium = 4.506 g / cm3 ) Calculate the porosity or porosity. Porosity (void ratio) (%) = (1-(electrode mass) / (electrode volume × metal specific gravity)) × 100 (2) mass per unit area (mg / cm2 ) Cut the electrode to a size of 130 mm × 100 mm and measure the mass with an electronic balance. Divide this value by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force per unit mass / area (1) (Adhesive force) (N / mg ・ cm2 )) [Method (i)] The measurement system used a tensile compression tester (Imada Manufacturing Co., Ltd., the tester body: SDT-52NA type tensile compression tester, load meter: SL-6001 load meter). A nickel plate having a thickness of 1.2 mm and a thickness of 200 mm was sprayed with alumina with a grain number of 320. The arithmetic average surface roughness (Ra) of the nickel plate after the blast treatment was 0.7 μm. Here, the surface roughness measurement uses a stylus-type surface roughness measuring machine SJ-310 (Mitutoyo Co., Ltd.). The measurement sample was set on a platform parallel to the ground, and the arithmetic average roughness Ra was measured under the following measurement conditions. When the measurement is performed 6 times, the average value is described. <Shape of Stylus> Conical, Taper Angle = 60 °, Tip Radius = 2 μm, Static Measuring Force = 0.75 mN <Roughness Standard> JIS2001 <Evaluation Curve> R <Filter> GAUSS <Critical Value λc> 0.8 mm <Critical The value λs> 2.5 μm <the number of intervals> 5 <forward sweep, backward sweep> There is a chuck for fixing the nickel plate to the lower side of the tensile compression tester so as to be vertical. The following ion exchange membrane A was used as a separator. As the reinforcing core material, a 90-denier monofilament (hereinafter referred to as PTFE yarn) made of polytetrafluoroethylene (PTFE) was used. As the sacrificial yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 6 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. First, a woven fabric is obtained by plain weaving with 24 PTFE yarns arranged in each of the two directions of TD and MD and two sacrificial yarns arranged between adjacent PTFE yarns. The obtained woven fabric was crimped by a roller to obtain a woven fabric having a thickness of 70 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.85 mg equivalent / g of dry resin, resin A, and CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer B had a resin B having an ion exchange capacity of 1.03 mg equivalent / g of the dry resin. Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 μm and a thickness of the resin B layer of 104 μm was obtained by a co-extrusion T-die method. Then, on a heating plate having a heating source and a vacuum source inside, and micropores on its surface, a release paper (cone-shaped embossing processing with a height of 50 μm), a reinforcing material, and a film X were sequentially laminated on the heating plate surface temperature. After heating and decompressing under the conditions of 223 ° C and a degree of reduced pressure of 0.067 MPa for 2 minutes, the release paper was removed to obtain a composite film. Saponification was performed by immersing the obtained composite film in an aqueous solution at 80 ° C. containing 30% by mass of dimethylsulfinium (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. After that, it was immersed in a 50 ° C aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour to replace the counter ion of the ion-exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC. Furthermore, 20% by mass of zirconia having a particle size of 1 μm was added to a 5% by mass ethanol solution of the acid type resin of the resin B to disperse it to prepare a suspension, and both sides of the composite film were prepared by a suspension spray method. Spraying was performed to form a coating of zirconia on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconia was measured by fluorescent X-ray measurement, and the result was 0.5 mg / cm2 . The average particle diameter is measured using a particle size distribution meter ("SALD (registered trademark) 2200" manufactured by Shimadzu Corporation). The ion exchange membrane (separator) obtained above was immersed in pure water for more than 12 hours and used in the test. It was made to contact the said nickel plate fully wetted with pure water, and it adhere | attached by the tension | tensile_strength of water. At this time, the nickel plate and the upper end of the ion-exchange membrane are aligned. The electrode sample (electrode) used for the measurement was cut into a 130 mm square. The ion exchange membrane A was cut into 170 mm squares. Two stainless steel plates (1 mm in thickness, 9 mm in length, and 170 mm in width) were sandwiched on one side of the electrode, aligned with the center of the stainless steel plate and the electrode, and uniformly fixed by 4 clamps. The center of the stainless steel plate was clamped by a clamp on the upper side of the tensile compression tester, and the electrode was suspended. At this time, the load to the testing machine was set to 0 N. Remove the stainless steel plate, electrode, and clamp assembly from the tensile compression tester temporarily. In order to fully wet the electrode with pure water, immerse it in a tank filled with pure water. Thereafter, the center of the stainless steel plate was clamped again to the chuck on the upper side of the tensile compression tester, and the electrode was suspended. The upper chuck of the tensile compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the ion exchange membrane using the surface tension of pure water. At this time, the bonding surface is 130 mm in width and 110 mm in length. The pure water filled in the washing bottle is blown to the electrode and the ion exchange membrane as a whole, and the diaphragm and the electrode are fully wetted again. After that, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (38 mm outer diameter) was gently pressed from above the electrode, and rolled from top to bottom to remove excess Remove pure water. The roller is applied only once. The electrode was raised at a speed of 10 mm / minute, and the load measurement was started. The overlapping portion of the electrode and the diaphragm was recorded as a load at a width of 130 mm and a length of 100 mm. This measurement was performed three times and the average value was calculated. The average value is divided by the area where the electrode overlaps with the ion exchange membrane and the electrode mass in the area where it overlaps with the ion exchange membrane to calculate the force per unit mass and area (1). The mass of the electrode overlapping the ion exchange membrane is based on the mass per unit area (mg / cm) of (2) above.2 The value obtained in) is calculated by ratio calculation. The environment of the measuring room is 23 ± 2 ℃ and relative humidity 30 ± 5%. In addition, the electrodes used in the examples and comparative examples can be attached independently without sagging or peeling when they are adhered to the ion exchange membrane of a nickel plate fixed vertically by surface tension. Fig. 79 shows a schematic diagram of a method for evaluating the bearing capacity (1). The measurement lower limit of the tensile tester is 0.01 (N). (4) Force per unit mass and unit area (2) (Adhesive force) (N / mg ・ cm2 )) [Method (ii)] The measurement system used a tensile compression tester (Imada Manufacturing Co., Ltd., the tester body: SDT-52NA type tensile compression tester, load meter: SL-6001 load meter). The nickel plate similar to the method (i) was fixed vertically to a chuck on the lower side of the tensile compression tester. The electrode sample (electrode) used for the measurement was cut into a 130 mm square. The ion exchange membrane A was cut into 170 mm squares. Two stainless steel plates (1 mm in thickness, 9 mm in length, and 170 mm in width) were sandwiched on one side of the electrode, aligned with the center of the stainless steel plate and the electrode, and uniformly fixed by 4 clamps. The center of the stainless steel plate was clamped by a clamp on the upper side of the tensile compression tester, and the electrode was suspended. At this time, the load to the testing machine was set to 0 N. Remove the stainless steel plate, electrode, and clamp assembly from the tensile compression tester temporarily. In order to fully wet the electrode with pure water, immerse it in a tank filled with pure water. Thereafter, the center of the stainless steel plate was clamped again to the chuck on the upper side of the tensile compression tester, and the electrode was suspended. The upper chuck of the tensile compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the nickel plate by the surface tension of the solution. At this time, the bonding surface is 130 mm in width and 110 mm in length. The pure water filled in the washing bottle is blown to the entire electrode and the nickel plate, and the nickel plate and the electrode are fully wetted again. After that, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (38 mm outer diameter) was gently pressed from above the electrode, and rolled from top to bottom to remove excess The solution was removed. The roller is applied only once. The electrode was raised at a speed of 10 mm / minute, and the load measurement was started. The load at the time when the longitudinal overlap between the electrode and the nickel plate became 100 mm was recorded. This measurement was performed three times and the average value was calculated. The average value is divided by the area where the electrode overlaps with the nickel plate and the mass of the electrode with the area overlapping with the nickel plate to calculate the force per unit mass and unit area (2). The mass of the electrode overlapping the diaphragm is based on the mass per unit area (mg / cm) of (2) above.2 The value obtained in) is calculated by ratio calculation. The environment of the measurement room was 23 ± 2 ° C and 30 ± 5% relative humidity. In addition, the electrodes used in the examples and comparative examples can be attached independently without sagging or peeling when they are adhered to a nickel plate that is fixed vertically by surface tension. The measurement lower limit of the tensile tester is 0.01 (N). (5) Evaluation method of cylindrical winding with a diameter of 280 mm (1) (%) (film and cylinder) Evaluation method (1) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. The electrodes in Examples 33 and 34 were integrated with the ion exchange membrane by hot pressing. Therefore, one body of the ion exchange membrane and the electrode was prepared (the electrode system was 130 mm square). The ion exchange membrane was fully immersed in pure water, and then placed on the curved surface of a plastic (polyethylene) tube made of 280 mm outside diameter. Thereafter, the excess solution was removed by a roller formed by winding an independent foaming type EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outer diameter of 38 mm). The roller system rolls on the ion exchange membrane from the left side to the right side of the pattern diagram shown in FIG. 80. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the plastic tube electrode with an outer diameter of 280 mm was measured. (6) Evaluation method of cylindrical winding with a diameter of 280 mm (2) (%) (film and electrode) Evaluation method (2) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into a 130 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. The ion exchange membrane and the electrode were fully immersed in pure water, and then laminated. The laminated body was placed on a curved surface of a plastic (polyethylene) tube having an outer diameter of 280 mm so that the electrodes became outside. Thereafter, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wrapped around a vinyl chloride tube (outer diameter of 38 mm) was gently pressed from above the electrode, and from the left side of the pattern diagram shown in FIG. 81 Scroll to the right to remove excess solution. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the electrode was measured. (7) 145 mm diameter cylindrical winding evaluation method (3) (%) (film and electrode) Evaluation method (3) was performed in the following order. The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into a 130 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. The ion exchange membrane and the electrode were fully immersed in pure water, and then laminated. The laminated body was placed on a curved surface of a plastic (polyethylene) tube having an outer diameter of 145 mm so that the electrodes became outside. Thereafter, a roller made of a 5 mm-thick, independent-foam EPDM sponge rubber wound around a vinyl chloride tube (38 mm outer diameter) was gently pressed from above the electrode, and from the left side of the pattern diagram shown in FIG. 82 Scroll to the right to remove excess solution. The roller is applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane was in close contact with the electrode was measured. (8) Operability (induction evaluation) (A) The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut into a size of 170 mm square, and the electrode was cut into 95 × 110 mm. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In each example, the ion exchange membrane and the electrode were fully immersed in three solutions of sodium bicarbonate aqueous solution, 0.1 N aqueous NaOH solution, and pure water, and then laminated, and then placed on a Teflon plate. The distance between the anode cell and the cathode cell used in the electrolytic evaluation was set to about 3 cm, and the stacked body that was left standing was lifted up to be inserted and sandwiched therebetween. When performing this operation, check whether the electrode is deviated or dropped while operating. (B) The ion exchange membrane A (diaphragm) produced in [Method (i)] was cut to a size of 170 mm square, and the electrode was cut to 95 × 110 mm. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. In each example, the ion exchange membrane and the electrode were fully immersed in three solutions of sodium bicarbonate aqueous solution, 0.1 N aqueous NaOH solution, and pure water, and then laminated, and then placed on a Teflon plate. Hold the corners of the two adjacent parts of the laminate, and lift up the laminate so that it is vertical. From this state, the two corners of the hand held are moved so that the film becomes convex or concave. This operation was repeated once more to confirm the followability of the electrode to the film. Based on the following indicators, the results were evaluated on four levels of 1-4. 1: good operation 2: able to operate 3: difficult to operate 4: generally inoperable Here, for the samples of Examples 4-28, dimensions of 1.3 m × 2.5 m with electrodes and 1.5 m × 2.8 m with ion exchange membrane The large electrolytic cell is operated in the same size. The evaluation result of Example 28 (hereinafter referred to as "3") is used as an index for evaluating the differences between the above-mentioned (A) and (B) and when the large-sized size is made. That is, in the case where the results obtained by evaluating a small laminated body are "1" and "2", it is evaluated that there is no problem in operability even in the case of making a large size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common salt concentration in caustic soda (ppm, 50% conversion)) The electrolytic performance was evaluated by the following electrolytic experiment. A titanium anode cell (anode termination cell) having an anode chamber provided with an anode was opposed to a cathode cell having a cathode chamber (cathode termination cell) made of nickel provided with a cathode. A pair of spacers are arranged between the cells, and a laminate (a laminate of the ion exchange membrane A and the electrode for electrolysis) is sandwiched between the pair of spacers. Here, both the ion exchange membrane A and the electrode for electrolysis were directly sandwiched between the spacers. Then, the anode cell, the gasket, the laminate, the gasket, and the cathode are closely contacted to obtain an electrolytic cell, and an electrolytic cell including the electrolytic cell is prepared. As the anode, a mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride was applied to a titanium substrate that had been subjected to spraying and acid etching treatment as a pretreatment, and was then dried and fired. The anode is fixed to the anode chamber by welding. As the cathode, those described in Examples and Comparative Examples were used. As the current collector of the cathode chamber, a porous metal made of nickel was used. The size of the current collector is 95 mm in length × 110 mm in width. As the metal elastic body, a pad woven with fine nickel wires is used. A metal elastomer was placed on the current collector. A nickel net made of a nickel wire with a diameter of 150 μm and a plain mesh with a 40-mesh mesh was covered thereon, and the four corners of the Ni net were fixed to the current collector by a rope made of Teflon (registered trademark). This Ni mesh was used as a power source. In this electrolytic cell, a zero-pitch structure is formed by utilizing the repulsive force of a pad of a metal elastomer. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As the separator, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used. Electrolysis of common salt is performed using the above electrolytic cell. The brine concentration (sodium chloride concentration) of the anode compartment was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode compartment was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell became 90 ° C. At current density of 6 kA / m2 Next, salt electrolysis was performed to measure voltage, current efficiency, and salt concentration in caustic soda. Here, the so-called current efficiency is the ratio of the amount of caustic soda generated to the flowing current. If the flowing current causes impurity ions or hydroxide ions instead of sodium ions to move in the ion exchange membrane, the current efficiency reduce. The current efficiency is obtained by dividing the Mohr number of caustic soda generated by a certain time by the Mohr number of electrons flowing in the meantime. The molar number of caustic soda is obtained by measuring the mass of caustic soda produced by electrolysis in a polymer tank. The salt concentration in caustic soda is a value obtained by converting the caustic soda concentration to 50%. In addition, Table 6 shows the specifications of the electrodes and power feeders used in the examples and comparative examples. (11) Measurement of the thickness of the catalyst layer, electrode substrate for electrolysis, and electrode thickness The thickness of the electrode substrate for electrolysis was measured uniformly on the surface using an electronic digital thickness gauge (manufactured by Mitutoyo Co., Ltd., showing at least 0.001 mm) Ten points were measured and the average value was calculated. This was used as the thickness (gauge thickness) of the electrode substrate for electrolysis. The thickness of the electrode is the same as that of the electrode substrate, and 10 points are uniformly measured in the plane by an electronic digital thickness meter, and the average value is calculated. This is used as the electrode thickness (gauge thickness). The thickness of the catalyst layer is determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. (12) Elastic deformation test of the electrode The ion exchange membrane A (diaphragm) produced in [Method (i)] and the electrode were cut into a size of 110 mm square. The ion-exchange membrane was immersed in pure water for more than 12 hours and used for the test. At a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, the ion-exchange membrane was laminated with the electrode to make a laminated body, as shown in FIG. 83, and wound to an outer diameter of f32 mm without gaps, 20 cm PVC tube. In order to prevent the wound laminate from peeling or loosening from the PVC pipe, a polyethylene strap is used for fixing. Hold in this state for 6 hours. After that, the straps were removed, and the laminated body was unrolled from the PVC pipe. Place the electrode only on the platform, and measure the height L of the part that protrudes from the platform1 , L2 And find the average. This value is used as an index of electrode deformation. That is, a smaller value means that it is difficult to deform. When a porous metal is used, there are two types of the SW direction and the LW direction during winding. In this test, it was wound in the SW direction. Moreover, about the electrode which deform | transformed (the electrode which did not return to the original flat state), the softness after plastic deformation was evaluated by the method shown in FIG. 84. That is, the deformed electrode is placed on a diaphragm that is fully immersed in pure water, one end is fixed, the opposite end of the floating is pressed against the diaphragm, the force is released, and the deformation electrode is evaluated to follow the diaphragm . (13) Evaluation of membrane damage The following ion exchange membrane B was used as a separator. As the reinforcing core material, polytetrafluoroethylene (PTFE) and a yarn of 100 denier twisted at 900 times / m into a yarn shape (hereinafter referred to as PTFE yarn) were used. As the sacrificial yarn of the warp yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 8 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. As the sacrificial yarn of the weft yarn, a yarn obtained by twisting polyethylene terephthalate (PET) with 35 deniers and 8 filaments at 200 times / m was used. First, plain weaving was performed by arranging 24 PTFE yarns per 24 inches and placing two sacrificial yarns between adjacent PTFE yarns to obtain a woven fabric with a thickness of 100 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.92 mg equivalent / g of dry resin polymer (A1),2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer (F1) had a polymer (B1) with an ion exchange capacity of 1.10 mg equivalent / g of dry resin. Using these polymers (A1) and (B1), a two-layer film with a thickness of 25 μm of a polymer (A1) layer and a thickness of 89 μm of a polymer (B1) layer was obtained by co-extrusion T-die method X . The ion exchange capacity of each polymer represents the ion exchange capacity when the ion exchange group precursor of each polymer is hydrolyzed and converted into an ion exchange group. Also, prepare separately with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer (F2) had a polymer (B2) with an ion exchange capacity of 1.10 mg equivalent / g of dry resin. This polymer single layer was extruded to obtain a film Y of 20 μm. Then, on a heating plate with a heating source and a vacuum source inside and micropores on the surface, the release paper, the film Y, the reinforcing material and the film X are sequentially laminated, and the conditions of the heating plate temperature 225 ° C and the decompression degree 0.022 MPa After depressurizing under heating for 2 minutes, the release paper was removed to obtain a composite film. The obtained composite membrane was immersed in an aqueous solution containing dimethylsulfine (DMSO) and potassium hydroxide (KOH) for 1 hour to perform saponification, and then immersed in 0.5 N NaOH for 1 hour to ion-exchange The attached ions were replaced with Na and then washed with water. Furthermore, it dried at 60 degreeC. Also, will start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The polymer (B3) of the copolymer (F) having an ion exchange capacity of 1.05 mg equivalent / g of the dried resin was hydrolyzed and then made into an acid form by hydrochloric acid. In a solution prepared by dissolving the acid polymer (B3 ') in a 50/50 (mass ratio) mixed solution of water and ethanol at a ratio of 5% by mass, the polymer (B3') and zirconia Zirconium oxide particles having an average particle diameter of 0.02 μm were added so that the mass ratio of the particles was 20/80. Thereafter, it was dispersed in a suspension of zirconia particles by a ball mill to obtain a suspension. This suspension was coated on both surfaces of the ion exchange membrane by a spray method and dried to obtain an ion exchange membrane B having a coating layer containing a polymer (B3 ′) and zirconia particles. The coating density of zirconia was measured by fluorescent X-ray measurement, and it was 0.35 mg / cm2 . For the anode system, the same one as in (9) electrolytic evaluation was used. For the cathode system, those described in Examples and Comparative Examples were used. The collector, pad and feed system of the cathode chamber are the same as those used in (9) Electrolytic Evaluation. In other words, the Ni mesh is used as a power feeder, and a zero-pitch structure is formed by using the repulsive force of a pad of a metal elastic body. The gasket was the same as that used in (9) Electrolytic Evaluation. As the separator, the ion exchange membrane B produced by the above method was used. That is, the same electrolytic cell as in (9) was prepared, except that the laminated body of the ion exchange membrane B and the electrode for electrolysis was sandwiched between a pair of spacers. Electrolysis of common salt is performed using the above electrolytic cell. The brine concentration (sodium chloride concentration) of the anode compartment was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode compartment was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell became 70 ° C. At current density of 8 kA / m2 Next, salt electrolysis was performed. After 12 hours from the start of the electrolysis, the electrolysis was stopped, the ion exchange membrane B was taken out, and the damage state was observed. "○" means no damage. “×” means that there is damage on almost the entire surface of the ion exchange membrane. (14) Ventilation resistance of the electrode The ventilation resistance of the electrode was measured using a permeability testing machine KES-F8 (trade name, Kato Tech Co., Ltd.). The unit of ventilation resistance value is kPa · s / m. The measurement was performed 5 times, and the average value is shown in Table 7. The measurement was performed under the following two conditions. The temperature in the measurement chamber was set to 24 ° C, and the relative humidity was set to 32%.・ Measurement condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Ventilation volume: 0.4 cc / cm2 / s Measurement range: SENSE L (low) Sample size: 50 mm × 50 mm • Measurement condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / cm2 / s Measurement range: SENSE M (medium) or H (high) Sample size: 50 mm × 50 mm [Example 4-1] As an electrode substrate for cathode electrolysis, an electrolytic nickel foil with a gauge thickness of 16 μm was prepared. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The nickel foil is punched to form a circular hole to form a porous foil. The opening ratio is 49%. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the electrode produced in Example 4-1 was 24 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The coating is also formed on the surface without roughening. It is the total thickness of ruthenium oxide and cerium oxide. Table 7 shows the measurement results of the adhesion force of the electrodes produced by the above methods. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. In order to use the electrode produced by the above method for electrolytic evaluation, it was cut into a size of 95 mm in length and 110 mm in width. Approximately the center of the carboxylic acid layer side of the ion-exchange membrane A (160 mm × 160 mm in size) of the ion exchange membrane A (160 mm × 160 mm) prepared in [Method (i)] with the roughened surface of the electrode equilibrated with a 0.1 N NaOH aqueous solution. The positions are opposite, and the surface tension of the aqueous solution makes them in close contact. Even if the four corners of the membrane part of the membrane-integrated electrode are grasped so that the electrode becomes the ground side and the membrane-integrated electrode is suspended parallel to the ground, there is no case of electrode peeling or deviation. In addition, even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not peel off or deviate. The membrane-integrated electrode is sandwiched between the anode cell and the cathode cell so that the electrode-attached surface becomes the cathode chamber side. The cross-sectional structure is a zero-pitch structure in which current collectors, pads, nickel grid feeders, electrodes, films, and anodes are sequentially arranged from the cathode chamber side. The obtained electrodes were subjected to electrolytic evaluation. The results are shown in Table 7. Shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF (fluorescence X-ray analysis), approximately 100% of the coating remained on the roughened surface, and the coating on the non-roughened surface decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 4-2] Example 4-2 uses an electrolytic nickel foil with a gauge thickness of 22 μm as the electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.96 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening rate is 44%. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 29 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 7 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0033 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 4-3] Example 4-3 uses an electrolytic nickel foil with a gauge thickness of 30 μm as the electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 1.38 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening rate is 44%. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 38 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 4-4] Example 4-4 uses an electrolytic nickel foil with a gauge thickness of 16 μm as the electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The porosity is 75%. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 24 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The measurement of the air flow resistance of the electrode was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on the roughened surface, and the coating on the surface without roughening decreased. This shows that the surface opposite to the film (the roughened surface) is helpful for electrolysis, and even if there is little or no coating on the opposite surface to the film, it can exhibit good electrolytic performance. [Example 4-5] In Example 4-5, an electrolytic nickel foil with a gauge thickness of 20 μm was prepared as an electrode substrate for cathode electrolysis. Both sides of the nickel foil are subjected to a roughening treatment by electrolytic nickel plating. The roughened surface has an arithmetic average roughness Ra of 0.96 μm. Both sides have the same roughness. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The opening ratio is 49%. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 30 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. The coating is also formed on the surface without roughening. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The measurement of the air flow resistance of the electrode was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. In addition, when the coating amount after electrolysis was measured by XRF, approximately 100% of the coating remained on both sides. In consideration of Comparative Examples 4-1 to 4-4, it is shown that even if there is little or no coating on the opposite side of the film, the electrolytic performance can be exhibited. Example 4-6 Example 4-6 was performed in the same manner as in Example 4-1 except that the electrode base material for cathode electrolysis was applied by ion plating, and the results are shown in Table 7. In addition, ion plating uses a Ru metal target at a heating temperature of 200 ° C, and a film formation pressure of 7 × 10 under an argon / oxygen environment.-2 Pa was formed into a film. The coating formed is ruthenium oxide. The thickness of the electrode is 26 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-7] Example 4-7 is an electrode base material for cathode electrolysis produced by an electroforming method. The shape of the photomask is a shape in which squares of 0.485 mm × 0.485 mm are arranged vertically and horizontally at intervals of 0.15 mm. By sequentially exposing, developing, and electroplating, a nickel porous foil having a gauge thickness of 20 μm and an opening ratio of 56% was obtained. The arithmetic average roughness Ra of the surface was 0.71 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 37 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis and is 17 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-8] The electrode base material for cathode electrolysis in Example 4-8 was produced by an electroforming method with a gauge thickness of 50 μm and an opening ratio of 56%. The arithmetic average roughness Ra of the surface was 0.73 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 60 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-9] In Example 4-9, a nickel non-woven fabric (manufactured by NIKKO TECHNO Co., Ltd.) having a gauge thickness of 150 μm and a porosity of 76% was used as an electrode substrate for cathode electrolysis. Non-woven nickel fiber with a diameter of about 40 μm and a basis weight of 300 g / m2 . Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 165 μm. The thickness of the catalyst layer is 15 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 29 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0612 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 4-10] In Example 4-10, a nickel nonwoven fabric (manufactured by NIKKO TECHNO Co., Ltd.) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode base material for cathode electrolysis. Non-woven nickel fiber with a diameter of about 40 μm and a basis weight of 500 g / m2 . Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 215 μm. The thickness of the catalyst layer is 15 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 40 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0164 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 4-11] In Example 4-11, a foamed nickel (manufactured by Mitsubishi Materials Co., Ltd.) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode base material for cathode electrolysis. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode was 210 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value was 17 mm, and it did not return to the original flat state. Therefore, the degree of softness after plastic deformation was evaluated. As a result, the electrode followed the separator by surface tension. From this, it was confirmed that the electrode can be brought into contact with the separator by a small force even if it is plastically deformed, and the operability of the electrode is good. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0402 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The film damage was evaluated as "0" and was relatively good. [Example 4-12] In Example 4-12, a nickel mesh having a wire diameter of 50 μm, a 200 mesh, a gauge thickness of 100 μm, and an opening ratio of 37% was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. Even if the blasting treatment is performed, the aperture ratio does not change. Because it is difficult to measure the surface roughness of the metal wire mesh, in Example 4-12, the nickel plate with a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface of the metal wire mesh. Roughness. The arithmetic average roughness Ra of one metal wire mesh was 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 110 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 0.5 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0154 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-13] In Example 4-13, a nickel mesh having a wire diameter of 65 μm, a 150 mesh, a gauge thickness of 130 μm, and an opening ratio of 38% was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. Even if the blasting treatment is performed, the aperture ratio does not change. Because it is difficult to measure the surface roughness of the metal mesh, in Example 4-13, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface of the metal mesh. Roughness. The arithmetic average roughness Ra is 0.66 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 133 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 3 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 6.5 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0124 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is "2", and it can be judged that it can be operated as a large laminated body. The evaluation of membrane damage was also "0", which was good. [Example 4-14] In Example 4-14, the same substrate (gauge thickness: 30 μm, open porosity: 44%) as that of Example 4-3 was used as an electrode substrate for cathode electrolysis. An electrolytic evaluation was performed with the same configuration as in Example 4-1, except that no nickel mesh power feeder was provided. That is, the cross-sectional structure of the electrolytic cell is a zero-pitch structure in which a current collector, a pad, a membrane-integrated electrode, and an anode are sequentially arranged from the cathode chamber side, and the pad functions as a power feeder. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-15] In Example 4-15, the same substrate (gauge thickness: 30 μm, open porosity: 44%) as that of Example 4-3 was used as the electrode substrate for cathode electrolysis. In place of the nickel grid feeder, a deteriorated cathode used in Reference Example 1 and an increased electrolytic voltage were provided. Other than that, electrolytic evaluation was performed with the same configuration as in Example 4-1. That is, the cross-sectional structure of the electrolytic cell starts from the cathode chamber side, and sequentially arranges the current collector, the pad, the deteriorated cathode (functioning as a power supply), the cathode, the separator, and the anode to form a zero-pitch structure, which deteriorates. And the cathode whose electrolysis voltage becomes high functions as a feeder. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-16] As an electrode substrate for anode electrolysis, a titanium foil having a gauge thickness of 20 μm was prepared. Both sides of the titanium foil are roughened. This titanium foil was punched, and round holes were made to form a porous foil. The diameter of the holes was 1 mm, and the opening ratio was 14%. The arithmetic average roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L and a iridium concentration of 100 g / L so that the molar ratios of ruthenium, iridium and titanium are 0.25: 0.25: 0.5 Iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed. This mixed solution was sufficiently stirred and used as an anode coating solution. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). After applying the coating solution to a titanium porous foil, drying was performed at 60 ° C for 10 minutes, and firing was performed at 475 ° C for 10 minutes. After repeating the series of operations of coating, drying, pre-firing, and firing, firing was performed at 520 ° C for 1 hour. In order to use the electrode produced by the above method for electrolytic evaluation, it was cut into a size of 95 mm in length and 110 mm in width. By the surface tension of the aqueous solution, it was brought into close contact with the approximate center of the sulfonic acid layer side of the ion-exchange membrane A (size: 160 mm × 160 mm) produced in [Method (i)] equilibrated with a 0.1 N NaOH aqueous solution. . The cathode was prepared in the following procedure. First, a nickel wire mesh having a wire diameter of 150 μm and 40 mesh was prepared as a base material. After performing a spray treatment with alumina as a pretreatment, it was immersed in 6 N hydrochloric acid for 5 minutes, and thoroughly washed and dried with pure water. Then, a ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) and cerium chloride (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L so that the molar ratio of the ruthenium element to the cerium element is 1: 0.25 To mix. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 300 ° C for 3 minutes, and firing was performed at 550 ° C for 10 minutes. Thereafter, firing was performed at 550 ° C for 1 hour. The series of operations of coating, drying, pre-firing and firing are repeated. As the current collector of the cathode chamber, a porous metal made of nickel was used. The size of the current collector is 95 mm in length × 110 mm in width. As the metal elastic body, a pad woven with fine nickel wires is used. A metal elastomer was placed on the current collector. The cathode produced by the above method was covered thereon, and the four corners of the net were fixed to the current collector by using a rope made of Teflon (registered trademark). Even if the four corners of the membrane part of the membrane-integrated electrode which is integrated with the membrane and the anode are grasped, the electrode becomes the ground side and the membrane-integrated electrode is suspended in a manner parallel to the ground, there is no peeling or deviation of the electrode. In addition, even if the membrane-integrated electrode is suspended perpendicularly to the ground by grasping both ends of one side, the electrode does not peel off or deviate. The anode used in Reference Example 3, which has been deteriorated and has an increased electrolytic voltage, is fixed to the anode cell by welding, and the membrane-integrated electrode is sandwiched between the anode cell and the cathode cell such that the electrode-attached surface becomes the anode chamber side. That is, the cross-sectional structure of the electrolytic cell is a zero-pitch structure in which a current collector, a pad, a cathode, a separator, a titanium porous foil anode, and an anode that has deteriorated and has an increased electrolytic voltage are sequentially arranged from the cathode chamber side. The anode that has deteriorated and has an increased electrolytic voltage functions as a power feeder. Furthermore, the anode of the titanium porous foil and the anode that has deteriorated and the electrolytic voltage becomes high are only in physical contact, and are not fixed by welding. With this configuration, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 26 μm. The thickness of the catalyst layer is 6 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 4 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0060 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-17] In Example 4-17, a titanium foil with a gauge thickness of 20 μm and a porosity of 30% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 4-16, and the result is shown in Table 7. The thickness of the electrode is 30 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 5 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0030 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-18] In Example 4-18, a titanium foil with a gauge thickness of 20 μm and an open porosity of 42% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.38 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 4-16, and the result is shown in Table 7. The thickness of the electrode is 32 μm. The thickness of the catalyst layer is 12 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 2.5 mm. It can be seen that the electrode has a wide elastic deformation area. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0022 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-19] In Example 4-19, a titanium foil with a gauge thickness of 50 μm and a porosity of 47% was used as an electrode substrate for anode electrolysis. The arithmetic average roughness Ra of the surface was 0.40 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 4-16, and the result is shown in Table 7. The thickness of the electrode is 69 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis and is 19 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 8 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0024 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-20] Example 4-20 uses a gauge with a thickness of 100 μm, a diameter of titanium fiber of about 20 μm, and a basis weight of 100 g / m2 The titanium non-woven fabric with a porosity of 78% is used as the electrode substrate for anode electrolysis. Other than that, evaluation was performed similarly to Example 4-16, and the result is shown in Table 7. The thickness of the electrode is 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average is 2 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-21] In Example 4-21, a titanium mesh with a thickness of 120 μm, a diameter of titanium fiber of about 60 μm, and a 150 mesh titanium wire mesh was used as the electrode substrate for anode electrolysis. The porosity is 42%. Spray treatment was performed with alumina of grain number 320. Because it is difficult to measure the roughness of the surface of the metal mesh, in Example 4-21, a titanium plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface of the metal mesh. Roughness. The arithmetic average roughness Ra is 0.60 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 4-16, and the result is shown in Table 7. The thickness of the electrode is 140 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 20 μm. Observed sufficient adhesion. Deformation test of electrode, result L1 , L2 The average value is 10 mm. It can be seen that the electrode has a wide elastic deformation area. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0132 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of membrane damage was also "0", which was good. [Example 4-22] Example 4-22 uses an anode that is degraded and has an increased electrolytic voltage in the same manner as in Example 4-16, and uses the same titanium nonwoven fabric as that in Example 4-20 as an anode. In the same manner as in Example 4-15, a cathode that was deteriorated and the electrolytic voltage became high was used as a cathode power source, and the same nickel foil electrode as in Example 4-3 was used as a cathode. The cross-sectional structure of the electrolytic cell is formed from the cathode chamber side in order to form a current collector, a pad, a deteriorated cathode with a higher voltage, a nickel porous foil cathode, a separator, a titanium non-woven anode, and a deteriorated anode with a higher electrolytic voltage. Pitch structure, the cathode and anode that are degraded and the electrolytic voltage becomes high function as a power feeder. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode (anode) is 114 μm, and the thickness of the catalyst layer is the thickness of the electrode (anode) minus the thickness of the electrode substrate for electrolysis to be 14 μm. The thickness of the electrode (cathode) is 38 μm, and the thickness of the catalyst layer is the thickness of the electrode (cathode) minus the thickness of the electrode base material for electrolysis to be 8 μm. Adequate adhesion was observed on both the anode and the cathode. Deformation test of electrode (anode), result L1 , L2 The average is 2 mm. Deformation test of electrode (cathode), result L1 , L2 The average is 0 mm. When the ventilation resistance of the electrode (anode) was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. When the ventilation resistance of the electrode (cathode) was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. In addition, it shows lower voltage, higher current efficiency, and lower caustic medium salt concentration. The operability is also "1", which is good. The evaluation of the anode and cathode membrane damage was also "0", which was good. Furthermore, in Example 4-22, the cathode was attached to one side of the separator, and the anode was attached to the opposite side. The cathode and the anode were combined to perform film damage evaluation. [Example 4-23] In Example 4-23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa was used. Zirfon membranes were immersed in pure water for more than 12 hours for testing. Except for the above, the evaluation was performed in the same manner as in Example 4-3, and the results are shown in Table 7. Deformation test of electrode, result L1 , L2 The average is 0 mm. It can be seen that the electrode has a wide elastic deformation area. Similar to the case of using an ion-exchange membrane as a separator, sufficient adhesion was observed, and the microporous membrane and the electrode were in close contact by surface tension, and the operability was "1", which was good. [Reference Example 1] In Reference Example 1, the cathode used in a large-scale electrolytic cell for 8 years as a cathode was deteriorated and the electrolytic voltage became high. The cathode was replaced by a nickel grid feeder on a pad of a cathode chamber, and electrolytic evaluation was performed through the ion exchange membrane A produced in [Method (i)]. In Reference Example 1, a membrane-integrated electrode is not used. The cross-sectional structure of the electrolytic cell is from the cathode chamber side, and the current collector, the pad, the deteriorated cathode, the ion exchange membrane A, and the anode are sequentially arranged to form a zero pitch. structure. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.04 V, the current efficiency was 97.0%, and the common salt concentration (50% conversion value) in caustic soda was 20 ppm. As a result of the deterioration of the cathode, the result was a higher voltage. [Reference Example 2] In Reference Example 2, a nickel grid feeder was used as the cathode. That is, electrolysis was performed using a nickel mesh without a catalyst coating. The nickel mesh cathode was placed on a pad of a cathode chamber, and electrolytic evaluation was performed through the ion exchange membrane A produced in [Method (i)]. The cross-sectional structure of the battery of Reference Example 2 is a zero-pitch structure in which a current collector, a pad, a nickel mesh, an ion exchange membrane A, and an anode are sequentially arranged from the cathode chamber side. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.38 V, the current efficiency was 97.7%, and the common salt concentration (50% conversion value) in caustic soda was 24 ppm. Since the cathode catalyst was not applied, the result was a higher voltage. [Reference Example 3] In Reference Example 3, the anode used in the large-scale electrolytic cell for about 8 years as the anode was deteriorated and the electrolytic voltage became high. The cross-sectional structure of the electrolytic cell in Reference Example 3 is formed from the cathode chamber side, in which the current collector, the pad, the cathode, the ion exchange membrane A produced in [Method (i)], and the anode that is degraded and has an increased electrolytic voltage are formed Zero-pitch structure. An electrolytic evaluation was performed with this configuration. As a result, the voltage was 3.18 V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 22 ppm. As the anode deteriorates, the result is a higher voltage. [Example 4-24] In Example 4-24, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 33% after full-roll processing was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 4-24, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.68 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. The mass per unit area is 67.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.05 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 64%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 22%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 13 mm. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2. [Example 4-25] In Example 4-25, a nickel porous metal with a gauge thickness of 100 μm and a porosity of 16% after full-roll processing was used as the electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 4-25, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 107 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis, and is 7 μm. Mass per unit area is 78.1 (mg / cm2 ). The force per unit mass and unit area (1) is 0.04 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 37%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 25%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 18.5 mm. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0176 (kPa · s / m) under measurement condition 2. [Example 4-26] In Example 4-26, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 40% after full-roll processing was used as an electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of the porous metal, in Example 4-26, the nickel plate with a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.70 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The electrode substrate for electrolysis was applied by the same ion plating as in Example 4-6. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 110 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. The force per unit mass and unit area (1) is 0.07 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 80%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 32%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "3", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 11 mm. When the ventilation resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0030 (kPa · s / m) under measurement condition 2. [Example 4-27] In Example 4-27, a nickel porous metal having a gauge thickness of 100 μm and a porosity of 58% after full-roll processing was used as the electrode substrate for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 4-27, the nickel plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the nickel plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 109 μm. The thickness of the catalyst layer is 9 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. The force per unit mass and unit area (1) is 0.06 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 69%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 39%, and the portion where the electrode was separated from the separator was increased. This has problems such as the electrode being easily peeled off when the film-integrated electrode is processed, and the electrode peeling off from the film during operation and the like. The operability is "3", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 11.5 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2. [Example 4-28] In Example 4-28, a nickel metal wire mesh with a gauge thickness of 300 μm and an opening ratio of 56% was used as an electrode substrate for cathode electrolysis. Because it is difficult to measure the surface roughness of the metal wire mesh, in Example 4-28, the nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface of the metal wire mesh. Roughness. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. The arithmetic average roughness Ra is 0.64 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for this, evaluation was performed in the same manner as in Example 4-1, and the results are shown in Table 7. The thickness of the electrode is 308 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Mass per unit area is 49.2 (mg / cm2 ). Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was 88%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was 42%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and during operation, the electrode is peeled off from the film, etc. The operability is "3" and there are problems. It can be evaluated as "3" when it is actually operated in a large size. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 23 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2. [Example 4-29] In Example 4-29, a nickel metal mesh with a gauge thickness of 200 μm and an opening ratio of 37% was used as the electrode base material for cathode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to determine the surface roughness of the metal mesh, in Example 4-29, the nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface of the metal mesh. Roughness. The arithmetic average roughness Ra is 0.65 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, the electrode electrolytic evaluation, the measurement result of the adhesion force, and the adhesiveness were performed in the same manner as in Example 4-1. The results are shown in Table 7. The thickness of the electrode is 210 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 10 μm. Mass per unit area is 56.4 mg / cm2 . Therefore, the result of the 145 mm diameter cylindrical winding evaluation method (3) was 63%, and the adhesion between the electrode and the separator was poor. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and during operation, the electrode is peeled off from the film, etc. The operability is "3" and there are problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 19 mm. When the airflow resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0096 (kPa · s / m) under measurement condition 2. [Example 4-30] In Example 4-30, a titanium porous metal having a gauge thickness of 500 μm and a porosity of 17% after full-roll processing was used as the electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of porous metal, in Example 4-30, a titanium plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.60 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Other than that, evaluation was performed similarly to Example 4-16, and the result is shown in Table 7. The thickness of the electrode was 508 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The mass per unit area is 152.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. When the air flow resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0072 (kPa · s / m) under measurement condition 2. [Example 4-31] In Example 4-31, a titanium porous metal having a gauge thickness of 800 μm and a porosity of 8% after full-roll processing was used as an electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Since it is difficult to measure the surface roughness of the porous metal, in Example 4-31, the titanium plate having a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.61 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Examples 4 to 16, and the results are shown in Table 7. The thickness of the electrode is 808 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. The mass per unit area is 251.3 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0172 (kPa · s / m) under measurement condition 2. [Example 4-32] In Example 4-32, a titanium porous metal having a gauge thickness of 1000 μm and a porosity of 46% after full-roll processing was used as an electrode substrate for anode electrolysis. Spray treatment was performed with alumina of grain number 320. The hole opening rate did not change after the blast treatment. Because it is difficult to measure the surface roughness of the porous metal, in Example 4-32, the titanium plate with a thickness of 1 mm was sprayed at the same time during spraying, and the surface roughness of the titanium plate was used as the surface roughness of the metal mesh. degree. The arithmetic average roughness Ra is 0.59 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. Except for the above, the evaluation was performed in the same manner as in Examples 4 to 16, and the results are shown in Table 7. The thickness of the electrode was 1011 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 11 μm. The mass per unit area is 245.5 (mg / cm2 ). The force per unit mass and unit area (1) is 0.01 (N / mg ・ cm2 ), Which is a smaller value. Therefore, the result of the cylindrical winding evaluation (2) with a diameter of 280 mm was less than 5%, and the result of the cylindrical winding evaluation (3) with a diameter of 145 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. This is because when the film-integrated electrode is processed, the electrode is easily peeled off, and the electrode is peeled off from the film during operation and the like. The operability is "4", and there are also problems. The film damage was evaluated as "0". The deformation test of the electrode was carried out. As a result, the electrode was curled into the shape of a PVC pipe and was not restored, and L was not measured.1 , L2 Value. As a result of measuring the ventilation resistance of the electrode, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2. [Example 4-33] In Example 4-33, a film electrode assembly obtained by thermocompression-bonding an electrode to a separator was prepared by referring to a previous document (an example of Japanese Patent Laid-Open No. Sho 58-48686). Electrode coating was performed in the same manner as in Example 4-1 using a nickel porous metal having a gauge thickness of 100 μm and an open porosity of 33% as an electrode substrate for cathode electrolysis. Thereafter, an inertization treatment was performed on one side of the electrode in the following order. A polyimide adhesive tape (Zhongxing Chemical Co., Ltd.) was attached to one side of the electrode, and a PTFE dispersion (DuPont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was coated on the opposite side at 120 ° C. Dry in a muffle furnace for 10 minutes. The polyimide tape was peeled off, and sintered in a muffle furnace set at 380 ° C for 10 minutes. This operation was repeated twice to inertize one side of the electrode. Made from terminal functional group "-COOCH3 "Perfluorocarbon polymer (C polymer) and end group is" -SO2 F "is a film formed of two layers of perfluorocarbon polymer (S polymer). The thickness of the C polymer layer is 3 mils, and the thickness of the S polymer layer is 4 mils. This two-layer membrane is subjected to a saponification treatment, and an ion exchange group is introduced into the end of the polymer by hydrolysis. The C polymer end is hydrolyzed to a carboxylic acid group, and the S polymer end is hydrolyzed to a sulfo group. The ion exchange capacity based on the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity based on the carboxylic acid group was 0.9 meq / g. The surface having a carboxylic acid group as an ion-exchange group is opposed to the inertized electrode surface, and hot pressing is performed to integrate the ion-exchange membrane with the electrode. One side of the electrode is also exposed after thermocompression bonding, and there is no part of the electrode penetration film. Thereafter, in order to suppress the adhesion of bubbles generated in the electrolysis to the film, a perfluorocarbon polymer mixture into which zirconia and a sulfo group were introduced was applied on both sides. Thus, the membrane-electrode assembly of Example 4-33 was produced. Using this membrane electrode assembly, the force per unit mass and unit area (1) was measured. As a result, the electrode was strongly bonded to the membrane by thermocompression bonding, so the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed without moving the electrode, and the electrode was pulled upward by a stronger force. As a result, the electrode was able to withstand 1.50 (N / mg · cm2 ), A part of the film was broken. The force (1) per unit mass and unit area of the membrane electrode assembly of Example 4-33 is at least 1.50 (N / mg · cm2 ), Being strongly engaged. A cylindrical winding evaluation (1) with a diameter of 280 mm was carried out. As a result, the contact area with the plastic pipe was less than 5%. On the other hand, a cylindrical winding evaluation (280) with a diameter of 280 mm was performed. As a result, although the electrode and the membrane were 100% bonded, the separator was not initially wound around the cylinder. The results of the cylindrical winding evaluation (3) with a diameter of 145 mm are the same. This result means that the operability of the film is impaired by the integrated electrode, and it is difficult to roll it into a roll or bend it. The operability is "3" and there are problems. The film damage was evaluated as "0". When electrolytic evaluation was performed, the voltage became higher, the current efficiency became lower, the salt concentration (50% conversion value) in caustic soda increased, and the electrolytic performance deteriorated. The thickness of the electrode was 114 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 14 μm. Deformation test of electrode, result L1 , L2 The average is 13 mm. The measurement of the ventilation resistance of the electrode was found to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2. [Example 4-34] In Example 4-34, a nickel mesh having a wire diameter of 150 μm, a 40 mesh, a gauge thickness of 300 μm, and an opening ratio of 58% was used as an electrode substrate for cathode electrolysis. Other than that, it carried out similarly to Example 4-33, and produced the membrane electrode assembly. Using this membrane electrode assembly, the force per unit mass and unit area (1) was measured. As a result, the electrode was strongly bonded to the membrane by thermocompression bonding, so the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed without moving the electrode, and the electrode was pulled upwards with a stronger force. As a result, the bearing capacity was 1.60 (N / mg · cm2 ), A part of the film was broken. The force (1) per unit mass and unit area of the membrane electrode assembly of Example 4-34 is at least 1.60 (N / mg · cm2 ), Being strongly engaged. Using this membrane electrode assembly, a cylindrical winding evaluation of 280 mm in diameter was performed (1). As a result, the contact area with the plastic pipe was less than 5%. On the other hand, a cylindrical winding evaluation (280) with a diameter of 280 mm was performed. As a result, although the electrode and the membrane were 100% bonded, the separator was not initially wound around the cylinder. The results of the cylindrical winding evaluation (3) with a diameter of 145 mm are the same. This result means that the operability of the film is impaired by the integrated electrode, and it is difficult to roll it into a roll or bend it. The operability is "3" and there are problems. When electrolytic evaluation was performed, the voltage became higher, the current efficiency became lower, the salt concentration in caustic soda increased, and the electrolytic performance deteriorated. The thickness of the electrode was 308 μm. The thickness of the catalyst layer is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis to be 8 μm. Deformation test of electrode, result L1 , L2 The average is 23 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2. [Example 4-35] A nickel wire having a gauge thickness of 150 μm was prepared as an electrode substrate for cathode electrolysis. A roughening process using this nickel wire is performed. Because it is difficult to measure the surface roughness of the nickel wire, in Example 4-35, the nickel plate having a thickness of 1 mm was sprayed at the same time during the spraying, and the surface roughness of the nickel plate was used as the surface roughness of the nickel wire. . Spray treatment was performed with alumina of grain number 320. The arithmetic average roughness Ra is 0.64 μm. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with a closed cell type wound around a cylinder made of PVC (polyvinyl chloride). The formed coating roller is arranged so that the coating liquid is always in contact with each other. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of one nickel wire produced in Example 4-35 was 158 μm. The nickel wire produced by the above method was cut into lengths of 110 mm and 95 mm. As shown in FIG. 85, a 110 mm nickel wire and a 95 mm nickel wire were vertically overlapped at the center of each nickel wire, and the intersection part was connected by Aron Alpha to produce an electrode. The electrodes were evaluated, and the results are shown in Table 7. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The opening rate is 99.7%. The mass per unit area of the electrode is 0.5 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 15 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measuring device was set to H (high), and the ventilation resistance value was 0.0002 (kPa · s / m). For the electrode, a structure shown in FIG. 86 was used, and the electrode (cathode) was set on a Ni grid power supply, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage became 3.16 V, which was high. [Example 4-36] In Example 4-36, the electrode prepared in Example 4-35 was used. As shown in FIG. 87, a 110 mm nickel wire and a 95 mm nickel wire were used for each of the nickel wires. The centers are placed vertically overlapping, and the intersections are connected by Aron Alpha to make electrodes. The electrodes were evaluated, and the results are shown in Table 7. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The porosity is 99.4%. The mass per unit area of the electrode is 0.9 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average value is 16 mm. The ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measurement device was set to H (high), and the ventilation resistance was 0.0004 (kPa · s / m). For the electrode, a structure shown in FIG. 88 was used, and the electrode (cathode) was placed on a Ni grid power supply, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage was 3.18 V, which was high. [Example 4-37] In Example 4-37, the electrode prepared in Example 4-35 was used. As shown in FIG. 89, a 110 mm nickel wire and a 95 mm nickel wire were used for each of the nickel wires. The centers are placed vertically overlapping, and the intersections are connected by Aron Alpha to make electrodes. The electrodes were evaluated, and the results are shown in Table 7. The portion of the electrode where the nickel wires overlap is the thickest, and the thickness of the electrode is 306 μm. The thickness of the catalyst layer is 6 μm. The porosity is 98.8%. The mass per unit area of the electrode is 1.9 (mg / cm2 ). The force (1) and (2) per unit mass and unit area are below the measurement lower limit of the tensile tester. Therefore, the result of the cylindrical winding evaluation (1) with a diameter of 280 mm was less than 5%, and the portion where the electrode was separated from the separator was increased. The operability is "4", and there are also problems. The film damage was evaluated as "0". Deformation test of electrode, result L1 , L2 The average is 14 mm. In addition, the ventilation resistance of the electrode was measured. As a result, it was 0.001 (kPa · s / m) or less under measurement condition 2. Under measurement condition 2, the SENSE (measurement range) of the ventilation resistance measurement device was set to H (high), and the ventilation resistance was 0.0005 (kPa · s / m). In addition, for the electrode, a structure shown in FIG. 90 was used, and the electrode (cathode) was set on a Ni grid feeder, and electrolytic evaluation was performed by the method described in (9) Electrolytic Evaluation. As a result, the voltage was 3.18 V, which was high. [Comparative Example 4-1] (Preparation of catalyst) 0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) were added to 150 ml of pure water to prepare Metal salt solution. 240 g of pure water was added to 100 g of a 15% tetramethylammonium hydroxide aqueous solution (Wako Pure Chemical Industries, Ltd.) to prepare an alkaline solution. While stirring the alkaline solution with a magnetic stirrer, the above-mentioned metal salt aqueous solution was added dropwise at 5 ml / min using a burette. The suspension containing the generated metal hydroxide fine particles was subjected to suction filtration, and then washed with water to remove alkaline components. Thereafter, the filtrate was transferred to 200 ml of 2-propanol (Kishida Chemical Co., Ltd.), and dispersed by an ultrasonic disperser (US-600T, Nippon Seiki Seisakusho Co., Ltd.) for another 10 minutes to obtain uniformity. Of suspension. A hydrophobic carbon black (DENKA BLACK (registered trademark) AB-7 (trade name), Denki Chemical Industry Co., Ltd.) 0.36 g, a hydrophilic carbon black (Ketjen Black (registered trademark) EC-600JD (trade name), Mitsubishi Chemical Co., Ltd.) was dispersed in 0.84 g of 100 ml of 2-propanol, and dispersed in an ultrasonic disperser for 10 minutes to obtain a suspension of carbon black. The suspension of the metal hydroxide precursor and the suspension of carbon black were mixed and dispersed by an ultrasonic disperser for 10 minutes. The suspension was subjected to suction filtration and dried at room temperature for half a day to obtain carbon black in which a metal hydroxide precursor was dispersed and fixed. Next, using an inert gas firing furnace (VMF165, Yamada Denki Co., Ltd.), firing was performed at 400 ° C for 1 hour in a nitrogen atmosphere to obtain carbon black A in which the electrode catalyst was dispersed and fixed. (Powder for reaction layer) To 1.6 g of carbon black A in which electrode catalyst was dispersed and immobilized, a surfactant Triton (registered trademark) X-100 (trade name, ICN Biomedical) diluted to 20% by weight with pure water was added. Co., Ltd.) 0.84 ml, pure water 15 ml, disperse by ultrasonic disperser for 10 minutes. To this dispersion was added 0.664 g of a PTFE (polytetrafluoroethylene) dispersion (PTFE30J (trade name), DuPont-Mitsui Fluorochemicals Co., Ltd.), and after stirring for 5 minutes, suction filtration was performed. Furthermore, it dried in the dryer at 80 degreeC for 1 hour, and grind | pulverized with the grinder, and obtained the powder A for reaction tanks. (Production of powder for gas diffusion layer) 20 g of hydrophobic carbon black (DENKA BLACK (registered trademark) AB-7 (trade name)) was diluted with pure water to 20% by weight of a surfactant using an ultrasonic disperser. 50 ml of Triton (registered trademark) X-100 (trade name) and 360 ml of pure water were dispersed for 10 minutes. 22.32 g of a PTFE dispersion was added to the obtained dispersion, and after stirring for 5 minutes, filtration was performed. Furthermore, it dried in the dryer at 80 degreeC for 1 hour, and grind | pulverized by the grinder, and obtained the powder A for gas diffusion layers. (Production of Gas Diffusion Electrode) 8.7 ml of ethanol was added to 4 g of powder A for gas diffusion layer, and the mixture was kneaded to form a maggot shape. The powder of the gas diffusion layer formed into a maggot shape was formed into a sheet shape by a roll forming machine, and a silver mesh (SW = 1, LW = 2, thickness = 0.3 mm) was embedded as a current collector, and the final shape was 1.8 mm Flakes. 2.2 ml of ethanol was added to 1 g of the powder A for the reaction layer, and the mixture was kneaded to obtain a maggot shape. The powder for the reaction layer formed into a maggot shape was formed into a sheet shape having a thickness of 0.2 mm by a roll forming machine. Further, the produced sheet obtained using the powder A for the gas diffusion layer and the two sheets obtained using the powder A for the reaction layer were laminated, and formed into a sheet shape of 1.8 mm by a roll forming machine. . The laminated sheet was dried at room temperature for one day and night, and ethanol was removed. Furthermore, in order to remove the remaining surfactant, a thermal decomposition treatment was performed in the air at 300 ° C for 1 hour. Wrapped in aluminum foil by a hot press (SA303 (trade name), TESTER SANGYO Co., Ltd.) at 50 kgf / cm at 360 ° C2 Hot pressing was performed for 1 minute to obtain a gas diffusion electrode. The thickness of the gas diffusion electrode is 412 μm. Using the obtained electrodes, electrolytic evaluation was performed. The cross-sectional structure of the electrolytic cell is a zero-pitch structure in which current collectors, pads, nickel grid feeders, electrodes, membranes, and anodes are sequentially arranged from the cathode chamber side. The results are shown in Table 7. Deformation test of electrode, result L1 , L2 The average value is 19 mm. The ventilation resistance of the electrode was measured. As a result, it was 25.88 (kPa · s / m) under measurement condition 1. In addition, the operability is "3" and there are problems. When electrolytic evaluation was performed, the current efficiency was lowered, the salt concentration in caustic soda was increased, and the electrolytic performance was significantly deteriorated. Membrane damage was evaluated as "3", which also had problems. From these results, it was found that if the gas diffusion electrode obtained in Comparative Example 4-1 was used, the electrolytic performance was significantly inferior. In addition, damage was observed on substantially the entire surface of the ion exchange membrane. The reason for this is considered to be that the gas resistance of the gas diffusion electrode of Comparative Example 4-1 was significantly large, and therefore, the NaOH generated in the electrode remained at the interface between the electrode and the separator and became a high concentration. [TABLE 6] [TABLE 7] In Table 7, all samples can be self-supported by surface tension before the measurement of "force per unit mass and unit area (1)" and "force per unit mass and unit area (2)" ( That is, there is no case of sagging). <Verification of Fifth Embodiment> An experimental example corresponding to the fifth embodiment (hereinafter referred to as "exemplary" in the following "Verification of the fifth embodiment") is prepared as follows, and does not correspond to the fifth embodiment. An experimental example corresponding to the embodiment (hereinafter referred to as "comparative example" in the item of "Verification of the fifth embodiment") was evaluated by the following method. The details will be described with reference to FIGS. 93 to 94 and 100 to 102 as appropriate. As the separator, an ion exchange membrane A manufactured in the following manner was used. As the reinforcing core material, a 90-denier monofilament (hereinafter referred to as PTFE yarn) made of polytetrafluoroethylene (PTFE) was used. As the sacrificial yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 6 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. First, a woven fabric is obtained by plain weaving with 24 PTFE yarns arranged in each of the two directions of TD and MD and two sacrificial yarns arranged between adjacent PTFE yarns. The obtained woven fabric was crimped by a roller to obtain a woven fabric having a thickness of 70 μm. Second, prepare to CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.85 mg equivalent / g of dry resin, resin A, and CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer B had a resin B having an ion exchange capacity of 1.03 mg equivalent / g of the dry resin. Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 μm and a thickness of the resin B layer of 104 μm was obtained by a co-extrusion T-die method. Then, on a heating plate having a heating source and a vacuum source inside, and micropores on its surface, a release paper (cone-shaped embossing processing with a height of 50 μm), a reinforcing material, and a film X were sequentially laminated on the heating plate surface temperature. After heating and decompressing under the conditions of 223 ° C and a degree of reduced pressure of 0.067 MPa for 2 minutes, the release paper was removed to obtain a composite film. Saponification was performed by immersing the obtained composite film in an aqueous solution at 80 ° C. containing 30% by mass of dimethylsulfinium (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. After that, it was immersed in a 50 ° C aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour to replace the counter ion of the ion-exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC. Furthermore, 20 mass% of zirconia having a particle size of 1 μm was added to a 5 mass% ethanol solution of an acid-type resin of resin B to disperse it, and a suspension was prepared. Spray spray on both sides to form a coating of zirconia on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconia was measured by fluorescent X-ray measurement, and the result was 0.5 mg / cm2 . Here, the average particle diameter is measured using a particle size distribution meter ("SALD (registered trademark) 2200" manufactured by Shimadzu Corporation). The following cathodes and anodes were used as electrodes. An electrolytic nickel foil having a gauge thickness of 22 μm was prepared as an electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.95 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The nickel foil is punched to form a circular hole to form a porous foil. The opening rate is 44%. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the fabricated electrode was 29 μm. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide is 7 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. The coating is also formed on the surface without roughening. Use a gauge thickness of 100 μm, titanium fiber diameter of about 20 μm, and weight per unit area of 100 g / m2 The titanium non-woven fabric with a porosity of 78% is used as the electrode substrate for anode electrolysis. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L and a iridium concentration of 100 g / L so that the molar ratios of ruthenium, iridium and titanium are 0.25: 0.25: 0.5 Iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed. This mixed solution was sufficiently stirred and used as an anode coating solution. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). After applying the coating solution to a titanium porous foil, drying was performed at 60 ° C for 10 minutes, and firing was performed at 475 ° C for 10 minutes. After repeating the series of operations of coating, drying, pre-firing, and firing, firing was performed at 520 ° C for 1 hour. [Example 5-1] (Example using a cathode-film laminated body) A wound body was prepared in advance in the following manner. First, an ion exchange membrane having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, by the method described above, four cathodes of 0.3 m in length and 2.4 m in width were prepared. After the ion-exchange membrane was immersed in a 2% sodium bicarbonate solution for one day and night, the cathode was arranged on the carboxylic acid layer side without gaps to prepare a laminate of the cathode and the ion-exchange membrane (see FIG. 100). If the cathode is placed on the membrane, the interface tension is exerted due to the contact with the sodium bicarbonate aqueous solution, and the cathode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. As shown in FIG. 101, the obtained laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. The rolled body has a cylindrical shape with an outer diameter of 84 mm and a length of 1.7 m, which can reduce the size of the laminated body. Then, in the existing large electrolytic cell (electrolytic cell having the same structure as that shown in Figs. 93 and 94), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press is released and taken out. There is a diaphragm and there is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained approximately perpendicular to the ground, but there was no case such as cathode peeling. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. When the wound body of the laminated body is prepared in advance during the electrolytic operation, it is evaluated that the electrode replacement and the diaphragm replacement can be completed in about tens of minutes for each electrolytic cell. [Example 5-2] (Example using an anode-film laminated body) A wound body was prepared in advance as follows. First, an ion exchange membrane having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, four anodes of 0.3 m in length and 2.4 m in width were prepared by the method described above. After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for one day and night, the anode was arranged on the sulfonic acid layer side without gaps in the same manner as in Example 5-1 to prepare a laminate of the anode and the ion exchange membrane. . If the cathode is placed on the membrane, the interface tension is exerted due to the contact with the sodium bicarbonate aqueous solution, and the cathode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The obtained laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m in the same manner as in Example 5-1 to prepare a wound body. The size of the wound body is a cylindrical shape with an outer diameter of 86 mm and a length of 1.7 m, which can reduce the size of the laminated body. Next, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained substantially perpendicular to the ground, but there was no case such as anodization. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. When the wound body of the laminated body is prepared in advance during the electrolytic operation, it is evaluated that the electrode replacement and the diaphragm replacement can be completed in about tens of minutes for each electrolytic cell. [Example 5-3] (Example using anode / cathode-film laminated body) A wound body was prepared in the following manner. First, an ion exchange membrane having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, four anodes and anodes each having a length of 0.3 m and a width of 2.4 m were prepared by the method described above. After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for one day and night, the cathode was arranged on the carboxylic acid layer side without gaps, and the anode was arranged on the sulfonic acid gap without gaps in the same way as in Example 5-1 Layered, and a laminated body of a cathode, an anode, and an ion exchange membrane was produced. If the cathode and the anode are placed on the membrane, the interface tension is exerted due to the contact with the sodium bicarbonate aqueous solution, and the cathode, the anode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The obtained laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m in the same manner as in Example 5-1 to prepare a wound body. The rolled body has a cylindrical shape with an outer diameter of 88 mm and a length of 1.7 m, which can reduce the size of the laminated body. Next, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained substantially perpendicular to the ground, but there was no case such as anodization. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. When the wound body of the laminated body is prepared in advance during the electrolytic operation, it is evaluated that the electrode replacement and the diaphragm replacement can be completed in about tens of minutes for each electrolytic cell. [Example 5-4] (Example using a cathode) A wound body was prepared in the following manner. First, by the method described above, four cathodes of 0.3 m in length and 2.4 m in width were prepared. The four cathodes were arranged without gaps so as to have a size of 1.2 m in length and 2.4 m in width. In order to prevent the cathodes from being separated from each other, as shown in FIG. 102, a PTFE rope is passed through an opening portion (not shown) of the cathode, thereby binding adjacent cathodes to each other and fixing them. In this operation, no pressure was applied and the temperature was 23 ° C. This cathode was wound around a polyvinyl chloride (PVC) tube having an outer diameter of 76 mm and a length of 1.7 m in the same manner as in Example 5-1 to prepare a wound body. The rolled body has a cylindrical shape with an outer diameter of 78 mm and a length of 1.7 m, which can reduce the size of the laminated body. Next, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released by pulling out the wound cathode from the state where the PVC pipe is standing upright. At this time, the cathode was maintained substantially perpendicular to the ground, but there was no case of cathode peeling. Then, after the cathode was inserted between the electrolytic cells, the electrolytic cells were moved, and the laminates were sandwiched between the electrolytic cells. Compared to the previous, the cathode can be easily replaced. If a cathode wound body is prepared in advance during the electrolytic operation, it is evaluated that the cathode can be renewed in several tens of minutes for each electrolytic cell. [Example 5-5] (Example using anode) A wound body was prepared in the following manner. First, four anodes of 0.3 m in length and 2.4 m in width were prepared by the method described above. The four anodes were arranged without gaps so as to have a size of 1.2 m in length and 2.4 m in width. In order to prevent the anodes from being separated from each other, adjacent anodes are tied to each other and fixed by a PTFE rope in the same manner as in Example 5-4. In this operation, no pressure was applied and the temperature was 23 ° C. This anode was wound around a polyvinyl chloride (PVC) tube having an outer diameter of 76 mm and a length of 1.7 m in the same manner as in Example 5-1 to prepare a wound body. The size of the wound body is a cylindrical shape with an outer diameter of 81 mm and a length of 1.7 m, which can reduce the size of the laminated body. Next, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released by pulling out the wound anode from the state where the PVC pipe is standing upright. At this time, the anode was maintained substantially perpendicular to the ground, but there was no such thing as peeling of the anode. Then, after the anode was inserted between the electrolytic cells, the electrolytic cells were moved, and the laminated bodies were sandwiched between the electrolytic cells. Compared with the previous, the anode can be easily replaced. If the anode wound body is prepared in advance during the electrolytic operation, it is evaluated that the anode can be updated in about tens of minutes for each electrolytic cell. [Comparative Example 5-1] (Previous electrode update) In an existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the adjacent electrolytic cell and ion exchange membrane formed by the press will be used The fixed state is released, and the existing diaphragm is taken out to become a state with a gap between the electrolytic cells. Thereafter, the electrolytic cell was lifted from the large electrolytic cell by a lift. Take out the electrolytic cell to a workshop where welding can be performed. After the anode that is fixed to the rib of the electrolytic cell by welding is peeled off, the burr of the peeled and removed part is polished with a mill or the like to smooth it. Regarding the cathode, the portion folded into the current collector and fixed was removed to peel off the cathode. After that, a new anode is set on the rib of the anode chamber, and the new anode is fixed to the electrolytic cell by spot welding. Regarding the cathode, a new cathode was similarly set on the cathode side, folded into a current collector, and fixed. Transfer the updated electrolytic cell to the place of the large electrolytic cell, and use an elevator to return the electrolytic cell to the electrolytic cell. The time required to release the fixed state of the electrolytic cell and the ion exchange membrane to fix the electrolytic cell again is 1 day or more. <Verification of the Sixth Embodiment> An experimental example corresponding to the sixth embodiment (hereinafter referred to as "exemplary" in the following "Verification of the sixth embodiment") is prepared as follows, and does not correspond to the sixth embodiment. The experimental example corresponding to the embodiment (hereinafter referred to as "comparative example" in the item of "Verification of the sixth embodiment") was evaluated by the following method. The details will be described with reference to FIGS. 105 to 106 as appropriate. As the separator, an ion exchange membrane b manufactured in the following manner was used. As the reinforcing core material, a 90-denier monofilament (hereinafter referred to as PTFE yarn) made of polytetrafluoroethylene (PTFE) was used. As the sacrificial yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 6 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. First, a woven fabric is obtained by plain weaving with 24 PTFE yarns arranged in each of the two directions of TD and MD and two sacrificial yarns arranged between adjacent PTFE yarns. The obtained woven fabric was crimped by a roller to obtain a woven fabric having a thickness of 70 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.85 mg equivalent / g of dry resin, resin A, and CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer B had a resin B having an ion exchange capacity of 1.03 mg equivalent / g of the dry resin. Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 μm and a thickness of the resin B layer of 104 μm was obtained by a co-extrusion T-die method. Then, on a heating plate having a heating source and a vacuum source inside, and micropores on its surface, a release paper (cone-shaped embossing processing with a height of 50 μm), a reinforcing material, and a film X were sequentially laminated on the heating plate surface temperature. After heating and decompressing under the conditions of 223 ° C and a degree of reduced pressure of 0.067 MPa for 2 minutes, the release paper was removed to obtain a composite film. Saponification was performed by immersing the obtained composite film in an aqueous solution at 80 ° C. containing 30% by mass of dimethylsulfinium (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. After that, it was immersed in a 50 ° C aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour to replace the counter ion of the ion-exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC. Furthermore, 20% by mass of zirconia having a particle size of 1 μm was added to a 5% by mass ethanol solution of the acid type resin of the resin B to disperse it to prepare a suspension, and both sides of the composite film were prepared by a suspension spray method. Spraying was performed to form a coating of zirconia on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconia was measured by fluorescent X-ray measurement, and the result was 0.5 mg / cm2 . Here, the average particle diameter is measured using a particle size distribution meter ("SALD (registered trademark) 2200" manufactured by Shimadzu Corporation). The following cathodes and anodes were used as electrodes. An electrolytic nickel foil having a gauge thickness of 22 μm was prepared as an electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.95 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The nickel foil is punched to form a circular hole to form a porous foil. The opening rate is 44%. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the fabricated electrode was 29 μm. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide is 7 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. The coating is also formed on the surface without roughening. Use a gauge thickness of 100 μm, titanium fiber diameter of about 20 μm, and weight per unit area of 100 g / m2 The titanium non-woven fabric with a porosity of 78% is used as the electrode substrate for anode electrolysis. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L and a iridium concentration of 100 g / L so that the molar ratios of ruthenium, iridium and titanium are 0.25: 0.25: 0.5 Iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed. This mixed solution was sufficiently stirred and used as an anode coating solution. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). After applying the coating solution to a titanium porous foil, drying was performed at 60 ° C for 10 minutes, and firing was performed at 475 ° C for 10 minutes. After repeating the series of operations of coating, drying, pre-firing, and firing, firing was performed at 520 ° C for 1 hour. [Example 6-1] (Example using a cathode-film laminate) A wound body was prepared in advance as follows. First, an ion exchange membrane b having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, by the method described above, four cathodes of 0.3 m in length and 2.4 m in width were prepared. After the ion-exchange membrane b was immersed in a 2% sodium bicarbonate solution for one day and night, the cathodes were arranged on the carboxylic acid layer side without gaps to prepare a laminate of the cathode and the ion-exchange membrane b. If the cathode is placed on the membrane, the interface tension is exerted due to the contact with the sodium bicarbonate aqueous solution, and the cathode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. In addition, in order to melt the ion exchange membrane b, the temperature must be 200 ° C. or higher, and the ion exchange membrane does not melt during integration in this example. Then, in the existing large electrolytic cell (electrolytic cell having the same structure as that shown in Figs. 105 and 106), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press is released and taken out. There is a diaphragm and there is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained approximately perpendicular to the ground, but there was no case such as cathode peeling. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. It is evaluated that for each electrolytic cell, electrode replacement and diaphragm replacement can be completed in tens of minutes. [Example 6-2] (Example using an anode-film laminated body) A wound body was prepared in the following manner. First, an ion exchange membrane b having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, four anodes of 0.3 m in length and 2.4 m in width were prepared by the method described above. After the ion exchange membrane b was immersed in a 2% sodium bicarbonate solution for one day and night, the anodes were arranged on the sulfonic acid layer side without gaps to prepare a laminate of the anode and the ion exchange membrane. If the anode is placed on the membrane, due to the contact with the aqueous sodium bicarbonate solution, the interfacial tension acts, and the anode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. Next, in the existing large electrolytic cell (the same electrolytic cell as in Example 6-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained substantially perpendicular to the ground, but there was no case such as anodization. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. It is evaluated that for each electrolytic cell, electrode replacement and diaphragm replacement can be completed in tens of minutes. [Example 6-3] (Example using anode / cathode-film laminate) A wound body was prepared in advance as follows. First, an ion exchange membrane b having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, four anodes and anodes each having a length of 0.3 m and a width of 2.4 m were prepared by the method described above. After the ion exchange membrane b was immersed in a 2% sodium bicarbonate solution for one day and night, the cathode was arranged without gaps on the carboxylic acid layer side, and the anode was arranged without gaps on the sulfonic acid layer side to prepare the cathode, anode, and ions Laminated body of exchange membrane b. If the cathode and the anode are placed on the membrane, the interface tension is exerted due to the contact with the sodium bicarbonate aqueous solution, and the cathode, the anode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. Next, in the existing large electrolytic cell (the same electrolytic cell as in Example 6-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained substantially perpendicular to the ground, but there was no case such as anodization. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. It is evaluated that for each electrolytic cell, electrode replacement and diaphragm replacement can be completed in tens of minutes. [Comparative Example 6-1] As described below, a film-electrode laminate in which an electrode was thermocompression-bonded to a separator was produced with reference to an example of Japanese Patent Laid-Open No. 58-48686. Electrode coating was performed in the same manner as in Example 6-1 using a nickel porous metal with a gauge thickness of 100 μm and an open porosity of 33% as an electrode base material for cathode electrolysis. The size of the electrode is 200 mm × 200 mm, and the number of pieces is 72 pieces. Thereafter, an inertization treatment was performed on one side of the electrode in the following order. A polyimide adhesive tape (Zhongxing Chemical Co., Ltd.) was attached to one side of the electrode, and a PTFE dispersion (DuPont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was coated on the opposite side at 120 ° C. Dry in a muffle furnace for 10 minutes. The polyimide tape was peeled off, and sintered in a muffle furnace set at 380 ° C for 10 minutes. This operation was repeated twice to inertize one side of the electrode. Made from terminal functional group "-COOCH3 "Perfluorocarbon polymer (C polymer) and end group is" -SO2 F "is a film formed of two layers of perfluorocarbon polymer (S polymer). The thickness of the C polymer layer is 3 mils, and the thickness of the S polymer layer is 4 mils. This two-layer membrane is subjected to a saponification treatment, and an ion exchange group is introduced into the end of the polymer by hydrolysis. The C polymer end is hydrolyzed to a carboxylic acid group, and the S polymer end is hydrolyzed to a sulfo group. The ion exchange capacity based on the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity based on the carboxylic acid group was 0.9 meq / g. The size of the obtained ion exchange membrane was the same as that of Example 6-1. The surface having a carboxylic acid group as an ion-exchange group is opposed to the inert electrode surface of the above-mentioned electrode, and hot pressing (thermocompression bonding) is performed to integrate the ion-exchange membrane with the electrode. That is, at a temperature at which the ion exchange membrane melts, 72 pieces of 200 mm square electrodes are integrated into one ion exchange membrane with a length of 1500 mm and a width of 2500 mm. One side of the electrode is also exposed after thermocompression bonding, and there is no part of the electrode penetration film. With a large size of 1500 mm × 2500 mm, the step of integrating the ion exchange membrane and the electrode by thermocompression requires more than one day. That is, when the electrode was renewed and the separator was replaced, it was evaluated in Comparative Example 6-1 that more time was required than in the Example. <Verification of the seventh embodiment> An experimental example corresponding to the seventh embodiment (hereinafter referred to as "exemplary" in the following "Verification of the seventh embodiment") is prepared as follows, and does not correspond to the seventh embodiment. The experimental example corresponding to the embodiment (hereinafter referred to as "comparative example" in the item of "Verification of the Seventh Embodiment") was evaluated by the following method. The details will be described with reference to FIGS. 114 to 115 as appropriate. As the separator, an ion exchange membrane manufactured in the following manner was used. As the reinforcing core material, a 90-denier monofilament (hereinafter referred to as PTFE yarn) made of polytetrafluoroethylene (PTFE) was used. As the sacrificial yarn, a yarn made of polyethylene terephthalate (PET) with 35 deniers and 6 filaments twisted at 200 times / m (hereinafter referred to as PET yarn) was used. First, a woven fabric is obtained by plain weaving with 24 PTFE yarns arranged in each of the two directions of TD and MD and two sacrificial yarns arranged between adjacent PTFE yarns. The obtained woven fabric was crimped by a roller to obtain a woven fabric having a thickness of 70 μm. Then, prepare to start with CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 COOCH3 The copolymer has an ion exchange capacity of 0.85 mg equivalent / g of dry resin, resin A, and CF2 = CF2 With CF2 = CFOCF2 CF (CF3 OCF2 CF2 SO2 The copolymer B had a resin B having an ion exchange capacity of 1.03 mg equivalent / g of the dry resin. Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 μm and a thickness of the resin B layer of 104 μm was obtained by a co-extrusion T-die method. Then, on a heating plate having a heating source and a vacuum source inside, and micropores on its surface, a release paper (cone-shaped embossing processing with a height of 50 μm), a reinforcing material, and a film X were sequentially laminated on the heating plate surface temperature. After heating and decompressing under the conditions of 223 ° C and a degree of reduced pressure of 0.067 MPa for 2 minutes, the release paper was removed to obtain a composite film. Saponification was performed by immersing the obtained composite film in an aqueous solution at 80 ° C. containing 30% by mass of dimethylsulfinium (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. After that, it was immersed in a 50 ° C aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour to replace the counter ion of the ion-exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC. Furthermore, 20% by mass of zirconia having a particle size of 1 μm was added to a 5% by mass ethanol solution of the acid type resin of the resin B to disperse it to prepare a suspension, and both sides of the composite film were prepared by a suspension spray method. Spraying was performed to form a coating of zirconia on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconia was measured by fluorescent X-ray measurement, and the result was 0.5 mg / cm2 . Here, the average particle diameter is measured using a particle size distribution meter ("SALD (registered trademark) 2200" manufactured by Shimadzu Corporation). The following cathodes and anodes were used as electrodes. An electrolytic nickel foil having a gauge thickness of 22 μm was prepared as an electrode base material for cathode electrolysis. A roughening process using electrolytic nickel plating was performed on one side of the nickel foil. The roughened surface has an arithmetic average roughness Ra of 0.95 μm. The measurement of the surface roughness was performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to the blast treatment. The nickel foil is punched to form a circular hole to form a porous foil. The opening rate is 44%. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium nitrate solution (FURUYA METAL Co., Ltd.) having a ruthenium concentration of 100 g / L and a cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of the ruthenium element to the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred, and this was used as a cathode coating liquid. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, pre-baking was performed at 150 ° C for 3 minutes, and firing was performed at 350 ° C for 10 minutes. These series of operations of coating, drying, pre-firing, and firing are repeated until a specific coating amount is obtained. The thickness of the fabricated electrode was 29 μm. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide is 7 μm, which is the thickness of the electrode minus the thickness of the electrode substrate for electrolysis. The coating is also formed on the surface without roughening. Use a gauge thickness of 100 μm, titanium fiber diameter of about 20 μm, and weight per unit area of 100 g / m2 The titanium non-woven fabric with a porosity of 78% is used as the electrode substrate for anode electrolysis. A coating solution for forming an electrode catalyst was prepared in the following procedure. A ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L and a iridium concentration of 100 g / L so that the molar ratios of ruthenium, iridium and titanium are 0.25: 0.25: 0.5 Iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed. This mixed solution was sufficiently stirred and used as an anode coating solution. A tank containing the coating liquid is provided at the lowermost part of the drum coating device. A coating roller made of a rubber (Inoac Corporation, E-4088, thickness 10 mm) made of a foamed EPDM (ethylene-propylene-diene rubber) with an independent cell type wound around a cylinder made of PVC (polyvinyl chloride). It is set so that it is always in contact with the coating liquid. A coating roller similarly wound with EPDM is provided on the upper part, and a roller made of PVC is further provided thereon. The electrode substrate was passed between the second coating roller and the uppermost PVC roller to apply a coating solution (roll coating method). After applying the coating solution to a titanium porous foil, drying was performed at 60 ° C for 10 minutes, and firing was performed at 475 ° C for 10 minutes. After repeating the series of operations of coating, drying, pre-firing, and firing, firing was performed at 520 ° C for 1 hour. [Example 7-1] (Example using a cathode-film laminate) A wound body was prepared in advance as follows. First, an ion exchange membrane having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, by the method described above, four cathodes of 0.3 m in length and 2.4 m in width were prepared. After the ion-exchange membrane was immersed in a 2% sodium bicarbonate solution for one day and night, the cathode was arranged on the carboxylic acid layer side without gaps to prepare a laminate of the cathode and the ion-exchange membrane. If the cathode is placed on the membrane, the interface tension is exerted due to the contact with the sodium bicarbonate aqueous solution, and the cathode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. Then, in the existing large electrolytic cell (electrolytic cell having the same structure as shown in Figs. 114 and 115), the fixed state of the adjacent electrolytic cell and the ion exchange membrane formed by the pressing device was released and taken out. There is a diaphragm and there is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained approximately perpendicular to the ground, but there was no case such as cathode peeling. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. When the wound body of the laminated body is prepared in advance during the electrolytic operation, it is evaluated that the electrode replacement and the diaphragm replacement can be completed in about tens of minutes for each electrolytic cell. [Example 7-2] (Example using an anode-film laminated body) A wound body was prepared in advance as follows. First, an ion exchange membrane having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, four anodes of 0.3 m in length and 2.4 m in width were prepared by the method described above. After the ion-exchange membrane was immersed in a 2% sodium bicarbonate solution for one day and night, the anode was arranged on the sulfonic acid layer side without gaps to prepare a laminate of the anode and the ion-exchange membrane. If the anode is placed on the membrane, due to the contact with the aqueous sodium bicarbonate solution, the interfacial tension acts, and the anode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. Then, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained substantially perpendicular to the ground, but there was no case such as anodization. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. When the wound body of the laminated body is prepared in advance during the electrolytic operation, it is evaluated that the electrode replacement and the diaphragm replacement can be completed in about tens of minutes for each electrolytic cell. [Example 7-3] (Example using anode / cathode-film laminate) A wound body was prepared in advance as follows. First, an ion exchange membrane having a length of 1.5 m and a width of 2.5 m was prepared by the method described above. In addition, four anodes and anodes each having a length of 0.3 m and a width of 2.4 m were prepared by the method described above. After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for one day and night, the cathode was arranged without gaps on the carboxylic acid layer side, and the anode was arranged without gaps on the sulfonic acid layer side to produce the cathode, anode, and ion exchange. Membrane laminate. If the cathode and the anode are placed on the membrane, the interface tension is exerted due to the contact with the sodium bicarbonate aqueous solution, and the cathode, the anode and the membrane are integrated by adsorption. No pressure is applied during integration in the manner described above. The temperature during integration was 23 ° C. The laminated body was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. Then, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released from the state of standing up the PVC pipe by pulling out the wound laminated body. At this time, the laminated body was maintained substantially perpendicular to the ground, but there was no case such as anodization. Then, after inserting the laminated body between the electrolytic cells, the electrolytic cell is moved, and the laminated bodies are sandwiched between the electrolytic cells. Compared with the previous, the electrode and the separator can be easily replaced. When the wound body of the laminated body is prepared in advance during the electrolytic operation, it is evaluated that the electrode replacement and the diaphragm replacement can be completed in about tens of minutes for each electrolytic cell. [Example 7-4] (Example using a cathode) A wound body was prepared in the following manner. First, by the method described above, four cathodes of 0.3 m in length and 2.4 m in width were prepared. The four cathodes were arranged without gaps so as to have a size of 1.2 m in length and 2.4 m in width. To prevent the cathodes from being separated from each other, adjacent cathodes are tied and fixed by PTFE ropes. In this operation, no pressure was applied and the temperature was 23 ° C. This cathode was wound around a polyvinyl chloride (PVC) tube having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. Then, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released by pulling out the wound cathode from the state where the PVC pipe is standing upright. At this time, the cathode was maintained substantially perpendicular to the ground, but there was no case of cathode peeling. Then, after the cathode was inserted between the electrolytic cells, the electrolytic cells were moved, and the laminates were sandwiched between the electrolytic cells. Compared to the previous, the cathode can be easily replaced. If a cathode wound body is prepared in advance during the electrolytic operation, it is evaluated that the cathode can be renewed in several tens of minutes for each electrolytic cell. [Example 7-5] (Example using anode) A wound body was prepared in advance in the following manner. First, four anodes of 0.3 m in length and 2.4 m in width were prepared by the method described above. The four anodes were arranged without gaps so as to have a size of 1.2 m in length and 2.4 m in width. To prevent the anodes from being separated from each other, adjacent anodes are tied and fixed by PTFE ropes. In this operation, no pressure was applied and the temperature was 23 ° C. This anode was wound around a polyvinyl chloride (PVC) tube having an outer diameter of 76 mm and a length of 1.7 m to prepare a wound body. Then, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixed state of the adjacent electrolytic cell and ion exchange membrane formed by the press was released, and the existing diaphragm was removed to become There is a gap between the electrolytic cells. Thereafter, the wound body is transferred to a large electrolytic cell. On a large electrolytic cell, the coiled state is released by pulling out the wound anode from the state where the PVC pipe is standing upright. At this time, the anode was maintained substantially perpendicular to the ground, but there was no such thing as peeling of the anode. Then, after the anode was inserted between the electrolytic cells, the electrolytic cells were moved, and the laminated bodies were sandwiched between the electrolytic cells. Compared with the previous, the anode can be easily replaced. If the anode wound body is prepared in advance during the electrolytic operation, it is evaluated that the anode can be updated in about tens of minutes for each electrolytic cell. [Comparative Example 7-1] (Previous electrode update) In the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the adjacent electrolytic cell and ion exchange membrane formed by the press will be used. The fixed state is released, and the existing diaphragm is taken out to become a state with a gap between the electrolytic cells. Thereafter, the electrolytic cell was lifted from the large electrolytic cell by a lift. Take out the electrolytic cell to a workshop where welding can be performed. After the anode that is fixed to the rib of the electrolytic cell by welding is peeled off, the burr of the peeled and removed part is polished with a mill or the like to smooth it. Regarding the cathode, the portion folded into the current collector and fixed was removed to peel off the cathode. After that, a new anode is set on the rib of the anode chamber, and the new anode is fixed to the electrolytic cell by spot welding. Regarding the cathode, a new cathode was similarly set on the cathode side, folded into a current collector, and fixed. Transfer the renewed electrolytic cell to the place of the large electrolytic cell, and use an elevator to return the electrolytic cell to the electrolytic cell. The time required from the release of the fixed state of the electrolytic cell and the ion exchange membrane to the fixing of the electrolytic cell is more than one day. This application is based on Japanese patent applications filed on March 22, 2017 (Japanese Patent Application No. 2017-056524 and Japanese Patent Application No. 2017-056525), and Japanese patent applications filed on March 20, 2018 Applications (Japanese Patent Application No. 2018-053217, Japanese Patent Application No. 2018-053146, Japanese Patent Application No. 2018-053144, Japanese Patent Application No. 2018-053231, Japanese Patent Application No. 2018-053145, Japanese Patent Japanese Patent Application No. 2018-053149 and Japanese Patent Application No. 2018-053139), the contents of which are incorporated herein by reference.

<與第1實施形態相對應之圖><Figure corresponding to the first embodiment>

針對圖1之符號之說明Explanation of the symbols in Figure 1

10‧‧‧電解用電極基材10‧‧‧ Electrode substrate for electrolysis

20‧‧‧第一層20‧‧‧ First floor

30‧‧‧第二層30‧‧‧Second floor

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖2~4之符號之說明Explanation of symbols in Figs. 2 to 4

1‧‧‧離子交換膜1‧‧‧ion exchange membrane

2‧‧‧羧酸層2‧‧‧carboxylic acid layer

3‧‧‧磺酸層3‧‧‧sulfonic acid layer

4‧‧‧強化芯材4‧‧‧ reinforced core material

10‧‧‧膜本體10‧‧‧ membrane body

11a‧‧‧塗佈層11a‧‧‧Coated layer

11b‧‧‧塗佈層11b‧‧‧Coated layer

21‧‧‧強化芯材21‧‧‧Reinforced core material

22‧‧‧強化芯材22‧‧‧ reinforced core material

52‧‧‧強化紗52‧‧‧ Reinforced yarn

100‧‧‧電解槽100‧‧‧ electrolytic cell

200‧‧‧陽極200‧‧‧Anode

300‧‧‧陰極300‧‧‧ cathode

504‧‧‧連通孔504‧‧‧Connecting hole

504a‧‧‧犧牲紗504a‧‧‧ sacrificial yarn

針對圖5~9之符號之說明Explanation of symbols in Figs. 5 to 9

1‧‧‧電解池1‧‧‧ electrolytic cell

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

4‧‧‧電解槽4‧‧‧ electrolytic cell

5‧‧‧壓製器5‧‧‧presser

6‧‧‧陰極端子6‧‧‧ cathode terminal

7‧‧‧陽極端子7‧‧‧Anode terminal

10‧‧‧陽極室10‧‧‧Anode Room

11‧‧‧陽極11‧‧‧Anode

12‧‧‧陽極墊片12‧‧‧Anode gasket

13‧‧‧陰極墊片13‧‧‧ cathode pad

18‧‧‧逆向電流吸收體18‧‧‧ reverse current sink

18a‧‧‧基材18a‧‧‧ substrate

18b‧‧‧逆向電流吸收層18b‧‧‧Reverse current absorption layer

19‧‧‧陽極室之底部19‧‧‧ bottom of anode chamber

20‧‧‧陰極室20‧‧‧ cathode chamber

21‧‧‧陰極21‧‧‧ cathode

22‧‧‧金屬彈性體22‧‧‧metal elastomer

23‧‧‧集電體23‧‧‧Current collector

24‧‧‧支持體24‧‧‧ support

30‧‧‧間隔壁30‧‧‧ partition

40‧‧‧電解用陰極結構體40‧‧‧ Electrolytic cathode structure

針對圖10之符號之說明Explanation of symbols in FIG. 10

1‧‧‧夾持治具(SUS)1‧‧‧ Holding fixture (SUS)

2‧‧‧電極2‧‧‧ electrode

3‧‧‧隔膜3‧‧‧ diaphragm

4‧‧‧鎳板(已實施粒編號320之氧化鋁噴擊)4‧‧‧nickel plate (alumina spraying with grain number 320 has been implemented)

100‧‧‧正面100‧‧‧ Positive

200‧‧‧側面200‧‧‧ side

針對圖11~13之符號之說明Explanation of symbols in FIGS. 11 to 13

1‧‧‧隔膜1‧‧‧ diaphragm

2a‧‧‧外徑280 mm之聚乙烯製管2a‧‧‧ polyethylene tube with outer diameter of 280 mm

2b‧‧‧外徑145 mm之聚乙烯製管2b‧‧‧ polyethylene tube with outer diameter of 145 mm

3‧‧‧剝離部3‧‧‧ stripping department

4‧‧‧密接部4‧‧‧ Adhesion Department

5‧‧‧電極5‧‧‧ electrode

針對圖14之符號之說明Explanation of symbols in FIG. 14

1‧‧‧PVC(聚氯乙烯)製管1‧‧‧PVC (polyvinyl chloride) pipe

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

3‧‧‧電極3‧‧‧ electrode

4‧‧‧平台4‧‧‧ platform

針對圖15之符號之說明Explanation of symbols in FIG. 15

1‧‧‧平台1‧‧‧ platform

2‧‧‧產生變形之電極2‧‧‧deformed electrode

10‧‧‧固定電極之治具10‧‧‧Fixed electrode fixture

20‧‧‧施加力之方向20‧‧‧ Direction of force

針對圖16~21之符號之說明Explanation of symbols in FIGS. 16 to 21

1‧‧‧110 mm之鎳線1‧‧‧110 mm nickel wire

2‧‧‧950 mm之鎳線2‧‧‧950 mm nickel wire

3‧‧‧架3‧‧‧

<與第2實施形態相對應之圖><Figure corresponding to the second embodiment>

針對圖22之符號之說明Explanation of symbols in FIG. 22

10‧‧‧電解用電極基材10‧‧‧ Electrode substrate for electrolysis

20‧‧‧第一層20‧‧‧ First floor

30‧‧‧第二層30‧‧‧Second floor

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖23~25之符號之說明Explanation of symbols in Figs. 23 to 25

1‧‧‧離子交換膜1‧‧‧ion exchange membrane

2‧‧‧羧酸層2‧‧‧carboxylic acid layer

3‧‧‧磺酸層3‧‧‧sulfonic acid layer

4‧‧‧強化芯材4‧‧‧ reinforced core material

10‧‧‧膜本體10‧‧‧ membrane body

11a‧‧‧塗佈層11a‧‧‧Coated layer

11b‧‧‧塗佈層11b‧‧‧Coated layer

21‧‧‧強化芯材21‧‧‧Reinforced core material

22‧‧‧強化芯材22‧‧‧ reinforced core material

52‧‧‧強化紗52‧‧‧ Reinforced yarn

100‧‧‧電解槽100‧‧‧ electrolytic cell

200‧‧‧陽極200‧‧‧Anode

300‧‧‧陰極300‧‧‧ cathode

504‧‧‧連通孔504‧‧‧Connecting hole

504a‧‧‧犧牲紗504a‧‧‧ sacrificial yarn

針對圖26~30之符號之說明Explanation of symbols in Figs. 26-30

1‧‧‧電解池1‧‧‧ electrolytic cell

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

4‧‧‧電解槽4‧‧‧ electrolytic cell

5‧‧‧壓製器5‧‧‧presser

6‧‧‧陰極端子6‧‧‧ cathode terminal

7‧‧‧陽極端子7‧‧‧Anode terminal

10‧‧‧陽極室10‧‧‧Anode Room

11‧‧‧陽極11‧‧‧Anode

12‧‧‧陽極墊片12‧‧‧Anode gasket

13‧‧‧陰極墊片13‧‧‧ cathode pad

18‧‧‧逆向電流吸收體18‧‧‧ reverse current sink

18a‧‧‧基材18a‧‧‧ substrate

18b‧‧‧逆向電流吸收層18b‧‧‧Reverse current absorption layer

19‧‧‧陽極室之底部19‧‧‧ bottom of anode chamber

20‧‧‧陰極室20‧‧‧ cathode chamber

21‧‧‧陰極21‧‧‧ cathode

22‧‧‧金屬彈性體22‧‧‧metal elastomer

23‧‧‧集電體23‧‧‧Current collector

24‧‧‧支持體24‧‧‧ support

30‧‧‧間隔壁30‧‧‧ partition

40‧‧‧電解用陰極結構體40‧‧‧ Electrolytic cathode structure

針對圖31之符號之說明Explanation of symbols in FIG. 31

1‧‧‧夾持治具(SUS)1‧‧‧ Holding fixture (SUS)

2‧‧‧電極2‧‧‧ electrode

3‧‧‧隔膜3‧‧‧ diaphragm

4‧‧‧鎳板(已實施粒編號320之氧化鋁噴擊)4‧‧‧nickel plate

100‧‧‧正面100‧‧‧ Positive

200‧‧‧側面200‧‧‧ side

針對圖32~34之符號之說明Explanation of symbols in Figs. 32 to 34

1‧‧‧隔膜1‧‧‧ diaphragm

2a‧‧‧外徑280 mm之聚乙烯製管2a‧‧‧ polyethylene tube with outer diameter of 280 mm

2b‧‧‧外徑145 mm之聚乙烯製管2b‧‧‧ polyethylene tube with outer diameter of 145 mm

3‧‧‧剝離部3‧‧‧ stripping department

4‧‧‧密接部4‧‧‧ Adhesion Department

5‧‧‧電極5‧‧‧ electrode

針對圖35之符號之說明Explanation of Symbols in Figure 35

1‧‧‧PVC(聚氯乙烯)製管1‧‧‧PVC (polyvinyl chloride) pipe

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

3‧‧‧電極3‧‧‧ electrode

4‧‧‧平台4‧‧‧ platform

針對圖36之符號之說明Explanation of Symbols in Figure 36

1‧‧‧平台1‧‧‧ platform

2‧‧‧產生變形之電極2‧‧‧deformed electrode

10‧‧‧固定電極之治具10‧‧‧Fixed electrode fixture

20‧‧‧施加力之方向20‧‧‧ Direction of force

針對圖37~42之符號之說明Explanation of symbols in Figs. 37 to 42

1‧‧‧110 mm之鎳線1‧‧‧110 mm nickel wire

2‧‧‧950 mm之鎳線2‧‧‧950 mm nickel wire

3‧‧‧架3‧‧‧

<與第3實施形態相對應之圖><Figure corresponding to the third embodiment>

針對圖43之符號之說明Explanation of Symbols in Figure 43

10‧‧‧電解用電極基材10‧‧‧ Electrode substrate for electrolysis

20‧‧‧第一層20‧‧‧ First floor

30‧‧‧第二層30‧‧‧Second floor

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖44~46之符號之說明Explanation of symbols in Figs. 44 to 46

1‧‧‧離子交換膜1‧‧‧ion exchange membrane

2‧‧‧羧酸層2‧‧‧carboxylic acid layer

3‧‧‧磺酸層3‧‧‧sulfonic acid layer

4‧‧‧強化芯材4‧‧‧ reinforced core material

10‧‧‧膜本體10‧‧‧ membrane body

11a‧‧‧塗佈層11a‧‧‧Coated layer

11b‧‧‧塗佈層11b‧‧‧Coated layer

21‧‧‧強化芯材21‧‧‧Reinforced core material

22‧‧‧強化芯材22‧‧‧ reinforced core material

52‧‧‧強化紗52‧‧‧ Reinforced yarn

100‧‧‧電解槽100‧‧‧ electrolytic cell

200‧‧‧陽極200‧‧‧Anode

300‧‧‧陰極300‧‧‧ cathode

504‧‧‧連通孔504‧‧‧Connecting hole

504a‧‧‧犧牲紗504a‧‧‧ sacrificial yarn

針對圖47~51之符號之說明Explanation of symbols in Figs. 47 to 51

1‧‧‧積層體1‧‧‧ laminated body

2‧‧‧電解用電極2‧‧‧electrode for electrolysis

2a‧‧‧電解用電極之內表面2a‧‧‧Inner surface of electrode for electrolysis

2b‧‧‧電解用電極之外表面2b‧‧‧Outer surface of electrode for electrolysis

3‧‧‧隔膜3‧‧‧ diaphragm

3a‧‧‧隔膜之內表面3a‧‧‧Inner surface of diaphragm

3b‧‧‧隔膜之外表面3b‧‧‧ Outside surface of diaphragm

7‧‧‧固定用構件7‧‧‧Fixing members

針對圖52~56之符號之說明Explanation of symbols in Figs. 52 to 56

1‧‧‧電解池1‧‧‧ electrolytic cell

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

4‧‧‧電解槽4‧‧‧ electrolytic cell

5‧‧‧壓製器5‧‧‧presser

6‧‧‧陰極端子6‧‧‧ cathode terminal

7‧‧‧陽極端子7‧‧‧Anode terminal

10‧‧‧陽極室10‧‧‧Anode Room

11‧‧‧陽極11‧‧‧Anode

12‧‧‧陽極墊片12‧‧‧Anode gasket

13‧‧‧陰極墊片13‧‧‧ cathode pad

18‧‧‧逆向電流吸收體18‧‧‧ reverse current sink

18a‧‧‧基材18a‧‧‧ substrate

18b‧‧‧逆向電流吸收層18b‧‧‧Reverse current absorption layer

19‧‧‧陽極室之底部19‧‧‧ bottom of anode chamber

20‧‧‧陰極室20‧‧‧ cathode chamber

21‧‧‧陰極21‧‧‧ cathode

22‧‧‧金屬彈性體22‧‧‧metal elastomer

23‧‧‧集電體23‧‧‧Current collector

24‧‧‧支持體24‧‧‧ support

30‧‧‧間隔壁30‧‧‧ partition

40‧‧‧電解用陰極結構體40‧‧‧ Electrolytic cathode structure

<與第4實施形態相對應之圖><Figure corresponding to the fourth embodiment>

針對圖63~67之符號之說明Explanation of symbols in Figs. 63 to 67

1‧‧‧電解池1‧‧‧ electrolytic cell

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

4‧‧‧電解槽4‧‧‧ electrolytic cell

5‧‧‧壓製器5‧‧‧presser

6‧‧‧陰極端子6‧‧‧ cathode terminal

7‧‧‧陽極端子7‧‧‧Anode terminal

10‧‧‧陽極室10‧‧‧Anode Room

11‧‧‧陽極11‧‧‧Anode

12‧‧‧陽極墊片12‧‧‧Anode gasket

13‧‧‧陰極墊片13‧‧‧ cathode pad

18‧‧‧逆向電流吸收體18‧‧‧ reverse current sink

18a‧‧‧基材18a‧‧‧ substrate

18b‧‧‧逆向電流吸收層18b‧‧‧Reverse current absorption layer

19‧‧‧陽極室之底部19‧‧‧ bottom of anode chamber

20‧‧‧陰極室20‧‧‧ cathode chamber

21‧‧‧陰極21‧‧‧ cathode

21a‧‧‧更新用陰極21a‧‧‧Renewal cathode

22‧‧‧金屬彈性體22‧‧‧metal elastomer

23‧‧‧集電體23‧‧‧Current collector

24‧‧‧支持體24‧‧‧ support

30‧‧‧間隔壁30‧‧‧ partition

40‧‧‧電解用陰極結構體40‧‧‧ Electrolytic cathode structure

針對圖68之符號之說明Explanation of the symbols in Figure 68

10‧‧‧電解用電極基材10‧‧‧ Electrode substrate for electrolysis

20‧‧‧第一層20‧‧‧ First floor

30‧‧‧第二層30‧‧‧Second floor

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖69~71之符號之說明Explanation of symbols in Figs. 69 to 71

1‧‧‧離子交換膜1‧‧‧ion exchange membrane

2‧‧‧羧酸層2‧‧‧carboxylic acid layer

3‧‧‧磺酸層3‧‧‧sulfonic acid layer

4‧‧‧強化芯材4‧‧‧ reinforced core material

10‧‧‧膜本體10‧‧‧ membrane body

11a‧‧‧塗佈層11a‧‧‧Coated layer

11b‧‧‧塗佈層11b‧‧‧Coated layer

21‧‧‧強化芯材21‧‧‧Reinforced core material

22‧‧‧強化芯材22‧‧‧ reinforced core material

52‧‧‧強化紗52‧‧‧ Reinforced yarn

100‧‧‧電解槽100‧‧‧ electrolytic cell

200‧‧‧陽極200‧‧‧Anode

300‧‧‧陰極300‧‧‧ cathode

504‧‧‧連通孔504‧‧‧Connecting hole

504a‧‧‧犧牲紗504a‧‧‧ sacrificial yarn

針對圖72~78之符號之說明Explanation of symbols in Figs. 72 to 78

1‧‧‧積層體1‧‧‧ laminated body

2‧‧‧電解用電極2‧‧‧ Electrolysis electrode

2a‧‧‧電解用電極之內表面2a‧‧‧Inner surface of electrode for electrolysis

2b‧‧‧電解用電極之外表面2b‧‧‧Outer surface of electrode for electrolysis

3‧‧‧隔膜3‧‧‧ diaphragm

3a‧‧‧隔膜之內表面3a‧‧‧Inner surface of diaphragm

3b‧‧‧隔膜之外表面3b‧‧‧ Outside surface of diaphragm

7‧‧‧固定用構件7‧‧‧Fixing members

A‧‧‧墊片A‧‧‧ Gasket

A1‧‧‧墊片之最外周緣A1‧‧‧ the outermost periphery of the gasket

B‧‧‧隔膜B‧‧‧ diaphragm

B1‧‧‧隔膜之最外周緣B1‧‧‧ the outermost periphery of the diaphragm

C‧‧‧電解用電極C‧‧‧ Electrolysis electrode

C1‧‧‧電解用電極之最外周緣C1‧‧‧ the outermost periphery of the electrode for electrolysis

針對圖79之符號之說明Explanation of Symbols in Figure 79

1‧‧‧夾持治具(SUS)1‧‧‧ Holding fixture (SUS)

2‧‧‧電極2‧‧‧ electrode

3‧‧‧隔膜3‧‧‧ diaphragm

4‧‧‧鎳板(已實施粒編號320之氧化鋁噴擊)4‧‧‧nickel plate (alumina spraying with grain number 320 has been implemented)

100‧‧‧正面100‧‧‧ Positive

200‧‧‧側面200‧‧‧ side

針對圖80~82之符號之說明Explanation of symbols in Figs. 80 to 82

1‧‧‧隔膜1‧‧‧ diaphragm

2a‧‧‧外徑280 mm之聚乙烯製管2a‧‧‧ polyethylene tube with outer diameter of 280 mm

2b‧‧‧外徑145 mm之聚乙烯製管2b‧‧‧ polyethylene tube with outer diameter of 145 mm

3‧‧‧剝離部3‧‧‧ stripping department

4‧‧‧密接部4‧‧‧ Adhesion Department

5‧‧‧電極5‧‧‧ electrode

針對圖84之符號之說明Explanation of Symbols in Figure 84

1‧‧‧平台1‧‧‧ platform

2‧‧‧產生變形之電極2‧‧‧deformed electrode

10‧‧‧固定電極之治具10‧‧‧Fixed electrode fixture

20‧‧‧施加力之方向20‧‧‧ Direction of force

針對圖85~90之符號之說明Explanation of symbols in Figs. 85 to 90

1‧‧‧110 mm之鎳線1‧‧‧110 mm nickel wire

2‧‧‧950 mm之鎳線2‧‧‧950 mm nickel wire

3‧‧‧架3‧‧‧

<與第5實施形態相對應之圖><Figure corresponding to the fifth embodiment>

針對圖91~95之符號之說明Explanation of Symbols in Figures 91 to 95

1‧‧‧電解池1‧‧‧ electrolytic cell

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

4‧‧‧電解槽4‧‧‧ electrolytic cell

5‧‧‧壓製器5‧‧‧presser

6‧‧‧陰極端子6‧‧‧ cathode terminal

7‧‧‧陽極端子7‧‧‧Anode terminal

10‧‧‧陽極室10‧‧‧Anode Room

11‧‧‧陽極11‧‧‧Anode

12‧‧‧陽極墊片12‧‧‧Anode gasket

13‧‧‧陰極墊片13‧‧‧ cathode pad

18‧‧‧逆向電流吸收體18‧‧‧ reverse current sink

18a‧‧‧基材18a‧‧‧ substrate

18b‧‧‧逆向電流吸收層18b‧‧‧Reverse current absorption layer

19‧‧‧陽極室之底部19‧‧‧ bottom of anode chamber

20‧‧‧陰極室20‧‧‧ cathode chamber

21‧‧‧陰極21‧‧‧ cathode

22‧‧‧金屬彈性體22‧‧‧metal elastomer

23‧‧‧集電體23‧‧‧Current collector

24‧‧‧支持體24‧‧‧ support

30‧‧‧間隔壁30‧‧‧ partition

40‧‧‧電解用陰極結構體40‧‧‧ Electrolytic cathode structure

針對圖96之符號之說明Explanation of Symbols in Figure 96

10‧‧‧電解用電極基材10‧‧‧ Electrode substrate for electrolysis

20‧‧‧第一層20‧‧‧ First floor

30‧‧‧第二層30‧‧‧Second floor

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖97~99之符號之說明Explanation of symbols in Figs. 97 to 99

1‧‧‧離子交換膜1‧‧‧ion exchange membrane

2‧‧‧羧酸層2‧‧‧carboxylic acid layer

3‧‧‧磺酸層3‧‧‧sulfonic acid layer

4‧‧‧強化芯材4‧‧‧ reinforced core material

10‧‧‧膜本體10‧‧‧ membrane body

11a‧‧‧塗佈層11a‧‧‧Coated layer

11b‧‧‧塗佈層11b‧‧‧Coated layer

21‧‧‧強化芯材21‧‧‧Reinforced core material

22‧‧‧強化芯材22‧‧‧ reinforced core material

52‧‧‧強化紗52‧‧‧ Reinforced yarn

100‧‧‧電解槽100‧‧‧ electrolytic cell

200‧‧‧陽極200‧‧‧Anode

300‧‧‧陰極300‧‧‧ cathode

504‧‧‧連通孔504‧‧‧Connecting hole

504a‧‧‧犧牲紗504a‧‧‧ sacrificial yarn

<與第6實施形態相對應之圖><Figure corresponding to the sixth embodiment>

針對圖103~107之符號之說明Explanation of symbols in Figs. 103 to 107

1‧‧‧電解池1‧‧‧ electrolytic cell

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

4‧‧‧電解槽4‧‧‧ electrolytic cell

5‧‧‧壓製器5‧‧‧presser

6‧‧‧陰極端子6‧‧‧ cathode terminal

7‧‧‧陽極端子7‧‧‧Anode terminal

10‧‧‧陽極室10‧‧‧Anode Room

11‧‧‧陽極11‧‧‧Anode

12‧‧‧陽極墊片12‧‧‧Anode gasket

13‧‧‧陰極墊片13‧‧‧ cathode pad

18‧‧‧逆向電流吸收體18‧‧‧ reverse current sink

18a‧‧‧基材18a‧‧‧ substrate

18b‧‧‧逆向電流吸收層18b‧‧‧Reverse current absorption layer

19‧‧‧陽極室之底部19‧‧‧ bottom of anode chamber

20‧‧‧陰極室20‧‧‧ cathode chamber

21‧‧‧陰極21‧‧‧ cathode

22‧‧‧金屬彈性體22‧‧‧metal elastomer

23‧‧‧集電體23‧‧‧Current collector

24‧‧‧支持體24‧‧‧ support

30‧‧‧間隔壁30‧‧‧ partition

40‧‧‧電解用陰極結構體40‧‧‧ Electrolytic cathode structure

針對圖108之符號之說明Explanation of symbols in Fig. 108

10‧‧‧電解用電極基材10‧‧‧ Electrode substrate for electrolysis

20‧‧‧第一層20‧‧‧ First floor

30‧‧‧第二層30‧‧‧Second floor

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖109~111之符號之說明Explanation of symbols in Figs. 109 to 111

1‧‧‧離子交換膜1‧‧‧ion exchange membrane

2‧‧‧羧酸層2‧‧‧carboxylic acid layer

3‧‧‧磺酸層3‧‧‧sulfonic acid layer

4‧‧‧強化芯材4‧‧‧ reinforced core material

10‧‧‧膜本體10‧‧‧ membrane body

11a‧‧‧塗佈層11a‧‧‧Coated layer

11b‧‧‧塗佈層11b‧‧‧Coated layer

21‧‧‧強化芯材21‧‧‧Reinforced core material

22‧‧‧強化芯材22‧‧‧ reinforced core material

52‧‧‧強化紗52‧‧‧ Reinforced yarn

100‧‧‧電解槽100‧‧‧ electrolytic cell

200‧‧‧陽極200‧‧‧Anode

300‧‧‧陰極300‧‧‧ cathode

504‧‧‧連通孔504‧‧‧Connecting hole

504a‧‧‧犧牲紗504a‧‧‧ sacrificial yarn

<與第7實施形態相對應之圖><Figure corresponding to the seventh embodiment>

針對圖112~118之符號之說明Explanation of symbols in Figs. 112 to 118

1‧‧‧電解池1‧‧‧ electrolytic cell

2‧‧‧離子交換膜2‧‧‧ion exchange membrane

2a‧‧‧新離子交換膜2a‧‧‧new ion exchange membrane

4‧‧‧電解槽4‧‧‧ electrolytic cell

5‧‧‧壓製器5‧‧‧presser

6‧‧‧陰極端子6‧‧‧ cathode terminal

7‧‧‧陽極端子7‧‧‧Anode terminal

8‧‧‧電解槽架8‧‧‧ electrolytic cell rack

9‧‧‧積層體9‧‧‧ laminated body

10‧‧‧陽極室10‧‧‧Anode Room

11‧‧‧陽極11‧‧‧Anode

12‧‧‧陽極墊片12‧‧‧Anode gasket

13‧‧‧陰極墊片13‧‧‧ cathode pad

18‧‧‧逆向電流吸收體18‧‧‧ reverse current sink

18a‧‧‧基材18a‧‧‧ substrate

18b‧‧‧逆向電流吸收層18b‧‧‧Reverse current absorption layer

19‧‧‧陽極室之底部19‧‧‧ bottom of anode chamber

20‧‧‧陰極室20‧‧‧ cathode chamber

21‧‧‧陰極21‧‧‧ cathode

22‧‧‧金屬彈性體22‧‧‧metal elastomer

23‧‧‧集電體23‧‧‧Current collector

24‧‧‧支持體24‧‧‧ support

30‧‧‧間隔壁30‧‧‧ partition

40‧‧‧電解用陰極結構體40‧‧‧ Electrolytic cathode structure

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖119之符號之說明Explanation of Symbols in Figure 119

10‧‧‧電解用電極基材10‧‧‧ Electrode substrate for electrolysis

20‧‧‧第一層20‧‧‧ First floor

30‧‧‧第二層30‧‧‧Second floor

100‧‧‧電解用電極100‧‧‧ Electrolysis electrode

針對圖120~122之符號之說明Explanation of symbols in Figs. 120 to 122

1‧‧‧離子交換膜1‧‧‧ion exchange membrane

2‧‧‧羧酸層2‧‧‧carboxylic acid layer

3‧‧‧磺酸層3‧‧‧sulfonic acid layer

4‧‧‧強化芯材4‧‧‧ reinforced core material

10‧‧‧膜本體10‧‧‧ membrane body

11a‧‧‧塗佈層11a‧‧‧Coated layer

11b‧‧‧塗佈層11b‧‧‧Coated layer

21‧‧‧強化芯材21‧‧‧Reinforced core material

22‧‧‧強化芯材22‧‧‧ reinforced core material

52‧‧‧強化紗52‧‧‧ Reinforced yarn

100‧‧‧電解槽100‧‧‧ electrolytic cell

200‧‧‧陽極200‧‧‧Anode

300‧‧‧陰極300‧‧‧ cathode

504‧‧‧連通孔504‧‧‧Connecting hole

504a‧‧‧犧牲紗504a‧‧‧ sacrificial yarn

圖1係本發明之一實施形態之電解用電極之模式性剖面圖。 圖2係表示離子交換膜之一實施形態之剖面模式圖。 圖3係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。 圖4係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 圖5係電解池之模式性剖面圖。 圖6係表示將2個電解池串聯連接之狀態之模式性剖面圖。 圖7係電解槽之模式圖。 圖8係表示組裝電解槽之步驟之模式性立體圖。 圖9係電解池所具備之逆向電流吸收體之模式性剖面圖。 圖10係實施例所記載之每單位質量•單位面積所承受之力(1)之評價方法的模式圖。 圖11係實施例所記載之直徑280 mm圓柱捲繞評價方法(1)之模式圖。 圖12係實施例所記載之直徑280 mm圓柱捲繞評價方法(2)之模式圖。 圖13係實施例所記載之直徑145 mm圓柱捲繞評價方法(3)之模式圖。 圖14係實施例所記載之電極之彈性變形試驗之模式圖。 圖15係塑性變形後之柔軟程度之評價方法之模式圖。 圖16係比較例13中所製作之電極之模式圖。 圖17係用以將比較例13中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖18係比較例14中所製作之電極之模式圖。 圖19係用以將比較例14中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖20係比較例15中所製作之電極之模式圖。 圖21係用以將比較例15中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖22係本發明之一實施形態中之電解用電極之模式性剖面圖。 圖23係表示離子交換膜之一實施形態之剖面模式圖。 圖24係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。 圖25係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 圖26係電解池之模式性剖面圖。 圖27係表示將2個電解池串聯連接之狀態之模式性剖面圖。 圖28係電解槽之模式圖。 圖29係表示組裝電解槽之步驟之模式性立體圖。 圖30係電解池所具備之逆向電流吸收體之模式性剖面圖。 圖31係實施例所記載之每單位質量•單位面積所承受之力(1)之評價方法的模式圖。 圖32係實施例所記載之直徑280 mm圓柱捲繞評價方法(1)之模式圖。 圖33係實施例所記載之直徑280 mm圓柱捲繞評價方法(2)之模式圖。 圖34係實施例所記載之直徑145 mm圓柱捲繞評價方法(3)之模式圖。 圖35係實施例所記載之電極之彈性變形試驗之模式圖。 圖36係塑性變形後之柔軟程度之評價方法之模式圖。 圖37係實施例34中所製作之電極之模式圖。 圖38係用以將實施例34中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖39係實施例35中所製作之電極之模式圖。 圖40係用以將實施例35中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖41係實施例36中所製作之電極之模式圖。 圖42係用以將實施例36中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖43係本發明之一實施形態中之電解用電極之模式性剖面圖。 圖44係例示離子交換膜之一實施形態之剖面模式圖。 圖45係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。 圖46係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 圖47中圖5A係例示電解用電極之至少一部分貫通隔膜而被固定之態樣之積層體的模式性剖面圖。圖5B係表示用以獲得圖5A之結構之步驟的說明圖。 圖48中圖6A係例示電解用電極之至少一部分位於隔膜之內部而被固定之態樣之積層體的模式性剖面圖。圖6B係表示用以獲得圖6A之結構之步驟的說明圖。 圖49中圖7A~C係例示使用紗狀之固定用構件作為用以固定隔膜與電解用電極之固定用構件進行固定之態樣之積層體的模式性剖面圖。 圖50係例示使用有機樹脂作為用以固定隔膜與電解用電極之固定用構件進行固定之態樣之積層體的模式性剖面圖。 圖51中圖9A係例示固定用構件之至少一部分從外部將隔膜與電解用電極固持並加以固定之態樣之積層體的模式性剖面圖。圖9B係例示固定用構件之至少一部分藉由磁力將隔膜與電解用電極加以固定之態樣之積層體的模式性剖面圖。 圖52係電解池之模式性剖面圖。 圖53係表示將2個電解池串聯連接之狀態之模式性剖面圖。 圖54係電解槽之模式圖。 圖55係表示組裝電解槽之步驟之模式性立體圖。 圖56係電解池可具備之逆向電流吸收體之模式性剖面圖。 圖57係表示實施例1中之積層體之說明圖。 圖58係表示實施例2中之積層體之說明圖。 圖59係表示實施例3中之積層體之說明圖。 圖60係表示實施例4中之積層體之說明圖。 圖61係表示實施例5中之積層體之說明圖。 圖62係表示實施例6中之積層體之說明圖。 圖63係電解池之模式性剖面圖。 圖64中圖2A係表示先前之電解槽中將2個電解池串聯連接之狀態之模式性剖面圖。圖2B係表示本實施形態之電解槽中將2個電解池串聯連接之狀態之模式性剖面圖。 圖65係電解槽之模式圖。 圖66係表示組裝電解槽之步驟之模式性立體圖。 圖67係電解池可具備之逆向電流吸收體之模式性剖面圖。 圖68係本發明之一實施形態中之電解用電極之模式性剖面圖。 圖69係例示離子交換膜之一實施形態之剖面模式圖。 圖70係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。 圖71係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 圖72係用以說明積層體與墊片之位置關係之說明圖。 圖73係用以說明積層體與墊片之位置關係之說明圖。 圖74中圖12A係例示電解用電極之至少一部分貫通隔膜而被固定之態樣之積層體的模式性剖面圖。圖12B係表示用以獲得圖12A之結構之步驟的說明圖。 圖75中圖13A係例示電解用電極之至少一部分位於隔膜之內部而被固定之態樣之積層體的模式性剖面圖。圖13B係表示用以獲得圖13A之結構之步驟的說明圖。 圖76中圖14A~C係例示使用紗狀之固定用構件作為用以固定隔膜與電解用電極之固定用構件進行固定之態樣之積層體的模式性剖面圖。 圖77係例示使用有機樹脂作為用以固定隔膜與電解用電極之固定用構件進行固定之態樣之積層體的模式性剖面圖。 圖78中圖16A係例示固定用構件之至少一部分從外部將隔膜與電解用電極固持並加以固定之態樣之積層體的模式性剖面圖。圖16B係例示固定用構件之至少一部分藉由磁力將隔膜與電解用電極加以固定之態樣之積層體的模式性剖面圖。 圖79係實施例所記載之每單位質量•單位面積所承受之力(1)之評價方法的模式圖。 圖80係實施例所記載之直徑280 mm圓柱捲繞評價方法(1)之模式圖。 圖81係實施例所記載之直徑280 mm圓柱捲繞評價方法(2)之模式圖。 圖82係實施例所記載之直徑145 mm圓柱捲繞評價方法(3)之模式圖。 圖83係實施例所記載之電極之柔軟性評價之模式圖。 圖84係塑性變形後之柔軟程度之評價方法之模式圖。 圖85係實施例35中所製作之電極之模式圖。 圖86係用以將實施例35中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖87係實施例36中所製作之電極之模式圖。 圖88係用以將實施例36中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖89係實施例37中所製作之電極之模式圖。 圖90係用以將實施例37中所製作之電極設置於鎳網饋電體上之結構體之模式圖。 圖91係電解池之模式性剖面圖。 圖92係表示將2個電解池串聯連接之狀態之模式性剖面圖。 圖93係電解槽之模式圖。 圖94係表示組裝電解槽之步驟之模式性立體圖。 圖95係電解池可具備之逆向電流吸收體之模式性剖面圖。 圖96係本發明之一實施形態中之電解用電極之模式性剖面圖。 圖97係例示離子交換膜之一實施形態之剖面模式圖。 圖98係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。 圖99係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 圖100係實施例1中所製作之積層體之模式圖。 圖101係將實施例1中所製作之積層體捲繞而製作捲繞體時之模式圖。 圖102係實施例4中所製作之積層體之模式圖。 圖103係電解池之模式性剖面圖。 圖104係表示將2個電解池串聯連接之狀態之模式性剖面圖。 圖105係電解槽之模式圖。 圖106係表示組裝電解槽之步驟之模式性立體圖。 圖107係電解池可具備之逆向電流吸收體之模式性剖面圖。 圖108係本發明之一實施形態中之電解用電極之模式性剖面圖。 圖109係例示離子交換膜之一實施形態之剖面模式圖。 圖110係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。 圖111係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。 圖112係電解池之模式性剖面圖。 圖113係表示將2個電解池串聯連接之狀態之模式性剖面圖。 圖114係電解槽之模式圖。 圖115係表示組裝電解槽之步驟之模式性立體圖。 圖116係電解池可具備之逆向電流吸收體之模式性剖面圖。 圖117中圖6(A)係用以說明本實施形態之第1態樣之各步驟之一例的電解槽之模式圖。圖6(B)係與圖6(A)相對應之模式性立體圖。 圖118中圖7(A)係用以說明本實施形態之第2態樣之各步驟之一例的電解槽之模式圖。圖7(B)係與圖7(A)相對應之模式性立體圖。 圖119係本發明之一實施形態中之電解用電極之模式性剖面圖。 圖120係例示離子交換膜之一實施形態之剖面模式圖。 圖121係用以對構成離子交換膜之強化芯材之開口率進行說明之概略圖。 圖122係用以對形成離子交換膜之連通孔之方法進行說明之模式圖。FIG. 1 is a schematic cross-sectional view of an electrode for electrolysis according to an embodiment of the present invention. Fig. 2 is a schematic sectional view showing an embodiment of an ion exchange membrane. FIG. 3 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 4 is a schematic diagram for explaining a method of forming a communication hole of an ion exchange membrane. Fig. 5 is a schematic sectional view of an electrolytic cell. Fig. 6 is a schematic sectional view showing a state where two electrolytic cells are connected in series. Fig. 7 is a schematic diagram of an electrolytic cell. Fig. 8 is a schematic perspective view showing a step of assembling an electrolytic cell. Fig. 9 is a schematic sectional view of a reverse current sink provided in the electrolytic cell. FIG. 10 is a schematic diagram of an evaluation method of the force (1) per unit mass and unit area described in the embodiment. FIG. 11 is a schematic diagram of the cylindrical winding evaluation method (1) with a diameter of 280 mm described in the examples. FIG. 12 is a schematic diagram of the cylindrical winding evaluation method (2) with a diameter of 280 mm described in the examples. FIG. 13 is a schematic diagram of the 145 mm diameter cylindrical winding evaluation method (3) described in the examples. FIG. 14 is a schematic diagram of an elastic deformation test of an electrode described in the examples. Fig. 15 is a schematic diagram of an evaluation method of softness after plastic deformation. FIG. 16 is a schematic view of an electrode produced in Comparative Example 13. FIG. FIG. 17 is a schematic diagram of a structure in which the electrode prepared in Comparative Example 13 is provided on a nickel mesh power feeder. FIG. 18 is a schematic view of an electrode produced in Comparative Example 14. FIG. FIG. 19 is a schematic view of a structure in which an electrode produced in Comparative Example 14 is provided on a nickel mesh power feeder. FIG. 20 is a schematic view of an electrode prepared in Comparative Example 15. FIG. FIG. 21 is a schematic view of a structure in which the electrode produced in Comparative Example 15 is provided on a nickel mesh power feeder. Fig. 22 is a schematic sectional view of an electrode for electrolysis in an embodiment of the present invention. Fig. 23 is a schematic sectional view showing an embodiment of an ion exchange membrane. FIG. 24 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. Fig. 25 is a schematic diagram for explaining a method of forming a communication hole of an ion exchange membrane. Fig. 26 is a schematic sectional view of an electrolytic cell. Fig. 27 is a schematic sectional view showing a state where two electrolytic cells are connected in series. Fig. 28 is a schematic diagram of an electrolytic cell. Fig. 29 is a schematic perspective view showing a step of assembling an electrolytic cell. Fig. 30 is a schematic sectional view of a reverse current sink provided in the electrolytic cell. FIG. 31 is a schematic diagram of an evaluation method of the force (1) per unit mass and unit area described in the embodiment. FIG. 32 is a schematic diagram of the cylindrical winding evaluation method (1) with a diameter of 280 mm described in the examples. FIG. 33 is a schematic diagram of the cylindrical winding evaluation method (2) with a diameter of 280 mm described in the examples. FIG. 34 is a schematic diagram of the 145 mm diameter cylindrical winding evaluation method (3) described in the examples. FIG. 35 is a schematic diagram of an elastic deformation test of the electrode described in the examples. Fig. 36 is a schematic diagram of an evaluation method of softness after plastic deformation. FIG. 37 is a schematic view of an electrode prepared in Example 34. FIG. FIG. 38 is a schematic view of a structure in which the electrode prepared in Example 34 is provided on a nickel grid feeder. FIG. 39 is a schematic view of an electrode fabricated in Example 35. FIG. FIG. 40 is a schematic diagram of a structure used for disposing the electrode prepared in Example 35 on a nickel mesh power feeder. FIG. 41 is a schematic view of an electrode prepared in Example 36. FIG. FIG. 42 is a schematic diagram of a structure for disposing the electrode prepared in Example 36 on a nickel mesh power feeder. Fig. 43 is a schematic sectional view of an electrode for electrolysis in an embodiment of the present invention. Fig. 44 is a schematic cross-sectional view illustrating an embodiment of an ion exchange membrane. Fig. 45 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. Fig. 46 is a schematic diagram for explaining a method of forming a communication hole of an ion exchange membrane. FIG. 5A in FIG. 47 is a schematic cross-sectional view illustrating a laminated body in which at least a part of the electrode for electrolysis passes through the separator and is fixed. Fig. 5B is an explanatory diagram showing steps for obtaining the structure of Fig. 5A. FIG. 6A in FIG. 48 is a schematic cross-sectional view illustrating a laminated body in which at least a part of the electrode for electrolysis is located inside the separator and is fixed. Fig. 6B is an explanatory diagram showing steps for obtaining the structure of Fig. 6A. 7A to 7C in FIG. 49 are schematic cross-sectional views illustrating a laminated body using a yarn-shaped fixing member as a fixing member for fixing a separator and an electrode for electrolysis. FIG. 50 is a schematic cross-sectional view illustrating a laminated body using an organic resin as a fixing member for fixing a separator and an electrode for electrolysis. FIG. 9A in FIG. 51 is a schematic cross-sectional view illustrating a laminated body in which at least a part of the fixing member holds and fixes the separator and the electrode for electrolysis from the outside. FIG. 9B is a schematic cross-sectional view illustrating a laminated body in which at least a part of the fixing member is fixed with a separator and an electrode for electrolysis by magnetic force. Fig. 52 is a schematic sectional view of an electrolytic cell. Fig. 53 is a schematic sectional view showing a state where two electrolytic cells are connected in series. Fig. 54 is a schematic diagram of an electrolytic cell. Fig. 55 is a schematic perspective view showing a step of assembling an electrolytic cell. Fig. 56 is a schematic cross-sectional view of a reverse current sink that can be provided in an electrolytic cell. FIG. 57 is an explanatory view showing a laminated body in Example 1. FIG. FIG. 58 is an explanatory diagram showing a laminated body in Example 2. FIG. FIG. 59 is an explanatory diagram showing a laminated body in Example 3. FIG. FIG. 60 is an explanatory view showing a laminated body in Example 4. FIG. FIG. 61 is an explanatory diagram showing a laminated body in Example 5. FIG. FIG. 62 is an explanatory diagram showing a laminated body in Example 6. FIG. Fig. 63 is a schematic sectional view of an electrolytic cell. FIG. 2A in FIG. 64 is a schematic sectional view showing a state in which two electrolytic cells are connected in series in a conventional electrolytic cell. FIG. 2B is a schematic cross-sectional view showing a state where two electrolytic cells are connected in series in the electrolytic cell according to this embodiment. Fig. 65 is a schematic diagram of an electrolytic cell. Fig. 66 is a schematic perspective view showing a step of assembling an electrolytic cell. Fig. 67 is a schematic cross-sectional view of a reverse current sink that can be provided in an electrolytic cell. Fig. 68 is a schematic sectional view of an electrode for electrolysis in an embodiment of the present invention. Fig. 69 is a schematic cross-sectional view illustrating an embodiment of an ion exchange membrane. FIG. 70 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 71 is a schematic diagram for explaining a method of forming a communication hole of an ion exchange membrane. Fig. 72 is an explanatory diagram for explaining a positional relationship between a laminated body and a gasket. Fig. 73 is an explanatory diagram for explaining a positional relationship between a laminated body and a gasket. FIG. 12A in FIG. 74 is a schematic cross-sectional view illustrating a laminated body in which at least a part of the electrode for electrolysis passes through the separator and is fixed. Fig. 12B is an explanatory diagram showing steps for obtaining the structure of Fig. 12A. FIG. 13A in FIG. 75 is a schematic cross-sectional view illustrating a laminated body in which at least a part of the electrode for electrolysis is located inside the separator and is fixed. FIG. 13B is an explanatory diagram showing steps for obtaining the structure of FIG. 13A. 14A to 14C in FIG. 76 are schematic cross-sectional views illustrating a laminated body using a yarn-shaped fixing member as a fixing member for fixing a separator and an electrode for electrolysis. FIG. 77 is a schematic cross-sectional view illustrating a laminated body using an organic resin as a fixing member for fixing a separator and an electrode for electrolysis. FIG. 16A in FIG. 78 is a schematic cross-sectional view illustrating a laminated body in which at least a part of the fixing member holds and fixes the separator and the electrode for electrolysis from the outside. FIG. 16B is a schematic cross-sectional view illustrating a laminated body in which at least a part of the fixing member is fixed with a separator and an electrode for electrolysis by magnetic force. FIG. 79 is a schematic diagram of an evaluation method of the force (1) per unit mass and unit area described in the embodiment. FIG. 80 is a schematic diagram of the cylindrical winding evaluation method (1) of 280 mm diameter described in the examples. FIG. 81 is a schematic diagram of the 280 mm diameter cylindrical winding evaluation method (2) described in the example. Fig. 82 is a schematic diagram of a method for evaluating a cylindrical winding with a diameter of 145 mm (3) according to the embodiment. Fig. 83 is a schematic diagram showing the evaluation of the flexibility of the electrodes described in the examples. Fig. 84 is a schematic diagram of an evaluation method of softness after plastic deformation. FIG. 85 is a schematic view of an electrode prepared in Example 35. FIG. FIG. 86 is a schematic diagram of a structure in which the electrode prepared in Example 35 is provided on a nickel grid feeder. FIG. 87 is a schematic view of an electrode prepared in Example 36. FIG. FIG. 88 is a schematic view of a structure used for disposing the electrode prepared in Example 36 on a nickel grid feeder. FIG. 89 is a schematic view of an electrode prepared in Example 37. FIG. FIG. 90 is a schematic diagram of a structure in which the electrode prepared in Example 37 is provided on a nickel grid feeder. Fig. 91 is a schematic sectional view of an electrolytic cell. Fig. 92 is a schematic sectional view showing a state where two electrolytic cells are connected in series. Fig. 93 is a schematic diagram of an electrolytic cell. Fig. 94 is a schematic perspective view showing a step of assembling an electrolytic cell. Fig. 95 is a schematic cross-sectional view of a reverse current sink that can be provided in an electrolytic cell. Fig. 96 is a schematic sectional view of an electrode for electrolysis in an embodiment of the present invention. Fig. 97 is a schematic cross-sectional view illustrating an embodiment of an ion exchange membrane. Fig. 98 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. Fig. 99 is a schematic diagram for explaining a method of forming a communication hole of an ion exchange membrane. FIG. 100 is a schematic view of a multilayer body produced in Example 1. FIG. FIG. 101 is a schematic view when a laminated body produced in Example 1 is wound to produce a wound body. FIG. 102 is a schematic view of a laminated body produced in Example 4. FIG. Fig. 103 is a schematic sectional view of an electrolytic cell. Fig. 104 is a schematic sectional view showing a state where two electrolytic cells are connected in series. Fig. 105 is a schematic diagram of an electrolytic cell. Fig. 106 is a schematic perspective view showing a step of assembling an electrolytic cell. Fig. 107 is a schematic cross-sectional view of a reverse current sink that can be provided in an electrolytic cell. Fig. 108 is a schematic sectional view of an electrode for electrolysis in an embodiment of the present invention. FIG. 109 is a schematic cross-sectional view illustrating an embodiment of an ion exchange membrane. FIG. 110 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. FIG. 111 is a schematic diagram for explaining a method of forming a communication hole of an ion exchange membrane. Fig. 112 is a schematic sectional view of an electrolytic cell. Fig. 113 is a schematic sectional view showing a state where two electrolytic cells are connected in series. Fig. 114 is a schematic view of an electrolytic cell. FIG. 115 is a schematic perspective view showing a step of assembling an electrolytic cell. FIG. 116 is a schematic cross-sectional view of a reverse current sink that can be provided in an electrolytic cell. FIG. 6 (A) in FIG. 117 is a schematic diagram of an electrolytic cell for explaining an example of each step in the first aspect of the present embodiment. FIG. 6 (B) is a schematic perspective view corresponding to FIG. 6 (A). FIG. 7 (A) in FIG. 118 is a schematic diagram of an electrolytic cell for explaining an example of each step in the second aspect of the embodiment. FIG. 7 (B) is a schematic perspective view corresponding to FIG. 7 (A). Fig. 119 is a schematic sectional view of an electrode for electrolysis in an embodiment of the present invention. Fig. 120 is a schematic cross-sectional view illustrating an embodiment of an ion exchange membrane. FIG. 121 is a schematic diagram for explaining the aperture ratio of a reinforced core material constituting an ion exchange membrane. Fig. 122 is a schematic diagram for explaining a method of forming a communication hole of an ion exchange membrane.

Claims (60)

一種電解用電極,其每單位面積之質量為48 mg/cm2 以下,每單位質量·單位面積所承受之力為0.08 N/mg・cm2 以上。An electrode for electrolysis, which has a mass per unit area of 48 mg / cm 2 or less, and a force per unit mass and unit area of 0.08 N / mg · cm 2 or more. 如請求項1之電解用電極,其中上述電解用電極包含電解用電極基材及觸媒層,該電解用電極基材之厚度為300 μm以下。The electrode for electrolysis according to claim 1, wherein the electrode for electrolysis includes an electrode substrate for electrolysis and a catalyst layer, and the thickness of the electrode substrate for electrolysis is 300 μm or less. 如請求項1或2之電解用電極,其中藉由以下之方法(3)所測得之比率為75%以上, [方法(3)] 依序積層於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之離子交換膜(170 mm見方)與電解用電極樣品(130 mm見方);於溫度23±2℃、相對濕度30±5%之條件下,以該積層體中之電解用電極樣品成為外側之方式,將積層體置於聚乙烯管(外徑145 mm)之曲面上,利用純水充分地浸漬積層體與管,將附著於積層體表面及管上之多餘之水分去除,1分鐘後測定於導入有離子交換基之全氟碳聚合物之膜之兩面塗佈有無機物粒子及結合劑之膜與電解用電極樣品密接之部分之面積的比率(%)。For example, if the electrode for electrolysis in claim 1 or 2 is used, the ratio measured by the following method (3) is 75% or more. [Method (3)] Polymerization of perfluorocarbon with ion exchange group introduced in order An ion exchange membrane (170 mm square) coated with inorganic particles and a binder and an electrode sample for electrolysis (130 mm square) are coated on both sides of the film; at a temperature of 23 ± 2 ° C and a relative humidity of 30 ± 5%, With the sample of the electrode for electrolysis in the laminated body turned outside, the laminated body was placed on a curved surface of a polyethylene tube (145 mm in outer diameter), and the laminated body and the tube were sufficiently impregnated with pure water to adhere to the surface of the laminated body And remove excess water from the tube. After 1 minute, measure the area of the portion where the membrane coated with the inorganic particles and the binding agent is adhered to the electrode sample for electrolysis on both sides of the membrane with the perfluorocarbon polymer introduced with the ion exchange group. ratio(%). 如請求項1至3中任一項之電解用電極,其係多孔結構,開孔率為5~90%。The electrode for electrolysis according to any one of claims 1 to 3 has a porous structure and has an open porosity of 5 to 90%. 如請求項1至4中任一項之電解用電極,其係多孔結構,開孔率為10~80%。The electrode for electrolysis according to any one of claims 1 to 4, which has a porous structure and an open porosity of 10 to 80%. 如請求項1至5中任一項之電解用電極,其中上述電解用電極之厚度為315 μm以下。The electrode for electrolysis according to any one of claims 1 to 5, wherein the thickness of the electrode for electrolysis is 315 μm or less. 如請求項1至6中任一項之電解用電極,其中藉由以下之方法(A)對上述電解用電極進行測定而獲得之值為40 mm以下, [方法(A)] 於溫度23±2℃、相對濕度30±5%之條件下,將積層離子交換膜與上述電解用電極而成之樣品捲繞並固定於外徑f32 mm之氯乙烯製芯材之曲面上,靜置6小時後將該電解用電極分離並載置於水平之板,測定此時該電解用電極之兩端部之垂直方向之高度L1 及L2 ,以該等之平均值作為測定值。The electrode for electrolysis according to any one of claims 1 to 6, wherein the value obtained by measuring the above electrode for electrolysis by the following method (A) is 40 mm or less, [Method (A)] at a temperature of 23 ± Under the conditions of 2 ° C and 30 ± 5% relative humidity, a sample formed by laminating an ion exchange membrane and the above-mentioned electrode for electrolysis was wound and fixed on a curved surface of a vinyl chloride core material having an outer diameter of f32 mm, and allowed to stand for 6 hours. Then, the electrode for electrolysis was separated and placed on a horizontal plate, and the heights L 1 and L 2 in the vertical direction at both ends of the electrode for electrolysis at this time were measured, and the average value of these was used as the measurement value. 如請求項1至7中任一項之電解用電極,其中將上述電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時之通氣阻力為24 kPa・s/m以下。The electrode for electrolysis according to any one of claims 1 to 7, wherein the electrode for electrolysis is set to a size of 50 mm × 50 mm and the temperature is 24 ° C, the relative humidity is 32%, the piston speed is 0.2 cm / s, and ventilation is performed. When the amount is 0.4 cc / cm 2 / s, the ventilation resistance is 24 kPa · s / m or less. 如請求項1至8中任一項之電解用電極,其中上述電解用電極基材含有選自鎳(Ni)及鈦(Ti)中之至少1種元素。The electrode for electrolysis according to any one of claims 1 to 8, wherein the electrode substrate for electrolysis contains at least one element selected from the group consisting of nickel (Ni) and titanium (Ti). 一種積層體,其包含如請求項1至9中任一項之電解用電極。A laminated body comprising the electrode for electrolysis according to any one of claims 1 to 9. 一種捲繞體,其包含如請求項1至9中任一項之電解用電極、或如請求項10之積層體。A rolled body comprising the electrode for electrolysis according to any one of claims 1 to 9 or a laminated body according to claim 10. 一種積層體,其具備 電解用電極、及 與上述電解用電極相接之隔膜或饋電體, 針對上述隔膜或饋電體之上述電解用電極之每單位質量·單位面積所承受之力未達1.5 N/mg・cm2A laminated body comprising an electrode for electrolysis, and a diaphragm or a power source connected to the electrode for electrolysis. The force per unit mass and unit area of the electrode for the electrolysis of the diaphragm or power source is not reached. 1.5 N / mg · cm 2 . 如請求項12之積層體,其中針對上述隔膜或饋電體之上述電解用電極之每單位質量·單位面積所承受之力超過0.005 N/mg・cm2For example, the laminated body according to claim 12, wherein the force per unit mass and unit area of the above-mentioned electrode for electrolysis for the above-mentioned separator or power feeder exceeds 0.005 N / mg · cm 2 . 如請求項12或13之積層體,其中上述饋電體為金屬絲網、金屬不織布、沖孔金屬、多孔金屬、或發泡金屬。For example, the laminated body of claim 12 or 13, wherein the above-mentioned power feeder is a metal wire mesh, a metal non-woven fabric, a punched metal, a porous metal, or a foamed metal. 如請求項12至14中任一項之積層體,其具有含有親水性氧化物粒子與導入有離子交換基之聚合物之混合物的層作為上述隔膜之至少一表面層。The laminated body according to any one of claims 12 to 14, which has a layer containing a mixture of hydrophilic oxide particles and a polymer into which an ion exchange group is introduced as at least one surface layer of the separator. 如請求項12至15中任一項之積層體,其中於上述電解用電極與上述隔膜或饋電體之間介置液體。The multilayer body according to any one of claims 12 to 15, wherein a liquid is interposed between the above-mentioned electrode for electrolysis and the above-mentioned separator or power supply. 一種積層體,其具有 隔膜、及 固定於上述隔膜之表面之至少一區域之電解用電極, 上述隔膜之表面中之上述區域之比率超過0%且未達93%。A laminated body comprising a separator and an electrode for electrolysis fixed to at least one area of a surface of the separator, and a ratio of the area in the surface of the separator exceeds 0% to less than 93%. 如請求項17之積層體,其中上述電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。The laminated body according to claim 17, wherein the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, At least one catalyst component in the group consisting of Sm, Eu, Gd, Tb and Dy. 如請求項17或18之積層體,其中於上述區域,上述電解用電極之至少一部分貫通上述隔膜而被固定。The multilayer body according to claim 17 or 18, wherein at least a part of the electrode for electrolysis penetrates the separator and is fixed in the region. 如請求項17至19中任一項之積層體,其中於上述區域,上述電解用電極之至少一部分位於上述隔膜之內部而被固定。The laminated body according to any one of claims 17 to 19, wherein at least a part of the electrode for electrolysis is located inside the separator and is fixed in the region. 如請求項17至20中任一項之積層體,其進而具有用以將上述隔膜與上述電解用電極加以固定之固定用構件。The laminated body according to any one of claims 17 to 20, further comprising a fixing member for fixing the separator and the electrode for electrolysis. 如請求項21之積層體,其中上述固定用構件之至少一部分從外部將上述隔膜與上述電解用電極固持。The laminated body according to claim 21, wherein at least a part of the fixing member holds the separator and the electrode for electrolysis from the outside. 如請求項21或22之積層體,其中上述固定用構件之至少一部分藉由磁力將上述隔膜與上述電解用電極加以固定。The laminated body according to claim 21 or 22, wherein at least a part of the fixing member fixes the separator and the electrode for electrolysis by magnetic force. 如請求項17至23中任一項之積層體,其中上述隔膜包含於表面層含有有機樹脂之離子交換膜, 上述有機樹脂存在於上述區域。The laminated body according to any one of claims 17 to 23, wherein the separator is included in an ion exchange membrane containing an organic resin in a surface layer, and the organic resin is present in the region. 如請求項17至24中任一項之積層體,其中上述隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之EW之第2離子交換樹脂層。The laminated body according to any one of claims 17 to 24, wherein the separator includes a first ion exchange resin layer and a second ion exchange resin layer having an EW different from the first ion exchange resin layer. 如請求項17至24中任一項之積層體,其中上述隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之官能基之第2離子交換樹脂層。The laminated body according to any one of claims 17 to 24, wherein the separator includes a first ion exchange resin layer and a second ion exchange resin layer having a functional group different from the first ion exchange resin layer. 一種電解槽,其具備 陽極、 支持上述陽極之陽極框、 配置於上述陽極框上之陽極側墊片、 與上述陽極相對向之陰極、 支持上述陰極之陰極框、 配置於上述陰極框上且與上述陽極側墊片相對向之陰極側墊片、及 配置於上述陽極側墊片與上述陰極側墊片之間之隔膜與電解用電極之積層體,且 上述積層體之至少一部分由上述陽極側墊片及上述陰極側墊片所夾持, 將上述電解用電極設為50 mm×50 mm之尺寸且設為溫度24℃、相對濕度32%、活塞速度0.2 cm/s及通氣量0.4 cc/cm2 /s之情形時之通氣阻力為24 kPa・s/m以下。An electrolytic cell includes an anode, an anode frame supporting the anode, an anode-side gasket disposed on the anode frame, a cathode facing the anode, a cathode frame supporting the cathode, and a cathode frame disposed on the cathode frame. A cathode-side gasket facing the anode-side gasket, and a laminated body of a separator and an electrode for electrolysis disposed between the anode-side gasket and the cathode-side gasket, and at least a part of the laminate is from the anode side Between the gasket and the cathode-side gasket, the size of the electrode for electrolysis was 50 mm × 50 mm, and the temperature was 24 ° C, the relative humidity was 32%, the piston speed was 0.2 cm / s, and the air flow rate was 0.4 cc /. In the case of cm 2 / s, the ventilation resistance is 24 kPa · s / m or less. 如請求項27之電解槽,其中上述電解用電極之厚度為315 μm以下。The electrolytic cell according to claim 27, wherein the thickness of the above-mentioned electrode for electrolysis is 315 μm or less. 如請求項27或28之電解槽,其中藉由以下之方法(A)對上述電解用電極進行測定而獲得之值為40 mm以下, [方法(A)] 於溫度23±2℃、相對濕度30±5%之條件下,將積層離子交換膜與上述電解用電極而成之樣品捲繞並固定於外徑f32 mm之氯乙烯製芯材之曲面上,靜置6小時後將該電解用電極分離並載置於水平之板,測定此時該電解用電極之兩端部之垂直方向之高度L1 及L2 ,以該等之平均值作為測定值。If the electrolytic cell of item 27 or 28 is requested, the value obtained by measuring the above electrode for electrolysis by the following method (A) is 40 mm or less, [method (A)] at a temperature of 23 ± 2 ° C and relative humidity Under the condition of 30 ± 5%, the sample formed by laminating the ion exchange membrane and the above-mentioned electrode for electrolysis was wound and fixed on the curved surface of a core material made of vinyl chloride with an outer diameter of f32 mm. After standing for 6 hours, the electrode was used for electrolysis. The electrodes are separated and placed on a horizontal plate, and the heights L 1 and L 2 in the vertical direction at both ends of the electrode for electrolysis at this time are measured, and the average of these is used as the measured value. 如請求項27至29中任一項之電解槽,其中上述電解用電極之每單位面積之質量為48 mg/cm2 以下。The electrolytic cell according to any one of claims 27 to 29, wherein the mass per unit area of the above-mentioned electrode for electrolysis is 48 mg / cm 2 or less. 如請求項27至30中任一項之電解槽,其中上述電解用電極之每單位質量·單位面積所承受之力超過0.005 N/mg・cm2The electrolytic cell according to any one of claims 27 to 30, wherein the force per unit mass and unit area of the above-mentioned electrode for electrolysis exceeds 0.005 N / mg · cm 2 . 如請求項27至31中任一項之電解槽,其中上述積層體之最外周緣位於較上述陽極側墊片及陰極側墊片之最外周緣更靠通電面方向外側之位置。For example, the electrolytic cell of any one of claims 27 to 31, wherein the outermost peripheral edge of the laminated body is located further outside the direction of the current-carrying surface than the outermost peripheral edges of the anode-side gasket and the cathode-side gasket. 如請求項27至32中任一項之電解槽,其中上述電解用電極含有選自由Ru、Rh、Pd、Ir、Pt、Au、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y,Zr、Nb、Mo、Ag、Ta、W、Re、Os、Al、In、Sn、Sb、Ga、Ge、B、C、N、O、Si、P、S、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb及Dy所組成之群中之至少一種觸媒成分。The electrolytic cell according to any one of claims 27 to 32, wherein the electrode for electrolysis contains a member selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, At least one catalyst component in the group consisting of Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy. 如請求項27至33中任一項之電解槽,其中於上述積層體中,上述電解用電極之至少一部分貫通上述隔膜而被固定。The electrolytic cell according to any one of claims 27 to 33, wherein in the laminated body, at least a part of the electrode for electrolysis penetrates the separator and is fixed. 如請求項27至33中任一項之電解槽,其中於上述積層體中,上述電解用電極之至少一部分位於上述隔膜之內部而被固定。The electrolytic cell according to any one of claims 27 to 33, wherein in the laminated body, at least a part of the electrode for electrolysis is located inside the separator and is fixed. 如請求項27至35中任一項之電解槽,其中於上述積層體中進而具有用以將上述隔膜與上述電解用電極加以固定之固定用構件。The electrolytic cell according to any one of claims 27 to 35, further comprising a fixing member for fixing the separator and the electrode for electrolysis in the laminated body. 如請求項36之電解槽,其中於上述積層體中,上述固定用構件之至少一部分貫通上述隔膜與上述電解用電極而加以固定。The electrolytic cell according to claim 36, wherein in the laminated body, at least a part of the fixing member penetrates the separator and the electrolytic electrode and is fixed. 如請求項36或37之電解槽,其中於上述積層體中,上述固定用構件含有可溶於電解液之可溶材料。The electrolytic cell according to claim 36 or 37, wherein in the laminated body, the fixing member contains a soluble material soluble in an electrolytic solution. 如請求項36至38中任一項之電解槽,其中於上述積層體中,上述固定用構件之至少一部分從外部將上述隔膜與上述電解用電極固持。The electrolytic cell according to any one of claims 36 to 38, wherein in the laminated body, at least a part of the fixing member holds the separator and the electrolytic electrode from the outside. 如請求項36至39中任一項之電解槽,其中於上述積層體中,上述固定用構件之至少一部分藉由磁力將上述隔膜與上述電解用電極加以固定。The electrolytic cell according to any one of claims 36 to 39, wherein in the laminated body, at least a part of the fixing member is fixed by a magnetic force to the separator and the electrode for electrolysis. 如請求項27至40中任一項之電解槽,其中上述隔膜包含於表面層含有有機樹脂之離子交換膜, 於上述有機樹脂中固定有上述電解用電極。The electrolytic cell according to any one of claims 27 to 40, wherein the separator includes an ion exchange membrane containing an organic resin in a surface layer, and the electrode for electrolysis is fixed to the organic resin. 如請求項27至41中任一項之電解槽,其中上述隔膜包含第1離子交換樹脂層及具有與該第1離子交換樹脂層不同之EW之第2離子交換樹脂層。The electrolytic cell according to any one of claims 27 to 41, wherein the separator includes a first ion exchange resin layer and a second ion exchange resin layer having an EW different from the first ion exchange resin layer. 一種如請求項27至42中任一項之電解槽之製造方法,其具有於上述陽極側墊片與陰極側墊片之間夾持上述積層體之步驟。A method for manufacturing an electrolytic cell according to any one of claims 27 to 42, comprising a step of sandwiching the laminated body between the anode-side gasket and the cathode-side gasket. 一種如請求項27至42中任一項之電解槽中之積層體之更新方法,其具有: 藉由將上述積層體從上述陽極側墊片及上述陰極側墊片分離而將該積層體從電解槽取出之步驟;及 於上述陽極側墊片與陰極側墊片之間夾持新的上述積層體之步驟。A method for updating a laminated body in an electrolytic cell according to any one of claims 27 to 42, comprising: separating the laminated body from the anode-side gasket and the cathode-side gasket from the laminated body from A step of taking out the electrolytic cell; and a step of clamping the new laminated body between the anode-side gasket and the cathode-side gasket. 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽配置電解用電極或該電解用電極與新隔膜之積層體而製造新電解槽之方法,並且 使用上述電解用電極或上述積層體之捲繞體。A method for manufacturing an electrolytic cell, which is used to arrange an electrode for electrolysis or to use the existing electrolytic cell with an anode, a cathode facing the anode, and a separator disposed between the anode and the cathode. A method for manufacturing a new electrolytic cell by laminating an electrode and a new separator, and using the above-mentioned electrode for electrolysis or a wound body of the above-mentioned laminated body. 如請求項45之電解槽之製造方法,其具有將上述電解用電極或上述積層體保持為捲繞狀態而獲得上述捲繞體之步驟(A)。The method for manufacturing an electrolytic cell according to claim 45, further comprising the step (A) of obtaining the wound body by maintaining the electrode for electrolysis or the laminated body in a wound state. 如請求項45或46之電解槽之製造方法,其具有解除上述捲繞體之捲繞狀態之步驟(B)。The method for manufacturing an electrolytic cell according to claim 45 or 46 has a step (B) of releasing the winding state of the above-mentioned wound body. 如請求項47之電解槽之製造方法,其具有於上述步驟(B)後於上述陽極及上述陰極之至少一者之表面上配置上述電解用電極或上述積層體之步驟(C)。The method for manufacturing an electrolytic cell according to claim 47, further comprising the step (C) of arranging the electrode for electrolysis or the laminate on the surface of at least one of the anode and the cathode after the step (B). 一種電極之更新方法,其係用以藉由使用電解用電極而更新既有之電極之方法,並且 使用上述電解用電極之捲繞體。An electrode updating method is a method for updating an existing electrode by using an electrode for electrolysis, and using the wound body of the above electrode for electrolysis. 如請求項49之電極之更新方法,其具有將上述電解用電極保持為捲繞狀態而獲得上述捲繞體之步驟(A')。The method for updating an electrode according to claim 49, further comprising the step (A ') of maintaining the electrode for electrolysis in a wound state to obtain the wound body. 如請求項49或50之電極之更新方法,其具有解除上述電解用電極之捲繞狀態之步驟(B')。If the method for updating the electrode of item 49 or 50 is requested, it has a step (B ') of releasing the winding state of the electrode for electrolysis. 如請求項51之電極之更新方法,其具有於上述步驟(B')後於既有電極之表面上配置上述電解用電極之步驟(C')。For example, the method for updating an electrode of item 51 has a step (C ') of disposing the electrode for electrolysis on a surface of an existing electrode after the step (B'). 一種捲繞體之製造方法,其係用以更新具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽的捲繞體之製造方法,並且 具有將電解用電極或該電解用電極與新隔膜之積層體捲繞而獲得上述捲繞體之步驟。A method for manufacturing a rolled body, which is used to update a method for manufacturing a rolled body of an existing electrolytic cell including an anode, a cathode facing the anode, and a separator disposed between the anode and the cathode, and The method includes a step of winding the electrode for electrolysis or a laminate of the electrode for electrolysis and a new separator to obtain the wound body. 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、及配置於上述陽極與上述陰極之間之隔膜的既有電解槽配置積層體而製造新電解槽之方法,並且具有: 藉由將電解用電極與新隔膜於該隔膜不熔融之溫度下進行一體化,而獲得上述積層體之步驟(A);及 於上述步驟(A)後將既有電解槽中之上述隔膜更換為上述積層體之步驟(B)。A method for manufacturing an electrolytic cell, which is used to manufacture a new electrolytic cell by arranging a laminate with an existing electrolytic cell provided with an anode, a cathode opposite to the anode, and a separator disposed between the anode and the cathode. A method (1) for obtaining the above-mentioned laminated body by integrating the electrode for electrolysis and a new separator at a temperature at which the separator is not melted, and the existing electrolysis after the step (A) Step (B) of replacing the diaphragm in the tank with the laminated body. 如請求項54之電解槽之製造方法,其中上述一體化係於常壓下進行。For example, the method for manufacturing an electrolytic cell according to claim 54, wherein the above-mentioned integration is performed under normal pressure. 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、固定於上述陽極與上述陰極之間之隔膜、以及支持上述陽極、上述陰極及上述隔膜之電解槽架的既有電解槽配置包含電解用電極及新隔膜之積層體而製造新電解槽之方法,並且具有: 於上述電解槽架內解除上述隔膜之固定之步驟(A);及 於上述步驟(A)後將上述隔膜與上述積層體交換之步驟(B)。A method for manufacturing an electrolytic cell, which is used to support an anode, the cathode, and the separator by using an anode, a cathode facing the anode, a diaphragm fixed between the anode and the cathode, and an electrolytic cell A method for manufacturing a new electrolytic cell by disposing a laminated body including an electrode for electrolysis and a new separator in an existing electrolytic cell of the rack, and comprising: a step (A) of releasing the fixation of the separator in the electrolytic cell rack; and A) The step (B) of exchanging the separator and the laminate. 如請求項56之電解槽之製造方法,其中上述步驟(A)係藉由使上述陽極及上述陰極分別沿該等之排列方向滑動而進行。For example, the method for manufacturing an electrolytic cell according to claim 56, wherein the step (A) is performed by sliding the anode and the cathode in the arrangement direction, respectively. 如請求項56或57之電解槽之製造方法,其中於上述步驟(B)後,藉由來自上述陽極及上述陰極之按壓,而將上述積層體固定於上述電解槽架內。For example, the method for manufacturing an electrolytic cell of item 56 or 57 is characterized in that after the step (B), the laminated body is fixed in the electrolytic cell rack by pressing from the anode and the cathode. 如請求項56至58中任一項之電解槽之製造方法,其中於上述步驟(B)中,於上述積層體不熔融之溫度下將該積層體固定於上述陽極及上述陰極之至少一者之表面上。The method for manufacturing an electrolytic cell according to any one of claims 56 to 58, wherein in step (B), the laminated body is fixed to at least one of the anode and the cathode at a temperature at which the laminated body does not melt. On the surface. 一種電解槽之製造方法,其係用以藉由對具備陽極、與上述陽極相對向之陰極、固定於上述陽極與上述陰極之間之隔膜、以及支持上述陽極、上述陰極及上述隔膜之電解槽架的既有電解槽配置電解用電極而製造新電解槽之方法,並且具有: 於上述電解槽架內解除上述隔膜之固定之步驟(A);及 於上述步驟(A)後,於上述隔膜與上述陽極或上述陰極之間配置上述電解用電極之步驟(B')。A manufacturing method of an electrolytic cell, which is used to support an anode, the cathode, and the separator by using an anode, a cathode facing the anode, a separator fixed between the anode and the cathode, and an electrolytic cell supporting the anode, the cathode, and the separator. A method for manufacturing a new electrolytic cell by disposing an electrolytic electrode in an existing electrolytic cell of the rack, and comprising: step (A) of releasing the fixation of the diaphragm in the electrolytic cell rack; and after the above step (A), The step (B ') of disposing the electrode for electrolysis with the anode or the cathode.
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