TW201240817A - Method for manufacturing sealing film, and sealing film - Google Patents

Method for manufacturing sealing film, and sealing film Download PDF

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Publication number
TW201240817A
TW201240817A TW100140963A TW100140963A TW201240817A TW 201240817 A TW201240817 A TW 201240817A TW 100140963 A TW100140963 A TW 100140963A TW 100140963 A TW100140963 A TW 100140963A TW 201240817 A TW201240817 A TW 201240817A
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Taiwan
Prior art keywords
resin
layer
sealing film
electrode
heat
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TW100140963A
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Chinese (zh)
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TWI480160B (en
Inventor
kousuke Kashima
Shirou Yamamoto
Shinichi Kobayashi
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Fujimori Kogyo Co
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Publication of TW201240817A publication Critical patent/TW201240817A/en
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Publication of TWI480160B publication Critical patent/TWI480160B/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/78Cases; Housings; Encapsulations; Mountings
    • H01G11/80Gaskets; Sealings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/74Terminals, e.g. extensions of current collectors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/183Sealing members
    • H01M50/186Sealing members characterised by the disposition of the sealing members
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/183Sealing members
    • H01M50/19Sealing members characterised by the material
    • H01M50/193Organic material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/183Sealing members
    • H01M50/19Sealing members characterised by the material
    • H01M50/197Sealing members characterised by the material having a layered structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00Polyalkenes
    • B32B2323/04Polyethylene
    • B32B2323/043HDPE, i.e. high density polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/16Capacitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/60Other road transportation technologies with climate change mitigation effect
    • Y02T10/70Energy storage systems for electromobility, e.g. batteries

Abstract

The method for manufacturing a sealing film (1) sandwiched between an electrode (11) of an electrical generation element stored in a bag (20) and an edge of the bag (20), comprising: a melt-kneading process in which both acid-modified polyolefin resin A in which carboxylic acid is graft polymerized and resin B having a functional group capable of reacting with a carboxyl group of the resin A are melted and kneaded, to denature the resin A and the resin B into resin C by chemical binding the carboxyl group of the resin A and the functional group of the resin B; a heat-resistant layer formation process in which a heat-resistant layer (3) is formed by shaping the resin C into a layer; an adhesive layer formation process in which a electrode adhesive layer (2) to be adhered to the electrode is formed by shaping carboxylic acid-modified polyolefin resin D into a layer; and a laminating process in which the heat-resistant layer (3) and the electrode adhesive layer (2) are directly laminated to each other in a molten state of either of or both the resin C and the resin D.

Description

201240817 六、發明說明: 【發明所屬之技術領域】 本發明係_於一種密封袋體所收納之二次電池或電容器 等發電元件之電極的密封膜之製造方法及密封膜。 本申請案基於20 10年11月11日於日本提出申請之日本專 利特願2010-252940號而主張優先權,並將其内容援用至 本文中。 【先前技術】 近年來,業界正逐步採用例如包含膜之袋體所收納之二 次電池或電容器等作為筆記型電腦或行動電話等電子機器 之電源或混合動力汽車、燃料電池汽車或電池汽車之電池 等。 先前’該等二:欠電池或電纟器係將扁I之發電元件密封 於包含將聚稀烴之密封層積層於Μ等金屬上而成之層 壓膜的平袋或拉伸成形之㈣巾而構成^於袋體之膜基材 係使使用於充放電之電極一端突出至外部並進行密 封。於密封時,係由袋體之膜基材夾持帶狀之電極並進行 熱密封(電極引板)。 厂該等二次電池等(以下,有稱為「電池組」之情形)電極 ur之雄封層’因此於密封時,難以使樹脂無間隙地 i產Μ極之!度方向之周圍,而於電極之厚度方向之周 高溫或夕右於電極之周圍產生⑽’則於長期使用、 :二ΐ::::環境等下,有密封部劣化,或密封部之 '、 者強度下降,導致電解液自密封部茂漏之 160004.doc 201240817 可能性。 針對該等問題’近年來使用利用密封膜夾持電極之表背 ,並與袋體之膜基材進行熱密封之方法^但是,若為了提 同心體與電極之密著性’而嚴格設定密封時之加熱或加麼 條件則有袋體之金屬箔與電極之間之樹脂變薄,或密 封膜變形,而引起短路之可能性。 又,於袋體之膜基材與電極之間夾持密封膜並進行熱密 于夺例如專利文獻2所揭示般,使密封膜自袋體之開口 端露出數毫米並進行熱密封。藉由上述方式露出密封膜, 可確實地防止短路。但是,於熱密封時,由於密封棒接觸 或接近該露出冑’故而有因高溫之密封棒之接觸或輻射熱 而使密封膜熔化或變形之情形。藉此,電極變得容易與袋 體之膜基材之金屬箔接觸。 為了解決該等問題,例如專利文獻丨甲揭示有利用被覆 材料被覆端子材料之熱密封部,而防止短路之構成,上述 被覆材料係具有利用熱接著性膜夾住包含織布、不織布、 或超高分子量聚乙烯之耐熱層而成之積層構造者。 又,專利文獻2令揭示有將經電子束交聯之聚烯烴層與 酸改性聚烯烴層積層而成之接著性膜。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開昭62-61268號公報 [專利文獻2]日本專利特開2001 -297748號公细 【發明内容】 160004.doc 201240817 t發明所欲解決之問題] 由於專利文獻1所揭示被霜 而翁料Μ 被㈣㈣利用織布或不織冲 ” ’故而作為織布或不織布 ^但是,由於織布或不織布不炫融,故而難以高密= 地將該等與熱接著性膜積層。因此,有容易形成針孔^ 封性不提高之可能性。右宓 有饴封性反而下降之情況。又,由 於超高分子量聚乙烯難以獲得,於成本方面不利。又,超 高分子量聚乙稀無法與包含聚丙㈣之樹脂之熱接著性膜 積層。因此,益法於你Μ …於叙體之密封層中採用聚丙烯系之樹 月曰,而難以提高袋體之耐熱性。 專利文獻2所揭不之接著性膜之耐熱性優異。但是,該 膜之製造方法係預先使聚烯烴膜電子束交聯並將酸改性聚 稀烴層擠出層^ ’或藉由共擠出而積層聚稀烴層與酸改性 聚稀烴層後進行電子束交聯。因&,採用任-方法均需要 電子束交聯之步驟。專利文獻2之段落GQi3中揭示有如下 情況:由於通常之聚丙烯藉由電子束照射而分解,故而需 要使用特定之樹脂。又,於藉由共擠出而積層聚烯煙層與 鷇改性聚烯烴層後進行電子束交聯之情形時,酸改性聚烯 烴亦發生交聯而使柔軟性下降’因此變得難以使樹脂無間 隙地迴繞於電極之厚度方向之周圍。 鑒於上述背景而完成之本發明係提供一種使用容易獲得 之材料,容易地使樹脂無間隙地迴繞於電極之厚度方向之 周圍,且可藉由簡單之步驟而以較高接著強度直接積層耐 熱層與電極接著層的耐熱性與密封性優異之密封膜之製造 160004.doc -6 · 201240817 方法及精由該製造方法所製造之密封膜β [解決問題之技術手段] 本發明之發明者於對耐熱性與密封性優異之密封膜之研 究中獲得如下知識見解:接枝聚合有羧酸之酸改性聚烯烴 樹脂之羧基容易與羥基、胺基、環氧基等反應,而可容易 地獲得改性。本發明係基於該知識見解而完成者。 即’根據本發明之第1態樣,可提供以下之密封膜之製 造方法9 (1)一種密封膜之製造方法’其係夾入袋體所收納之發電元 件之電極與袋體之邊緣之間的密封膜之製造方法,其具有 如下步驟: 熔融混練步驟,其係藉由將接枝聚合有羧酸之酸改性聚 烯烴樹脂Α與具有可與樹脂Α之羧基反應之官能基的樹脂β 兩者進行熔融混練,使樹脂Α之羧基與樹脂Β之官能基進 行化學鍵結而改性為樹脂C ; 耐熱層製膜步驟,其係將樹脂c成形為層狀而形成耐熱 層; ‘、’、 接著層製膜步驟,其係將羧酸改性聚烯烴樹脂D成形為 層狀而形成接著於電極之電極接著層; 積層步驟,其係於樹脂C與樹脂D中之任一者或兩者為 熔融狀態時直接積層上述耐熱層與上述電極接著層。 ⑺如(1)之密封膜之製造方法’其中上述熔融混練步驟係 於擠出機内進行。 ’ ⑺如⑴或⑺之密封膜之製造方法,其中上μ融混練步 160004.doc 201240817 驟與上述耐熱層製膜步驟係連續進行。 (4) 如(1)至(3)中任一項之密封膜之製造方法,其中上述積 層步驟係與上述耐熱層製膜步驟與上述接著層製膜步驟中 之任一者或兩者連續進行。 (5) 如⑴至(4)令任一項之密封膜之製造方法,纟中上述積 層步驟係於共擠出模内進行。 ⑷如⑴至(5)中任一項之密封膜之製造方法,#中上述熔 融混練步驟係以相對於樹脂A為99〜9〇而樹脂B成為1〜之 重量百分比進行調配而進行。 ⑺如(1)至(6)中任一項之密封膜之製造方法,纟中使用具 有與樹脂A之熔點相同或低於其之熔點之樹脂作為樹脂 D ° 又,根據本發明之第2態樣,可提供以下之密封膜。 (8)種社、封膜,其係夾入袋體所收納之發電元件之電極與 袋體之邊緣之間者’並且具有將包含樹脂C之耐熱層直接 積層於包含羧酸改性聚烯烴樹脂D之電極接著層上而成之 積層構造,該樹脂C係藉由將接枝聚合有羧酸之酸改性聚 稀煙樹脂讀具有可與樹脂A之緩基反應之官能基之樹㈣ 兩者進行熔融I練,使樹脂A之叛基與樹脂B之官能基化 學鍵結進行改性而成者。 ⑼如(8)之密封膜’纟中樹脂B係選自具有rn基、胺基或環 氧基之樹脂中之一種或兩種以上。 (10)如(8)或(9)之密封膜,其中樹脂A係使順丁烯二酸酐接 枝聚合於聚丙烯上而成之酸改性聚烯烴樹脂。 160004.doc 201240817 (11) 如(8)至(10)中任一項之密封膜,其中上述積層構造係 藉由樹脂C與樹脂D之共擠出而形成》 (12) 如(8)至(11)中任一項之密封膜,其係於上述耐熱層上 積層有與袋體之最内層熱熔接之密封層者。 [發明之效果][Brief Description of the Invention] [Technical Field] The present invention relates to a method for producing a sealing film for an electrode of a power generating element such as a secondary battery or a capacitor housed in a sealed bag body, and a sealing film. The present application claims priority based on Japanese Patent Application No. 2010-252940, filed on Jan. [Prior Art] In recent years, the industry is gradually adopting a secondary battery or a capacitor housed in a bag containing a film as a power source for an electronic device such as a notebook computer or a mobile phone, or a hybrid car, a fuel cell car, or a battery car. Battery, etc. Previously, the second class: the under-battery or the electric-powered device is used to seal the power-generating element of the flat I to a flat bag or stretch-formed film comprising a laminate film in which a sealing layer of a polythene hydrocarbon is laminated on a metal such as tantalum. The film base material of the bag body is such that one end of the electrode for charging and discharging protrudes to the outside and is sealed. At the time of sealing, the strip-shaped electrode is held by the film substrate of the bag body and heat-sealed (electrode guide plate). In the case of such a secondary battery or the like (hereinafter, there is a case called "battery pack"), the male seal layer of the electrode ur is therefore difficult to make the resin produce a bungee without a gap in the direction of the seal. When the thickness of the electrode is high in the circumferential direction or the periphery of the electrode is generated (10)', the sealing portion is deteriorated during the long-term use, or the environment of the sealing portion, or the strength of the sealing portion is lowered, resulting in electrolysis. The liquid leaks from the seal part 160004.doc 201240817 possibility. In response to these problems, in recent years, a method of holding the front and back of the electrode with a sealing film and heat-sealing the film substrate of the bag body has been used. However, the sealing is strictly set in order to improve the adhesion between the concentric body and the electrode. In the case of heating or addition, the resin between the metal foil of the bag body and the electrode is thinned, or the sealing film is deformed, which may cause a short circuit. Further, the sealing film is sandwiched between the film substrate of the bag and the electrode, and heat-sealed, as disclosed in Patent Document 2, and the sealing film is exposed from the opening end of the bag by several millimeters and heat-sealed. By exposing the sealing film in the above manner, the short circuit can be surely prevented. However, in the case of heat sealing, the sealing film is melted or deformed due to contact or radiant heat of the high temperature due to contact or proximity of the sealing bar. Thereby, the electrode becomes easy to come into contact with the metal foil of the film substrate of the bag. In order to solve such problems, for example, the patent document discloses that a heat-sealed portion of a terminal material is coated with a covering material to prevent short-circuiting, and the covering material has a woven fabric, a non-woven fabric, or a super-adhesive film. A laminated structure made of a heat-resistant layer of high molecular weight polyethylene. Further, Patent Document 2 discloses an adhesive film in which an electron beam crosslinked polyolefin layer and an acid-modified polyolefin are laminated. [Prior Art] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. SHO-62-61268 [Patent Document 2] Japanese Patent Laid-Open No. 2001-297748 (Summary of the Invention) 160004.doc 201240817 t Invention The problem to be solved] The patent document 1 discloses that it is frosted and the material is used. (4) (4) Using woven fabric or non-woven fabric, it is used as a woven fabric or a non-woven fabric. However, since the woven fabric or the non-woven fabric is not glazed, it is difficult to be dense. = The layer is laminated with the thermal adhesive film. Therefore, there is a possibility that the pinhole sealing property is not easily improved. The right crucible has a decrease in the sealing property. Further, since the ultrahigh molecular weight polyethylene is difficult to obtain, In terms of cost, the ultra-high molecular weight polyethylene cannot be laminated with the thermal adhesive film of the resin containing polypropylene (IV). Therefore, it is advantageous to use the polypropylene tree in the sealing layer of the body. It is difficult to improve the heat resistance of the bag. The adhesive film disclosed in Patent Document 2 is excellent in heat resistance. However, the film is produced by cross-linking a polyolefin film with an electron beam and acid-modified poly (hydrocarbon). Layer extrusion layer ^ 'Or by electron-crosslinking after laminating a polythene hydrocarbon layer and an acid-modified polythene hydrocarbon layer by co-extrusion. The steps of electron beam cross-linking are required for any method using &. Paragraph of Patent Document 2 GQi3 discloses that since a usual polypropylene is decomposed by electron beam irradiation, it is necessary to use a specific resin. Further, after the polyene layer and the yttrium-modified polyolefin layer are laminated by co-extrusion, In the case of electron beam crosslinking, the acid-modified polyolefin is also crosslinked to lower the flexibility. Therefore, it becomes difficult to rewind the resin around the thickness direction of the electrode without a gap. The present invention completed in view of the above background is Providing a material which is easily obtained, which can easily wrap the resin around the thickness direction of the electrode without a gap, and can directly laminate the heat resistance and sealing of the heat-resistant layer and the electrode-attached layer with a high bonding strength by a simple procedure. Manufacture of a sealing film having excellent properties 160004.doc -6 · 201240817 Method and sealing film manufactured by the manufacturing method β [Technical means for solving the problem] The inventors of the present invention are resistant to heat In the study of the sealing film excellent in the property and the sealing property, the following knowledge is obtained: the carboxyl group of the acid-modified polyolefin resin having a carboxylic acid is easily reacted with a hydroxyl group, an amine group, an epoxy group or the like, and can be easily obtained. The present invention has been completed based on this knowledge. That is, according to the first aspect of the present invention, the following method for producing a sealing film can be provided. (1) A method for producing a sealing film, which is sandwiched into a bag body. A method for producing a sealing film between an electrode of a power generating element housed and an edge of a bag body, comprising the steps of: a melt-kneading step by graft-polymerizing a carboxylic acid-modified polyolefin resin with The resin β having a functional group reactive with the carboxyl group of the resin oxime is melt-kneaded, and the carboxyl group of the resin ruthenium is chemically bonded to the functional group of the resin oxime to be modified into the resin C. The heat-resistant layer film-forming step is The resin c is formed into a layer to form a heat-resistant layer; ',', and a subsequent film forming step of forming the carboxylic acid-modified polyolefin resin D into a layer to form an electrode subsequent layer which is followed by an electrode; Based on either resin C and the resin D in the one or both of the heat laminated directly to the electrode layer and the adhesion layer when a molten state. (7) The method for producing a sealing film according to (1) wherein the melt-kneading step is carried out in an extruder. (7) The method for producing a sealing film according to (1) or (7), wherein the step of the above-mentioned heat-resistant layer is continuously carried out in the step of the above-mentioned heat-resistant layer forming step 160004.doc 201240817. (4) The method for producing a sealing film according to any one of (1) to (3) wherein the laminating step is continuous with either or both of the heat-resistant layer forming step and the subsequent layer forming step get on. (5) The method for producing a sealing film according to any one of (1) to (4), wherein the laminating step is carried out in a co-extrusion mold. (4) The method for producing a sealing film according to any one of (1) to (5), wherein the melting and kneading step is carried out by mixing the resin A to 99 to 9 Torr and the resin B to a weight percentage of 1 to 1. (7) The method for producing a sealing film according to any one of (1) to (6), wherein a resin having a melting point equal to or lower than a melting point of the resin A is used as the resin D°, and according to the second aspect of the present invention In the same way, the following sealing film is available. (8) a vegetable or a sealing film which is sandwiched between the electrode of the power generating element housed in the bag body and the edge of the bag body' and has a heat-resistant layer containing the resin C directly laminated to the carboxylic acid-modified polyolefin a layered structure formed by the electrode of the resin D on a layer which is read by a resin which is graft-polymerized with a carboxylic acid and which is modified to have a functional group capable of reacting with the slow group of the resin A (4) The two are melted and practiced to modify the chemical bond between the resin group of the resin A and the resin of the resin B. (9) The sealing film of (8), wherein the resin B is one or more selected from the group consisting of resins having a rn group, an amine group or an epoxy group. (10) A sealing film according to (8) or (9), wherein the resin A is an acid-modified polyolefin resin obtained by graft-polymerizing maleic anhydride onto polypropylene. The sealing film according to any one of (8) to (10), wherein the above-mentioned laminated structure is formed by co-extrusion of the resin C and the resin D (12) as in (8) to The sealing film according to any one of (11), wherein the heat-resistant layer is provided with a sealing layer which is thermally welded to the innermost layer of the bag body. [Effects of the Invention]

本發明之密封膜之製造方法係使樹脂A之羧基與樹脂B 之官能基化學鍵結而改性為樹脂c,因此不需要電子束交 聯等交聯步驟。因此,可藉由簡單之步驟而賦予耐熱層耐 熱性。 由於僅將樹脂A與樹脂B之兩者熔融混練,故而可於製 膜步驟所使用之通常擠出機内改性為樹脂c。 於本發明中,於樹脂C與樹脂D中之任一者或兩者為熔 融狀態時,直接積層耐熱層與電極接著層。積層方法係組 合擠出機與製膜模頭而形成一個層後,擠出層壓另一層。 另一積層方法係將耐熱層與電極接著層共擠出。藉由該等 方法於本發明中’可藉由簡單之步驟而以較高接著強度 直接積層耐熱層與電極接著層。藉由該等方法之密封膜^ 熱被封時,難以產生因高溫之密封棒之接觸或輻射熱而引 起之密封膜熔化’或變形。藉此,難以引起電極與袋體之 金屬箔之短路。 、 尤其是耐熱層與電極接著層之共擠出可藉由更為簡單之 步驟,而以更高接著強度直接積層耐熱層與電極接著層。 本發明之密封膜之耐熱層具有使樹脂八之緩基與樹脂B 之官能基化學鍵結進行改性而成之炼融流動性較小之樹脂 160004.doc 201240817 c。藉此,於熱密封時,耐熱層難以變薄,或密封膜難以 熱變形。因此’難以引起電極與袋體之金屬箔之短路。 若樹脂B為選自具有經基、胺基或環氧基之樹脂中之一 種或兩種以上’則樹脂A之羧基與樹脂6之官能基容易化 =鍵結,而順利地改性為樹脂。。由於藉由將樹脂A與樹 脂:熔融混練而改性為樹脂C ’故而樹脂A之羧基與樹脂B 之官能基容易均勻地化學鍵結。 若樹脂A為使順丁烯二酸酐接枝聚合於聚丙烯上而成之 西文改性聚烯烴樹脂,則樹脂A之羧基與樹脂B之官能基容 易化學鍵結,變得更順利地改性為樹脂C。 右密封膜之積層構造係藉由樹脂c與樹脂D之共擠出而 形成,則積層構造之接著強度較高,於熱密封時密封膜不 會熱變形,或難以引起電極與袋體之金屬箔之短路。 右將與袋體之最内層熱熔接之密封層積層於耐熱層上, 則可提尚袋體之最内層與密封膜之熱熔接強度。又,若將 拉封層直接積層於耐熱層上,則可防止由電解液引起之接 著界面之剝離。 【實施方式】 以下’基於實施形態對本發明進行詳細說明。 圖1係表示本發明之密封膜丨之概略構成之剖面圖。 圖2係表示將圖1所示之密封膜1插入袋體之層壓膜2〇與 電極11之間並熔接之狀態,且沿電極丨丨之長度方向之剖面 圖。 圖3A係表示將圖1所示之密封膜丨接著於電極丨丨上而成之 160004.doc 201240817 附有密封膜之電極1G之立體圖。圓3B係表示时相同密封 膜之電極10之與電極11之長度方向正交之方向上之剖面 圖。 本發明之密封膜丨係夾入袋體所收納之發電元件之電極 與袋體之邊緣之間。該膜之基本層構成如圖1及圖2所示, 具有由電極接著層2與耐熱層3積層而成之包含至少2層之 積層構造。本形態例之密封膜丨係於基本層構成之耐熱層3 上進而直接積層與袋體之最内層之密封層22熱熔接之密封 層4。 本發明之密封膜1之厚度較佳為50 μιη〜300 μιη。若密封 膜1之厚度小於該範圍,則有絕緣性降低之情況。再者, 密封膜1之厚度亦可大於該範圍。但是,無法期待絕緣性 之進一步提高,而且反而變得難以進行熱密封。 耐熱層3包含樹脂c,該樹脂c係藉由將接枝聚合有羧酸 之酸改性聚烯烴樹脂A與具有可與樹脂八之羧基反應之官 能基之樹脂B兩者進行熔融混練,使樹脂A之羧基與樹脂B 之官能基進行化學鍵結而改性者。 此時之樹脂之調配比例較佳為相對於99〜90重量。/。之樹 月曰A,樹脂B為1〜1〇重量%。若樹脂B之調配比例低於該範 圍,則有樹脂C之改性效果較小,而變得缺乏密封膜丨之耐 熱性之情況。若樹脂B之調配比例高於該範圍,則耐熱層3 办易變脆。因此,於裝有電池組時,有因電極11之彎折而 於耐熱層3上產生裂痕之情況。 耐熱層3確保袋體之層壓膜20之金屬箔21與電極11之絕 160004.doc -11 - 201240817 ' 耐熱層3防止於熱熔接時密封膜1之熱變形,只要可 確保絕緣性’ ’則較佳為較薄。耐熱層3之厚度較佳為% ㈣〜150㈣。若耐熱層3之厚度未達50 μιη,則有時密封膜 會發生熱變形’或於熱熔接時變薄,而變得缺乏絕緣 性:再者’耐熱層3之厚度亦可超過15〇叫。但是無法 /寺、’邑緣〖生之進一步提尚。構成耐熱層3之樹脂與樹脂Α相 比樹月曰B僅化學鍵結於樹脂八上之部分與樹脂a相比高分 子化,相對較硬而熔融流動性較低。因此,若耐熱層3變 厚為必需以上,則於將電極丨丨夾入兩片密封膜丨、丨之間 時由電極11之厚度之階差所產生之間隙於熱熔接時難以 填滿。藉此,有時於密封膜1、1之間產生針孔。 酸改性聚烯烴樹脂A係藉由將使伸烷基單體' 例如乙 烯丙烯等之1種或2種以上聚合而成之聚烯烴作為基礎樹 月曰,接枝聚合不飽和羧酸或其衍生物而獲得。 作為聚烯烴’例如使用聚丙烯或聚乙烯之均聚物及共聚 物。作為共聚物,使用丙烯與1〜5重量%之乙烯之無規共 聚物(無規PP)或嵌段共聚物(嵌段pp)、乙烯與卜⑺重量0/〇 之丙烯之無規或嵌段共聚物、丙烯或乙烯與卜1〇重量%之 碳數為4以上之α-烯烴之共聚物、及該等之混合物等。 為了將袋體之層壓膜20之密封層22設為聚乙烯系樹脂, 而於密封膜1之耐熱層3中使用聚乙烯系樹脂作為樹脂a之 基礎樹脂之情形時,較佳為使用溶點為13〇〜14〇°C左右之 直鏈狀低密度聚乙烯或高密度聚乙烯。 酸改性聚烯烴樹脂A之基礎樹脂較佳為使用熔融流動速 160004.docIn the method for producing a sealing film of the present invention, the carboxyl group of the resin A is chemically bonded to the functional group of the resin B to be modified into the resin c. Therefore, a crosslinking step such as electron beam crosslinking is not required. Therefore, the heat resistance of the heat-resistant layer can be imparted by a simple procedure. Since only the resin A and the resin B are melted and kneaded, they can be modified into the resin c in a usual extruder used in the film forming step. In the present invention, when either or both of the resin C and the resin D are in a molten state, the heat-resistant layer and the electrode-attached layer are directly laminated. The lamination method combines an extruder and a film forming die to form a layer, and then extrusion lamination of another layer. Another method of lamination is to coextrude the heat resistant layer with the electrode back layer. By the methods in the present invention, the heat-resistant layer and the electrode-attached layer can be directly laminated with a higher bonding strength by a simple step. When the sealing film of these methods is sealed, it is difficult to cause the sealing film to melt or deform due to the contact of the high temperature sealing rod or the radiant heat. Thereby, it is difficult to cause a short circuit between the electrode and the metal foil of the bag body. In particular, the co-extrusion of the heat-resistant layer and the electrode-attached layer can directly laminate the heat-resistant layer and the electrode-attached layer with a higher bonding strength by a simpler process. The heat-resistant layer of the sealing film of the present invention has a resin having a small smelting fluidity which is obtained by chemically bonding a resin group of a resin and a functional group of the resin B. 160004.doc 201240817 c. Thereby, the heat-resistant layer is hard to be thinned at the time of heat sealing, or the sealing film is hard to be thermally deformed. Therefore, it is difficult to cause a short circuit between the electrode and the metal foil of the bag body. If the resin B is one or more selected from the group consisting of a resin having a trans group, an amine group or an epoxy group, the carboxyl group of the resin A and the functional group of the resin 6 are easily converted to a bond, and are smoothly modified into a resin. . . Since the resin A and the resin are melt-kneaded to be modified into the resin C', the carboxyl group of the resin A and the functional group of the resin B are easily and chemically bonded uniformly. If the resin A is a Western modified polyolefin resin obtained by graft-polymerizing maleic anhydride onto polypropylene, the carboxyl group of the resin A and the functional group of the resin B are easily chemically bonded, and the modification is more smoothly performed. For resin C. The laminated structure of the right sealing film is formed by co-extrusion of the resin c and the resin D, and the subsequent strength of the laminated structure is high, the sealing film is not thermally deformed during heat sealing, or the metal of the electrode and the bag body is hard to be caused. Short circuit of the foil. The sealing layer which is thermally welded to the innermost layer of the bag body is laminated on the heat-resistant layer on the right side, thereby improving the heat fusion strength of the innermost layer of the bag body and the sealing film. Further, when the zipper layer is directly laminated on the heat-resistant layer, peeling of the interface due to the electrolytic solution can be prevented. [Embodiment] Hereinafter, the present invention will be described in detail based on embodiments. Fig. 1 is a cross-sectional view showing a schematic configuration of a sealing film crucible of the present invention. Fig. 2 is a cross-sectional view showing the state in which the sealing film 1 shown in Fig. 1 is inserted between the laminated film 2'' of the bag body and the electrode 11 and welded, and along the longitudinal direction of the electrode. Fig. 3A is a perspective view showing the electrode 1G with a sealing film attached to the sealing film shown in Fig. 1 which is attached to the electrode crucible 160004.doc 201240817. The circle 3B is a cross-sectional view in the direction in which the electrode 10 of the same sealing film is orthogonal to the longitudinal direction of the electrode 11. The sealing film of the present invention is sandwiched between the electrode of the power generating element housed in the bag body and the edge of the bag body. As shown in Fig. 1 and Fig. 2, the basic layer structure of the film has a laminated structure including at least two layers formed by laminating the electrode underlayer 2 and the heat-resistant layer 3. The sealing film of the present embodiment is attached to the heat-resistant layer 3 of the base layer, and the sealing layer 4 which is thermally welded to the innermost layer of the sealing layer 22 of the bag body is directly laminated. The thickness of the sealing film 1 of the present invention is preferably from 50 μm to 300 μm. If the thickness of the sealing film 1 is less than this range, the insulation property may be lowered. Furthermore, the thickness of the sealing film 1 may also be larger than this range. However, the insulation property cannot be expected to be further improved, and on the contrary, it becomes difficult to perform heat sealing. The heat-resistant layer 3 contains a resin c which is melt-kneaded by both an acid-modified polyolefin resin A graft-polymerized with a carboxylic acid and a resin B having a functional group reactive with a carboxyl group of the resin. The carboxyl group of the resin A is chemically bonded to the functional group of the resin B to be modified. The blending ratio of the resin at this time is preferably from 99 to 90% by weight. /. The tree Moon A, the resin B is 1 to 1% by weight. If the blending ratio of the resin B is lower than this range, the modification effect of the resin C is small, and the heat resistance of the sealing film is lacking. If the blending ratio of the resin B is higher than the range, the heat-resistant layer 3 is easily brittle. Therefore, when the battery pack is mounted, cracks may occur in the heat-resistant layer 3 due to the bending of the electrode 11. The heat-resistant layer 3 ensures the metal foil 21 of the laminated film 20 of the bag body and the electrode 11 160004.doc -11 - 201240817 ' The heat-resistant layer 3 prevents thermal deformation of the sealing film 1 during heat fusion, as long as insulation is ensured ' ' It is preferably thinner. The thickness of the heat-resistant layer 3 is preferably from % (four) to 150 (four). If the thickness of the heat-resistant layer 3 is less than 50 μm, the sealing film may be thermally deformed or thinned during heat welding, and the insulation may be lacking: in addition, the thickness of the heat-resistant layer 3 may exceed 15 〇 . However, it is impossible to make a further mention of the temple. The resin constituting the heat-resistant layer 3 is higher in molecular weight than the resin a than the resin a, and is relatively hard and has low melt fluidity. Therefore, if the heat-resistant layer 3 is thicker than necessary, the gap caused by the step of the thickness of the electrode 11 when the electrode 丨丨 is sandwiched between the two sealing films 丨 and 丨 is difficult to fill at the time of heat fusion. Thereby, pinholes may be formed between the sealing films 1 and 1. The acid-modified polyolefin resin A is obtained by polymerizing one or two or more kinds of alkylene monomers such as ethylene propylene, etc., as a base tree, graft-polymerized unsaturated carboxylic acid or Obtained from the derivative. As the polyolefin, for example, a homopolymer and a copolymer of polypropylene or polyethylene are used. As the copolymer, a random or embedded propylene of propylene and 1 to 5% by weight of a random copolymer of ethylene (random PP) or a block copolymer (block pp), ethylene and (7) weight of 0/〇 of propylene is used. A copolymer of a segment copolymer, propylene or ethylene, and an α-olefin having a carbon number of 4 or more by weight, and a mixture thereof. In order to use the sealing layer 22 of the laminated film 20 of the bag body as a polyethylene resin and the polyethylene resin as the base resin of the resin a in the heat-resistant layer 3 of the sealing film 1, it is preferred to use a solvent. The point is a linear low-density polyethylene or high-density polyethylene of about 13 〇 14 〇 ° C. The base resin of the acid-modified polyolefin resin A preferably uses a melt flow rate 160004.doc

S 201240817 率(MFR)為0.5〜30 g/10 min,尤其是5〜15 g/l〇 min之均聚 丙烯及丙烯-乙烯無規共聚物或’ MFR為0.3〜30 g/10 min之 聚乙稀及乙稀-α稀烴共聚物。 形成耐熱層3之樹脂C之MFR較佳為〇.5 g/1〇 min〜3 g/1〇 nun之範圍。若MFR小於該範圍,則有難以成形之情況。 若MFR大於該範圍,則有於熱熔接時,耐熱層3會變形, 或變薄,而導致絕緣性下降之情況。 對於耐熱層3,謀求於將本發明之密封膜丨熱熔接於電極 11上時難以熔融或軟化。因此,形成其之樹脂(:之熔點越 高越好。具體而言,於包含聚丙烯系樹脂之密封膜之情形 時,較佳為藉由JIS K6921_2 DSC法所測得之熔點為 130〜170eC之樹脂。 為了獲得此種樹脂C,較佳使用以聚丙烯(pp)之均聚 物、乙稀與丙烯之無規共聚物或嵌段共聚物或該等之聚合 物合金作為基礎樹脂的酸改性聚烯烴樹脂作為樹脂A。p p ㈣脂通常於低溫環境下容易變脆。由於乙烯與丙稀之嵌 段共聚物即便熔點較高錄性亦優異,且於低溫環境下亦 不變脆(耐寒性),故而較佳。 作為接枝聚合於酸改性聚稀烴樹脂A之基礎樹脂上之不 飽和㈣,例如可列舉:丙㈣、甲基丙賴、順丁稀二 酸、反丁烯二酸、衣康酸、檸康酸、該等之酸酐、及該等 之醋、醯胺、酿亞胺、金屬鹽等衍生物。料不飽和缓酸 中,較佳為順丁稀二酸,最佳為順丁稀二酸野。又,為了 促進聚烯烴與該等不飽和㈣之反應,例如較佳為使用過 I60004.doc 201240817 氧化苯甲醯、過氧化月桂醯耸古 π往離寺有機過氧化物或偶氮二異丁 腈等自由基聚合起始劑。 作為接枝聚合之不飽和錄酸夕县 π规蛟之量,通常相對於單體之總 重量為0.5〜5重量〇/〇。 於聚稀烴上接枝聚合不飽和複酸之方法例如有如下方 法:於炼融狀態下使聚稀烴與不飽和㈣反應之方法;於 漿料狀態下使㈣烴與不飽和_反應之方法;於氣相狀 態下使聚烯烴與不飽和羧酸反應之方法等。該等方法中, 於熔融狀態下反應之方法由於操作容易,故而較佳。具體 而言,利用滾筒、亨舍爾混合機等充分混合上述所示之聚 烯烴 '不飽和羧酸、有機過氧化物等聚合起始劑。其後 熔融混練而進行接枝化反應。 熔融混練之方法並無特別限制,例如可使用螺旋擠出 機、班伯裏混煉機、混煉輥等進行。該等方法巾,螺旋擠 錢由於操作簡便,故而可較佳地使ρ螺旋擠出機可為 單軸、雙轴、或其以上之多轴螺旋m練之溫度較佳 為所使用之聚稀烴之溶點以上且所使用之有機過氧化物之 刀解m·度以下。具體之溫度及時間通常為於“ο〜下 0.3〜30分鐘,較佳為於^(^^(^下丨〜…分鐘。 將於酸改性聚稀烴樹脂A中炼融混練樹脂B而改性之樹 脂c成形為層狀,而形成賦予密封膜耐熱性之耐熱層3。形 成耐熱層3之方法可列舉:將樹脂〇於複數個輥間進行壓延 之壓光法;利用T模或環模將熔融之樹脂(:擠出之擠出法。 該等方法中,擠出法由於可利用改性步驟所使用之擠出機 160004.doc 201240817 而將熔融混練而成之樹脂c直接擠出,故而較佳。 於向樹脂c之改性步驟之前階段,較佳為增加將聚烯烴 與不飽和羧酸類投入擠出機中進行熔融混練,而改性為酸 改性聚烯烴樹脂A之步驟。其後,較佳為進而將樹脂B投 入此擠出機中’將樹脂A改性為樹脂c。 再者,將不飽和羧酸接枝聚合而成之酸改性聚烯烴樹脂 在市面上有售’因此亦可使用市售品。 與不飽和羧酸接枝聚合而成之PP系聚合物包括利用金屬 氫氧化物、氧化物、低級脂肪酸鹽等中和羧基而成之離子 聚合物。 作為樹脂B所具有之可與樹脂八之羧基反應的官能基, 可列舉羥基、胺基、羧基、曱醯基、環氧基等。作為具有 該等官能基之樹脂B,並無特別限制,較佳為容易獲得之 通用樹脂。作為此種通用樹脂,可列舉:乙烯_乙烯醇共 聚物(EVOH ’ ethylene Vinyi alc〇h〇1)、聚乙烯醇(pvA, polyvinyl alc〇h〇l)、尼龍6或尼龍66等聚醯胺(pA, polyamide)、乙烯·曱基丙烯酸縮水甘油醋共聚物 (E-GMA,ethylene-glycidyl methacrylatee 含環氧基樹脂 等。因此,作為可與樹脂A之羧基反應之較佳官能基,可 列舉羥基、胺基、環氧基。 於使用EV0H作為樹脂B之情形時,就與樹脂八之相溶性 或加工性之觀點而言,MFR較佳為 MFR更佳為卜20 g/l〇 min、尤佳為3〜16 g/1〇 —。作為 EVOH中之乙烯含量,乙烯較佳為2〇〜6〇莫耳%,更佳為 160004.doc 15 201240817 25〜50莫耳%。 於使用聚酿胺作為樹脂B之梧形吐 <馆t時’就為了實現穩定化 而封阻末端胺基從而減少末踹脸Λ 不鳊胺基量之聚醯胺而言,較佳 為使用末端胺基量與末端羧基孴相π 坟丞重相问之聚醯胺,或末端羧 基相對於末端胺基之莫耳比Α ? 吁比為2以上且末端胺基量為 8.〇xl 0-5莫耳/g以上之聚酿胺。此錄 妝此種聚醯胺可提高樹脂C之 炫融黏度之资切速率依賴性》聚酿胺之熔點在通用樹脂中 相對較高,因此所獲得之樹脂c之針對熱變形之财性提 高。S 201240817 rate (MFR) is 0.5~30 g/10 min, especially 5~15 g/l〇min homopolypropylene and propylene-ethylene random copolymer or 'MFR 0.3~30 g/10 min Ethylene and ethylene-α dilute hydrocarbon copolymers. The MFR of the resin C forming the heat-resistant layer 3 is preferably in the range of 〇.5 g / 1 〇 min 〜 3 g / 1 〇 nun. If the MFR is smaller than the range, it may be difficult to form. When the MFR is larger than the range, the heat-resistant layer 3 may be deformed or thinned during heat fusion, resulting in a decrease in insulation properties. In the heat-resistant layer 3, it is difficult to melt or soften when the sealing film of the present invention is thermally welded to the electrode 11. Therefore, the resin forming the same (the higher the melting point, the better. Specifically, in the case of a sealing film comprising a polypropylene-based resin, the melting point measured by the JIS K6921_2 DSC method is preferably 130 to 170 eC. In order to obtain such a resin C, it is preferred to use a homopolymer of polypropylene (pp), a random copolymer or block copolymer of ethylene and propylene or a polymer alloy of the above as a base resin. The modified polyolefin resin is used as the resin A. The pp (iv) grease is easily brittle in a low temperature environment. Since the block copolymer of ethylene and propylene is excellent in the high melting point and is not brittle in a low temperature environment ( Cold resistance is preferred. As the unsaturated (four) which is graft-polymerized on the base resin of the acid-modified polyolefin resin A, for example, C (tetra), methyl propyl lysine, cis-butyl diacid, and anti-butyl Adipic acid, itaconic acid, citraconic acid, such acid anhydrides, and derivatives of such vinegar, guanamine, flavonoid, metal salt, etc., in the unsaturated acid, preferably butadiene Acid, the best is cis-succinic acid field. Also, in order to promote polyolefins and these For the reaction of saturating (4), for example, it is preferred to use a free radical polymerization initiator such as oxidized benzamidine, oxidized laurel, guaranium, π, shoji organic peroxide or azobisisobutyronitrile. The amount of the π 蛟 蛟 不 , , , , , , , , , π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π Method: a method for reacting a polyhydrocarbon with an unsaturated (4) in a smelting state; a method for reacting a (tetra) hydrocarbon with an unsaturated _ in a slurry state; reacting a polyolefin with an unsaturated carboxylic acid in a gas phase In the above methods, the method of reacting in a molten state is preferred because it is easy to handle. Specifically, the above-described polyolefin 'unsaturated carboxylic acid is sufficiently mixed by a roll, a Henschel mixer, or the like. A polymerization initiator such as an organic peroxide, followed by melt-kneading to carry out a grafting reaction. The method of melt-kneading is not particularly limited, and for example, a screw extruder, a Banbury mixer, a kneading roller, or the like can be used. The method towel Since the screwing is easy to operate, the ρ screw extruder can preferably be uniaxially, biaxially or more, and the temperature of the multi-axis spiral m is preferably above the melting point of the polythene used. And the organic peroxide used is not less than m·degree of the solution. The specific temperature and time are usually "Oh ~ 0.3~30 minutes, preferably ^ (^^(^下丨~...min. The resin c modified by kneading the kneaded resin B in the acid-modified polysulfide resin A is formed into a layer shape to form a heat-resistant layer 3 which imparts heat resistance to the sealing film. The method of forming the heat-resistant layer 3 is as follows: Calendering method for rolling between a plurality of rolls; melting of the resin by a T-die or a ring mold (extrusion extrusion method. In the methods, the extrusion method is performed by extrusion using the modification step It is preferable to directly extrude the resin c which is melt-kneaded by the machine 160004.doc 201240817. In the stage before the modification step of the resin c, it is preferred to add a step of modifying the polyolefin-modified polyolefin resin A by introducing the polyolefin and the unsaturated carboxylic acid into an extruder for melt-kneading. Thereafter, it is preferred to further inject the resin B into the extruder to modify the resin A into the resin c. Further, an acid-modified polyolefin resin obtained by graft-polymerizing an unsaturated carboxylic acid is commercially available. Therefore, a commercially available product can also be used. The PP-based polymer obtained by graft-polymerizing an unsaturated carboxylic acid includes an ionic polymer obtained by neutralizing a carboxyl group with a metal hydroxide, an oxide or a lower fatty acid salt. Examples of the functional group which the resin B can react with the carboxyl group of the resin include a hydroxyl group, an amine group, a carboxyl group, a mercapto group, an epoxy group and the like. The resin B having such functional groups is not particularly limited, and is preferably a general-purpose resin which is easily available. Examples of such a general-purpose resin include polyamines such as ethylene-vinyl alcohol copolymer (EVOH 'ethylene Vinyi alc〇h〇1), polyvinyl alcohol (pvA, polyvinyl alc〇h〇l), nylon 6 or nylon 66. (pA, polyamide), ethylene-mercaptoacrylic acid glycidyl vinegar copolymer (E-GMA, ethylene-glycidyl methacrylatee containing epoxy resin, etc. Therefore, as a preferred functional group reactive with the carboxyl group of the resin A, Hydroxy group, amine group, epoxy group. When EV0H is used as the resin B, MFR is preferably MFR more preferably 20 g/l〇min from the viewpoint of compatibility with resin or processability. More preferably, it is 3~16 g/1 〇-. As the ethylene content in EVOH, ethylene is preferably 2 〇~6 〇 mol%, more preferably 160004.doc 15 201240817 25~50 mol%. When the amine is used as the resin B, it is preferred to use a terminal amine in order to stabilize the terminal amine group and thereby reduce the amount of the terminal amine. The base amount and the terminal carboxyl group π phase 丞 the tomb of the polyamine, or the terminal carboxyl group relative to the end The molar ratio of the amine group is 2 or more and the amount of the terminal amine group is 8. 〇xl 0-5 mol/g or more of the poly-amine. This kind of polyamide can improve the resin C Rate dependence of the viscosity of the melt viscosity The melting point of the polystyrene is relatively high in the general-purpose resin, so that the obtained resin c has an improved property against thermal deformation.

於使用含環氧基樹脂作為樹脂3之情形時,就與樹脂B 之相溶性或加工性之觀點而言,較佳為將乙烯單體共聚合 而成者。樹脂A之羧基將含環氧基樹脂之環氧基開環,而 將由開環所生成之録S旨化。該S旨化反覆進行。結果樹脂 C之分子構造成為交聯構造,而使針對熱變形之耐性提 高。 電極接著層2係將密封膜丨於電極丨!上加熱加壓進行熱熔 接而成之層。電極接著層2包含與金屬之接著性優異之羧 酸改性聚烯烴樹脂D。 樹脂D係使烷烯單體、例如乙烯、丙烯等之1種或2種以 上與不飽和羧酸或其衍生物之1種或2種以上共聚合而成之 樹脂。作為共聚物’可列舉嵌段共聚物 '接枝共聚物或無 規共聚物。於使用接枝共聚物之情形時,可將與樹脂A相 同之聚烯烴和與樹脂A相同之不飽和羧酸接枝聚合而製成 羧酸改性聚烯烴樹脂D。 160004.doc -16 · 201240817 電極接著層2只要確保與電極11之熱熔接’則較佳為較 薄。通常電極接著層2之厚度為2〇 μπι〜60 μιη。若電極接著 層2之厚度小於該範圍,則有電極接著層2與電極丨丨之接著 強度降低之情況。若電極接著層2之厚度大於該範圍,則 有變得缺乏密封膜1之耐熱性之情況。 形成電極接著層2之樹脂D之熔點較佳為低於形成耐熱層 3之樹脂C之熔點。於包含聚丙烯系樹脂之密封膜1之情形 時,樹脂D之熔點較佳為130〇c〜150〇c。若樹脂d之熔點低 於該範圍’則有變得缺乏密封膜1之耐熱性之情況。若樹 脂D之溶點高於該範圍’則難以增大與形成耐熱層3之樹脂 C之熔點差。若樹脂d與樹脂c之熔點差為1 〇。(:以上,則熱 熔接時之溫度管理變得容易,故而較佳。 樹脂D之熔點較佳為等於或低於樹脂a之炫點。若將樹 月曰A改性為樹脂C,則樹脂B之分子鍵結於樹脂a之分子 上,而使樹脂C之分子量增大,從而使樹脂c之熔點變得 向於樹脂A。藉此,變得容易使樹脂d與樹脂ς;之熔點差成 為10 C以上。若將樹脂D與樹脂A採用相同之樹脂,則樹 脂之管理變得容易。 形成電極接著層2之方法可列舉使用擠出機將熔融之樹 脂D自T模或環模擠出之擠出法。使用接枝共聚物作為樹 脂D之情形時,以與樹脂A相同之方式利用擠出機擠出 時’可使聚烯烴與不飽和羧酸類接枝聚合。 為了製成包含聚乙烯系樹脂之密封膜,於電極接著層2 令採用酸改性聚乙稀之情形時’較佳為熔點為90M2〇<>c左 160004.doc 17 201240817 右之順丁烯二酸酐接枝共聚合聚乙烯。酸改性聚乙烯包含 將羧基中和而成之離子聚合物。 形成電極接著層2之酸改性聚烯烴樹脂D之MFR較佳為3 g/10 min 〜30 g/l〇 min 之範圍。MFR 更佳為 5 g/l〇 min 〜10 g/10 min之範圍。若MFR小於該等範圍,則於熱熔接時, 酸改性聚烯烴難以充分迴繞於電極丨丨之周圍。若MFR大於 該等範圍,則電極接著層2變薄,而使接著強度不足。 本發明中’ MFR係依據JIS K7210,於聚丙烯系樹脂之 情形時均於230°C下進行測定,於聚乙烯系樹脂之情形時 均於190°C下進行測定。 再者,羧酸改性聚烯烴樹脂在市面上有售,因此亦可使 用市售品。 電極接著層2與耐熱層3係直接積層,並非於層間經由接 著劑層或增黏劑層進行積層。藉此,可防止由電解液向積 層界面之侵入所引起之剝離及密封膜丨之柔軟性之下降。 於密封膜1中,不僅電極接著層2,耐熱層3之向電極“周 圍之迴繞亦重要。只要不影響柔軟性或與電解液之相互作 用,亦可使用接著劑進行乾式層壓。又,於進行擠出層壓 之情形時’亦可使用增黏劑。 作為直接積層之方法,可列舉:將所成形之電極接著層 2與耐熱層3重4並進行加㈣接之熱層壓;㈣成形電二 接著層2與耐熱層3中之任一者,一面自丁模將另一者以炫 融狀態擠出’-面進行積層之擠出層星法;於電極 2與耐熱層3兩者為嫁融狀態時,一面自共擠出模擠出,二 160004.doc -18· 201240817 7進行積層之共擠出層壓法1等方法中,共擠出層壓法 糸藉由將一面進行炫融混練而改性為樹脂c一面擠出樹脂 之擠出機、與擠出樹脂D之另一擠出機連接於共擠出模 上’而於共擠出模内進行直接積層。藉此,可使向樹脂c 之改性耐熱層3之形成、電極接著層2之形成、電極接著 層2與耐熱層3之積層於—個步驟中進行,故而較佳。 於本形態例中,將密封層4積層於耐熱層3之與電極接著 層相反面上。被封層4係與袋體之層壓膜2〇之密封層進 行加熱加壓而熔接之層。 作為積層方法,基於與電極接著層2與耐熱層3之積層相 同之原因而採用相同之方法。該等方法中,可將電極接著 層2與耐熱層3與密封層4 一次性積層,因此較佳為利用共 擠出層壓法進行積層。 密封層4只要確保與袋體之密封層22之熔接,則較佳為 較薄。通常密封層4之厚度為20 μηι〜4〇 μιηβ若密封層4之 厚度小於該等範圍,則密封層4與袋體之密封層22之熔接 強度降低。若密封層4之厚度大於該範圍,則變得缺乏密 封膜1之财熱性。 就容易與袋體之層壓膜20之密封層22熔接之情況而言, 形成密封層4之樹脂(以下,稱為樹脂Ε)較佳為與構成密封 層22之樹脂同種或相同之樹脂。通常就耐熱性優異方面而 言,密封膜1係由ΡΡ系樹脂所構成。 於雄、封膜1由ΡΡ系樹脂所構成之情形時,樹脂Ε可列舉·· ΡΡ之均聚物、乙烯與丙烯之無規共聚物或嵌段共聚物或該 160004.doc -19· 201240817 等之混合物、或該等之聚合物合金等。該等之中,就柔軟 性優異方面而言,較佳為乙烯與丙烯之無規共聚物。 於包含pp系樹脂之密封膜之情形時,形成密封層4之樹 脂£之熔點較佳為130它〜170。(:〇若樹脂]^之熔點低於該範 圍,則有變得缺乏密封膜丨之耐熱性之情況。若形成密封 層4之樹脂E之熔點高於該範圍,則難以增大與形成耐熱層 3之樹脂C之熔點差。若樹脂E之熔點與樹脂c之熔點之差 為10 C以上,則向袋體熔接層壓膜2〇時之溫度管理變得容 易,故而較佳。 於將密封膜1製成聚乙稀系樹脂而於密封層4中採用聚乙 烯系樹脂之情形時,較佳為使用熔點為1〇〇〜12〇ec左右之 低密度聚乙烯或直鍵狀低密度聚乙稀。 於包含PP系樹脂之密封膜之情形時,形成密封層4之樹 脂E之MFR較佳為3 g/10 min〜3〇 g/1〇 min之範圍,更佳 g/l〇 min〜10 g/10 min之範圍。若樹脂E2Mfr小於該等範 圍,則難以利用擠出層壓或共擠出層壓 以驗大於該等範圍,則難以利用共擠出環模進= 形。 再者,密封層4為任意之層,於確保耐熱層3與袋體之密 封層22之熔接之情形時,亦可不設置密封層4。 將本發明之密封膜i炫接於袋體之密封層22與電極叹 間。熔接密封膜!時,如圖2所示,使特定寬度之密封膜】 自層壓膜20之端部露出並進行熔接。此時,為了使密封膜 【之定位變得容易,較佳為預先著色2片密封膜丨中之至少^ 160004.docWhen an epoxy group-containing resin is used as the resin 3, it is preferred to copolymerize the ethylene monomer from the viewpoint of compatibility with the resin B or workability. The carboxyl group of the resin A is opened by ring-opening of the epoxy group-containing resin, and the ring formed by the ring opening is obtained. This S is carried out in succession. As a result, the molecular structure of the resin C became a crosslinked structure, and the resistance against thermal deformation was improved. The electrode is then layer 2 to seal the sealing film to the electrode 丨! A layer obtained by heat-pressing and heat-melting. The electrode adhesive layer 2 contains a carboxylic acid-modified polyolefin resin D excellent in adhesion to a metal. Resin D is a resin obtained by copolymerizing one or more kinds of an alkene monomer, for example, ethylene or propylene, with one or more of an unsaturated carboxylic acid or a derivative thereof. The copolymer ' can be exemplified by a block copolymer 'graft copolymer or a random copolymer. In the case of using a graft copolymer, a polyolefin similar to the resin A and an unsaturated carboxylic acid similar to the resin A may be graft-polymerized to form a carboxylic acid-modified polyolefin resin D. 160004.doc -16 · 201240817 The electrode adhesion layer 2 is preferably thin as long as it is thermally bonded to the electrode 11. Usually, the thickness of the electrode layer 2 is 2 〇 μπι to 60 μιη. If the thickness of the electrode layer 2 is smaller than the range, there is a case where the adhesion strength between the electrode layer 2 and the electrode layer is lowered. If the thickness of the electrode underlayer 2 is larger than the range, the heat resistance of the sealing film 1 may become insufficient. The melting point of the resin D forming the electrode subsequent layer 2 is preferably lower than the melting point of the resin C forming the heat-resistant layer 3. In the case of the sealing film 1 comprising a polypropylene resin, the melting point of the resin D is preferably from 130 〇 c to 150 〇 c. If the melting point of the resin d is lower than this range, the heat resistance of the sealing film 1 may become insufficient. If the melting point of the resin D is higher than the range ', it is difficult to increase the difference in melting point of the resin C which forms the heat-resistant layer 3. If the melting point difference between the resin d and the resin c is 1 〇. (The above is preferable because the temperature management at the time of heat fusion is easy, and the melting point of the resin D is preferably equal to or lower than the sleek point of the resin a. If the resin is modified to the resin C, the resin The molecule of B is bonded to the molecule of the resin a, and the molecular weight of the resin C is increased, so that the melting point of the resin c becomes toward the resin A. Thereby, the difference in melting point between the resin d and the resin is easily obtained. When the resin D and the resin A are the same resin, the management of the resin becomes easy. The method of forming the electrode back layer 2 is to extrude the molten resin D from the T die or the ring die using an extruder. Extrusion method. When a graft copolymer is used as the resin D, when it is extruded by an extruder in the same manner as the resin A, the polyolefin can be graft-polymerized with an unsaturated carboxylic acid. The sealing film of the polyethylene resin is preferably a melting point of 90 M2 when the electrode is layer 2 is made of acid-modified polyethylene. <c left 160004.doc 17 201240817 Right maleic anhydride Graft copolymerized polyethylene. Acid-modified polyethylene contains a carboxyl group to neutralize The ionic polymer. The MFR of the acid-modified polyolefin resin D forming the electrode subsequent layer 2 is preferably in the range of 3 g/10 min to 30 g/l 〇 min. The MFR is more preferably 5 g/l 〇 min 〜10 The range of g/10 min. If the MFR is less than the above range, the acid-modified polyolefin is difficult to sufficiently wrap around the electrode crucible during heat fusion. If the MFR is larger than the range, the electrode layer 2 is thinned. In the present invention, the 'MFR is measured at 230 ° C in the case of a polypropylene resin in accordance with JIS K7210, and is measured at 190 ° C in the case of a polyethylene resin. Further, since the carboxylic acid-modified polyolefin resin is commercially available, a commercially available product can also be used. The electrode adhesive layer 2 and the heat-resistant layer 3 are directly laminated, and are not laminated between the layers via the adhesive layer or the tackifier layer. Thereby, it is possible to prevent the peeling caused by the intrusion of the electrolytic solution into the laminated interface and the decrease in the flexibility of the sealing film 。. In the sealing film 1, not only the electrode subsequent layer 2 but also the electrode of the heat-resistant layer 3 is wound around the electrode. Also important as long as it does not affect the softness or the electrolyte For the interaction, it is also possible to use an adhesive for dry lamination. Also, in the case of extrusion lamination, a tackifier can also be used. As a method of direct lamination, the formed electrode is layer 2 and The heat-resistant layer 3 is heavy 4 and is subjected to thermal bonding by (4) bonding; (4) forming any one of the electric two-layer 2 and the heat-resistant layer 3, and one side is extruded from the butting die to the other side in a dazzling state. Extrusion layer star method of lamination; when both electrode 2 and heat-resistant layer 3 are in a state of being married, one side is extruded from a co-extrusion die, and two layers of co-extrusion lamination are carried out on a layer of 160004.doc -18·201240817 7 In the first method, the co-extrusion lamination method is carried out by co-extruding an extruder which extrudes a resin while being modified into a resin c by one side, and is connected to another extruder of the extruded resin D. Directly laminating in the co-extrusion die. Thereby, the formation of the modified heat-resistant layer 3 of the resin c, the formation of the electrode underlayer 2, and the lamination of the electrode underlayer 2 and the heat-resistant layer 3 can be carried out in a single step, which is preferable. In the present embodiment, the sealing layer 4 is laminated on the opposite surface of the heat-resistant layer 3 from the electrode layer. The layer to be sealed 4 is a layer in which the sealing layer of the laminated film 2 of the bag body is heated and pressurized to be welded. As the lamination method, the same method is employed for the same reason as the lamination of the electrode underlayer 2 and the heat-resistant layer 3. In these methods, the electrode underlayer 2 and the heat-resistant layer 3 and the sealing layer 4 can be laminated at one time, and therefore it is preferable to laminate by the co-extrusion lamination method. The sealing layer 4 is preferably thin as long as it is welded to the sealing layer 22 of the bag body. Usually, the thickness of the sealing layer 4 is 20 μηι to 4 μm μηβ. If the thickness of the sealing layer 4 is less than the above range, the welding strength of the sealing layer 4 and the sealing layer 22 of the bag body is lowered. If the thickness of the sealing layer 4 is larger than the range, the heat of the sealing film 1 becomes insufficient. In the case where the sealing layer 22 of the laminated film 20 of the bag body is easily welded, the resin forming the sealing layer 4 (hereinafter referred to as resin enamel) is preferably the same or the same resin as the resin constituting the sealing layer 22. Generally, the sealing film 1 is composed of a lanthanum resin in terms of excellent heat resistance. In the case where Yu Xiong and the sealing film 1 are composed of a lanthanoid resin, the resin Ε can be exemplified by a homopolymer of ruthenium, a random copolymer of ethylene and propylene or a block copolymer or the 160004.doc -19·201240817 Mixtures, etc., or such polymer alloys, and the like. Among these, a random copolymer of ethylene and propylene is preferred in terms of excellent flexibility. In the case of a sealing film comprising a pp-based resin, the melting point of the resin forming the sealing layer 4 is preferably 130 to 170. (If the melting point of the resin is lower than the range, the heat resistance of the sealing film may be insufficient. If the melting point of the resin E forming the sealing layer 4 is higher than the range, it is difficult to increase and form heat resistance. The difference in melting point of the resin C of the layer 3. If the difference between the melting point of the resin E and the melting point of the resin c is 10 C or more, the temperature management when the laminated body is welded to the bag body is easy, so it is preferable. When the sealing film 1 is made of a polyethylene resin and a polyethylene resin is used for the sealing layer 4, it is preferable to use a low density polyethylene having a melting point of about 1 〇〇 12 〇 ec or a low density of a straight bond. In the case of a sealing film comprising a PP-based resin, the MFR of the resin E forming the sealing layer 4 is preferably in the range of 3 g/10 min to 3 〇g/1 〇 min, more preferably g/l 〇 The range of min~10 g/10 min. If the resin E2Mfr is smaller than the above range, it is difficult to use extrusion lamination or co-extrusion lamination to test more than these ranges, and it is difficult to use the co-extrusion ring mold. Further, the sealing layer 4 is an arbitrary layer, and may be omitted when the heat-resistant layer 3 is welded to the sealing layer 22 of the bag body. The sealing layer 4 is disposed. The sealing film i of the present invention is slidably connected to the sealing layer 22 of the bag body and the electrode sigh. When the sealing film is welded, as shown in FIG. 2, a sealing film of a specific width is made from the laminated film 20 The end portion is exposed and welded. At this time, in order to facilitate the positioning of the sealing film, it is preferable to pre-color at least two of the two sealing films.

S •20- 201240817 片。著色之方法可使用對構成密封膜1之層之至少一層進 行印刷、染色、染料或顏料等著色劑之捏合等方法。該等 方法中,因著色劑之捏合簡便,故而較佳。著色之層亦可 用於確認與袋體之密封層22之熔接是否良好。因此,著色 之層較佳為於熔接時無變形或熔融之耐熱層3。 本形態例之密封膜於熔接時為了實現密封膜1之定位與 使樹脂無間隙地迴繞於電極之厚度方向之周圍,而如圖3 A 所示’較佳為預先使用密封膜1之電極接著層2而將本發明 之密封膜1熱熔接於電極11之至少1面,較佳為兩面。藉 此’可使用密封膜1之密封層4或耐熱層3’容易且確實地 向袋體之密封層22進行熔接。此時,若將密封膜1著色, 則於將密封膜與袋體之最内層熔接而成之電極引板之熱熔 接時,可於自動化之熔接組裝線中使用感光器而將電極引 板與密封膜1進行正確定位。 於密封膜1與電極11之熱熔接中,可使用熱封機或瞬間 封口機等’並利用密封棒加熱而進行壓接。又,於密封膜 1之加熱時,若使用電磁感應加熱或通電加熱而直接加熱 電極11,則抑制由密封層4或耐熱層3之外側部分之熔融所 引起之流動,並促進耐熱層3之内侧部分或電極接著層2之 軟化或熔融,故而較佳。 電極11之形狀可例示帶狀或圓棒等。電極11之大小並無 特別限制,例如若為帶狀,則厚度為5〇 μιη〜5〇〇 μπι,寬度 為5 mm〜1〇〇 mm,長度為4〇 爪爪左右。帶狀之電 極11亦可將其稜線(角緣部)變圓。又,雖然其表面亦可為 I60004.doc 201240817 經壓延加工之加工面之狀態,但較佳為藉由喷砂或蝕刻等 表面處理進行粗面化。藉由進行粗面化,密封膜1之接著 強度會提高.又,亦可實施化成處理等底層處理。 作為電極11之材質,例如可使用鋁、銅、鎳、鉄、金、 @或各種合金等金屬。豸等之中,就導電性優異,且對成 本亦有利之方面而言,較佳為使用鋁或銅。其中,鋁或銅 存在如下情況:於電池組中,對於擔憂會於電解液中產生 之氟化氫(氫氟酸)的耐性不充分。又,若pp系樹脂與銅接 觸,則有促進樹脂劣化之可能性。因此,較佳為將導電性 較高且對氫氟酸之耐性優異之鎳鍍敷於鋁或銅之底層金屬 上。 .熔接有本發明之密封臈i之袋體之層壓膜2 〇例如可列舉 如圖2所示,於金屬箱21之一面上積層密封層22,並於另 面上積層膜基材23而成之積層膜等。層壓膜2〇亦可積層 其他層。 心體之層壓膜20係成形為經拉伸成形之袋或平袋等。作 為金屬箔21,可列舉鋁箔、不鏽鋼箔、銅箔、鐵箔等。金 屬fl 21亦可實施化成處理等底層處理。 形成袋體之層壓膜2 0之密封層2 2的樹脂係選擇可與密封 膜1之密封層4熔接之樹脂。作為此種樹脂,例如於密封膜 1之密封層4為PP系樹脂之情形時,可使用pp之均聚物或 pp與乙烯之共聚物等。於聚乙烯系樹脂之情形時可使用 低密度聚乙烯或直鏈狀低密度聚乙烯等。構成膜基材23之 樹月曰並無特別限制,較佳為使用強度較大之聚醯胺、聚對 160004.docS •20- 201240817 pieces. The method of coloring may be carried out by, for example, kneading a coloring agent such as printing, dyeing, dye, or pigment on at least one layer of the layer constituting the sealing film 1. Among these methods, it is preferred because the kneading of the coloring agent is simple. The colored layer can also be used to confirm whether the sealing of the sealing layer 22 with the bag body is good. Therefore, the colored layer is preferably a heat-resistant layer 3 which is not deformed or melted at the time of welding. In the sealing film of the present embodiment, in order to achieve the positioning of the sealing film 1 and to wrap the resin around the thickness direction of the electrode without a gap, as shown in FIG. 3A, it is preferable to use the electrode of the sealing film 1 in advance. The sealing film 1 of the present invention is thermally welded to at least one side of the electrode 11, preferably two sides. By this, the sealing layer 4 or the heat-resistant layer 3' of the sealing film 1 can be easily and surely welded to the sealing layer 22 of the bag body. At this time, when the sealing film 1 is colored, when the sealing film is thermally welded to the electrode tab which is welded to the innermost layer of the bag, the photoreceptor can be used in the automated fusion bonding line to bond the electrode tab The sealing film 1 is correctly positioned. In the heat fusion of the sealing film 1 and the electrode 11, a heat sealer or an instant sealer or the like can be used and heated by a sealing rod to be pressure-bonded. Further, when the electrode 11 is directly heated by electromagnetic induction heating or electric heating during heating of the sealing film 1, the flow caused by the melting of the sealing layer 4 or the outer portion of the heat-resistant layer 3 is suppressed, and the heat-resistant layer 3 is promoted. The inner portion or the electrode is preferably softened or melted by the layer 2, so that it is preferred. The shape of the electrode 11 can be exemplified by a belt shape or a round bar or the like. The size of the electrode 11 is not particularly limited. For example, if it is a strip shape, the thickness is 5 〇 μηη to 5 〇〇 μπι, the width is 5 mm to 1 mm, and the length is 4 〇 claws. The strip-shaped electrode 11 can also round its ridge line (corner edge portion). Further, although the surface thereof may be in the state of a processed surface of I60004.doc 201240817, which is subjected to calendering, it is preferably roughened by surface treatment such as sand blasting or etching. By roughening, the strength of the sealing film 1 is improved. Further, an underlayer treatment such as a chemical conversion treatment can be carried out. As the material of the electrode 11, for example, a metal such as aluminum, copper, nickel, rhodium, gold, @ or various alloys can be used. Among the crucibles and the like, aluminum or copper is preferably used in terms of excellent electrical conductivity and advantageous in terms of cost. Among them, aluminum or copper has a problem that in the battery pack, resistance to hydrogen fluoride (hydrofluoric acid) which is generated in the electrolytic solution is insufficient. Further, when the pp-based resin is in contact with copper, there is a possibility that the resin is deteriorated. Therefore, it is preferred to plate nickel having high conductivity and excellent resistance to hydrofluoric acid on the underlying metal of aluminum or copper. The laminate film 2 to which the bag body of the sealing container of the present invention is welded, for example, as shown in Fig. 2, a sealing layer 22 is laminated on one surface of the metal case 21, and the film substrate 23 is laminated on the other surface. A laminated film or the like. The laminate film 2 can also be laminated with other layers. The core body laminate film 20 is formed into a stretch-formed bag or a flat bag or the like. Examples of the metal foil 21 include an aluminum foil, a stainless steel foil, a copper foil, and an iron foil. The metal fl 21 can also be subjected to an underlayer treatment such as a chemical conversion treatment. The resin forming the sealing layer 2 2 of the laminated film 20 of the bag body is selected from a resin which can be welded to the sealing layer 4 of the sealing film 1. When the sealing layer 4 of the sealing film 1 is a PP-based resin, for example, a homopolymer of pp or a copolymer of pp and ethylene can be used. In the case of a polyethylene resin, low density polyethylene or linear low density polyethylene can be used. The sapphire constituting the film substrate 23 is not particularly limited, and it is preferred to use a polyamine having a high strength and a poly-pair.

S • 22- 201240817 本一甲酸乙二酯(PET)或pp等。若將該等樹脂延伸而形成 膜,則可獲得較高之物理強度。該等膜亦可積層複數層。 以上,雖然基於較佳之實施形態對本發明進行說明,但 本發明並不限定於上述實施形態,可進行各種變更。 例如密封膜1為了提高各樹脂層間之接著性、物理性強 度或絕緣性等,亦可進而含有樹脂層等其他層。於該情形 時,其他層較佳為於熱熔接時難以熔融且柔軟性較高之 層。又,亦可將各層間之層壓強度控制為適當範圍,而對 密封膜1賦予於袋體内之溫度或壓力異常上升之情形時具 備之安全閥之功能。 [實施例] 使用以下所示之樹脂而製作表1所示之密封膜1之實施例 及比較例。 樹脂A :將順丁烯二酸酐接枝聚合於無規pp上而成之順丁 烯一酸酐改性 PP(MFR 2.4 g/l〇 min(23〇eC )、熔點 143°C )S • 22- 201240817 Ben-ethylene formate (PET) or pp. When the resin is stretched to form a film, a high physical strength can be obtained. The films may also be laminated in multiple layers. The present invention has been described above based on preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made. For example, the sealing film 1 may further contain another layer such as a resin layer in order to improve adhesion between the respective resin layers, physical strength, insulation, and the like. In this case, the other layer is preferably a layer which is difficult to melt and has high flexibility at the time of heat fusion. Further, the lamination strength between the layers can be controlled to an appropriate range, and the sealing film 1 can be provided with a function as a safety valve when the temperature or pressure in the bag rises abnormally. [Examples] Examples and comparative examples of the sealing film 1 shown in Table 1 were produced using the resins shown below. Resin A: cis-butene-anhydride modified PP obtained by graft polymerization of maleic anhydride onto random pp (MFR 2.4 g/l〇 min (23〇eC), melting point 143 ° C)

樹脂B 樹脂 B-l :乙烯比率 48 mol% 之 EVOH(MFR 15 g/10 min(230°C )、熔點 160°C ) 樹脂 B-2 :乙烯比率 32 mol% 之 EVOH(MFR 3.6 g/10 min(230°C )、熔點 183°C ) 樹脂B-3 :尼龍6(相對黏度3.37、熔點22(TC ) 樹脂B-4 :尼龍6(相對黏度4_08、溶點22(TC ) 樹脂B-5 :甲基丙稀酸縮水甘油i旨含有率6 wt%之E-GMA共 聚物(MFR 3 g/10 min(190°C )、熔點 1〇5。〇 ) 160004.doc •23- 201240817Resin B Resin B1: EVOH having an ethylene ratio of 48 mol% (MFR 15 g/10 min (230 ° C), melting point 160 ° C) Resin B-2: EVOH having an ethylene ratio of 32 mol% (MFR 3.6 g/10 min ( 230 ° C), melting point 183 ° C) Resin B-3: Nylon 6 (relative viscosity 3.37, melting point 22 (TC) Resin B-4: Nylon 6 (relative viscosity 4_08, melting point 22 (TC) Resin B-5: Methyl acrylate glycidol is an E-GMA copolymer having a content of 6 wt% (MFR 3 g/10 min (190 ° C), melting point 1〇5. 〇) 160004.doc •23- 201240817

樹脂D 樹脂D-l :將順丁稀二酸酐接枝聚合於無規pp上而成之順 丁烯二酸酐改性PP(MFR 7 5 g/1〇 min(23〇ec)、熔點 135。〇 樹脂D-2 ··將順丁燥二酸酐接枝聚合於無規pp上而成之順 丁烯二酸酐改性PP(MFR 7.〇 g/1〇以叩抓)、熔點14(Γ(:) 樹脂 E : | 段PP(MFR 2.3 g(23(rc)/1() _、炼點 i63〇c ) <實施例1~15> 將樹脂A與樹脂B以表丨所示之調配比添加至擠出機之料 斗中 面以表1所示之擠出溫度使之改性為樹脂c: 一面擠 出並於/、擠出τ模内與自另一擠出機擠出之樹脂D進行 積層,而澆鑄成形密封膜實施例卜15。 於表1之層構成之攔為3層之實施例中,於共擠线鑄成 形時,進而自^ -擠出機擠出樹脂E而進行共擠出積層。 又’於表1之者色劑之攔為3份之實施例巾,於調配樹脂A 與樹脂B之情形時添加3重量份之叩基礎之顏料母料。 樹脂D與樹脂E之擠出溫度均設為24〇β(:。 以上述之方式成形將包含4〇㈣之電極接著層2與表1之 财熱層之欄所不之厚度之耐熱層3的2層構造之#層膜1 20 μηι之密封層4積層而# +,駐w 成之3層構造之積層膜。將該積層 膜切割成25 mm之寬声,☆制仏^ 見度’而製作密封膜1之實施例丨〜丨5。 <比較例1 > 於240°c下分別擠屮始+ 、 樹月s D-1與樹脂E,並於共擠出丁模 内進行積層’而成形句冬〇 乂办包3 20 μιη之電極接著層2與8〇 密封層4之2層構造的穑呙 曰膜洗鑄。將該積層膜切割成25 J 60004.docResin D Resin Dl: maleic anhydride modified PP obtained by graft-polymerizing cis-butyl dianhydride onto random pp (MFR 7 5 g/1〇min (23〇ec), melting point 135. oxime resin D-2 ·· Maleic anhydride modified PP (MFR 7.〇g/1〇), which is obtained by graft polymerization of cis-butyl dianhydride onto random pp, melting point 14 (Γ: Resin E: | Section PP (MFR 2.3 g (23(rc)/1() _, refining point i63〇c) <Examples 1 to 15> The ratio of the resin A and the resin B shown in Table 丨The hopper in the extruder was modified to the resin c at the extrusion temperature shown in Table 1: one side extruded and/or extruded in a τ mold and resin D extruded from another extruder In the embodiment in which the layer is formed into three layers, in the embodiment in which the layer of the layer of the first embodiment is formed by three layers, the resin E is extruded from the extruder. Co-extruded laminates. In addition, in the case of the toner of Table 1, three parts of the sample towel were added, and in the case of the preparation of the resin A and the resin B, 3 parts by weight of the base pigment masterbatch was added. Resin D and resin The extrusion temperature of E is set to 24 〇 β (:. Forming a layered film of 20 layers of a heat-resistant layer 3 having a thickness of 4 〇 (4) and a heat-resistant layer 3 of a thickness of the layer 2 of the heat-producing layer of Table 1 and a layer of film 1 20 μηι w A laminated film of a three-layer structure. The laminated film is cut into a wide sound of 25 mm, and the sealing film 1 is produced in an example of 宽~丨5. <Comparative Example 1 > At 240 °c, the extrusion starts +, the tree s D-1 and the resin E, and the layers are formed in the co-extrusion dies. The formed segments are 3 20 μιη electrodes, followed by layers 2 and 8 〇. The enamel film of the two-layer structure of the sealing layer 4 is cut. The laminated film is cut into 25 J 60004.doc

S -24· 201240817 mm之寬度,而製作比較例1之密封膜1。 [表1] 樹脂A 樹脂B 樹脂D 著色劑 擠出溫度 时熱層 層構成 實施例1 95份 B-1 5份 D-1 無 240〇C 40 μιη 3層 實施例2 93份 B-1 7份 D-1 無 240〇C 40 μηι 3層 實施例3 90份 B-1 10份 D-1 無 240°C 40 μπι 3層 實施例4 95份 B-1 5份 D-1 無 240〇C 50 μτη 3層 實施例5 95份 B-1 5份 D-1 無 240。。 50 μιη 2層 實施例6 95份 B-1 5份 D-1 無 260〇C 40 μΐΏ 3層 實施例7 95份 B-1 5份 D-2 無 240〇C 40 μιη 2層 實施例8 95份 B-2 5份 D-1 無 260〇C 50 μιη 2層 實施例9 90份 B-2 10份 D-1 無 260〇C 40 μιη 3層 實施例10 90份 B-2 7份 D-1 3份 260〇C 40 μιη 3層 實施例11 92份 B-3 5份 D-1 3份 270〇C 40 μιη 3層 實施例12 90份 B-3 10份 D-1 無 270〇C 50 μιυ 2層 實施例13 92份 B-4 5份 D-1 3份 260〇C 40 μηι 3層 實施例14 92份 B-5 5份 D-1 3份 260〇C 40 μηι 3層 實施例15 90份 B-5 10份 D-1 無 260〇C 50 μιη 2層 比較例1 無 無 D-1 無 240〇C 無 2層 再者,表1中之「份」均指「重量份」。 <電極接著強度之測定> 使用厚度50 μηι、寬度50 mm、長度50 mm之正方形之在呂 箔作為電極11。分別將密封膜1之實施例1〜15及比較例1切 斷成60 mm之長度。以密封膜1之電極接著層2為内側而重 疊於電極11上。使用熱封機,於200°C、0.2 MPa、3秒鐘 之條件下自鋁箔側進行加熱,於一端殘留未熔接部,並熱 炫接另一端。 使用Instron型拉伸試驗機對各密封膜1之電極接著層2與 160004.doc -25- 201240817 電極11之剝離強度進行測定。於剝離強度之測定時,將未 炫接於電極11上之密封膜丨之端部與電極丨丨之端部固定於 拉伸試驗機之兩個夾頭上,並以300 mm/min之速度進行拉 伸,而對1 80度剝離強度進行測定。各密封膜i之電極接著 層2與電極11係以27.5〜32.8 N/25 mm之密封強度進行熱密 封。 <層壓膜熔接強度之測定> 藉由乾式層壓將作為膜基材23之厚度12 μιη之雙軸延伸 PET膜、作為金屬箔21之厚度4〇 之鋁箔及作為密封層 22之厚度40 μιη之乙烯與丙烯之無規共聚物膜進行積層。 將所得之積層膜切割成邊長為1〇〇 mm之正方形,而製作2 片之袋體之層壓膜2〇。 分別將密封膜1之實施例丨〜丨5及比較例i切割成6〇爪爪之 長度。使2片之袋體之層壓膜2〇之密封層22彼此相對,並 於其之間夾入密封膜丨。於挾入密封膜丨時,使密封膜i自 層壓膜20之端部露出5 mm。 於與電極接著強度之測定相同之條件下自2片之袋體之 層壓膜20之兩側進行加熱,並將密封膜1露出之側之一端 進订炫接。另一端作為未熔接部而殘留。於密封膜1之熔 夺使也、封膜1之露出部分之根部約2 mm與密封棒接 觸。 以與電極接著強度之測定相同之方式,將密封膜1之未 熔接部之端部與層壓膜2〇之端部固定於拉伸試驗機之兩個 夾頭上,於與電極接著強度之測定相同之條件下,對各密 160004.docThe sealing film 1 of Comparative Example 1 was produced by the width of S - 24 · 201240817 mm. [Table 1] Resin A Resin B Resin D Colorant At the extrusion temperature, the thermal layer layer was constructed. Example 1 95 parts B-1 5 parts D-1 No 240 〇 C 40 μη 3 layers Example 2 93 parts B-1 7 Part D-1 No 240〇C 40 μηι 3 layer Example 3 90 parts B-1 10 parts D-1 No 240°C 40 μπι 3 layer Example 4 95 parts B-1 5 parts D-1 No 240〇C 50 μτη 3 layer Example 5 95 parts B-1 5 parts D-1 No 240. . 50 μηη 2 layer Example 6 95 parts B-1 5 parts D-1 No 260〇C 40 μΐΏ 3 layers Example 7 95 parts B-1 5 parts D-2 No 240〇C 40 μη 2 layer Example 8 95 Part B-2 5 parts D-1 No 260〇C 50 μιη 2 layers Example 9 90 parts B-2 10 parts D-1 No 260〇C 40 μιη 3 layers Example 10 90 parts B-2 7 parts D- 1 3 parts 260〇C 40 μηη 3 layers Example 11 92 parts B-3 5 parts D-1 3 parts 270〇C 40 μη 3 layers Example 12 90 parts B-3 10 parts D-1 No 270〇C 50 Μιυ 2 layer Example 13 92 parts B-4 5 parts D-1 3 parts 260 〇C 40 μηι 3 layers Example 14 92 parts B-5 5 parts D-1 3 parts 260 〇C 40 μηι 3 layer Example 15 90 parts B-5 10 parts D-1 No 260 〇C 50 μιη 2 layers Comparative Example 1 No D-1 No 240 〇C No 2 layers Further, the "parts" in Table 1 means "parts by weight". <Measurement of electrode adhesion strength> A prism having a thickness of 50 μm, a width of 50 mm, and a length of 50 mm was used as the electrode 11. Examples 1 to 15 and Comparative Example 1 of the sealing film 1 were cut into lengths of 60 mm, respectively. The electrode 11 is laminated on the electrode 11 with the electrode 2 of the sealing film 1 as the inner side. The heat-sealing machine was used to heat the aluminum foil side at 200 ° C, 0.2 MPa, and 3 seconds, and the unwelded portion was left at one end, and the other end was thermally glazed. The peel strength of the electrode back layer 2 of each sealing film 1 and the electrode 11 of 160004.doc -25 - 201240817 was measured using an Instron type tensile tester. In the measurement of the peeling strength, the end portion of the sealing film which is not stunned on the electrode 11 and the end of the electrode 固定 are fixed to the two chucks of the tensile testing machine, and are carried out at a speed of 300 mm/min. Tensile, and the peel strength of 180 degrees was measured. The electrode underlayer 2 of each sealing film i and the electrode 11 were heat-sealed at a sealing strength of 27.5 to 32.8 N/25 mm. <Measurement of Laminated Film Welding Strength> A biaxially stretched PET film having a thickness of 12 μm as the film substrate 23, an aluminum foil having a thickness of 4 Å as the metal foil 21, and a thickness as the sealing layer 22 by dry lamination A 40 μm ethylene and propylene random copolymer film was laminated. The obtained laminated film was cut into a square having a side length of 1 mm, and a laminated film of 2 sheets of a bag was produced. The examples of the sealing film 1 and the comparative example i were respectively cut into the lengths of 6 jaws. The sealing layer 22 of the laminated film 2 of the two-piece bag body was opposed to each other with the sealing film 夹 interposed therebetween. When the sealing film was inserted, the sealing film i was exposed from the end of the laminated film 20 by 5 mm. Heating was performed from both sides of the laminated film 20 of the two-piece bag under the same conditions as the measurement of the adhesive strength of the electrode, and one end of the side on which the sealing film 1 was exposed was spliced. The other end remains as an unwelded portion. The sealing film 1 is melted and the root portion of the exposed portion of the sealing film 1 is brought into contact with the sealing bar by about 2 mm. The end portion of the unfused portion of the sealing film 1 and the end portion of the laminate film 2 are fixed to the two chucks of the tensile tester in the same manner as the measurement of the adhesive strength of the electrode, and the strength of the electrode is measured. Under the same conditions, for each secret 160004.doc

S -26- 201240817 封膜1之密封層4或耐熱層3與層壓膜2()之熱密封強度進行 測定。各密封膜!與層麼膜2〇係以124 2〜i43 3 n/25 _之 密封強度進行熱密封。 又任實施例中之密封臈1之自層壓膜20露出之部分 .纟見熱變形或熔融之跡象。另一方面,於比較例中,自層 .壓膜20露出之部分根部稍有縮小。 <混練品之MFR> 將95重量份之樹脂八與5重量份之樹脂B_i之熔融混練品 (樹知C-1)、95重量份之樹脂入與5重量份之樹脂Β·3之熔融 混練品(樹脂C-3)分別單獨擠出’並測定23〇〇c下之MFR。 原始之樹脂A之MFR為2.0樹脂(:_1之1^1^為1.9,與樹脂 八相㈣叹下降。再者,樹脂C-3之MFR為2.5,與樹脂a相 比MFR上升。由此推測,於本發明中密封膜1之耐熱性提 高之原因不僅在於因樹脂A之羧基與樹脂B之官能基之化 學鍵結而使分子量變大,亦受到部分交聯影響。 [產業上之可利用性] 本發明可廣泛應用於密封袋體所收納之二次電池或電容 器等發電元件之電極之密封膜的製造方法及密封膜。 【圖式簡單說明】 圖1係表示本發明之密封膜之一例之剖面圖。 圖2係表示使用圖丨所示密封膜而接合袋體之層壓膜與電 極之狀態之剖面圖。 圖3A係表示將圖1所示密封膜接著於電極上而成之附有 密封膜之電極的立體圖。 160004.doc •27- 201240817 圖3B係表示將圖1所示密封膜接著於電極上而成之附有 密封膜之電極的剖面圖。 【主要元件符號說明】 1 密封膜 2 電極接著層 3 耐熱層 4 密封層 10 附有密封膜之電極 11 電極 20 袋體之層壓膜 21 層壓膜之金屬箔 22 層壓膜之密封層 23 層壓膜之膜基材S -26- 201240817 The sealing strength of the sealing layer 4 or the heat-resistant layer 3 of the sealing film 1 and the laminated film 2 () was measured. Each sealing film! The film is heat-sealed with a sealing strength of 124 2 to i43 3 n/25 Å. Further, in the embodiment, the portion of the sealing crucible 1 which is exposed from the laminate film 20 is seen as an indication of thermal deformation or melting. On the other hand, in the comparative example, the portion of the root portion from which the laminate 20 was exposed was slightly reduced. <MFR of kneaded product> A melt-kneaded product of 95 parts by weight of resin VIII and 5 parts by weight of resin B_i (Shu C-1), 95 parts by weight of resin, and 5 parts by weight of resin Β·3 The kneaded product (resin C-3) was separately extruded ' and the MFR at 23 〇〇 c was measured. The MFR of the original resin A was 2.0 resin (: 1 to 1^1 of _1 was 1.9, and the octet of the resin was decreased by octave (four). Further, the MFR of the resin C-3 was 2.5, and the MFR was higher than that of the resin a. It is presumed that the heat resistance of the sealing film 1 is improved in the present invention not only because the molecular weight of the carboxyl group of the resin A and the functional group of the resin B are increased, but also the molecular weight is increased, and it is also affected by partial crosslinking. The present invention can be widely applied to a method for producing a sealing film for an electrode of a power generating element such as a secondary battery or a capacitor housed in a sealed bag body, and a sealing film. [Fig. 1] Fig. 1 shows a sealing film of the present invention. Fig. 2 is a cross-sectional view showing a state in which a laminate film and an electrode of a bag body are joined by using a sealing film shown in Fig. 2. Fig. 3A shows a sealing film shown in Fig. 1 attached to an electrode. Fig. 3B is a cross-sectional view showing an electrode with a sealing film formed by attaching the sealing film shown in Fig. 1 to an electrode. [Description of main component symbols] 1 sealing film 2 electrode layer 3 Heat-sealing layer 4 with the film substrate layer 10 of the film 23 layer laminate film 22 of the laminate film 21 of the electrode 11 of the electrode film 20 sealing the bag film layer of a metal foil seal body layer

160004.doc -28- Λ S160004.doc -28- Λ S

Claims (1)

201240817 七、申請專利範圍·· u 一種密封膜之製造方法,其係夾入袋體所收納之發電元 件之電極與袋體之邊緣之間的密封膜之製造方法,其具 有如下步驟: • '溶融混練步驟’其係藉由將接枝聚合有羧酸之酸改性 , 聚烯烴樹脂A與具有可與樹脂A之羧基反應之官 能基的樹 脂B兩者進行溶融混練’使樹脂a之羧基與樹脂b之官能 基進行化學鍵結而改性為樹脂C ; 耐熱層製膜步驟’其係將樹脂C成形為層狀而形成耐 熱層; 接著層製膜步驟’其係將羧酸改性聚烯烴樹脂D成形 為層狀而形成接著於電極之電極接著層; 積層步驟,其係於樹脂c與樹脂D中之任一者或兩者為 熔融狀態時直接積層上述耐熱層與上述電極接著層。 2.如請求項1之密封膜之製造方法,其中上述熔融混練步 驟係於擠出機内進行。 3_如請求項1之密封膜之製造方法,其中上述熔融混練步 驟與上述耐熱層製膜步驟係連續進行。 _ 4.如請求項1至3中任一項之密封膜之製造方法,其中上述 . 積層步驟係與上述耐熱層製膜步驟與上述接著層製膜步 驟中之任一者或兩者連續進行。 5. 如請求項1至3中任一項之密封膜之製造方法,其中上述 積層步驟係於共擠出模内進行。 6. 如請求項1至3中任一項之密封膜之製造方法,其中上述 160004.doc 201240817 炫融/昆練步驟係以相對於樹脂A為99〜9〇而樹脂b成為 1 10之重量百分比進行調配而進行。 如凊求項1至3中任—項之密封膜之製造方法,其中使用 具有與樹脂A之熔點相同或低於其之炫點之樹脂作為樹 脂D。 8· -種密封| ’其係夹入袋體所收納《發電元件之電極與 ▲體之邊緣之間者,並且具有 將包含樹脂C之耐熱層直接積層於包含羧酸改性聚烯 煙樹脂D之電極接著層上而成之積層構造,該樹脂c係藉 由將接枝聚合有羧酸之酸改性聚烯烴樹脂A與具有可與 樹脂A之羧基反應之官能基之樹脂B兩者進行熔融混練, 使樹脂A之羧基與樹脂B之官能基化學鍵結進行改性而成 者。 9·如請求項8之密封膜,其中樹脂B係選自具有羥基胺基 或環氧基之樹脂中之一種或兩種以上。 10. 如請求項8之密封膜,其中樹脂a係使順丁烯二酸酐接枝 聚合於聚丙烯上而成之酸改性聚烯烴樹脂。 11. 如請求項8至10中任一項之密封膜,装φ 丁联具中上述積層構造 係藉由樹脂C與樹脂D之共擠出而形成。 12 ·如請求項8至1 0中任一項之密封膜,1总 了膜其係於上述耐熱層 上積層與袋體之最内層熱熔接之密封層者_。 160004.doc S201240817 VII. Patent Application Range·· u A method for manufacturing a sealing film, which is a method for manufacturing a sealing film which is sandwiched between an electrode of a power generating element housed in a bag body and an edge of a bag body, and has the following steps: The melt-kneading step 'by the graft-polymerization of a carboxylic acid-modified acid, and the polyolefin resin A and the resin B having a functional group reactive with the carboxyl group of the resin A are melt-kneaded to make the carboxyl group of the resin a It is chemically bonded to the functional group of the resin b to be modified into a resin C; the heat-resistant layer forming step "forms the resin C into a layer to form a heat-resistant layer; and the subsequent film-forming step" is to modify the carboxylic acid. The olefin resin D is formed into a layer to form an electrode subsequent layer which is followed by an electrode; and a laminating step of directly laminating the heat-resistant layer and the electrode subsequent layer when either or both of the resin c and the resin D are in a molten state . 2. The method of producing a sealing film according to claim 1, wherein the melt-kneading step is carried out in an extruder. The method for producing a sealing film according to claim 1, wherein the melt-kneading step and the heat-resistant layer forming step are continuously performed. The method for producing a sealing film according to any one of claims 1 to 3, wherein the step of laminating is performed continuously with either or both of the heat-resistant layer forming step and the subsequent layer forming step . 5. The method of producing a sealing film according to any one of claims 1 to 3, wherein the laminating step is carried out in a co-extrusion mold. 6. The method for producing a sealing film according to any one of claims 1 to 3, wherein the above-mentioned 160004.doc 201240817 glaze/stamping step is 99 to 9 Torr with respect to Resin A and the resin b becomes 1 10 by weight. The percentage is adjusted. The method for producing a sealing film according to any one of items 1 to 3, wherein a resin having a smear point which is the same as or lower than the melting point of the resin A is used as the resin D. 8· - Type of seal | 'It is sandwiched between the electrode of the power generating element and the edge of the ▲ body, and has a heat-resistant layer containing the resin C directly laminated on the carboxylic acid-modified olefin resin. a laminated structure formed by an electrode of D which is obtained by graft-polymerizing a carboxylic acid-modified polyolefin resin A with a resin B having a functional group reactive with a carboxyl group of the resin A. The melt kneading is carried out to chemically bond the carboxyl group of the resin A with the functional group of the resin B to be modified. 9. The sealing film of claim 8, wherein the resin B is one or more selected from the group consisting of hydroxylamine groups or epoxy groups. 10. The sealing film of claim 8, wherein the resin a is an acid-modified polyolefin resin obtained by graft-polymerizing maleic anhydride onto polypropylene. 11. The sealing film according to any one of claims 8 to 10, wherein the laminated structure is formed by co-extrusion of a resin C and a resin D. The sealing film according to any one of claims 8 to 10, wherein the film is a sealing layer which is laminated on the heat-resistant layer and thermally welded to the innermost layer of the bag. 160004.doc S
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