JP2020050924A - Gasket for electrolytic cell and electrolytic cell - Google Patents
Gasket for electrolytic cell and electrolytic cell Download PDFInfo
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- JP2020050924A JP2020050924A JP2018182712A JP2018182712A JP2020050924A JP 2020050924 A JP2020050924 A JP 2020050924A JP 2018182712 A JP2018182712 A JP 2018182712A JP 2018182712 A JP2018182712 A JP 2018182712A JP 2020050924 A JP2020050924 A JP 2020050924A
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- electrolytic cell
- gasket
- chamber frame
- cathode
- anode
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Links
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 23
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- 239000000758 substrate Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- -1 alkali hydroxide compound Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004823 Reactive adhesive Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000005405 multipole Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BASYJLWAYAUJBW-UHFFFAOYSA-N [Ti].[Ir].[Ru].[Pt] Chemical compound [Ti].[Ir].[Ru].[Pt] BASYJLWAYAUJBW-UHFFFAOYSA-N 0.000 description 1
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical class OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
本発明は、電解槽に用いられるガスケット、及びガスケットを用いてなる電解槽に関する。 The present invention relates to a gasket used for an electrolytic cell and an electrolytic cell using the gasket.
電気分解法を用いて、工業的に塩素、水素及び水酸化アルカリ化合物を製造する設備として、選択的に特定イオンを透過させるイオン交換膜を備えた電解槽が使用されている。当該電解槽は給電方法により単極式と複極式の２方式が存在するが、いずれもイオン交換膜を挟んで陽極及び陰極を備えた電極室を有する構造となっている。また、陽極と陰極の極間距離の関係により、ギャップ式、ナローギャップ式、ファイナイトギャップ式、ゼロギャップ式といった区別もあるが、いずれもイオン交換膜を挟んで陽極及び陰極を備えるという構成については同一である。製造目的物により陽極室及び陰極室に満たされる電解液が異なるが、アルカリ塩や水酸化アルカリ化合物の水溶液を用いることが一般的である。 BACKGROUND ART As equipment for industrially producing chlorine, hydrogen, and an alkali hydroxide compound using an electrolysis method, an electrolytic cell provided with an ion exchange membrane that selectively allows specific ions to pass therethrough is used. The electrolytic cell has two types, a monopolar type and a bipolar type, depending on the power supply method. Both types have a structure having an electrode chamber having an anode and a cathode with an ion exchange membrane interposed therebetween. In addition, depending on the relationship between the distance between the anode and the cathode, there is also a distinction such as a gap type, a narrow gap type, a finite gap type, and a zero gap type. Are the same. Although the electrolyte solution filled in the anode compartment and the cathode compartment differs depending on the production object, it is common to use an aqueous solution of an alkali salt or an alkali hydroxide compound.
当該電解槽は電極室からの液漏れを防ぐためにイオン交換膜を挟んで陽極ガスケットと陰極ガスケットが備わっており、ガスケットには水、アルカリ塩、水酸化アルカリ化合物、次亜塩素酸化合物、塩素酸化合物などに対する耐薬品性が求められている。また、電気分解反応を効率よく行うために、加温運転を行う場合もあり、耐熱性も求められている。これらの条件を満たす軟質材料としてガスケットにはＥＰＤＭ等が用いられることが広く普及している。（特許文献１、２参照） The electrolytic cell has an anode gasket and a cathode gasket with an ion exchange membrane interposed between them to prevent liquid leakage from the electrode chamber.The gasket contains water, alkali salts, alkali hydroxide compounds, hypochlorous acid compounds, chloric acid compounds. Chemical resistance to compounds and the like is required. In addition, a heating operation may be performed in order to perform the electrolysis reaction efficiently, and heat resistance is also required. As a soft material that satisfies these conditions, the use of EPDM or the like for gaskets has become widespread. (See Patent Documents 1 and 2)
電解槽に使用されるイオン交換膜や電極は定期的な交換を必要とする部品であり、これらの部品交換の際にはガスケットを交換することが望まれる。電解槽に組み付けられるガスケットはイオン交換膜の性能維持のために、陽極側ガスケットと陰極側ガスケットには好ましい位置関係があり、電解槽型式によりガスケットを組み付ける規定位置は異なるが、規定位置に対し数ｍｍの寸法公差範囲内で双方のガスケットを配置する必要がある。ガスケット位置関係が好ましくない状態で電解槽に通電するとイオン交換膜にブリスター状の損傷が発生し、電解性能の低下や電解槽内で発生したガスが混合して爆発する危険性が有った。 The ion exchange membranes and electrodes used in the electrolytic cell are components that require periodic replacement, and it is desirable to replace the gasket when replacing these components. In order to maintain the performance of the ion exchange membrane, the gasket assembled in the electrolytic cell has a favorable positional relationship between the anode gasket and the cathode gasket. It is necessary to arrange both gaskets within a dimensional tolerance of mm. If electricity is supplied to the electrolytic cell in a state where the gasket positional relationship is not favorable, blister-like damage occurs in the ion exchange membrane, and there is a risk that the electrolytic performance is reduced and gas generated in the electrolytic cell mixes and explodes.
ガスケットには、イオン交換膜と接触する面にはいわゆるギャザーといわれる凹凸差０．６〜１．５ｍｍを設けることが一般的ではあるが、このギャザーの劣化が激しく、改善が求められていた。 The gasket is generally provided with a so-called gather having an unevenness of 0.6 to 1.5 mm on a surface in contact with the ion exchange membrane. However, the gather is greatly deteriorated, and improvement has been demanded.
本発明はギャザーを有することにより、ガスケットが劣化しやすくなるという問題を解決することを課題とする。 An object of the present invention is to solve the problem that a gasket is easily deteriorated by having a gather.
本発明者らは鋭意検討を重ねた結果、イオン交換膜との接触する面の凹凸差を０．３ｍｍ未満とする電解槽用ガスケット、及び該ガスケットを有する電解槽を用いることで上記課題が解決することを見出し、本発明を完成するに至った。 The inventors of the present invention have made intensive studies and as a result, the above-mentioned problem is solved by using an electrolytic cell gasket having an unevenness difference of less than 0.3 mm on the surface in contact with the ion exchange membrane, and an electrolytic cell having the gasket. And completed the present invention.
項１ イオン交換膜との接触する面の凹凸差を０．３ｍｍ未満とする電解槽用ガスケット。
項２ 陰極室枠、及び陽極室枠に項１に記載の電解槽用ガスケットを具備する電解槽。
項３ 陰極室枠、及び陽極室枠に具備される電解槽用ガスケットが同一である項２に記載の電解槽。
項４ 押し型面に接触して成型されるガスケット面が対面する関係となる項３に記載の電解槽。
項５ イオン交換膜を介して対面する関係となる項４に記載の電解槽。
項６ 陰極室枠、及び陽極室枠と請求項１に記載の電解槽用ガスケットの間に接着剤層、又は粘着剤層を有する項２〜５いずれかに記載の電解槽。
項７ ガスケットがエチレン−プロピレン系ゴムにより構成される項１〜６いずれかに記載の電解槽用ガスケット、電解槽。
項８ 過酸化物架橋剤により架橋されてなる項７に記載の電解槽用ガスケット、電解槽。
Item 1. A gasket for an electrolytic cell in which a difference in unevenness of a surface in contact with an ion exchange membrane is less than 0.3 mm.
Item 2 An electrolytic cell comprising the electrolytic cell gasket according to Item 1 in a cathode chamber frame and an anode chamber frame.
Item 3. The electrolytic cell according to Item 2, wherein a gasket for an electrolytic cell provided in the cathode chamber frame and the anode chamber frame is the same.
Item 4 The electrolytic cell according to Item 3, wherein a gasket surface formed in contact with the pressing mold surface has a facing relationship.
Item 5 The electrolytic cell according to Item 4, which has a face-to-face relationship via an ion exchange membrane.
Item 6. The electrolytic cell according to any one of Items 2 to 5, further comprising an adhesive layer or a pressure-sensitive adhesive layer between the cathode chamber frame and the anode chamber frame and the gasket for an electrolytic cell according to Claim 1.
Item 7. The gasket for an electrolytic cell or the electrolytic cell according to any one of Items 1 to 6, wherein the gasket is made of ethylene-propylene rubber.
Item 8. The gasket for an electrolytic cell and the electrolytic cell according to Item 7, which are crosslinked with a peroxide crosslinking agent.
本発明によれば、ギャザーを有することにより劣化することがないために、メンテナンスの頻度を低減することができる。 ADVANTAGE OF THE INVENTION According to this invention, since it does not deteriorate by having a gather, the frequency of maintenance can be reduced.
本発明はイオン交換膜との接触する面の凹凸差を０．３ｍｍ未満とする電解槽用ガスケットである。 The present invention is a gasket for an electrolytic cell in which the unevenness of the surface in contact with the ion exchange membrane is less than 0.3 mm.
ガスケットの材料の具体例としては、天然ゴム、イソプレンゴム、スチレン・ブタジエンゴム、ブチルゴム、ブタジエンゴム、エチレン・プロピレンゴム（ＥＰＭゴム）、エチレン・プロピレン・ジエンゴム（ＥＰＤＭゴム）、クロロプレンゴム、シリコーンゴム、フッ素ゴム、アクリルゴム、多孔質ＰＴＦＥ（ポリテロラフルオロエチレン）等が挙げられる。それらの中でも、耐薬品性や硬度の観点から、エチレン・プロピレン・ジエンゴム（ＥＰＤＭゴム）、エチレン・プロピレンゴム（ＥＰＭゴム）等のエチレン−プロピレン系ゴム、及びこれらの架橋体からなる１種であることが好ましい。架橋方法は、材料の種類に応じて、硫黄加硫、過酸化物架橋等の公知の方法を用いることができる。 Specific examples of gasket materials include natural rubber, isoprene rubber, styrene / butadiene rubber, butyl rubber, butadiene rubber, ethylene / propylene rubber (EPM rubber), ethylene / propylene / diene rubber (EPDM rubber), chloroprene rubber, silicone rubber, Fluorine rubber, acrylic rubber, porous PTFE (polytellorafluoroethylene) and the like are included. Among them, ethylene-propylene rubbers such as ethylene-propylene-diene rubber (EPDM rubber) and ethylene-propylene rubber (EPM rubber), and one of crosslinked products thereof, from the viewpoint of chemical resistance and hardness. Is preferred. As the crosslinking method, a known method such as sulfur vulcanization or peroxide crosslinking can be used depending on the type of the material.
本発明のガスケットは電極室枠フランジ面に配置され、電解液やガスのリークを防止する。そのため、ガスケットには電気化学反応により電極室で発生したイオン種がイオン交換膜を透過するために電極面積と同程度の大きさの開口部が形成されている。通常、電解槽は上面視で長方形状であるため、ガスケットも長方形状の開口部を有する長方形状になっていることが好ましい。 The gasket of the present invention is disposed on the flange surface of the electrode chamber frame to prevent leakage of the electrolyte or gas. For this reason, the gasket is formed with an opening having a size approximately equal to the electrode area for the ionic species generated in the electrode chamber by the electrochemical reaction to pass through the ion exchange membrane. Usually, since the electrolytic cell is rectangular in a top view, it is preferable that the gasket also has a rectangular shape having a rectangular opening.
本発明のガスケットは、イオン交換膜との接触する面の凹凸差は０．３ｍｍ未満であり、０．２５ｍｍ未満であることが好ましく、０〜０．２ｍｍであることがより好ましい。 In the gasket of the present invention, the unevenness of the surface in contact with the ion exchange membrane is less than 0.3 mm, preferably less than 0.25 mm, and more preferably 0 to 0.2 mm.
本発明のガスケットは、後述する陽極室枠、陰極室枠に具備するガスケットに用いることができるが、陽極室枠に具備するガスケット、陰極室枠に具備するガスケットは同一であっても異なってもよい。陽極室枠に具備するガスケット、陰極室枠に具備するガスケットを同一にすることにより、生産コストや在庫管理コストを低減することができる。さらに、電解槽を組み立てる再に陽極側部品と陰極側部品が異なる場合には、細心の注意を払って組み立てることが求められるが、同一のすなわち陽極側と陰極側の部品を共通化することで、電解槽組立作業の管理を簡便かつ間違いの起こらない様にすることができる。「ガスケットを同一にする」とは同一の寸法を有するように成形されることを指し、具体的には同一の寸法を有する金型から成形されることが好ましい。この際、同一の材質の金型を用い、同一の条件で成形されることがより好ましい。 The gasket of the present invention can be used as a gasket provided in the anode chamber frame and the cathode chamber frame described later, but the gasket provided in the anode chamber frame and the gasket provided in the cathode chamber frame may be the same or different. Good. By using the same gasket for the anode chamber frame and the gasket for the cathode chamber frame, production costs and inventory management costs can be reduced. Furthermore, when the anode part and the cathode part are different when assembling the electrolytic cell, it is necessary to assemble with great care.However, by sharing the same parts, ie, the anode and cathode parts, In addition, the management of the electrolytic cell assembling operation can be performed easily and without error. “Making the gaskets the same” means that they are molded so as to have the same dimensions, and specifically, it is preferable to mold them from a mold having the same dimensions. At this time, it is more preferable that the molds are formed using the same material and under the same conditions.
電極室枠
本発明の電極室枠は電極室枠のフランジ面に本発明の電解槽用ガスケットを具備してなる。電極室枠は陽極、又は陰極を備えてなり、陽極を備える電極室枠を陽極室枠、陰極を備える電極室枠を陰極室枠と記載することができる。本発明の電極室枠は電解槽を作製後に電極室となる部分を指す。
Electrode chamber frame The electrode chamber frame of the present invention is provided with the electrolytic cell gasket of the present invention on the flange surface of the electrode chamber frame. The electrode chamber frame includes an anode or a cathode. An electrode chamber frame including an anode can be referred to as an anode chamber frame, and an electrode chamber frame including a cathode can be referred to as a cathode chamber frame. The electrode chamber frame of the present invention refers to a portion that becomes an electrode chamber after an electrolytic cell is manufactured.
陰極室枠、陽極室枠と電解槽用ガスケットの間に接着剤層・粘着剤層を有することが好ましい。接着剤層・粘着剤層に用いる接着剤・粘着剤としては、乾燥固化型クロロプレン系接着剤等の有機溶剤を含む接着剤・粘着剤、有機溶剤を含まない接着剤・粘着剤いずれも使用することができるが、物性変化を招かない点で有機溶剤を含まない接着剤・粘着剤であることが好ましい。 It is preferable to have an adhesive layer and a pressure-sensitive adhesive layer between the cathode chamber frame, the anode chamber frame and the gasket for the electrolytic cell. As the adhesive / adhesive used for the adhesive layer / adhesive layer, any adhesive / adhesive containing an organic solvent, such as a dry-solidified chloroprene-based adhesive, or any adhesive / adhesive containing no organic solvent is used. However, adhesives and pressure-sensitive adhesives containing no organic solvent are preferable because they do not cause a change in physical properties.
有機溶剤を含まない接着剤としては、反応系接着剤が好ましく、エポキシ樹脂系接着剤（１液系・２液混合系）、シアノアクリレート系接着剤、ポリウレタン系接着剤、アクリル系接着剤、アクリル樹脂系接着剤、その他の反応系接着剤、エポキシ変成シリコーン系、アクリル変成シリコーン系等の変成シリコーン系接着剤、シリル化ウレタン系接着剤等が挙げられる。有機溶剤を含まない粘着剤としてはアクリル系粘着剤や、ウレタン系粘着剤、シリコーン系粘着剤が例示できる。 As the adhesive containing no organic solvent, a reactive adhesive is preferable, and an epoxy resin-based adhesive (one-component / two-component mixed), a cyanoacrylate-based adhesive, a polyurethane-based adhesive, an acrylic-based adhesive, acrylic Examples include resin-based adhesives, other reactive adhesives, modified silicone-based adhesives such as epoxy-modified silicone-based, and acrylic-modified silicone-based adhesives, and silylated urethane-based adhesives. Examples of the adhesive containing no organic solvent include an acrylic adhesive, a urethane adhesive, and a silicone adhesive.
電解槽
本発明の電解槽は、本発明の電極室枠により構成される電極室を具備する。好ましくは、本発明の電極室枠により構成される電極室、イオン交換膜を具備する。
Electrolyzer The electrolyzer of the present invention includes an electrode chamber constituted by the electrode chamber frame of the present invention. Preferably, an electrode chamber constituted by the electrode chamber frame of the present invention and an ion exchange membrane are provided.
本発明の陽極室枠に具備された陽極は、開口を有する導電性基体とその導電性基体上に設けられる触媒層とを有する。 The anode provided in the anode chamber frame of the present invention has a conductive substrate having an opening and a catalyst layer provided on the conductive substrate.
導電性基体としては、耐食性を有するチタニウム製エキスパンドメタル、チタニウム製織網又はチタニウム製パンチングメタルが好ましく、均一導電性と経済性の観点から、チタン製エキスパンドメタルが特に好ましい。導電性基体の開口率は、機械的強度と通液性とを両立させるために、２５〜７５％であることが好ましい。 As the conductive substrate, a titanium expanded metal, a titanium woven mesh or a titanium punched metal having corrosion resistance is preferable, and a titanium expanded metal is particularly preferable from the viewpoint of uniform conductivity and economy. The aperture ratio of the conductive substrate is preferably 25 to 75% in order to achieve both mechanical strength and liquid permeability.
陽極の触媒層、即ち、導電性基体の表面に被覆する電極活性物質として、イリジウム、ルテニウム、白金、パラジウム等の白金族金属と、チタン、タンタル、ニオブ、タングステン、ジルコニウム等のバルブ金属及び錫からなる群より選ばれた１種類以上の金属の酸化物との混合酸化物が好ましい。一例として、イリジウム−ルテニウム−チタン混合酸化物、イリジウム−ルテニウム−白金−チタン混合酸化物、白金及びイリジウム酸化物が挙げられる。また、水酸化アルカリ化合物の水溶液を陽極液として電解する場合にはニッケルを含む化合物を電極活性物質として用いることができる。 The catalyst layer of the anode, that is, as an electrode active material coated on the surface of the conductive substrate, iridium, ruthenium, platinum, platinum group metals such as palladium, and titanium, tantalum, niobium, tungsten, valve metals such as zirconium and tin. Preference is given to mixed oxides with oxides of one or more metals selected from the group consisting of: Examples include iridium-ruthenium-titanium mixed oxide, iridium-ruthenium-platinum-titanium mixed oxide, platinum and iridium oxide. When electrolysis is performed using an aqueous solution of an alkali hydroxide compound as an anolyte, a compound containing nickel can be used as the electrode active material.
導電性基体に行う表面処理として、機械的表面処理及び化学的表面処理が挙げられる。機械的表面処理法として、微細な研磨材を使用し、基材の表面を緻密に凹凸化するブラスト処理法があり、また、化学的表面処理の方法として、シュウ酸、硝酸、硫酸、塩酸、フッ酸等の浴中で化学エッチング処理を行う方法がある。 Examples of the surface treatment performed on the conductive substrate include a mechanical surface treatment and a chemical surface treatment. As a mechanical surface treatment method, there is a blast treatment method in which a fine abrasive is used and the surface of the base material is made finely uneven, and as a chemical surface treatment method, oxalic acid, nitric acid, sulfuric acid, hydrochloric acid, There is a method of performing a chemical etching treatment in a bath of hydrofluoric acid or the like.
斯かる表面処理は、前記化学的表面処理を単独に又は前記機械的表面処理を単独に行ってもよく、両処理法を組み合わせてもよい。なお、陽極の表面に形成される凹凸の高低差の最大値は、通液性の確保とイオン交換膜の保護とを両立させるために、３〜５０μｍであることが好ましく、５〜４０μｍであることがより好ましい。 In such a surface treatment, the chemical surface treatment may be performed alone or the mechanical surface treatment may be performed alone, or both treatment methods may be combined. In addition, the maximum value of the height difference of the unevenness formed on the surface of the anode is preferably 3 to 50 μm, and more preferably 5 to 40 μm, in order to ensure both liquid permeability and protection of the ion exchange membrane. Is more preferable.
本発明の陰極室枠に具備された陰極は、開口を有する導電性基体とその導電性基体上に設けられる触媒層とを有する。 The cathode provided in the cathode chamber frame of the present invention has a conductive substrate having an opening and a catalyst layer provided on the conductive substrate.
また、陰極の導電性基体は、鉄、銅、ステンレス、ニッケル等を使うことが可能であり、特に耐食性等の点からはニッケルを使うことが好ましい。導電性基体の形状は通液性を確保し、均一な導電性が保たれることが望まれ、具体的にはエキスパンドメタル、パンチングメタル、ファインメッシュ、平織メッシュがよく、例えば、ニッケル製ファインメッシュ又はニッケル製平織メッシュであることが好ましい。斯かる陰極の導電性基体における開口率は、２５〜７５％であることが好ましい。 The conductive base of the cathode can be made of iron, copper, stainless steel, nickel, or the like. It is particularly preferable to use nickel from the viewpoint of corrosion resistance and the like. It is desired that the shape of the conductive substrate ensure liquid permeability and maintain uniform conductivity. Specifically, expanded metal, punched metal, fine mesh, and plain woven mesh are preferable. Alternatively, it is preferably a nickel plain woven mesh. The aperture ratio of the cathode in the conductive substrate is preferably 25 to 75%.
陰極の触媒層、即ち、導電性基体の表面に被覆する電極活性物質として、白金、パラジウム、ルテニウム、イリジウム、銅、銀、錫、ニッケル、コバルト及び鉛等の金属又はそれらの単一もしくは混合物や混合酸化物の使用が好ましい。 As a cathode catalyst layer, that is, as an electrode active material coated on the surface of the conductive substrate, metals such as platinum, palladium, ruthenium, iridium, copper, silver, tin, nickel, cobalt and lead, or a single or mixture thereof, The use of mixed oxides is preferred.
本発明の電解槽は、陽極と、陰極と、それらの間に配置されるイオン交換膜と、を備えており、陽極を有する陽極室、及び陰極を有する陰極室を構成する。電解槽内に所定数の電極ユニットが同一極性で縦列的に配置され、隣接するユニットにイオン交換膜が配置されることにより複極式電解槽を形成することができる。また、単極式電解槽の場合、１つの電極ユニットの両側に、陽極又は陰極の何れかが形成され、それぞれの電極ユニットがイオン交換膜を介して交互に配置されることで単極式電解槽を形成することができる。本発明の電解槽は、単極式又は複極式の電解槽の何れの方式にも適用することができる。また、電解槽組立状態で陽極と陰極の極間距離により、ギャップ式、ナローギャップ式、ファイナイトギャップ式、ゼロギャップ式といった分類をする場合もあるが、ガスケットの位置関係においては電極間距離の影響を受けないため、いずれの方式にも本発明の電解槽を適用することができる。 The electrolytic cell of the present invention includes an anode, a cathode, and an ion-exchange membrane disposed therebetween, and forms an anode chamber having an anode and a cathode chamber having a cathode. A bipolar electrode tank can be formed by arranging a predetermined number of electrode units in the electrolytic cell in tandem with the same polarity, and arranging an ion exchange membrane in an adjacent unit. In the case of a monopolar electrolytic cell, either an anode or a cathode is formed on both sides of one electrode unit, and the respective electrode units are alternately arranged via an ion exchange membrane, so that the monopolar electrolytic cell is formed. A bath can be formed. The electrolytic cell of the present invention can be applied to any of a monopolar electrolytic cell and a bipolar electrolytic cell. In addition, depending on the distance between the anode and the cathode in the assembled state of the electrolytic cell, there are cases where the gap type, narrow gap type, finite gap type, and zero gap type are classified. Since it is not affected, the electrolytic cell of the present invention can be applied to any of the methods.
本発明の電解槽は、陰極室枠、及び陽極室枠に具備される電解槽用ガスケットが同一であることが好ましく、更に押し型面に接触して成型されるガスケット面が対面する（向い合う）関係となるように配置することが好ましい。尚、本願発明においては、ガスケット面には、金型を用いてプレス成型する際には、押し型面に接触して成型されるガスケット面と受け型面に接触して成型されるガスケット面が存在する。この際、ガスケットを金型等で成形する場合には、製造上の公差が発生する。同一のガスケットを用いて、押し型面に接触して成型されるガスケット面が対面する（向い合う）関係となるように配置することにより、公差を低減することができ、電解槽に用いられるガスケットの枚数が多くなるほど効果が大きくなる。 In the electrolytic cell of the present invention, it is preferable that the gaskets for the electrolytic cell provided in the cathode chamber frame and the anode chamber frame are the same, and the gasket surfaces formed in contact with the pressing mold surface face each other (facing each other). It is preferable to arrange them so as to have a relationship. In the present invention, the gasket surface has a gasket surface formed by contacting the pressing die surface and a gasket surface formed by contacting the receiving die surface when press-molding using a mold. Exists. At this time, when the gasket is formed by a mold or the like, a manufacturing tolerance occurs. By using the same gasket and arranging the gasket surface formed in contact with the pressing die surface so as to have a facing (facing) relationship, the tolerance can be reduced, and the gasket used in the electrolytic cell The effect increases as the number of images increases.
電極室枠、電解槽の製造方法
本発明の電極室枠、電解槽の製造方法は、ガスケットを電極室枠のフランジ面に具備する工程を含み、具備させる工程としては接着剤や粘着剤を塗布する工程（塗布工程）であることが好ましい。接着剤、粘着剤は段落「００１８」に記載されている接着剤、粘着剤を用いることができる。
Method for producing electrode chamber frame and electrolytic cell The method for producing an electrode chamber frame and electrolytic cell of the present invention includes a step of providing a gasket on a flange surface of the electrode chamber frame, and the step of applying a gasket includes applying an adhesive or a pressure-sensitive adhesive. (A coating step). The adhesive and the pressure-sensitive adhesive described in paragraph “0018” can be used as the adhesive and the pressure-sensitive adhesive.
塗布工程により、ガスケットを具備させる場合には、ガスケット、電極室枠のフランジ面の両方又は片方に塗布すればよく、具備させる面の全部、又は一部に塗布することができる。尚、粘着剤は一般的にはフィルム等の支持体を用い、支持体に塗工された両面テープ等の粘着製品を貼り付ける等により塗布される。 When a gasket is provided in the application step, the gasket may be applied to both or one of the flange surfaces of the electrode chamber frame, and may be applied to all or a part of the provided surface. The pressure-sensitive adhesive is generally applied by using a support such as a film and attaching an adhesive product such as a double-sided tape applied to the support.
また、本発明の電極室枠、電解槽の製造方法においては、電極室にガスケットを具備する工程（塗布工程）の前にガスケットをエタノール等のアルコール系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、及び水から選択される溶剤で洗浄する工程（洗浄工程）を含むことが好ましい。ガスケットの材料であるゴム成形品は、一般的に金型を使用した加硫工程を経て製造され、加硫工程で金型からゴム成形品を取り外しやすくするために離型剤が使用される。ガスケットを電極室枠のフランジ面に具備させる際に、ガスケット表面に離型剤が残存していると粘着剤・接着剤の効果が低下する場合がある。そこで、ガスケット表面に残存する離型剤を拭き取り（洗浄により）除去することで粘着剤・接着剤の効果が改善される。ガスケット表面を拭き取る際には、ガスケットの損傷を引き起こしにくい水、アルコール、揮発性の高いケトン系溶剤を使用することが好ましく、フッ素系やケイ素系の離型剤を効率よく簡便に除去するためにエタノールやアセトンを使用することが好ましい。尚、電極室枠のフランジ面における不純物を除去する目的で、アルコール系溶剤、ケトン系溶剤、及び水から選択される溶剤で洗浄してもよく、洗浄することが好ましい。 In the method for manufacturing an electrode chamber frame and an electrolytic cell according to the present invention, the gasket may be placed on an alcohol-based solvent such as ethanol, a ketone-based solvent such as acetone or methyl ethyl ketone before a step (coating step) of providing a gasket in the electrode chamber, And a step of washing with a solvent selected from water and water (washing step). A rubber molded product, which is a material of a gasket, is generally manufactured through a vulcanization process using a mold, and a release agent is used to facilitate removal of the rubber molded product from the mold in the vulcanization process. When the gasket is provided on the flange surface of the electrode chamber frame, if the release agent remains on the gasket surface, the effect of the pressure-sensitive adhesive / adhesive may be reduced. Therefore, the effect of the pressure-sensitive adhesive / adhesive is improved by wiping (by washing) the release agent remaining on the gasket surface. When wiping the gasket surface, it is preferable to use water, alcohol, or a highly volatile ketone-based solvent that does not easily damage the gasket, in order to efficiently and easily remove the fluorine-based or silicon-based release agent. Preferably, ethanol or acetone is used. In addition, in order to remove impurities on the flange surface of the electrode chamber frame, the electrode chamber may be washed with a solvent selected from an alcohol-based solvent, a ketone-based solvent, and water, and is preferably washed.
本発明により、ギャザーを有することにより劣化することがないために、メンテナンスの頻度を低減することができる電解槽を提供できるために有用である。 INDUSTRIAL APPLICABILITY The present invention is useful because it can provide an electrolytic cell that can reduce the frequency of maintenance because it does not deteriorate due to having gathers.
１０１ 陽極室枠（陽極室）
１０２ 陽極
１０３ 陽極フランジ面
１０４ 陽極ガスケット
１０５ イオン交換膜
１０６ 陰極室枠（陰極室）
１０７ 陰極
１０８ 陰極フランジ面
１０９ 陰極ガスケット
２０１ 複極室枠における陽極室
２０２ 陽極
２０３ 陽極室枠フランジ面
２０４ 陰極ガスケット
２０５ イオン交換膜
２０６ 複極室枠における陰極室
２０７ 陰極
２０８ 陰極フランジ面
２０９ 陽極ガスケット
２１０ 隔壁
101 Anode compartment frame (Anode compartment)
102 Anode 103 Anode flange surface 104 Anode gasket 105 Ion exchange membrane 106 Cathode chamber frame (cathode chamber)
107 Cathode 108 Cathode flange surface 109 Cathode gasket 201 Anode chamber 202 in multipole chamber frame Anode 203 Anode chamber frame flange face 204 Cathode gasket 205 Ion exchange membrane 206 Cathode chamber 207 in multipole chamber frame Cathode 208 Cathode flange face 209 Anode gasket 210 Partition
Claims (8)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018182712A JP7440999B2 (en) | 2018-09-27 | 2018-09-27 | Gasket for electrolytic cell and electrolytic cell |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018182712A JP7440999B2 (en) | 2018-09-27 | 2018-09-27 | Gasket for electrolytic cell and electrolytic cell |
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| Publication Number | Publication Date |
|---|---|
| JP2020050924A true JP2020050924A (en) | 2020-04-02 |
| JP7440999B2 JP7440999B2 (en) | 2024-02-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2018182712A Active JP7440999B2 (en) | 2018-09-27 | 2018-09-27 | Gasket for electrolytic cell and electrolytic cell |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6156290A (en) * | 1984-08-28 | 1986-03-20 | Showa Denko Kk | Method for attaching ion exchange membrane |
| JPS63216990A (en) * | 1987-02-27 | 1988-09-09 | ザ ダウ ケミカル カンパニ− | Hermetical seal method of electrolytic cell, electrolytic assembly and electrolytic cell hermetical seal method |
| JPH0364490A (en) * | 1989-07-31 | 1991-03-19 | Asahi Chem Ind Co Ltd | Gasket for filter press-type electrolytic cell, its production and the cell provided with the gasket |
| JPH03285984A (en) * | 1990-03-30 | 1991-12-17 | Toyo Tire & Rubber Co Ltd | Gasket for electrolysis tank and preparation thereof |
| JPH059772A (en) * | 1991-07-04 | 1993-01-19 | Asahi Chem Ind Co Ltd | Electrolytic cell for alkali chloride solution |
| JP2000178780A (en) * | 1998-12-14 | 2000-06-27 | Asahi Chem Ind Co Ltd | Gasket for electrolyzing alkali chloride |
| JP2001280504A (en) * | 2000-03-31 | 2001-10-10 | Nichias Corp | Rubber gasket structure and manufacturing method therefor |
| JP2001335981A (en) * | 2000-05-29 | 2001-12-07 | Showa Rubber Co Ltd | Gasket for electrolytic cell of ion exchange membrane |
| JP2004223766A (en) * | 2003-01-20 | 2004-08-12 | Moon Star Co | Gasket manufacturing method and press mold structure used in the method |
-
2018
- 2018-09-27 JP JP2018182712A patent/JP7440999B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6156290A (en) * | 1984-08-28 | 1986-03-20 | Showa Denko Kk | Method for attaching ion exchange membrane |
| JPS63216990A (en) * | 1987-02-27 | 1988-09-09 | ザ ダウ ケミカル カンパニ− | Hermetical seal method of electrolytic cell, electrolytic assembly and electrolytic cell hermetical seal method |
| JPH0364490A (en) * | 1989-07-31 | 1991-03-19 | Asahi Chem Ind Co Ltd | Gasket for filter press-type electrolytic cell, its production and the cell provided with the gasket |
| JPH03285984A (en) * | 1990-03-30 | 1991-12-17 | Toyo Tire & Rubber Co Ltd | Gasket for electrolysis tank and preparation thereof |
| JPH059772A (en) * | 1991-07-04 | 1993-01-19 | Asahi Chem Ind Co Ltd | Electrolytic cell for alkali chloride solution |
| JP2000178780A (en) * | 1998-12-14 | 2000-06-27 | Asahi Chem Ind Co Ltd | Gasket for electrolyzing alkali chloride |
| JP2001280504A (en) * | 2000-03-31 | 2001-10-10 | Nichias Corp | Rubber gasket structure and manufacturing method therefor |
| JP2001335981A (en) * | 2000-05-29 | 2001-12-07 | Showa Rubber Co Ltd | Gasket for electrolytic cell of ion exchange membrane |
| JP2004223766A (en) * | 2003-01-20 | 2004-08-12 | Moon Star Co | Gasket manufacturing method and press mold structure used in the method |
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|---|---|
| JP7440999B2 (en) | 2024-02-29 |
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