JP2001262471A - Radical decomposition-resistant fiber structure and polymer electrolytic membrane composite using the same as a reinforcing material - Google Patents
Radical decomposition-resistant fiber structure and polymer electrolytic membrane composite using the same as a reinforcing materialInfo
- Publication number
- JP2001262471A JP2001262471A JP2000073662A JP2000073662A JP2001262471A JP 2001262471 A JP2001262471 A JP 2001262471A JP 2000073662 A JP2000073662 A JP 2000073662A JP 2000073662 A JP2000073662 A JP 2000073662A JP 2001262471 A JP2001262471 A JP 2001262471A
- Authority
- JP
- Japan
- Prior art keywords
- radical
- decomposition
- fibrous base
- base material
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 62
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 title claims description 10
- 239000002131 composite material Substances 0.000 title claims description 7
- 239000012779 reinforcing material Substances 0.000 title abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 87
- 238000000576 coating method Methods 0.000 claims abstract description 56
- 239000011248 coating agent Substances 0.000 claims abstract description 55
- 229920001281 polyalkylene Polymers 0.000 claims abstract description 49
- 239000004745 nonwoven fabric Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 21
- 239000002759 woven fabric Substances 0.000 claims description 19
- 239000005518 polymer electrolyte Substances 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 6
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 6
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 claims description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 5
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 229920006120 non-fluorinated polymer Polymers 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 16
- 239000000446 fuel Substances 0.000 abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 229920001940 conductive polymer Polymers 0.000 abstract description 6
- 238000004364 calculation method Methods 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012783 reinforcing fiber Substances 0.000 abstract 2
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 abstract 1
- 229920005594 polymer fiber Polymers 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 37
- 230000015556 catabolic process Effects 0.000 description 28
- 238000006731 degradation reaction Methods 0.000 description 28
- -1 polytetrafluoroethylene Polymers 0.000 description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 description 15
- 238000009864 tensile test Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 8
- 230000001737 promoting effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 230000002542 deteriorative effect Effects 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012028 Fenton's reagent Substances 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CHDVXKLFZBWKEN-UHFFFAOYSA-N C=C.F.F.F.Cl Chemical compound C=C.F.F.F.Cl CHDVXKLFZBWKEN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OEJFYPLFUBTHDI-UHFFFAOYSA-N CC=C.C=C.C=C(F)F.F.F.F.F.F.F Chemical group CC=C.C=C.C=C(F)F.F.F.F.F.F.F OEJFYPLFUBTHDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101000856234 Clostridium acetobutylicum (strain ATCC 824 / DSM 792 / JCM 1419 / LMG 5710 / VKM B-1787) Butyrate-acetoacetate CoA-transferase subunit A Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- DXXYTBCIXZGERI-UHFFFAOYSA-N O.O.O.O.O.O.O.[Fe] Chemical compound O.O.O.O.O.O.O.[Fe] DXXYTBCIXZGERI-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Nonwoven Fabrics (AREA)
- Woven Fabrics (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な耐ラジカル
分解性繊維構造物に関する。更に詳しくは、耐ラジカル
分解性が要求される水溶液中での用途、例えば、電気分
解、一次電池や二次電池のセパレーターとして、あるい
は燃料電池に用いられる水素イオン伝導性高分子膜の補
強材として、有用な耐ラジカル分解性繊維構造物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel radical-decomposition resistant fiber structure. More specifically, use in an aqueous solution in which radical decomposition resistance is required, such as electrolysis, as a separator for a primary battery or a secondary battery, or as a reinforcing material for a hydrogen ion conductive polymer membrane used in a fuel cell. And a useful radical-decomposition-resistant fiber structure.
【０００２】[0002]
【従来の技術】近年、電気分解、一次電池や二次電池に
おけるセパレーター、あるいは燃料電池に用いられる水
素イオン伝導性高分子膜の補強材等として、合成繊維の
不織布、織布、短繊維等の繊維質基材を使用することが
検討されている。2. Description of the Related Art In recent years, synthetic fibers such as nonwoven fabrics, woven fabrics and short fibers have been used as separators in electrolysis, primary batteries and secondary batteries, or as reinforcing materials for hydrogen ion conductive polymer membranes used in fuel cells. The use of fibrous substrates is being considered.
【０００３】現在、高分子電解質膜の材料としては、デ
ュポン社の「ナフィオン」に代表される、パーフルオロ
アルキルスルホン酸や、米国特許第５,３６２,８３６号
に記載されるスルホン酸基を置換したポリエーテルエー
テルケトン、特開平１０−４５９１３号公報に記載され
るポリエーテルスルホン等がある。At present, as a material for a polymer electrolyte membrane, perfluoroalkylsulfonic acid represented by "Nafion" of DuPont or a sulfonic acid group described in US Pat. No. 5,362,836 is substituted. And polyether sulfone described in JP-A-10-45913.
【０００４】しかしながら、これらから製膜された高分
子電解質膜の水素イオン伝導性を発現させるためには、
水による膨潤が必須である。このような膨潤した膜は機
械強度的に非常に弱く、高いスルホン酸基置換量では水
に溶解してしまう物もある。そのため、これらの高分子
電解質膜では、実際に高分子電解質型燃料電池を構成し
た場合、耐久性が悪いというのが実状である。However, in order to make the polymer electrolyte membrane formed from these materials exhibit hydrogen ion conductivity,
Swelling with water is essential. Such a swollen film is very weak in mechanical strength, and there are some which dissolve in water at a high sulfonic acid group substitution amount. Therefore, in reality, these polymer electrolyte membranes have poor durability when a polymer electrolyte fuel cell is actually constructed.
【０００５】このような課題に対し、米国特許第５,５
４７,５５１号、特開平６−２３０７８０号公報、第３
回国際燃料電池会議（１９９９年）要項集Ａ３−６、Ａ
４−１、Ａ４−２等に記載されるように、ポリ四フッ化
エチレンの多孔膜、織布、短繊維分散による補強が検討
されている。In order to solve such a problem, US Pat.
47,551, JP-A-6-230780, No. 3
International Fuel Cell Conference (1999) Essentials A3-6, A
As described in 4-1 and A4-2, reinforcement by dispersion of a polytetrafluoroethylene porous film, a woven fabric, and short fibers has been studied.
【０００６】しかしながら、高分子電解質型燃料電池の
実用性からは、ポリ四フッ化エチレンは高価で経済的な
問題がある。また、材料の選択性が無く、補強材にはポ
リ四フッ化エチレンの特性が強いられることとなる。例
えば、ポリ四フッ化エチレンの表面張力が小さいことに
より、電解質複合膜を作製しても界面密着が不十分とな
ってしまうことがある。However, from the practicality of the polymer electrolyte fuel cell, polytetrafluoroethylene has an expensive and economical problem. Further, there is no material selectivity, and the properties of polytetrafluoroethylene are imposed on the reinforcing material. For example, due to the low surface tension of polytetrafluoroethylene, interfacial adhesion may be insufficient even when an electrolyte composite membrane is produced.
【０００７】ポリ四フッ化エチレン以外の補強材とし
て、特開昭６４−２２９３２号公報ではポリオレフィン
からなる多孔性薄膜が紹介されている。しかしながら、
この多孔性薄膜は、高分子電解質型燃料電池が実際に使
用される温度、湿度環境での耐久性について充分に耐え
られる物とは言い難い。As a reinforcing material other than polytetrafluoroethylene, JP-A-64-22932 introduces a porous thin film made of polyolefin. However,
It is hard to say that this porous thin film can sufficiently withstand the durability in a temperature and humidity environment where the polymer electrolyte fuel cell is actually used.
【０００８】一方、その他の既存の合成繊維からなる繊
維質基材、例えば、ポリエステル、ポリアミド等の不織
布、織布を用いた場合は、耐久性とりわけ耐ラジカル分
解性が悪く、長時間ラジカル環境下に置かれた場合、繊
維を構成する高分子重合体自体の分解劣化が進行して、
強度が顕著に低下してしまう。On the other hand, when other existing fibrous base materials made of synthetic fibers, for example, non-woven fabrics or woven fabrics such as polyester and polyamide, are used, the durability, especially the resistance to radical decomposition, is poor, and the use in a radical environment for a long time is difficult. When placed in, the degradation of the polymer itself constituting the fiber progresses,
The strength is significantly reduced.
【０００９】特開平１０−３１２８１５号公報において
は、合成繊維を含めた各種の繊維補強材が利用可能とさ
れており、特に、このような補強材を異種材料で塗工被
覆して、特定の用途に要求される特性を付与することが
できると記載されているが、具体的に耐久性を向上させ
る手段は開示されていない。[0009] In Japanese Patent Application Laid-Open No. 10-321815, various fiber reinforcements including synthetic fibers can be used. In particular, such reinforcements are coated and coated with different materials to obtain a specific material. Although it is described that properties required for use can be imparted, there is no specific disclosure of means for improving durability.
【００１０】ところで、高分子電解質型燃料電池の汎用
性が阻害されている要因として、高分子電解質膜の耐久
性を含めた実用性が不十分という点と各構成材料が高価
であるという点が挙げられる。耐久性の観点からは特に
耐ラジカル分解性が該膜に使用される材料への特性とし
て要求されるが、ポリ四フッ化エチレン以外の基材は長
時間ラジカル環境下に置かれた場合、高分子重合体自体
の分解劣化が進行して、該基材の強度が顕著に低下して
しまう。[0010] By the way, factors that hinder the versatility of the polymer electrolyte fuel cell are that the practicality including the durability of the polymer electrolyte membrane is insufficient, and that each constituent material is expensive. No. From the viewpoint of durability, radical decomposition resistance is particularly required as a property of the material used for the film. However, a substrate other than polytetrafluoroethylene has a high The degradation of the molecular polymer itself progresses, and the strength of the base material is significantly reduced.
【００１１】また、同様に水の存在下で使用される電気
分解や一次又は二次電池のセパレータとしても同じ問題
がある。[0011] Similarly, there is the same problem as the separator used in the electrolysis or primary or secondary battery used in the presence of water.
【００１２】[0012]
【発明が解決しようとする課題】したがって、本発明の
主たる目的は、このラジカル分解性を改善することによ
り、ポリ四弗化エチレン以外の各種繊維質基材を用いて
固体高分子型電解質膜の補強材等として有用なものを提
供することにある。SUMMARY OF THE INVENTION Accordingly, a main object of the present invention is to improve the radical decomposability and to improve the solid polymer electrolyte membrane using various fibrous substrates other than polytetrafluoroethylene. It is to provide a useful material such as a reinforcing material.
【００１３】[0013]
【課題を解決するための手段】本発明に係る新規な耐ラ
ジカル分解性繊維構造物は、熱変形開始温度が８０℃以
上の非フッ素系高分子重合体繊維よりなる繊維質基材の
繊維表面に、計算化学による炭素−フッ素の２中心結合
エネルギー絶対値がいずれも１６．５ｅＶより大きく、
かつ、溶媒可溶なフッ素化ポリアルキレン溶液を含む被
覆材により、繊維質基材の重量に対し１〜３０重量％の
範囲の被覆量で被覆されていることを特徴とするもので
ある。SUMMARY OF THE INVENTION The novel radical-decomposition resistant fiber structure according to the present invention provides a fiber surface of a fibrous base material made of non-fluorinated high molecular weight polymer fibers having a heat deformation initiation temperature of 80 ° C. or higher. In addition, the absolute value of the two-center bond energy of carbon-fluorine by computational chemistry is larger than 16.5 eV,
The fibrous base material is coated with a coating material containing a solvent-soluble fluorinated polyalkylene solution in a coating amount of 1 to 30% by weight based on the weight of the fibrous base material.
【００１４】本発明では、このような耐ラジカル分解性
繊維構造物に関し、次の各発明も包含する。 １）繊維質基材が、不織布あるいは織布であることを特
徴とする、上記の耐ラジカル分解性繊維構造物。 ２）繊維質基材が、ポリアルキレン、塩化ポリアルキレ
ン、ポリエステルあるいはこれらの共重合体よりなる非
フッ素系高分子重合体の繊維を１種類以上用いて形成さ
れていることを特徴とする、上記の耐ラジカル分解性繊
維構造物。 ３）溶媒可溶なフッ素化ポリアルキレンが、四フッ化エ
チレン、六フッ化プロピレン、フッ化ビニリデン、三フ
ッ化塩化エチレンの少なくとも１種をモノマーとする、
単一重合体、共重合体あるいはこれらの重合体同士の混
合物であることを特徴とする、上記の耐ラジカル分解性
繊維構造物。 ４）溶媒可溶なフッ素化ポリアルキレンの溶液を含む被
覆材による被覆量が、繊維質基材の重量に対し４〜２０
重量％であることを特徴とする、上記の耐ラジカル分解
性繊維構造物。 ５）非フッ素系高分子繊維よりなる繊維質基材の繊維表
面に溶媒可溶なフッ素化ポリアルキレンの溶液を含む被
覆材により被覆し、溶媒を除去した後、さらに放射線照
射を施したことを特徴とする、上記の耐ラジカル分解性
繊維構造物。 ６）上記の耐ラジカル分解性繊維構造物で補強したこと
を特徴とする水の存在下で使用される高分子電解質膜複
合体。The present invention relates to such a radically degradable fiber structure, and includes the following inventions. 1) The above radical-resistant fiber structure, wherein the fibrous base material is a nonwoven fabric or a woven fabric. 2) The fibrous base material is formed by using one or more kinds of non-fluorinated high molecular weight fibers made of polyalkylene, polyalkylene chloride, polyester or a copolymer thereof. Radical resistant fiber structure. 3) The solvent-soluble fluorinated polyalkylene has at least one of ethylene tetrafluoride, propylene hexafluoride, vinylidene fluoride and ethylene trifluoride chloride as a monomer,
The fibrous structure resistant to radical decomposition described above, which is a homopolymer, a copolymer, or a mixture of these polymers. 4) The coating amount of the coating material containing the solvent-soluble fluorinated polyalkylene solution is 4 to 20 with respect to the weight of the fibrous base material.
The above radical-resistant fiber structure is characterized in that the fiber structure is in weight%. 5) The fiber surface of the fibrous base material made of non-fluorinated polymer fiber was coated with a coating material containing a solution of a solvent-soluble fluorinated polyalkylene, the solvent was removed, and then radiation irradiation was performed. The radical-resistant fiber structure as described above, which is characterized by the following. 6) A polymer electrolyte membrane composite used in the presence of water, which is reinforced with the radical decomposition resistant fiber structure described above.
【００１５】このような本発明の耐ラジカル分解性繊維
構造物は、水の存在下でラジカルに曝される用途、例え
ば、電気分解、一次電池又は二次電池のセパレーターと
して、あるいは燃料電池に用いられる水素イオン伝導性
高分子膜の補強材として、有効に使用できる。また、本
発明の耐ラジカル分解性繊維構造物は、これを用いて、
機械強度的に耐久性のある固体高分子電解質膜複合体を
作製することができる。Such a fibrous structure resistant to radical decomposition according to the present invention is used in applications where it is exposed to radicals in the presence of water, for example, as a separator for electrolysis, primary batteries or secondary batteries, or used in fuel cells. Can be effectively used as a reinforcing material for the hydrogen ion conductive polymer membrane to be obtained. Further, the radical decomposition resistant fiber structure of the present invention, using this,
A solid polymer electrolyte membrane composite having mechanical strength and durability can be produced.
【００１６】[0016]
【発明の実施の形態】本発明は、特定の繊維質基材の繊
維表面が、特定の溶媒可溶なフッ素化ポリアルキレンを
含む被覆材で被覆されている耐ラジカル分解性の繊維構
造物である。以下、繊維質基材、被覆材、この両者から
実質的になる耐ラジカル分解性繊維構造物及びその評価
の順で、本発明の具体的内容を説明する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fibrous structure resistant to radical decomposition, in which the fiber surface of a specific fibrous base material is coated with a coating material containing a specific solvent-soluble fluorinated polyalkylene. is there. Hereinafter, the specific contents of the present invention will be described in the order of the fibrous base material, the coating material, the radically decomposable fiber structure substantially consisting of both, and the evaluation thereof.
【００１７】（１）繊維質基材 水の存在下（水溶液中あるいは水溶液を含浸させた状
態）で使用され耐ラジカル劣化性が要求される本発明の
繊維構造物は、水の沸点以下の比較的高い温度で使用さ
れる。例えば、固体高分子型燃料電池の場合、作動温度
としては８０℃前後が設定される。そのため、それより
も低い温度で熱変形、特に自己収縮を起こす繊維質基材
を用いた場合、実際の使用環境下において顕著に変形を
起こすため、特に補強材として使用する場合、寸法変化
の観点から好ましくない。したがって、本発明では熱変
形開始温度が８０℃以上の非フッ素系高分子重合体繊維
よりなる繊維質基材が使用される。(1) Fibrous base material The fibrous structure of the present invention which is used in the presence of water (in an aqueous solution or in a state impregnated with an aqueous solution) and which is required to have resistance to radical deterioration is compared with the boiling point of water or lower. Used at very high temperatures. For example, in the case of a polymer electrolyte fuel cell, the operating temperature is set at around 80 ° C. Therefore, when a fibrous base material that undergoes thermal deformation at a lower temperature, especially self-shrinkage, is used to cause significant deformation in an actual use environment. Is not preferred. Therefore, in the present invention, a fibrous base material made of non-fluorinated high molecular weight polymer fibers having a heat deformation initiation temperature of 80 ° C. or higher is used.
【００１８】ここで「熱変形開始温度」とは、配向緩
和、溶融等により繊維質基材の形状が顕著に変形を開始
する温度のことであり、ここではティー・エイ・インス
ツルメント社製の熱機械分析装置ＴＭＡ２９４０型を用
いて測定される。測定条件は１００ｃｃ／分窒素気流下
で４ｍｍ幅１２．５ｍｍ間隔にセットした試験片に０．
００５Ｎの荷重を加え、１０℃／分の昇温速度で試験片
の間隔変化を測定し、そして、収縮方向、延伸方向いず
れでも変形が顕著に発生した時の温度−変位曲線の変曲
点を熱変形開始温度とする。Here, the term "thermal deformation starting temperature" means a temperature at which the shape of the fibrous base material remarkably starts to deform due to orientation relaxation, melting, and the like, and is herein manufactured by TA Instruments. Is measured using a thermomechanical analyzer TMA2940. The measurement conditions were as follows: a test piece set at 4 mm width and 12.5 mm interval under a nitrogen flow of 100 cc / min.
A load of 005N was applied, and the change in the interval between the test pieces was measured at a rate of temperature rise of 10 ° C./min. The heat deformation starting temperature.
【００１９】本発明で繊維質基材に用いる非フッ素系高
分子繊維としては、各種の合成繊維が有効であり、例え
ば、ポリエチレン繊維、ポリプロピレン繊維、ポリエス
テル繊維、ポリ塩化ビニル繊維、ポリアミド繊維、アラ
ミド繊維、ポリフェニレンスルフィド繊維等が挙げら
れ、なかでもポリエチレン繊維、ポリプロピレン繊維、
ポリエステル繊維、ポリ塩化ビニル繊維が好適である。As the non-fluorinated polymer fiber used for the fibrous base material in the present invention, various synthetic fibers are effective, for example, polyethylene fiber, polypropylene fiber, polyester fiber, polyvinyl chloride fiber, polyamide fiber, aramid fiber. Fiber, polyphenylene sulfide fiber, etc., among which polyethylene fiber, polypropylene fiber,
Polyester fibers and polyvinyl chloride fibers are preferred.
【００２０】繊維質基材の形態としては不織布、織布、
単独短繊維等の、どのような形状に対しても本発明は適
用することが可能であるが、構造物として用いる観点か
ら、高い強度が実現できる不織布あるいは織布が好まし
い。Non-woven fabric, woven fabric,
The present invention can be applied to any shape such as a single short fiber, but a nonwoven fabric or a woven fabric that can realize high strength is preferable from the viewpoint of use as a structure.
【００２１】そのような不織布、織布からなる繊維質基
材の特性としては、電解質膜の補強材として用いる場
合、イオン伝導性が要求される理由から、目付が５〜５
０ｇ／ｍ2、厚みが５〜１００μｍの不織布又は織布が
好適である。目付が５ｇ／ｍ2よりも低い、あるいは厚
みが５μｍよりも薄い場合は、補強材としての強度を充
分に保つことが困難である。また、目付が５０ｇ／ｍ2
よりも高い場合、空孔率が極端に低くなるか厚みが厚く
なり１００μｍを超えてしまうことがある。この場合、
イオン伝導複合膜とした場合のイオン伝導抵抗が高くな
ってしまう。なお、ここで言う不織布、織布の目付は、
後述する被覆処理後の繊維構造物としての目付である。The characteristics of such a fibrous base material made of a nonwoven fabric or a woven fabric are as follows: when used as a reinforcing material for an electrolyte membrane, the basis weight is 5 to 5 because of the requirement of ionic conductivity.
A nonwoven or woven fabric having a thickness of 0 g / m 2 and a thickness of 5 to 100 μm is suitable. When the basis weight is less than 5 g / m 2 or the thickness is less than 5 μm, it is difficult to sufficiently maintain the strength as a reinforcing material. Also, the basis weight is 50 g / m 2.
If the porosity is higher than the above range, the porosity may be extremely low or the thickness may be large, and may exceed 100 μm. in this case,
In the case of an ion conductive composite membrane, the ion conductive resistance is increased. In addition, the basis weight of the nonwoven fabric and the woven fabric mentioned here is
This is a basis weight as a fiber structure after a coating process described later.
【００２２】（２）被覆材 本発明では上記のような繊維質基材の耐ラジカル分解性
を改善する目的で、特定の被覆材で繊維表面を被覆する
が、本発明者らの研究の結果、該被覆材の構成成分とし
ては、計算化学による炭素−フッ素の２中心結合エネル
ギー絶対値がいずれも１６．５ｅＶより大きく、かつ溶
媒に可溶性を有するフッ素化ポリアルキレンを選択する
ことで効果的に耐ラジカル分解性が改善されることが判
った。(2) Coating material In the present invention, the fiber surface is coated with a specific coating material for the purpose of improving the radical decomposition resistance of the above fibrous base material. Effectively, as a component of the coating material, a fluorinated polyalkylene having a carbon-fluorine two-center binding energy absolute value of greater than 16.5 eV and a solubility in a solvent is selected by computational chemistry. It was found that the radical decomposition resistance was improved.
【００２３】かかるフッ素化ポリアルキレンとして、炭
素−フッ素の２中心結合エネルギー絶対値が１７．０ｅ
Ｖ以上となる炭素−フッ素結合が全炭素−フッ素結合の
５％以上あるフッ素化ポリアルキレンが好ましい。As such a fluorinated polyalkylene, the absolute value of the two-center bond energy of carbon-fluorine is 17.0 e.
A fluorinated polyalkylene having a carbon-fluorine bond of V or more of 5% or more of the total carbon-fluorine bond is preferred.
【００２４】ここで「２中心結合エネルギー」は分子軌
道計算によって求められる２中心エネルギーであり、分
子軌道計算結果は富士通製の分子軌道法プログラムＭＯ
ＰＡＣ９３のＡＭ１法による構造最適化計算により得ら
れる。そして、２中心結合エネルギーはＭｕｌｌｉｋｅ
ｎのエネルギー解析手法によって求められる値である。
なお、同解析法は上記プログラムＭＯＰＡＣのＥＮＰＡ
ＲＴ計算によって得られる。Here, the "two-center binding energy" is the two-center energy obtained by molecular orbital calculation, and the result of molecular orbital calculation is based on the MO program MO
It is obtained by the structure optimization calculation by the PAC93 AM1 method. And the two-center binding energy is Mullike
n is a value obtained by the energy analysis method.
The analysis method is based on the ENPA program MOPAC.
Obtained by RT calculation.
【００２５】計算化学による炭素−フッ素の２中心結合
エネルギー絶対値がいずれも１６．５ｅＶより大きいフ
ッ素化ポリアルキレンには、ポリ四フッ化エチレンも包
含されるが、ポリ四フッ化エチレンの場合、あらゆる溶
媒に対して安定であり、均一な溶媒溶液を調製すること
が困難である。これに対し、ポリ四フッ化エチレンのコ
ロイド分散液がポリ四フッ化エチレンの塗工溶液として
公知であり、例えば、ダイキン工業（株）製ポリフロン
ディスパージョンＤ−１，Ｄ−２がある。しかしなが
ら、この場合でもポリ四フッ化エチレンは微粒子として
塗工表面に添着されるため、繊維表明への均一な被覆が
困難である。Fluorinated polyalkylenes having a carbon-fluorine two-center binding energy absolute value of greater than 16.5 eV by computational chemistry also include polytetrafluoroethylene. In the case of polytetrafluoroethylene, It is difficult to prepare a homogeneous solvent solution that is stable to all solvents. On the other hand, a colloidal dispersion of polytetrafluoroethylene is known as a coating solution of polytetrafluoroethylene, and examples thereof include polyflon dispersions D-1 and D-2 manufactured by Daikin Industries, Ltd. However, even in this case, since polytetrafluoroethylene is attached to the coating surface as fine particles, it is difficult to uniformly coat the fiber surface.
【００２６】そのため、本発明者らは、さきに特願平１
１−２９４９１９号において、耐熱性が非常に高いアラ
ミド樹脂からなる基材にポリ四フッ化エチレン微粒子を
添着後、ポリ四フッ化エチレンの溶融温度以上に加熱し
て添着微粒子を溶解して均一塗膜化する技術を提案し
た。For this reason, the inventors of the present invention have previously disclosed Japanese Patent Application No.
In Japanese Patent No. 1-294919, after adhering polytetrafluoroethylene microparticles to a substrate made of aramid resin having extremely high heat resistance, the mixture is heated to a temperature equal to or higher than the melting temperature of polytetrafluoroethylene to dissolve the adhered microparticles and uniformly coat A technology for film formation was proposed.
【００２７】しかしながら、この場合は、繊維質基材と
しては少なくとも２５０℃以上の熱変形開始温度、熱分
解温度を示すものが必要となり、繊維質基材としての材
料選択の幅が狭くなると共に、２５０℃以上の高温での
熱処理を要するため、生産性が低減する。However, in this case, the fibrous base material needs to have a thermal deformation initiation temperature and a pyrolysis temperature of at least 250 ° C. or more, and the range of material selection as the fibrous base material is reduced. Since heat treatment at a high temperature of 250 ° C. or more is required, productivity is reduced.
【００２８】そのため、本発明では、生産性の観点から
溶媒可溶なフッ素化ポリアルキレンを用いる。上記のよ
うな溶媒可溶なフッ素化ポリアルキレンとしては、四フ
ッ化エチレン、六フッ化プロピレン、フッ化ビニリデ
ン、三フッ化塩化エチレンから選ばれる少なくとも１種
を、ポリマー構造の繰り返し単位で５０モル％以上有す
る単一重合体、共重合体あるいはこのような高分子重合
体同士の混合物で、有機溶媒に容易に溶解し得るものが
選択される。上記のように四フッ化エチレンの単一重合
体は、溶媒に溶解させることが困難という観点から本発
明では使用に適さない。Therefore, in the present invention, a solvent-soluble fluorinated polyalkylene is used from the viewpoint of productivity. As the solvent-soluble fluorinated polyalkylene as described above, at least one selected from ethylene tetrafluoride, propylene hexafluoride, vinylidene fluoride, and ethylene trifluoride chloride is used in an amount of 50 mol per repeating unit of the polymer structure. % Or a mixture of such high-molecular polymers which can be easily dissolved in an organic solvent. As described above, the homopolymer of ethylene tetrafluoride is not suitable for use in the present invention from the viewpoint that it is difficult to dissolve it in a solvent.
【００２９】ここで「溶媒可溶な」とは、少なくとも１
種類の溶媒に、２５℃で５重量％以上の溶質が均一に溶
解することを意味し、その溶解に当たっては攪拌、超音
波、加熱、濃縮等の各種の溶解手段を用いることができ
る。Here, “solvent-soluble” means that at least 1
This means that 5% by weight or more of solute is uniformly dissolved at 25 ° C. in various kinds of solvents, and various kinds of dissolving means such as stirring, ultrasonic waves, heating, and concentration can be used for the dissolution.
【００３０】四フッ化エチレンの単一重合体以外の有機
溶媒可溶性フッ素化ポリアルキレン、例えば、ポリフッ
化ビニリデン、フッ化ビニリデン−四フッ化エチレン共
重合体、フッ化ビニリデン−六フッ化プロピレン共重合
体、フッ化ビニリデン−四フッ化エチレン−三フッ化塩
化エチレン３元共重合体、フッ化ビニリデン−六フッ化
プロピレン−三フッ化塩化エチレン３元共重合体あるい
はこれらの混合物等が、本発明で使用し得る溶媒可溶な
フッ素化ポリアルキレンとしてあげられる。Organic solvent-soluble fluorinated polyalkylenes other than homopolymer of ethylene tetrafluoride, for example, polyvinylidene fluoride, vinylidene fluoride-ethylene tetrafluoride copolymer, vinylidene fluoride-propylene hexafluoride copolymer In the present invention, vinylidene fluoride-ethylene tetrafluoride-ethylene trifluorochloride terpolymer, terpolymer of vinylidene fluoride-propylene hexafluoride-ethylene trifluorochloride or a mixture thereof are used in the present invention. Examples of the usable solvent-soluble fluorinated polyalkylene include:
【００３１】なかでも、フッ化ビニリデンと水素がフッ
素置換された炭素数２〜４のフッ素化ポリアルキレンと
の共重合体が好適なものとしてあげられる。ただし、置
換水素のうち１〜２個が塩素で置換されたものでもよ
い。Among them, a copolymer of vinylidene fluoride and a fluorinated polyalkylene having 2 to 4 carbon atoms in which hydrogen is substituted by hydrogen is mentioned as a preferable example. However, one in which one or two of the substituted hydrogens have been replaced by chlorine may be used.
【００３２】また、上記のフッ素化ポリアルキレンを溶
解する溶媒としては、繊維質基材を溶解、劣化させるこ
と無くフッ素化ポリアルキレンが溶解することができ、
かつ、熱処理乾燥、真空乾燥等で容易に揮発除去できる
溶媒が選択される。そのような溶媒としては沸点が２５
０℃以下の有機極性溶媒が挙げられる。このような有機
極性溶媒としては、アセトン、メチルエチルケトン、シ
クロヘキサノン等に代表されるケトン系溶媒、酢酸メチ
ル、酢酸エチル等のエステル系溶媒、ジメチルホルムア
ミド、ジメチルアセトアミド、Ｎ−メチル−ピロリドン
等のアミド系溶媒等が例示される。これらの溶媒は単一
組成で用いることができるが、フッ素化ポリアルキレン
の溶解性、フッ素化ポリアルキレンの繊維質基材への塗
工性等を調整する目的で複数組成の混合溶媒を用いるこ
ともできる。As the solvent for dissolving the fluorinated polyalkylene, the fluorinated polyalkylene can be dissolved without dissolving or deteriorating the fibrous base material.
In addition, a solvent that can be easily volatilized and removed by heat treatment drying, vacuum drying, or the like is selected. Such solvents have a boiling point of 25.
Organic polar solvents having a temperature of 0 ° C. or lower are mentioned. Examples of such organic polar solvents include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as methyl acetate and ethyl acetate, and amide solvents such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone. Etc. are exemplified. These solvents can be used in a single composition, but a mixed solvent of a plurality of compositions is used for the purpose of adjusting the solubility of the fluorinated polyalkylene, the coating property of the fluorinated polyalkylene on the fibrous base material, and the like. Can also.
【００３３】更に、これらの有機極性溶媒には、塗工性
の調整、繊維質基材の劣化抑制の目的で、貧溶媒等の他
の種類の溶媒や添加剤を副成分として添加混合すること
もできる。そのような溶媒としては水、アルコール、グ
リコール、アルカン等が挙げられ、添加剤としては油
剤、界面活性剤等が挙げられる。Further, for the purpose of adjusting coatability and suppressing deterioration of the fibrous base material, these types of organic polar solvents may be mixed with other types of solvents and additives such as poor solvents as additives. Can also. Examples of such a solvent include water, alcohol, glycol, and alkane, and examples of the additive include an oil agent and a surfactant.
【００３４】なお、被覆材として、このようなフッ素化
ポリアルキレンの溶液に、前述したポリ四フッ化エチレ
ンの微粒子や酸化珪素、酸化アルミ、ガラス等の無機微
粒子あるいはシランカップリング剤等を添加混合したも
のを用いることもできる。ただし、この場合、添加剤の
重量はフッ素化ポリアルキレンの重量より少なくすべき
であり、フッ素化ポリアルキレンの５０重量％以下、特
に３０重量％以下にするのが好ましい。As a coating material, the above-mentioned fluorinated polyalkylene solution is mixed with the above-mentioned fine particles of polytetrafluoroethylene, inorganic fine particles such as silicon oxide, aluminum oxide and glass, or a silane coupling agent. It can also be used. However, in this case, the weight of the additive should be smaller than the weight of the fluorinated polyalkylene, and is preferably 50% by weight or less, particularly preferably 30% by weight or less of the fluorinated polyalkylene.
【００３５】（３）繊維構造物 本発明の構造物では、繊維質基材を構成する繊維表面に
上記フッ素化ポリアルキレンの溶液を含む被覆材を被覆
し溶媒を除去・乾燥するが、その被覆量としては、繊維
質基材の重量を基準にして、固形分重量にして１〜３０
重量％、好適には４〜２０重量％の範囲とする。各種添
加剤を含む場合は、これらの添加剤を含めた被覆量とし
て繊維質基材の重量に対し１〜３０重量％の範囲が好ま
しい。(3) Fiber Structure In the structure of the present invention, the surface of the fiber constituting the fibrous base material is coated with a coating material containing the solution of the above-mentioned fluorinated polyalkylene, and the solvent is removed and dried. The amount is 1 to 30 in terms of solid weight based on the weight of the fibrous base material.
% By weight, preferably 4 to 20% by weight. When various additives are contained, the coating amount including these additives is preferably in the range of 1 to 30% by weight based on the weight of the fibrous base material.
【００３６】ここで「被覆量」とは、被覆する全組成物
から溶媒を除いた所謂固形分の合計重量を意味する。す
なわち、被覆処理後に溶媒を除去した後の被覆材の合計
重量の、繊維質基材の重量(乾燥重量）に対する割合
（重量％）で表わされる。本発明では、被覆量が繊維質
基材の重量の１％重量よりも少ない場合、繊維質基材表
面を均一に被覆するのが困難になり、そのため、被覆さ
れない繊維質基材表面から選択的にラジカル分解が発生
してしまう。The term "coating amount" as used herein means the total weight of so-called solid contents excluding the solvent from the entire composition to be coated. That is, it is expressed as a ratio (% by weight) of the total weight of the coating material after removing the solvent after the coating treatment to the weight (dry weight) of the fibrous base material. In the present invention, when the coating amount is less than 1% by weight of the weight of the fibrous base material, it becomes difficult to uniformly coat the fibrous base material surface, and therefore, it is possible to selectively select from the uncoated fibrous base material surface. Radical decomposition occurs.
【００３７】耐ラジカル分解性の向上の観点からは、フ
ッ素化ポリアルキレンを用いた被覆材の被覆量は多い方
が好ましいが、被覆量が繊維質基材の３０重量％より多
い場合、繊維質基材自体の特性が充分に発揮されなくな
るようになる上、特に不織布、織布の形状の繊維質基材
の場合は、繊維間の空孔が被覆材で顕著に封塞されてし
まい、イオン伝導性を必要特性とするセパレーター、高
分子電解質補強材としては使用に適さないものとなる。
被覆量のより好ましい範囲は繊維質基材の重量の４〜２
０重量％の範囲である。From the viewpoint of improving the radical decomposition resistance, the coating amount of the coating material using the fluorinated polyalkylene is preferably large, but when the coating amount is more than 30% by weight of the fibrous base material, The characteristics of the base material itself will not be sufficiently exhibited, and in particular, in the case of a fibrous base material in the form of a nonwoven fabric or a woven fabric, the pores between the fibers will be remarkably sealed with the coating material. It is unsuitable for use as a separator or a polymer electrolyte reinforcing material that requires conductivity.
A more preferable range of the coating amount is 4 to 2 parts by weight of the fibrous base material.
The range is 0% by weight.
【００３８】上記のような溶媒に溶解したフッ素化ポリ
アルキレン溶液は、各種の手段により繊維質基材表面に
塗工することができる。その手段としてはスプレー法、
ディッピング法等が一般的に簡便な手段として知られて
いる。もちろんこれ以外のマイヤーバーコート、グラビ
アコート等も、フィルム支持体を用いる等の工夫により
活用することができる。この塗工では、繊維質基材にお
いて、セパレーター、補強材等の使用時に水に接する繊
維表面の全体をフッ素化ポリアルキレンで覆うようにす
るのが好ましい。The fluorinated polyalkylene solution dissolved in the above solvent can be applied to the surface of the fibrous base material by various means. The spray method,
A dipping method or the like is generally known as a simple means. Of course, other Meyer bar coats, gravure coats, and the like can also be used by devising a film support or the like. In this coating, it is preferable that the entire surface of the fibrous base material that comes into contact with water when a separator, a reinforcing material, or the like is used is covered with fluorinated polyalkylene.
【００３９】そして、上記のような手段を用いて被覆材
を塗工した繊維質基材は、熱処理乾燥、真空乾燥等の公
知の乾燥手段で溶媒を揮発除去させることができる。こ
れにより繊維質基材表面に均一にフッ素化ポリアルキレ
ンを被覆することができる。The fibrous base material to which the coating material is applied by using the above-described means can be volatilized and removed by a known drying means such as heat treatment drying and vacuum drying. As a result, the surface of the fibrous base material can be uniformly coated with the fluorinated polyalkylene.
【００４０】なお、繊維質基材と被覆材の密着性向上、
被覆材の塗工性向上を目的として、塗工、被覆をする前
に繊維質基材表面にシランカップリング剤処理、コロナ
放電処理等の前処理をすることも可能である。It should be noted that the adhesion between the fibrous base material and the coating material can be improved,
For the purpose of improving the coating property of the coating material, it is also possible to perform a pretreatment such as a silane coupling agent treatment or a corona discharge treatment on the surface of the fibrous base material before coating and coating.
【００４１】更には、このように繊維表面にフッ素化ポ
リアルキレンを被覆した後に放射線照射を行い、照射に
よるフッ素化ポリアルキレンの架橋、不溶化により、被
覆したフッ素化ポリアルキレンの再溶解を抑制すること
も可能である。この場合、更に耐ラジカル分解性も改善
することも判った。Further, after the fiber surface is coated with the fluorinated polyalkylene as described above, irradiation is performed, and the re-dissolution of the coated fluorinated polyalkylene is suppressed by crosslinking and insolubilization of the fluorinated polyalkylene by irradiation. Is also possible. In this case, it was also found that the radical decomposition resistance was further improved.
【００４２】ここで使用する放射線照射としては、γ
線、電子線照射が好ましい。生産性の観点からは電子線
照射がより好ましい。適当な照射量は繊維質基材の耐久
性により変わるが、１００００ｋＧｙ以下、好ましくは
２０００ｋＧｙ以下であれば、繊維質基材自体を劣化さ
せることがない。また、電子線照射による被覆材変性に
は、１ｋＧｙ以上の照射量が好ましい。The radiation irradiation used here is γ
Beam and electron beam irradiation are preferred. From the viewpoint of productivity, electron beam irradiation is more preferable. The appropriate dose depends on the durability of the fibrous base material, but if it is 10,000 kGy or less, preferably 2,000 kGy or less, the fibrous base material itself does not deteriorate. For modifying the coating material by electron beam irradiation, an irradiation amount of 1 kGy or more is preferable.
【００４３】上述のような本発明の繊維構造物は、優れ
た耐ラジカル分解性を有するため、水溶液中で又は水も
しくは水溶液を含浸させてラジカル発生下にて使用する
用途、例えば電気分解、一次電池もしくは二次電池のセ
パレーターとして、また、燃料電池に用いられる水素イ
オン伝導性高分子膜の補強材等として、有効に使用可能
である。Since the fiber structure of the present invention as described above has excellent resistance to radical decomposition, it is used in an aqueous solution or when impregnated with water or an aqueous solution to generate radicals, such as electrolysis, primary electrolysis, and the like. It can be effectively used as a separator of a battery or a secondary battery, or as a reinforcing material for a hydrogen ion conductive polymer membrane used in a fuel cell.
【００４４】該繊維構造物の厚みは、用途によって適宜
選択されるが、一般には、１００μｍ以下が好ましい。The thickness of the fibrous structure is appropriately selected depending on the application, but is generally preferably 100 μm or less.
【００４５】（４）特性の評価 以上のような本発明の繊維構造物における耐ラジカル分
解性は次のようにして評価することができる。まず、ラ
ジカルによる分解処理であるが、これは「膜」１０
（１）（１９８５年）４２頁に記載されているように、
ヒドロキシラジカルを発生するフェントン試薬中に基材
を浸漬するという、ラジカル分解劣化促進処理をするこ
とで行う。具体的には、まず、３０重量％濃度の過酸化
水素水１００重量部に第二鉄イオンが２０ｐｐｍとなる
ように硫酸鉄（II）・七水和物を０．００９９６重量部
添加溶解してフェントン試薬を調製し、そして評価材料
をその試薬に浸漬し、６８℃で２４時間放置する。な
お、フェントン試薬のヒドロキシラジカル発生量は時間
と共に低下するため、途中の５時間経過した時点で、新
たなフェントン試薬と入れ替える。すなわち、６８℃で
５時間浸漬後、新たなフェントン試薬に浸漬し直して６
８℃で１９時間放置する。このようにラジカル分解劣化
促進処理を行った後、評価材料を充分な超純水中で洗浄
し、過剰に付着した水分を拭取り、分解劣化度を評価す
る。(4) Evaluation of Characteristics The radical decomposition resistance of the fiber structure of the present invention as described above can be evaluated as follows. First, the decomposition treatment by radicals is performed using the “film” 10
(1) As described on page 42 (1985),
This is performed by performing a radical decomposition degradation promoting treatment of immersing the substrate in a Fenton reagent that generates hydroxyl radicals. Specifically, first, 0.00996 parts by weight of iron (II) sulfate / heptahydrate was added and dissolved in 100 parts by weight of a 30% by weight aqueous hydrogen peroxide solution so that ferric ion became 20 ppm. A Fenton reagent is prepared and the evaluation material is immersed in the reagent and left at 68 ° C. for 24 hours. Since the amount of hydroxyl radical generated by the Fenton reagent decreases with time, a new Fenton reagent is replaced when five hours have passed halfway. That is, after immersion at 68 ° C. for 5 hours,
Leave at 8 ° C. for 19 hours. After performing the radical decomposition degradation promotion treatment in this way, the evaluation material is washed in a sufficient amount of ultrapure water, excess moisture is wiped off, and the degradation degradation degree is evaluated.
【００４６】分解劣化度は各種の手段で評価できるが、
ここでは引張り試験により、機械強度的に分解劣化度を
評価する手段が用いられる。この引張り試験による分解
劣化度の測定は以下のようにして行われる。まず、引張
り試験は、ＪＩＳ規格Ｋ７１２７に準じて、２５℃で１
０ｃｍ／分の引張り速度で行う。測定サンプルは測定方
向に、長さ２０ｃｍとなるように切り出し、１０ｃｍ間
隔で引張り試験を実施し、その測定値を次の３つのパラ
メーター：引張り弾性率（但し、サンプル形状により単
位異なる。）、最大点荷重（但し、サンプル形状により
単位異なる。）、最大点伸度で表わす。そしてラジカル
分解劣化促進処理前と後でのそれらパラメーターを比較
し、処理前の値に対する低下量の割合(劣化率）をそれ
ぞれのパラメーターにおける分解劣化度とする。The degree of degradation can be evaluated by various means.
Here, means for evaluating the degree of degradation by mechanical strength using a tensile test is used. The measurement of the degree of degradation by the tensile test is performed as follows. First, the tensile test was performed at 25 ° C. in accordance with JIS K7127.
It is performed at a pulling speed of 0 cm / min. The measurement sample is cut out in the measurement direction so as to have a length of 20 cm, a tensile test is performed at 10 cm intervals, and the measured value is measured by the following three parameters: tensile elastic modulus (however, the unit varies depending on the sample shape), and the maximum. Point load (however, the unit varies depending on the sample shape) and maximum point elongation. Then, the parameters before and after the radical decomposition degradation promotion processing are compared, and the ratio of the amount of reduction (deterioration rate) to the value before the processing is defined as the degree of degradation for each parameter.
【００４７】[0047]
【実施例】以下、参考例、実施例及び比較例により、本
発明の構成及び効果を具体的に説明する。ただし、本発
明はこれらによって何ら限定されるものではない。な
お、実施例、比較例の測定値は何れも上記の方法で測定
したものである。EXAMPLES Hereinafter, the structure and effects of the present invention will be described in detail with reference to Reference Examples, Examples and Comparative Examples. However, the present invention is not limited by these. Note that the measured values of the examples and comparative examples are all measured by the above method.
【００４８】［参考例１：ポリ塩化ビニル繊維質基材の
製造］帝人（株）製のポリ塩化ビニル繊維「テビロン」
（ＷＢ５６Ｔ１５、熱変形開始温度９１℃）を用い、目
付量４１ｇ／ｍ2、厚み９０μｍとなるように平織りし
た織布を作製した。この織布について、糸方向に引張り
試験を行った。試験サンプルは糸２０本分に織布を切り
出して行った。そして、各測定パラメーターは糸２０本
当たりでの値として示した。その結果を表１に示す。次
いで、この織布に、ラジカル分解劣化促進処理を行った
後、同様に糸方向に引張り試験を行った。その結果は表
１のようになった。Reference Example 1: Production of polyvinyl chloride fibrous base material "Tevilon", a polyvinyl chloride fiber manufactured by Teijin Limited
(WB56T15, heat deformation start temperature: 91 ° C.), a woven fabric was plain-woven so as to have a basis weight of 41 g / m 2 and a thickness of 90 μm. This woven fabric was subjected to a tensile test in the yarn direction. The test sample was prepared by cutting a woven fabric into 20 yarns. Each measurement parameter was shown as a value per 20 yarns. Table 1 shows the results. Next, the woven fabric was subjected to a radical decomposition degradation promoting treatment, and then a tensile test was similarly performed in the yarn direction. The results are shown in Table 1.
【００４９】［実施例１］参考例１で作製したポリ塩化
ビニル織布に、次のようにフッ素化ポリアルキレンを被
覆した。まず、フッ素化ポリアルキレンとして、フッ化
ビニリデン−ヘキサフルオロプロピレン共重合体（エル
フ・アトケム社製「カイナー」２８０１、フッ化ビニリ
デン／ヘキサフルオロプロピレン＝９／１重量比共重合
体、重量平均分子量３８．５万）を用いた。このポリマ
ーの成分であるフッ化ビニリデンの環状８量体構造及び
ヘキサフルオロプロピレンの環状８量体構造でそれぞれ
炭素−フッ素2中心結合エネルギー絶対値を計算したと
ころ、最小値は１６．７ｅＶであった。Example 1 The polyvinyl chloride woven fabric produced in Reference Example 1 was coated with a fluorinated polyalkylene as follows. First, as a fluorinated polyalkylene, a vinylidene fluoride-hexafluoropropylene copolymer (“Kyner” 2801 manufactured by Elf Atochem Co., a vinylidene fluoride / hexafluoropropylene = 9/1 weight ratio copolymer, a weight average molecular weight of 38) 50,000). When the absolute value of carbon-fluorine two-center bond energy was calculated for each of the cyclic octamer structure of vinylidene fluoride and hexafluoropropylene, which are the components of this polymer, the minimum value was 16.7 eV. .
【００５０】そして、このフッ素化ポリアルキレンをジ
メチルアセトアミド２５重量部、メチルエチルケトン２
５重量部及び１−メトキシ−２−プロパノール５０重量
部からなる混合溶媒に、ポリマー濃度４重量％となるよ
うに攪拌混合して、均一な塗工溶液を調製した。Then, the fluorinated polyalkylene was added to 25 parts by weight of dimethylacetamide and methyl ethyl ketone 2
A uniform coating solution was prepared by stirring and mixing with a mixed solvent consisting of 5 parts by weight and 1 part by weight of 1-methoxy-2-propanol so that the polymer concentration became 4% by weight.
【００５１】そして、ステンレス板の上に置いたポリ塩
化ビニル織布に、この塗工溶液を＃１０のマイヤーバー
で塗工、それを釣り下げ、２５℃、５０％ＲＨの環境下
で１０分間放置した後、８０℃で５分間熱処理すること
でフッ素化ポリアルキレンによる被覆を行った。このと
きの被覆量は２．１ｇ／ｍ2であり、織布基材に対し
５．１重量％であった。Then, the coating solution was applied to a polyvinyl chloride woven cloth placed on a stainless steel plate with a # 10 Meyer bar, and the coating solution was hung down for 10 minutes in an environment of 25 ° C. and 50% RH. After standing, the coating was treated with fluorinated polyalkylene by heat treatment at 80 ° C. for 5 minutes. At this time, the coating amount was 2.1 g / m 2 , which was 5.1% by weight based on the woven fabric substrate.
【００５２】このようにして作製した被覆織布につい
て、参考例１と同じく引張り試験による分解劣化度を評
価した。その結果を表１に示す。これより、ラジカル分
解劣化促進環境で殆ど強度劣化の無い織布であることが
わかった。The coated woven fabric thus manufactured was evaluated for the degree of degradation by a tensile test in the same manner as in Reference Example 1. Table 1 shows the results. From this, it was found that the woven fabric had almost no strength deterioration in the environment where radical decomposition and deterioration were promoted.
【００５３】［参考例２：ポリエステル繊維質基材の製
造］広瀬製紙製ポリエステル（ＰＥＴ）不織布（０５Ｔ
Ｈ１２、目付量１２ｇ／ｍ 2、厚み３４μｍ、熱変形開
始温度８５℃）について、ＭＤ方向に引張り試験を行っ
た結果を表１に示す。次いでこの不織布に、ラジカル分
解劣化促進処理を行った後、ＭＤ方向１ｃｍ幅にサンプ
ルを切り出して引張り試験を行った。そして、各パラメ
ーターは１ｃｍ幅で厚みを含めた値とした。その試験結
果を表１に示す。このようにポリエステル不織布は顕著
に劣化することが判った。[Reference Example 2: Production of polyester fibrous base material]
Zose] Hirose Paper-made polyester (PET) non-woven fabric (05T
H12, basis weight 12g / m Two, Thickness 34μm, thermal deformation open
(Temperature: 85 ° C), tensile test in MD direction
The results are shown in Table 1. Next, the non-woven fabric
After performing the degradation degradation treatment, the sample is pumped to a width of 1 cm in the MD direction.
And a tensile test was performed. And each parameter
The value of the data was 1 cm width and the thickness was included. The test result
The results are shown in Table 1. Polyester nonwoven is remarkable like this
It turned out to be deteriorated.
【００５４】［実施例２］参考例２のポリエステル（Ｐ
ＥＴ）不織布に、次のようにフッ素化ポリアルキレンを
被覆した。すなわち、フッ素化ポリアルキレンとして
は、実施例１のフッ化ビニリデン−ヘキサフルオロプロ
ピレン共重合体を用いた。そして、このフッ素化ポリア
ルキレンをジメチルアセトアミド溶媒に、ポリマー濃度
０．７重量％となるように攪拌混合し、均一な塗工溶液
を得た。そして、ステンレス板の上に置いたポリエチレ
ンテレフタレート（ＰＥＴ）繊維不織布に、この塗工溶
液を＃１０のマイヤーバーで塗工し、それを釣り下げ、
２５℃，５０％ＲＨ環境下で１０分間放置した後、８０
℃で１０分間熱処理することでフッ素化ポリアルキレン
による被覆を行った。この時の被覆量は０．１７ｇ／ｍ
2であり、不織布基材に対し１．４重量％であった。こ
のようにして作製した被覆不織布について、参考例２と
同じく引張り試験による分解劣化度を評価した。分解劣
化その結果を表１に示す。これより、ラジカル分解劣化
促進環境で分解劣化が抑制された不織布であることがわ
かった。Example 2 The polyester of Reference Example 2 (P
ET) The nonwoven fabric was coated with a fluorinated polyalkylene as follows. That is, the vinylidene fluoride-hexafluoropropylene copolymer of Example 1 was used as the fluorinated polyalkylene. Then, the fluorinated polyalkylene was stirred and mixed with a dimethylacetamide solvent so as to have a polymer concentration of 0.7% by weight to obtain a uniform coating solution. Then, this coating solution was applied to a polyethylene terephthalate (PET) fiber non-woven fabric placed on a stainless steel plate using a # 10 Meyer bar, and it was hung down.
After leaving for 10 minutes at 25 ° C and 50% RH, 80
The coating with fluorinated polyalkylene was performed by heat treatment at 10 ° C. for 10 minutes. The coating amount at this time is 0.17 g / m
2 , which was 1.4% by weight based on the nonwoven fabric substrate. About the coated nonwoven fabric produced in this manner, the degree of degradation by a tensile test was evaluated in the same manner as in Reference Example 2. Table 1 shows the results of the degradation. From this, it was found that the nonwoven fabric was inhibited from degrading and deteriorating in a radical decomposition and degradation promoting environment.
【００５５】［実施例３］実施例２においてジメチルア
セトアミド溶媒に溶解するフッ素化ポリアルキレン量を
５重量％とした。このときの被覆量は１．２ｇ／ｍ2で
あり、不織布基材に対し１０重量％であった。このよう
にして作製した被覆不織布について、参考例２と同じく
引張り試験による分解劣化度を評価した。その結果を表
１に示す。これより、ラジカル分解劣化促進環境で分解
劣化が抑制された不織布であることがわかった。Example 3 The amount of the fluorinated polyalkylene dissolved in the dimethylacetamide solvent in Example 2 was 5% by weight. The coating amount at this time was 1.2 g / m 2 , which was 10% by weight based on the nonwoven fabric substrate. About the coated nonwoven fabric produced in this manner, the degree of degradation by a tensile test was evaluated in the same manner as in Reference Example 2. Table 1 shows the results. From this, it was found that the nonwoven fabric was inhibited from degrading and deteriorating in a radical decomposition and degradation promoting environment.
【００５６】[実施例４]実施例３において作製したフッ
素化ポリアルキレン被覆ポリエステル（ＰＥＴ）不織布
に１０ｋＧｙの電子線を照射した。このようにして作製
した被覆不織布について、参考例２と同じく引張り試験
による分解劣化度を評価した。その結果を表１に示す。
これより、ラジカル分解劣化促進環境で分解劣化が抑制
された不織布であることがわかった。Example 4 The fluorinated polyalkylene-coated polyester (PET) nonwoven fabric produced in Example 3 was irradiated with an electron beam of 10 kGy. About the coated nonwoven fabric produced in this manner, the degree of degradation by a tensile test was evaluated in the same manner as in Reference Example 2. Table 1 shows the results.
From this, it was found that the nonwoven fabric was inhibited from degrading and deteriorating in a radical decomposition and degradation promoting environment.
【００５７】[実施例５]実施例３において作製したフッ
素化ポリアルキレン被覆ポリエステル（ＰＥＴ）不織布
に２００ｋＧｙの電子線を照射した。このようにして作
製した被覆不織布について、参考例２と同じく引張り試
験による分解劣化度を評価した。その結果を表１に示
す。これより、ラジカル分解劣化促進環境で分解劣化が
抑制された不織布であることがわかった。Example 5 The fluorinated polyalkylene-coated polyester (PET) nonwoven fabric produced in Example 3 was irradiated with an electron beam of 200 kGy. About the coated nonwoven fabric produced in this manner, the degree of degradation by a tensile test was evaluated in the same manner as in Reference Example 2. Table 1 shows the results. From this, it was found that the nonwoven fabric was inhibited from degrading and deteriorating in a radical decomposition and degradation promoting environment.
【００５８】［比較例１：エポキシ樹脂による被覆］参
考例２のポリエステル（ＰＥＴ）不織布に、次のように
してエポキシ樹脂硬化物を被覆した。すなわち、水分散
エポキシ（ナガセ化成製、５％濃度エポキシクレゾール
ノボラック樹脂）１００重量部に、硬化触媒として１,
８−ジアザビシクロ［５,４,０］−７−ウンデセンを
０．１重量部添加混合し、塗工液を調製した。そして、
ステンレス板の上に置いた不織布に、この塗工溶液を＃
１０のマイヤーバーで塗工、それを釣り下げ８０℃の乾
燥機で３０分間、更に１００℃で５分間熱処理すること
で、不織布にエポキシ樹脂硬化物を積層した。このとき
の被覆量は２．０ｇ／ｍ2であり、不織布基材に対し１
６．７重量％であった。Comparative Example 1: Coating with Epoxy Resin The polyester (PET) nonwoven fabric of Reference Example 2 was coated with a cured epoxy resin as follows. That is, 100 parts by weight of a water-dispersed epoxy (Nagase Chemical Co., Ltd., 5% epoxy cresol novolak resin) was added with 1,1 as a curing catalyst.
0.1 part by weight of 8-diazabicyclo [5,4,0] -7-undecene was added and mixed to prepare a coating solution. And
Apply this coating solution to a non-woven fabric placed on a stainless steel plate.
The coated epoxy resin was laminated on the nonwoven fabric by coating with a 10 Meyer bar, hanging it down, and heat-treating it with a dryer at 80 ° C. for 30 minutes and at 100 ° C. for 5 minutes. The coating amount at this time was 2.0 g / m 2 ,
6.7% by weight.
【００５９】このようにして作製した被覆不織布につい
て、参考例２と同じく引張り試験による分解劣化度を評
価した。その結果を表１に示す。これより、ラジカル分
解劣化促進環境で分解劣化度は被覆処理を施していない
ポリエステル不織布の試験結果と同ような値であり、ラ
ジカル分解劣化が抑制されていなかった。The coated nonwoven fabric thus manufactured was evaluated for the degree of degradation by a tensile test in the same manner as in Reference Example 2. Table 1 shows the results. As a result, the degree of degradation in the environment promoting radical degradation was similar to the test result of the polyester non-woven fabric not subjected to the coating treatment, and the radical degradation was not suppressed.
【００６０】[0060]
【表１】 [Table 1]
【００６１】[0061]
【発明の効果】本発明によれば、各種の繊維質基材のラ
ジカル分解性が改善され、水溶液中での用途、例えば、
電気分解、一次電池、二次電池のセパレーターとして、
また、燃料電池に用いられる水素イオン伝導性高分子膜
等の補強材として有用な補強構造物が提供される。According to the present invention, the radical decomposability of various fibrous base materials is improved, and the use in aqueous solutions, for example,
As separator for electrolysis, primary battery, secondary battery,
Further, a reinforcing structure useful as a reinforcing material such as a hydrogen ion conductive polymer membrane used for a fuel cell is provided.
【００６２】例えば、通常、燃料電池用の高分子電解質
膜はいわゆるイオン交換膜で水に膨潤させて使用される
が、この膜はそのため極端に低い強度しかなく、機械強
度的が問題となっている。本発明の繊維構造物は、これ
に高分子電解質組成を含浸（具体的には高分子電解質溶
液を含浸して乾燥させる）させて使用することができ、
また、本発明の繊維構造物を電解質膜に貼り合わせる
か、あるいは複数の高分子電解質膜間に挿入して、プレ
ス加工することにより補強材として使用可能である。For example, a polymer electrolyte membrane for a fuel cell is usually a so-called ion exchange membrane which is used by being swollen in water. However, this membrane has an extremely low strength, and the mechanical strength is problematic. I have. The fiber structure of the present invention can be used by impregnating it with a polymer electrolyte composition (specifically, impregnating and drying a polymer electrolyte solution),
Further, the fibrous structure of the present invention can be used as a reinforcing material by bonding it to an electrolyte membrane or inserting it between a plurality of polymer electrolyte membranes and pressing it.
【００６３】また、セパレータでは、本発明の繊維構造
物がそれ自体でセパレーターとなりうるが、別のセパレ
ーターの補強材として使用することもできる。In the separator, the fibrous structure of the present invention can be a separator by itself, but can also be used as a reinforcing material for another separator.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｄ０６Ｍ 101:20 Ｄ０６Ｍ 101:20 101:22 101:22 101:32 101:32 (72)発明者 大道 高弘 山口県岩国市日の出町２番１号 帝人株式 会社岩国研究センター内 Ｆターム(参考） 4L033 AB01 AB05 AB07 AC15 CA17 CA70 4L047 AA14 AA21 BB06 CB10 CC12 DA00 4L048 AA17 AA20 AA56 BA01 BA02 CA00 CA15 DA24 5H026 AA06 BB04 BB08 BB10 CX02 CX03 EE18 EE19 HH06 HH08Continuation of the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) D06M 101: 20 D06M 101: 20 101: 22 101: 22 101: 32 101: 32 (72) Inventor Takahiro Omichi Iwakuni, Yamaguchi Prefecture No. 2-1, Hinode-cho, Teijin Co., Ltd. F-term in Iwakuni Research Center, Teijin Limited 4L033 AB01 AB05 AB07 AC15 CA17 CA70 4L047 AA14 AA21 BB06 CB10 CC12 DA00 4L048 AA17 AA20 AA56 BA01 BA02 CA00 CA15 DA24 5H026 AA06 BB04 BB08 BB04 BB08 EE19 HH06 HH08
Claims (7)
系高分子重合体繊維よりなる繊維質基材の繊維表面を、
計算化学による炭素−フッ素の２中心結合エネルギー絶
対値がいずれも１６．５ｅＶより大きく、かつ、溶媒可
溶なフッ素化ポリアルキレンの溶液を含む被覆材により
繊維質基材の重量に対し１〜３０重量％の被覆量で被覆
したことを特徴とする、耐ラジカル分解性繊維構造物。1. The fiber surface of a fibrous base material made of a non-fluorinated high molecular weight polymer fiber having a heat deformation initiation temperature of 80 ° C. or higher,
The absolute value of the two-center bond energy of carbon-fluorine by computational chemistry is greater than 16.5 eV, and the coating material containing a solvent-soluble fluorinated polyalkylene solution is 1 to 30 parts by weight based on the weight of the fibrous base material. A radical-decomposition-resistant fiber structure, characterized in that the fiber structure is coated with a coating amount of weight%.
ことを特徴とする、請求項１に記載の耐ラジカル分解性
繊維構造物。2. The radical-decomposition-resistant fibrous structure according to claim 1, wherein the fibrous base material is a nonwoven fabric or a woven fabric.
リアルキレン、ポリエステルあるいはこれらの共重合体
よりなる非フッ素系高分子重合体繊維を１種類以上用い
て形成されていることを特徴とする、請求項１〜請求項
２のいずれかに記載の耐ラジカル分解性繊維構造物。3. The fibrous base material is formed by using at least one kind of non-fluorinated high molecular weight polymer fiber composed of polyalkylene, polyalkylene chloride, polyester or a copolymer thereof. The radical-decomposition-resistant fiber structure according to claim 1.
四フッ化エチレン、六フッ化プロピレン、フッ化ビニリ
デン、三フッ化塩化エチレンの少なくとも１種をモノマ
ーとする、単一重合体、共重合体あるいはこれらの重合
体同士の混合物であることを特徴とする、請求項１〜請
求項３のいずれかに記載の耐ラジカル分解性繊維構造
物。4. A solvent-soluble fluorinated polyalkylene,
It is characterized by being a homopolymer, a copolymer or a mixture of these polymers, using at least one of ethylene tetrafluoride, propylene hexafluoride, vinylidene fluoride and ethylene trifluoride as a monomer. The radical-decomposition-resistant fiber structure according to any one of claims 1 to 3.
液を含む被覆材による被覆量が、繊維質基材の重量に対
し４〜２０重量％であることを特徴とする、請求項１〜
請求項４のいずれかに記載の耐ラジカル分解性繊維構造
物。5. The coating amount of the coating material containing the solvent-soluble fluorinated polyalkylene solution is 4 to 20% by weight based on the weight of the fibrous base material.
The radical-decomposition-resistant fiber structure according to claim 4.
材の繊維表面に溶媒可溶なフッ素化ポリアルキレンの溶
液を含む被覆材により被覆し、溶媒を除去した後、さら
に放射線照射を施したことを特徴とする、請求項１〜請
求項５に記載の耐ラジカル分解性繊維構造物。6. The fiber surface of a fibrous base material made of non-fluorinated polymer fiber is coated with a coating material containing a solution of a solvent-soluble fluorinated polyalkylene, and after removing the solvent, it is further irradiated with radiation. The radical-decomposition-resistant fiber structure according to any one of claims 1 to 5, wherein the fibrous structure is resistant to radical decomposition.
耐ラジカル分解性繊維構造物で補強したことを特徴とす
る水の存在下で使用される高分子電解質膜複合体。7. A polymer electrolyte membrane composite used in the presence of water, wherein the composite is reinforced with the radical-decomposition-resistant fiber structure according to claim 1. Description:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000073662A JP2001262471A (en) | 2000-03-16 | 2000-03-16 | Radical decomposition-resistant fiber structure and polymer electrolytic membrane composite using the same as a reinforcing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000073662A JP2001262471A (en) | 2000-03-16 | 2000-03-16 | Radical decomposition-resistant fiber structure and polymer electrolytic membrane composite using the same as a reinforcing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001262471A true JP2001262471A (en) | 2001-09-26 |
Family
ID=18591876
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000073662A Pending JP2001262471A (en) | 2000-03-16 | 2000-03-16 | Radical decomposition-resistant fiber structure and polymer electrolytic membrane composite using the same as a reinforcing material |
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| Country | Link |
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| JP (1) | JP2001262471A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006307394A (en) * | 2005-05-02 | 2006-11-09 | Teijin Techno Products Ltd | Woven fabric for ion exchange membrane |
| WO2007145176A1 (en) * | 2006-06-12 | 2007-12-21 | Toyota Jidosha Kabushiki Kaisha | Electrolyte film and method of selecting the same |
| JP5338316B2 (en) * | 2006-08-28 | 2013-11-13 | トヨタ自動車株式会社 | REINFORCED ELECTROLYTE MEMBRANE FOR FUEL CELL, METHOD FOR PRODUCING THE SAME, MEMBRANE-ELECTRODE ASSEMBLY FOR FUEL CELL, AND SOLID POLYMER FUEL CELL HAVING THE SAME |
-
2000
- 2000-03-16 JP JP2000073662A patent/JP2001262471A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006307394A (en) * | 2005-05-02 | 2006-11-09 | Teijin Techno Products Ltd | Woven fabric for ion exchange membrane |
| WO2007145176A1 (en) * | 2006-06-12 | 2007-12-21 | Toyota Jidosha Kabushiki Kaisha | Electrolyte film and method of selecting the same |
| US8128836B2 (en) | 2006-06-12 | 2012-03-06 | Toyota Jidosha Kabushiki Kaisha | Electrolyte membrane and method of selecting the same |
| JP5338316B2 (en) * | 2006-08-28 | 2013-11-13 | トヨタ自動車株式会社 | REINFORCED ELECTROLYTE MEMBRANE FOR FUEL CELL, METHOD FOR PRODUCING THE SAME, MEMBRANE-ELECTRODE ASSEMBLY FOR FUEL CELL, AND SOLID POLYMER FUEL CELL HAVING THE SAME |
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