JP2003022823A - Proton conductive membrane or film, and fuel cell using it - Google Patents

Proton conductive membrane or film, and fuel cell using it

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Publication number
JP2003022823A
JP2003022823A JP2001207547A JP2001207547A JP2003022823A JP 2003022823 A JP2003022823 A JP 2003022823A JP 2001207547 A JP2001207547 A JP 2001207547A JP 2001207547 A JP2001207547 A JP 2001207547A JP 2003022823 A JP2003022823 A JP 2003022823A
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JP
Japan
Prior art keywords
acid group
membrane
polymer
proton
monomer
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.)
Granted
Application number
JP2001207547A
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Japanese (ja)
Other versions
JP4827331B2 (en
Inventor
Shigeru Fujita
茂 藤田
Masao Abe
正男 阿部
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Nitto Denko Corp
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Nitto Denko Corp
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Conductive Materials (AREA)
  • Fuel Cell (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a proton conductive membrane or film having durability and mechanical strength and its manufacturing method, and to provide a fuel cell using this membrane or film as a proton exchange membrane. SOLUTION: This proton conductive membrane is obtained by polymerizing a single functional monomer having a phosphate group, a phosphonate group or a phosphinate group in the side and a single functional monomer having an amine salt of the phosphate group, the phosphonate group or the phosphinate group in the side chain, in the void of a porous membrane, by producing a polymer having a part of the phosphate group in the form of an amine salt, the phosphonate group or the phosphinate group in the side chain, and by carrying the polymer in the voids of the porous membrane. The proton conductive film formed by blocking at least a part of the remaining voids of the voids of the proton conductive membrane and the manufacturing method of the proton conductive film are provided. In addition, the fuel cell using the proton conductive film as the proton exchange membrane is provided.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、プロトン伝導性を有す
るプロトン伝導性膜、これより得られるプロトン伝導性
フィルムとそれらの製造方法、更には、それらプロトン
伝導性膜又はフィルムをプロトン交換膜として用いてな
る燃料電池に関する。FIELD OF THE INVENTION The present invention relates to a proton conductive membrane having proton conductivity, a proton conductive film obtained from the same, a method for producing the same, and a proton exchange membrane or a proton conductive membrane. The present invention relates to a fuel cell used.

【０００２】[0002]

【従来の技術】従来、プロトン伝導性膜は、イオン交換
膜や湿度センサー等の用途に用いられているが、近年、
固体高分子型燃料電池における固体電解質膜としての用
途においても注目を集めている。例えば、デュポン社の
ナフィオン（登録商標）を代表とするスルホン酸基含有
フッ素樹脂膜は、電気自動車や分散型電源用燃料電池に
おける固体電解質としての利用が検討されているが、従
来より知られているこれらのフッ素樹脂系プロトン伝導
性膜は、価格が非常に高いという欠点がある。プロトン
伝導性膜を燃料電池等の新たな用途において実用化を図
るには、プロトン伝導性を高く、しかも価格を低くする
ことが不可欠である。2. Description of the Related Art Conventionally, proton conductive membranes have been used for applications such as ion exchange membranes and humidity sensors.
Attention has also been paid to its use as a solid electrolyte membrane in polymer electrolyte fuel cells. For example, a sulfonic acid group-containing fluororesin membrane typified by DuPont Nafion (registered trademark) has been studied for use as a solid electrolyte in fuel cells for electric vehicles and dispersed power sources, but has been known so far. These fluororesin-based proton conductive membranes have the drawback of being extremely expensive. In order to put the proton conductive membrane into practical use in new applications such as fuel cells, it is essential to have high proton conductivity and low cost.

【０００３】そこで、従来、空孔を有する多孔質膜に電
解質ポリマーを含有させて、プロトン伝導性膜を得る方
法が種々提案されている。例えば、特開平９−１９４６
０９号公報には、フッ素樹脂、ポリエチレン樹脂、ポリ
プロピレン樹脂等の疎水性樹脂からなる多孔質膜の空孔
内に同じく疎水性のポリマーの溶液を含浸させ、乾燥さ
せて、上記ポリマーを多孔質膜に担持させた後、このポ
リマーにスルホン酸基、プロトン化アミノ基、カルボキ
シル基等のイオン交換基を導入し、かくして、イオン交
換膜を製造する方法が提案されている。しかし、このよ
うな方法によれば、イオン交換基を多孔質膜中に均一に
分布させることは困難であり、延いては、プロトン伝導
性も十分ではない。Therefore, conventionally, various methods have been proposed for obtaining a proton conductive membrane by incorporating an electrolyte polymer into a porous membrane having pores. For example, Japanese Patent Laid-Open No. 9-1946
No. 09, a solution of the same hydrophobic polymer is impregnated into the pores of a porous film made of a hydrophobic resin such as a fluororesin, a polyethylene resin, and a polypropylene resin, and the porous polymer is dried to obtain the above polymer. A method for producing an ion exchange membrane by introducing an ion exchange group such as a sulfonic acid group, a protonated amino group, or a carboxyl group into the polymer after supporting it on the polymer has been proposed. However, according to such a method, it is difficult to uniformly disperse the ion exchange groups in the porous membrane, and the proton conductivity is not sufficient.

【０００４】そこで、最近、イオン交換基としてリン酸
エステル基を有するポリマー、即ち、側鎖にリン酸エス
テル基を有するメタクリル酸誘導体から導かれるポリマ
ーを固体高分子型燃料電池用プロトン交換膜として用い
ることが「高分子学会予稿集」第４８巻第３号第４１４
頁（１９９９年）、「高分子学会予稿集」第４８巻第１
０号第２３９３頁（１９９９年）、「高分子学会予稿
集」第４９巻第４号第７５１頁（２０００年）等に提案
されている。Therefore, recently, a polymer having a phosphoric acid ester group as an ion exchange group, that is, a polymer derived from a methacrylic acid derivative having a phosphoric acid ester group in a side chain is used as a proton exchange membrane for a polymer electrolyte fuel cell. The “Proceedings of the Polymer Society of Japan” Vol. 48, No. 3, No. 414
Page (1999), "Proceedings of the Polymer Society of Japan", Vol. 48, No. 1
No. 0, page 2393 (1999), “Proceedings of the Polymer Society of Japan,” Vol. 49, No. 4, page 751 (2000), etc.

【０００５】これら文献によれば、側鎖にリン酸エステ
ル基を有するメタクリル酸誘導体から導かれるポリマー
は、上記リン酸エステル基のプロトン解離度が大きく、
強い酸性を示すので、高いプロトン伝導性を有してお
り、しかも、主鎖が炭化水素でありながら、耐熱性を有
すると共に、水に殆ど溶解しないという特性を有する。
このように、リン酸エステル基を置換基として側鎖に有
するポリマーが水不溶性であるのは、リン酸エステル基
がそれぞれの間に形成する水素結合によって、ポリマー
鎖間に強いネットワークが形成されるためであるとみら
れる。According to these documents, a polymer derived from a methacrylic acid derivative having a phosphoric acid ester group in its side chain has a large degree of proton dissociation of the phosphoric acid ester group,
Since it exhibits strong acidity, it has a high proton conductivity, and has a characteristic that it has heat resistance even though the main chain is a hydrocarbon and it is hardly dissolved in water.
Thus, the water-insoluble polymer having a phosphate ester group as a substituent is water-insoluble because the hydrogen bond formed between the phosphate ester groups forms a strong network between the polymer chains. It seems to be because of it.

【０００６】しかしながら、側鎖にリン酸エステル基を
有するメタクリル酸誘導体から導かれる上記ポリマー自
体は、機械的強度が低く、脆いので、燃料電池用プロト
ン交換膜として用いることは困難である。また、上記ポ
リマーは、その製造時にしばしばゲル化したり、また、
得られたポリマーが溶解性に乏しい等、実用化のために
は、製造面や成形性の面で尚、多くの問題がある。However, the above-mentioned polymer itself derived from a methacrylic acid derivative having a phosphate ester group in its side chain has low mechanical strength and is brittle, so that it is difficult to use it as a proton exchange membrane for fuel cells. In addition, the above-mentioned polymer often gels during its production, and
There are still many problems in terms of production and moldability for practical use, such as poor solubility of the obtained polymer.

【０００７】一般に、多孔質膜にプロトン伝導性を付与
するためには、膜内にプロトン発生源又は輸送サイトを
有することが必要であり、先に言及したスルホン酸基は
そのようなプロトン発生源又は輸送サイトの代表例であ
る。しかし、スルホン酸基を有するポリマーは、代表的
には、ポリスチレンスルホン酸やポリビニルスルホン酸
等であり、これらはすべて水溶性である。従って、水素
ガスや酸素ガスを水蒸気加湿して用いる燃料電池のプロ
トン交換膜としては、これらのポリマーは、そのままで
は、用いることが困難である。即ち、燃料電池のプロト
ン交換膜として用いるには、ポリマーに何らかの水不溶
性化処理を施すことが必要である。Generally, in order to impart proton conductivity to the porous membrane, it is necessary to have a proton generating source or a transport site in the membrane, and the sulfonic acid group mentioned above is such a proton generating source. Or, it is a typical example of a transportation site. However, the polymer having a sulfonic acid group is typically polystyrene sulfonic acid, polyvinyl sulfonic acid, or the like, and all of them are water-soluble. Therefore, it is difficult to use these polymers as they are as a proton exchange membrane of a fuel cell in which hydrogen gas or oxygen gas is humidified. That is, in order to use it as a proton exchange membrane of a fuel cell, it is necessary to subject the polymer to some kind of water insolubilization treatment.

【０００８】水溶性ポリマーを水不溶化するためには、
架橋処理をするか、又はスルホン酸基を有するモノマー
と共に水不溶性ポリマーを与えるようなモノマーと共重
合を行なって、共重合体とする必要がある。To make a water-soluble polymer insoluble in water,
It is necessary to carry out a crosslinking treatment or copolymerize with a monomer having a sulfonic acid group to give a water-insoluble polymer to obtain a copolymer.

【０００９】しかし、水溶性ポリマーに架橋処理を施す
ことによって、水に完全に溶解することは避けることが
できても、水に接触したとき、ポリマーが膨潤すること
は避けられない。かくして、水溶性ポリマーの架橋によ
る水不溶化は、それと引換えにポリマーの機械的強度の
低下をもたらすので、そのように、水溶性ポリマーを水
不溶化したポリマーを燃料電池用プロトン交換膜として
用いることも困難である。However, by subjecting the water-soluble polymer to a crosslinking treatment, it is possible to avoid complete dissolution in water, but it is unavoidable that the polymer swells when contacted with water. Thus, water insolubilization due to cross-linking of the water-soluble polymer causes a decrease in the mechanical strength of the polymer in exchange for that, and thus it is also difficult to use the water-insoluble polymer as a proton exchange membrane for fuel cells. Is.

【００１０】他方、水不溶性ポリマーを与えるモノマー
との共重合によって、水不溶性ポリマーを得るには、重
合に供するモノマー中のスルホン酸基含有モノマーの割
合を相対的に低くせざるを得ず、そうすれば、本来、プ
ロトン交換膜として求められるプロトン伝導性が損なわ
れるので、高いプロトン伝導性を有するポリマーを得る
ことはできない。On the other hand, in order to obtain a water-insoluble polymer by copolymerization with a monomer which gives a water-insoluble polymer, the proportion of the sulfonic acid group-containing monomer in the monomers to be polymerized must be relatively low. If so, the proton conductivity originally required for the proton exchange membrane is impaired, so that a polymer having high proton conductivity cannot be obtained.

【００１１】[0011]

【発明が解決しようとする課題】本発明は、プロトン伝
導性膜又はフィルムにおける上述した問題を解決するた
めになされたものであって、耐久性と機械的強度を有す
るプロトン伝導性膜又はフィルムとそれらの製造方法、
更には、それらをプロトン交換膜として用いてなる燃料
電池を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in a proton conductive membrane or film, and a proton conductive membrane or film having durability and mechanical strength. Their manufacturing method,
Furthermore, it aims at providing the fuel cell which uses them as a proton exchange membrane.

【００１２】[0012]

【問題を解決するための手段】本発明によれば、側鎖の
リン酸基、ホスホン酸基又はホスフィン酸基が一部、ア
ミン塩化されたポリマーを多孔質膜の空孔内に担持させ
てなることを特徴とするプロトン伝導性膜が提供され
る。According to the present invention, a polymer in which a phosphoric acid group, a phosphonic acid group or a phosphinic acid group of a side chain is partly amine chlorinated is supported in the pores of a porous membrane. A proton-conducting membrane is provided.

【００１３】更に、本発明によれば、上記プロトン伝導
性膜の空孔の残余の空隙の少なくとも一部が閉塞されて
なるプロトン伝導性フィルムが提供される。Further, according to the present invention, there is provided a proton conductive film in which at least a part of the remaining voids of the pores of the proton conductive membrane is closed.

【００１４】また、本発明によれば、側鎖にリン酸基、
ホスホン酸基又はホスフィン酸基を有する単官能性モノ
マーと側鎖のリン酸基、ホスホン酸基又はホスフィン酸
基がアミン塩化された単官能性モノマーとを多孔質膜の
空孔内で重合させて、側鎖のリン酸基、ホスホン酸基又
はホスフィン酸基が一部、アミン塩化されたポリマーを
生成させると共に、このポリマーを上記多孔質膜の空孔
内に担持させることを特徴とするプロトン伝導性膜の製
造方法が提供される。Further, according to the present invention, a phosphate group is contained in the side chain,
By polymerizing a monofunctional monomer having a phosphonic acid group or a phosphinic acid group and a monofunctional monomer having an amine salt of a phosphoric acid group, a phosphonic acid group or a phosphinic acid group of a side chain, in the pores of the porous membrane. Proton conduction characterized by producing a polymer in which a phosphoric acid group, a phosphonic acid group or a phosphinic acid group of a side chain is partially amine chloride and supporting the polymer in the pores of the porous membrane. A method for manufacturing a permeable membrane is provided.

【００１５】更に、本発明によれば、側鎖にリン酸基、
ホスホン酸基又はホスフィン酸基を有する単官能性モノ
マーを多孔質膜の空孔内で重合させて、側鎖にリン酸
基、ホスホン酸基又はホスフィン酸基を有するポリマー
を生成させると共に、このポリマーを上記多孔質膜の空
孔内に担持させ、更に、このポリマーの上記側鎖のリン
酸基、ホスホン酸基又はホスフィン酸基を一部、アミン
塩化することを特徴とするプロトン伝導性膜の製造方法
が提供される。Further, according to the present invention, a phosphate group is contained in the side chain,
A monofunctional monomer having a phosphonic acid group or a phosphinic acid group is polymerized in the pores of a porous membrane to produce a polymer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain, and the polymer. Is supported in the pores of the porous membrane, and further, the side chain phosphoric acid group, phosphonic acid group or phosphinic acid group of the polymer is partially amine-chlorided to form a proton conductive membrane. A manufacturing method is provided.

【００１６】また、本発明によれば、側鎖にリン酸基、
ホスホン酸基又はホスフィン酸基を有する単官能性モノ
マーと側鎖のリン酸基、ホスホン酸基又はホスフィン酸
基がアミン塩化された単官能性モノマーとを含むモノマ
ー混合物を多孔質膜の空孔内で重合させて、側鎖のリン
酸基、ホスホン酸基又はホスフィン酸基が一部、アミン
塩化されたポリマーを生成させると共に、このポリマー
を上記多孔質膜の空孔内に担持させて、プロトン伝導性
膜を得、次いで、このプロトン伝導性膜の空孔の残余の
空隙の少なくとも一部を閉塞することを特徴とするプロ
トン伝導性フィルムの製造方法が提供される。Further, according to the present invention, a phosphate group on the side chain,
A monomer mixture containing a monofunctional monomer having a phosphonic acid group or a phosphinic acid group and a monofunctional monomer in which a phosphoric acid group, a phosphonic acid group or a phosphinic acid group of a side chain is amine-chlorided, in a pore of a porous membrane. And a side chain of a phosphoric acid group, a phosphonic acid group or a phosphinic acid group is partially polymerized to form an amine salt, and the polymer is supported in the pores of the porous membrane to generate a proton. There is provided a method for producing a proton conductive film, which comprises obtaining a conductive membrane and then closing at least a part of the remaining voids of the pores of the proton conductive membrane.

【００１７】更に、本発明によれば、側鎖にリン酸基、
ホスホン酸基又はホスフィン酸基を有する単官能性モノ
マーを多孔質膜の空孔内で重合させて、側鎖にリン酸
基、ホスホン酸基又はホスフィン酸基を有するポリマー
を生成させると共に、このポリマーを上記多孔質膜の空
孔内に担持させ、更に、このポリマーの上記側鎖のリン
酸基、ホスホン酸基又はホスフィン酸基を一部、アミン
塩化して、プロトン伝導性膜を得、次いで、このプロト
ン伝導性膜の空孔の残余の空隙の少なくとも一部を閉塞
することを特徴とするプロトン伝導性フィルムの製造方
法が提供される。Furthermore, according to the present invention, a phosphate group is contained in the side chain,
A monofunctional monomer having a phosphonic acid group or a phosphinic acid group is polymerized in the pores of a porous membrane to produce a polymer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain, and the polymer. Is supported in the pores of the porous membrane, and the side chain phosphoric acid group, phosphonic acid group or phosphinic acid group of the polymer is partly amine-chlorinated to obtain a proton conductive membrane, There is provided a method for producing a proton conductive film, which comprises closing at least a part of the remaining voids of the pores of the proton conductive film.

【００１８】上記のほか、本発明によれば、上記プロト
ン伝導性膜又はプロトン伝導性フィルムをプロトン交換
膜として用いてなる燃料電池が提供される。In addition to the above, according to the present invention, there is provided a fuel cell using the above proton conductive membrane or the proton conductive film as a proton exchange membrane.

【００１９】[0019]

【発明の実施の形態】本発明によるプロトン伝導性膜
は、側鎖のリン酸基、ホスホン酸基又はホスフィン酸基
が一部、アミン塩化されたポリマーを多孔質膜の空孔内
に担持させてなるものである。BEST MODE FOR CARRYING OUT THE INVENTION The proton-conducting membrane according to the present invention has a polymer in which a side-chain phosphoric acid group, phosphonic acid group or phosphinic acid group is partially aminated and which is supported in the pores of the porous membrane. It will be.

【００２０】以下、本発明において、側鎖にリン酸基、
ホスホン酸基又はホスフィン酸基を有するポリマーを
「Ｐ−ポリマー」といい、上記側鎖のリン酸基、ホスホ
ン酸基又はホスフィン酸基が一部、アミン塩化されたポ
リマーを「Ｐ−ポリマーの部分アミン塩」という。Hereinafter, in the present invention, the side chain has a phosphate group,
A polymer having a phosphonic acid group or a phosphinic acid group is referred to as a "P-polymer", and a polymer in which a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in the side chain is partly amine-chlorided is referred to as a "P-polymer part". Amine salt ".

【００２１】本発明によれば、このようなプロトン伝導
性膜は、好ましくは、側鎖にリン酸基、ホスホン酸基又
はホスフィン酸基を有する単官能性モノマーと側鎖のリ
ン酸基、ホスホン酸基又はホスフィン酸基がアミン塩化
された単官能性モノマーを多孔質膜の空孔内で重合させ
て、側鎖のリン酸基、ホスホン酸基又はホスフィン酸基
が一部、アミン塩化されたポリマーを生成させると共
に、このポリマーを上記多孔質膜の空孔内に担持させる
ことによって得ることができる。According to the present invention, such a proton conductive membrane is preferably a monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain and a phosphoric acid group or a phosphon group in a side chain. A monofunctional monomer in which an acid group or a phosphinic acid group was amine-chlorinated was polymerized in the pores of the porous membrane to partially phosphorylate a side-chain phosphoric acid group, phosphonic acid group or phosphinic acid group. It can be obtained by producing a polymer and supporting the polymer in the pores of the porous membrane.

【００２２】以下、本発明において、側鎖にリン酸基、
ホスホン酸基又はホスフィン酸基を有する単官能性モノ
マーを「Ｐ−モノマー」といい、側鎖のリン酸基、ホス
ホン酸基又はホスフィン酸基がアミン塩化された単官能
性モノマーを「Ｐ−塩モノマー」という。また、上記リ
ン酸基、ホスホン酸基又はホスフィン酸基を「Ｐ−酸
基」という。Hereinafter, in the present invention, the side chain has a phosphate group,
A monofunctional monomer having a phosphonic acid group or a phosphinic acid group is referred to as a "P-monomer", and a monofunctional monomer in which a phosphoric acid group, a phosphonic acid group or a phosphinic acid group of a side chain is amine-chlorided is referred to as a "P-salt". "Monomer". The phosphoric acid group, phosphonic acid group or phosphinic acid group is referred to as "P-acid group".

【００２３】また、Ｐ−塩モノマーとＰ−モノマーとの
混合物を「Ｐ−モノマーの部分アミン塩」という。A mixture of P-salt monomer and P-monomer is referred to as "a partial amine salt of P-monomer".

【００２４】本発明によるプロトン伝導性膜において、
基材として用いる多孔質膜は、特に、限定されることな
く、種々の樹脂からなるものを用いることができる。そ
のような樹脂として、例えば、ポリテトラフルオロエチ
レン等のフッ素樹脂、６，６−ナイロンほか、種々のポ
リアミド樹脂、ポリエチレンテレフタレート等のポリエ
ステル樹脂、ジメチルフェニレンオキサイド、ポリエー
テルエーテルケトン等のポリエーテル樹脂、エチレン、
プロピレン等のα−オレフィン、ノルボルネン等の脂環
式不飽和炭化素、ブタジエン、イソプレン等の共役ジエ
ン等の（共）重合体、例えば、ポリエチレン樹脂、ポリ
プロピレン樹脂や、また、エチレン−プロピレンゴム、
ブタジエンゴム、イソプレンゴム、ブチルゴム、ノルボ
ルネンゴム等のエラストマーやそれらの水添物等の脂肪
族炭化水素樹脂を挙げることができる。これらの樹脂
は、単独で、又は２種以上を併用して、上記多孔質膜を
形成していてよい。In the proton conductive membrane according to the present invention,
The porous film used as the substrate is not particularly limited, and various resins made of various resins can be used. Examples of such a resin include fluororesins such as polytetrafluoroethylene, 6,6-nylon, various polyamide resins, polyester resins such as polyethylene terephthalate, dimethylphenylene oxide, polyether resins such as polyetheretherketone, and the like. ethylene,
(Co) polymers such as α-olefins such as propylene, alicyclic unsaturated hydrocarbons such as norbornene, conjugated dienes such as butadiene and isoprene, for example, polyethylene resin, polypropylene resin, and ethylene-propylene rubber,
Examples thereof include elastomers such as butadiene rubber, isoprene rubber, butyl rubber, norbornene rubber, and aliphatic hydrocarbon resins such as hydrogenated products thereof. These resins may be used alone or in combination of two or more to form the porous membrane.

【００２５】本発明によれば、上記した種々の樹脂から
なる多孔質膜のなかでも、ポリオレフィン樹脂、特に、
重量平均分子量５．０×１０5 以上、好ましくは、１．
０×１０6 以上の高分子量ポリエチレン樹脂からなる多
孔質膜が強度や耐熱性にすぐれるところから、好ましく
用いられる。また、ポリテトラフルオロエチレンやポリ
フッ化ビニリデン等のフッ素樹脂からなる多孔質膜も、
そのすぐれた耐薬品性と耐熱性から、本発明において、
好ましく用いられる。According to the present invention, among the above-mentioned porous films made of various resins, polyolefin resins, particularly,
Weight average molecular weight 5.0 × 10 5 or more, preferably 1.
A porous membrane made of a high molecular weight polyethylene resin of 0 × 10 6 or more is preferably used because it is excellent in strength and heat resistance. In addition, a porous film made of a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride,
Due to its excellent chemical resistance and heat resistance, in the present invention,
It is preferably used.

【００２６】本発明によれば、基材多孔質膜は、従来よ
り知られている適宜の手段によって親水化されていても
よい。このような親水化された多孔質膜は、例えば、ス
ルホン酸基、リン酸基、カルボキシル基、アミノ基、ア
ミド基、水酸基等の親水性基を有する重合体やそのブレ
ンドを原料に用いて製膜することによって得ることがで
きる。また、そのような親水性基をもたない重合体を多
孔質膜に製膜した後に、その多孔質膜に、例えば、スル
ホン化処理を施したり、また、界面活性剤を担持させる
等の方法によって得ることができる。According to the present invention, the base porous membrane may be hydrophilized by any suitable means known in the art. Such a hydrophilized porous membrane is produced, for example, by using a polymer having a hydrophilic group such as a sulfonic acid group, a phosphoric acid group, a carboxyl group, an amino group, an amide group or a hydroxyl group or a blend thereof as a raw material. It can be obtained by filming. In addition, a method in which a polymer having no such hydrophilic group is formed into a porous film, and then the porous film is subjected to, for example, a sulfonation treatment or a surfactant is carried. Can be obtained by

【００２７】本発明において、基材多孔質膜は、通常、
２０〜９０％、好ましくは、３０〜８５％の範囲の空孔
率を有する。多孔質膜の空孔率が２０％よりも小さいと
きは、このような多孔質膜の空孔にＰ−ポリマーの部分
アミン塩を担持させても、高いプロトン伝導性を有する
膜を得ることができない。しかし、多孔質膜の空孔率が
９０％よりも大きいときは、そのような多孔質膜の空孔
にＰ−ポリマーの部分アミン塩を担持させて得られるプ
ロトン伝導性膜は、強度が十分でなく、取り扱いや種々
の用途での使用に困難が伴う。In the present invention, the substrate porous membrane is usually
It has a porosity in the range of 20-90%, preferably 30-85%. When the porosity of the porous membrane is less than 20%, even if the partial amine salt of P-polymer is carried in the pores of such a porous membrane, a membrane having high proton conductivity can be obtained. Can not. However, when the porosity of the porous membrane is greater than 90%, the proton conductive membrane obtained by supporting the partial amine salt of P-polymer in the pores of such a porous membrane has sufficient strength. However, it is difficult to handle and use for various purposes.

【００２８】また、基材多孔質膜は、Ｐ−ポリマーの部
分アミン塩を多孔質膜中に保持することができれば、特
に、限定されるものではないが、その平均孔径は、通
常、０．００１〜１００μｍの範囲であり、０．００５
〜１０μｍの範囲にあることが好ましい。同様に、多孔
質膜の厚みも、特に、限定されるものではないが、通
常、１ｍｍ以下であり、好ましくは、５〜５００μｍの
範囲である。The base porous membrane is not particularly limited as long as it can retain the partial amine salt of P-polymer in the porous membrane, but the average pore diameter thereof is usually 0. 001 to 100 μm, and 0.005
It is preferably in the range of 10 μm. Similarly, the thickness of the porous film is not particularly limited, but is usually 1 mm or less, preferably 5 to 500 μm.

【００２９】本発明によるプロトン伝導性膜は、好まし
くは、Ｐ−モノマーの部分アミン塩を多孔質膜に含浸さ
せ、この多孔質膜の空孔内で重合させて、Ｐ−ポリマー
の部分アミン塩を生成させると共に、このＰ−ポリマー
の部分アミン塩を上記多孔質膜の空孔内に担持させるこ
とによって得ることができる。In the proton-conducting membrane according to the present invention, preferably, the partial amine salt of P-monomer is impregnated into the porous membrane, and the partial amine salt of P-polymer is polymerized in the pores of the porous membrane. And the partial amine salt of the P-polymer is supported in the pores of the porous membrane.

【００３０】本発明によれば、上記Ｐ−モノマーのう
ち、リン酸基を有するモノマーの好ましい例として、一
般式（Ｉ）According to the present invention, among the above P-monomers, as a preferable example of the monomer having a phosphoric acid group, a compound represented by the general formula (I)

【００３１】[0031]

【化１】 [Chemical 1]

【００３２】（式中、Ｒは水素原子又はメチル基を示
し、Ｘは基の両末端が炭素原子である２価の有機基を示
す。）で表わされる化合物を挙げることができる。(Wherein R represents a hydrogen atom or a methyl group, and X represents a divalent organic group having carbon atoms at both ends of the group).

【００３３】特に、本発明においては、上記基Ｘは、好
ましくは、一般式（Ａ）Particularly, in the present invention, the group X is preferably a compound represented by the general formula (A)

【００３４】[0034]

【化２】 [Chemical 2]

【００３５】（式中、Ｒ’はエチレン基又はプロピレン
基を示し、Ｒ”は炭素原子数１〜１０、好ましくは、２
〜６の直鎖状又は分岐鎖状アルキレン基を示し、ｐは１
〜１０の整数であり、ｑは０、１又は２である。）で表
わされる２価基か、又は一般式（Ｂ）(In the formula, R'represents an ethylene group or a propylene group, and R "has 1 to 10 carbon atoms, preferably 2
To 6 are linear or branched alkylene groups, and p is 1
Is an integer of 10 and q is 0, 1 or 2. ) Or a divalent group represented by the general formula (B)

【００３６】[0036]

【化３】 [Chemical 3]

【００３７】（式中、Ａｒ及びＡｒ’はそれぞれ独立に
２価の芳香族炭化水素基、好ましくは、フェニレン基を
示し、Ｒ'"は炭素原子数１〜１０、好ましくは、２〜６
の直鎖状又は分岐鎖状アルキレン基を示し、ｒは０又は
１であり、ｒが１のとき、ｓは０又は１である。）で表
わされる２価基を示す。(In the formula, Ar and Ar 'each independently represent a divalent aromatic hydrocarbon group, preferably a phenylene group, and R'"has 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms.
Is a linear or branched alkylene group, and r is 0 or 1, and when r is 1, s is 0 or 1. ) Represents a divalent group.

【００３８】従って、上記一般式（Ｉ）で表わされるＰ
−モノマーの好ましい具体例としては、例えば、２−メ
タクリロイルオキシエチルホスフェート、メタクリロイ
ルテトラ（オキシエチレン）ホスフェート、メタクリロ
イルペンタ（オキシプロピレン）ホスフェート、４−ス
チリルメトキシブチルホスフェート等を挙げることがで
きる。Therefore, P represented by the above general formula (I)
-Examples of preferable monomers include 2-methacryloyloxyethyl phosphate, methacryloyl tetra (oxyethylene) phosphate, methacryloyl penta (oxypropylene) phosphate, 4-styryl methoxybutyl phosphate, and the like.

【００３９】ホスホン酸基を有するモノマーの好ましい
例としては、一般式（II）Preferred examples of the monomer having a phosphonic acid group include those represented by the general formula (II)

【００４０】[0040]

【化４】 [Chemical 4]

【００４１】（式中、Ｒは水素原子又はメチル基を示
し、Ｙは基の両末端が炭素原子である２価の有機基を示
す。）で表わされる化合物を挙げることができる。(In the formula, R represents a hydrogen atom or a methyl group, and Y represents a divalent organic group having carbon atoms at both ends of the group.).

【００４２】特に、本発明においては、上記基Ｙは、好
ましくは、一般式（Ｂ）Particularly in the present invention, the above-mentioned group Y is preferably the general formula (B).

【００４３】[0043]

【化５】 [Chemical 5]

【００４４】（式中、Ａｒ及びＡｒ’はそれぞれ独立に
２価の芳香族炭化水素基、好ましくは、フェニレン基を
示し、Ｒ'"は炭素原子数１〜１０、好ましくは、２〜６
の直鎖状又は分岐鎖状アルキレン基を示し、ｒは０又は
１であり、ｒが１のとき、ｓは０又は１である。）で表
わされる２価基を示す。(In the formula, Ar and Ar 'each independently represent a divalent aromatic hydrocarbon group, preferably a phenylene group, and R'"has 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms.
Is a linear or branched alkylene group, and r is 0 or 1, and when r is 1, s is 0 or 1. ) Represents a divalent group.

【００４５】従って、上記一般式（II）で表わされるホ
スホン酸基を有するモノマーの好ましい具体例として
は、例えば、４−（２−スチリルメトキシエチル）フェ
ニルホスホン酸、４−（スチリルメトキシ）ブチルホス
ホン酸、スチリルメチルホスホン酸等の化合物を挙げる
ことができる。Therefore, preferred specific examples of the monomer having a phosphonic acid group represented by the above general formula (II) include, for example, 4- (2-styrylmethoxyethyl) phenylphosphonic acid and 4- (styrylmethoxy) butylphosphone. Examples thereof include compounds such as acid and styrylmethylphosphonic acid.

【００４６】また、ホスフィン酸基を有するモノマーの
好ましい例としては、一般式（III)Preferred examples of the monomer having a phosphinic acid group include those represented by the general formula (III)

【００４７】[0047]

【化６】 [Chemical 6]

【００４８】（式中、Ｒは水素原子又はメチル基を示
し、Ｚは基の両末端が炭素原子である２価の有機基を示
す。）で表わされる化合物を挙げることができる。(In the formula, R represents a hydrogen atom or a methyl group, and Z represents a divalent organic group having carbon atoms at both ends of the group.).

【００４９】特に、本発明においては、上記基Ｚは、好
ましくは、一般式（Ｂ）Particularly, in the present invention, the above-mentioned group Z is preferably the general formula (B).

【００５０】[0050]

【化７】 [Chemical 7]

【００５１】（式中、Ａｒ及びＡｒ’はそれぞれ独立に
２価の芳香族炭化水素基、好ましくは、フェニレン基を
示し、Ｒ'"は炭素原子数１〜１０、好ましくは、２〜６
の直鎖状又は分岐鎖状アルキレン基を示し、ｒは０又は
１であり、ｒが１のとき、ｓは０又は１である。）で表
わされる２価基を示す。(In the formula, Ar and Ar 'each independently represent a divalent aromatic hydrocarbon group, preferably a phenylene group, and R'"has 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms.
Is a linear or branched alkylene group, and r is 0 or 1, and when r is 1, s is 0 or 1. ) Represents a divalent group.

【００５２】従って、上記一般式（III)で表わされるホ
スフィン酸基を有するモノマーの具体例としては、例え
ば、４−（２−スチリルメトキシエチル）フェニルホス
フィン酸、４−（スチリルメトキシ）ブチルホスフィン
酸、スチリルメチルホスフィン酸等の化合物を挙げるこ
とができる。Therefore, specific examples of the monomer having a phosphinic acid group represented by the general formula (III) include 4- (2-styrylmethoxyethyl) phenylphosphinic acid and 4- (styrylmethoxy) butylphosphinic acid. Examples thereof include compounds such as styrylmethylphosphinic acid.

【００５３】本発明によれば、Ｐ−ポリマーの部分アミ
ン塩の製造において、Ｐ−モノマーの部分アミン塩と共
に、Ｐ−酸基を有する多官能性モノマー（以下、多官能
性Ｐ−モノマーということがある。）を用いることがで
きる。According to the present invention, in the production of a partial amine salt of a P-polymer, a polyfunctional monomer having a P-acid group (hereinafter referred to as a polyfunctional P-monomer) together with a partial amine salt of a P-monomer. Can be used.

【００５４】このような多官能性Ｐ−モノマーの好まし
い例として、例えば、一般式（IV）Preferred examples of such polyfunctional P-monomers include those represented by the general formula (IV)

【００５５】[0055]

【化８】 [Chemical 8]

【００５６】（式中、ＲとＸは前記と同じであり、ｍは
２又は３である。）で表わされるリン酸ジエステル又は
トリエステルを挙げることができる。(In the formula, R and X are the same as above, and m is 2 or 3.) and the phosphoric acid diester or triester can be mentioned.

【００５７】本発明においては、このような多官能性Ｐ
−モノマーのうち、特に、基Ｘが前記一般式（Ａ）で表
わされる基であるものが好ましい。In the present invention, such a polyfunctional P
Among the monomers, those in which the group X is a group represented by the above general formula (A) are particularly preferable.

【００５８】従って、このような多官能性Ｐ−モノマー
の具体例として、例えば、ビス（メタクリロイルオキシ
エチル）ホスフェート、ビス｛５−（メタクリロイルオ
キシエチルオキシカルボニル）ペンチル｝ホスフェート
等のリン酸ジエステルを挙げることができる。Therefore, specific examples of such polyfunctional P-monomers include phosphoric acid diesters such as bis (methacryloyloxyethyl) phosphate and bis {5- (methacryloyloxyethyloxycarbonyl) pentyl} phosphate. be able to.

【００５９】Ｐ−モノマーの部分アミン塩がこのような
多官能性Ｐ−モノマーを含むとき、この多官能性Ｐ−モ
ノマーの割合は５０モル％以下であり、好ましくは、４
５モル％以下である。When the partial amine salt of the P-monomer contains such a polyfunctional P-monomer, the proportion of the polyfunctional P-monomer is 50 mol% or less, preferably 4
It is 5 mol% or less.

【００６０】このように、Ｐ−モノマーの部分アミン塩
と共に多官能性Ｐ−モノマーを用いることによって、得
られるＰ−ポリマーの部分アミン塩は、上記多官能性Ｐ
−モノマーの架橋反応によって、三次元構造、即ち、架
橋構造を有し、かくして、Ｐ−ポリマーの部分アミン塩
の耐水性や耐溶剤性等の物性を更に改善することができ
る。Thus, the partial amine salt of the P-polymer obtained by using the polyfunctional P-monomer together with the partial amine salt of the P-monomer has the above-mentioned polyfunctional P-monomer.
-By the crosslinking reaction of the monomer, it has a three-dimensional structure, that is, a crosslinking structure, and thus the physical properties such as water resistance and solvent resistance of the partial amine salt of the P-polymer can be further improved.

【００６１】また、本発明によれば、Ｐ−モノマーの部
分アミン塩と共に、Ｐ−酸基のいずれをも有しない多官
能性モノマー（以下、多官能性非Ｐ−モノマーというこ
とがある。）を用いることができる。このように、Ｐ−
モノマー部分アミン塩が多官能性非Ｐ−モノマーを含む
とき、この多官能性非Ｐ−モノマーの割合は５０モル％
以下であり、好ましくは、４５モル％以下である。Further, according to the present invention, a polyfunctional monomer having neither a P-acid group nor a partial amine salt of a P-monomer (hereinafter may be referred to as a polyfunctional non-P-monomer). Can be used. Thus, P-
When the monomeric partial amine salt contains a polyfunctional non-P-monomer, the proportion of the polyfunctional non-P-monomer is 50 mol%.
It is below, preferably 45 mol% or below.

【００６２】このように、Ｐ−モノマーの部分アミン塩
と共に多官能性非Ｐ−モノマーを用いることによって、
得られるＰ−ポリマーの部分アミン塩は、種々の物性、
例えば、ガラス転移温度、親水性の程度、柔軟性、機械
的強度等を調整することもできる。Thus, by using a polyfunctional non-P-monomer with a partial amine salt of a P-monomer,
The partial amine salt of the obtained P-polymer has various physical properties,
For example, the glass transition temperature, the degree of hydrophilicity, flexibility, mechanical strength and the like can be adjusted.

【００６３】しかし、本発明によるプロトン伝導性膜に
おいて、Ｐ−ポリマーの部分アミン塩に架橋構造をもた
せるための手段は、上記に限定されるものではなく、例
えば、官能基間の反応、過酸化物による架橋、電子線等
の照射、オゾンの作用等、従来より知られている適宜の
手段を利用することができる。However, in the proton conductive membrane according to the present invention, the means for imparting a crosslinked structure to the partial amine salt of the P-polymer is not limited to the above, and examples thereof include reaction between functional groups and peroxidation. Appropriate means known in the related art such as crosslinking by a substance, irradiation with an electron beam or the like, action of ozone and the like can be used.

【００６４】更に、本発明によれば、Ｐ−モノマーの部
分アミン塩と共に、Ｐ−酸基のいずれをも有しない単官
能性モノマー（以下、単官能性非Ｐ−モノマーというこ
とがある。）を用いて、Ｐ−モノマーの部分アミン塩と
共重合体を形成させてもよい。Further, according to the present invention, a monofunctional monomer having neither a P-acid group nor a partial amine salt of a P-monomer (hereinafter sometimes referred to as a monofunctional non-P-monomer). May be used to form a copolymer with the partial amine salt of the P-monomer.

【００６５】このような単官能性非Ｐ−モノマーとして
は、例えば、スチレン、ビニルスルホン酸、スチレンス
ルホン酸ナトリウム等のビニルモノマー類、エチルビニ
ルエーテル等のビニルエーテル類、アクリル酸ブチル、
メトキシエチルアクリレート、２−エチルヘキシルメタ
クリレート、アクリル酸等のアクリルモノマー類、Ｎ，
Ｎ−ジメチルアミノプロピルアクリルアミド、２−アク
リルアミド−２−メチルプロパンスルホン酸等のアクリ
ルアミド類を挙げることができる。Examples of such monofunctional non-P-monomers include vinyl monomers such as styrene, vinyl sulfonic acid, sodium styrene sulfonate, vinyl ethers such as ethyl vinyl ether, butyl acrylate, and the like.
Acrylic monomers such as methoxyethyl acrylate, 2-ethylhexyl methacrylate, acrylic acid, N,
Examples thereof include acrylamides such as N-dimethylaminopropyl acrylamide and 2-acrylamido-2-methylpropane sulfonic acid.

【００６６】本発明において、Ｐ−モノマーの部分アミ
ン塩（多官能性Ｐ−モノマーを含む。）と共に単官能性
非Ｐ−モノマーを用いる場合、その単官能性非Ｐ−モノ
マーの割合は、用いる基材多孔質膜の空孔率にもよる
が、通常、Ｐ−モノマーの部分アミン塩（多官能性Ｐ−
モノマーを含む。）に対して、９０モル％以下の範囲で
あり、好ましくは、８０モル％以下の範囲である。単官
能性非Ｐ−モノマーの割合がＰ−モノマーの部分アミン
塩（多官能性Ｐ−モノマーを含む。）に対して９０モル
％よりも多いときは、高プロトン伝導性膜を得ることが
できない。In the present invention, when a monofunctional non-P-monomer is used together with a partial amine salt of P-monomer (including a polyfunctional P-monomer), the proportion of the monofunctional non-P-monomer is used. Although it depends on the porosity of the substrate porous membrane, it is usually a partial amine salt of P-monomer (polyfunctional P-
Contains monomers. ) To 90 mol% or less, preferably 80 mol% or less. When the proportion of the monofunctional non-P-monomer is more than 90 mol% with respect to the partial amine salt of the P-monomer (including the polyfunctional P-monomer), a high proton conductive membrane cannot be obtained. .

【００６７】本発明において、Ｐ−モノマーのＰ−酸基
をアミン塩化するには、即ち、Ｐ−酸基がアミン塩化さ
れたＰ−モノマーを得るには、Ｐ−モノマーにアミンを
作用させる。In the present invention, an amine is allowed to act on the P-monomer in order to aminate the P-acid group of the P-monomer, that is, to obtain a P-monomer in which the P-acid group is aminated.

【００６８】ここに、上記アミンは、特に、限定される
ものではないが、例えば、ピリジン、キノリン、アクリ
ジン、イミダゾール、ピラゾール、ピペリジン、ピペラ
ジン等の複素環式アミンやその誘導体、アニリン、トル
イジン、ベンジルアミン、ジフェニルアミン、ナフチル
アミン等の芳香族アミンやその誘導体、ｎ−ブチルアミ
ン、ｎ−ヘキシルアミン等の脂肪族アミンやその誘導
体、モノエタノールアミン、ジエタノールアミン等のア
ルカノールアミン、グリシン、グルタミン酸等のアミノ
酸、ベタイン等の両性物質等を挙げることができる。Here, the above-mentioned amine is not particularly limited, but for example, heterocyclic amines such as pyridine, quinoline, acridine, imidazole, pyrazole, piperidine, piperazine and their derivatives, aniline, toluidine, benzyl. Aromatic amines and their derivatives such as amines, diphenylamine and naphthylamine, aliphatic amines and their derivatives such as n-butylamine and n-hexylamine, alkanolamines such as monoethanolamine and diethanolamine, amino acids such as glycine and glutamic acid, betaine and the like. The amphoteric substance and the like can be mentioned.

【００６９】本発明によれば、前記Ｐ−モノマーの部分
アミン塩は、好ましくは、アミンのアミノ基／Ｐ−モノ
マーの有するＰ−酸基の比率Ｒが０＜Ｒ＜１となるよう
に、Ｐ−モノマーにアミンを作用させて、アミン塩化し
ていないＰ−モノマーとアミン塩化したＰ−モノマーと
の混合物として得ることができる。特に、本発明によれ
ば、Ｐ−モノマーの部分アミン塩において、アミンのア
ミノ基／Ｐ−モノマーの有するＰ−酸基の比率Ｒは、
０．１≦Ｒ≦０．９の範囲であることが好ましい。According to the present invention, the partial amine salt of the P-monomer preferably has a ratio R of amino group of amine / P-acid group of P-monomer of 0 <R <1. The amine can be reacted with the P-monomer to obtain a mixture of the non-amine-salt P-monomer and the amine-salt P-monomer. In particular, according to the present invention, in the partial amine salt of P-monomer, the ratio R of the amino group of amine / P-acid group of P-monomer is:
The range of 0.1 ≦ R ≦ 0.9 is preferable.

【００７０】しかし、本発明によれば、Ｐ−モノマーを
すべて、アミン塩化し、このアミン塩化Ｐ−モノマー
と、アミン塩化していないＰ−モノマーとを混合し、こ
れをＰ−モノマーの部分アミン塩とすることもできる。
従って、この場合には、アミン塩化したＰ−モノマーと
アミン塩化していないＰ−モノマーにおいて、それぞれ
のＰ−モノマーは同じでもよく、異なっていてもよい。However, according to the present invention, all P-monomers are amine salified, and the amine-salted P-monomers and unaminated P-monomers are mixed, and this is a partial amine of the P-monomers. It can also be salt.
Therefore, in this case, in the aminized P-monomer and the non-aminated P-monomer, the respective P-monomers may be the same or different.

【００７１】本発明によれば、かくして、プロトン伝導
性膜は、好ましくは、Ｐ−モノマーの部分アミン塩と、
必要に応じて、上述した多官能性Ｐ−モノマーや多官能
性非Ｐ−モノマー、単官能性非Ｐ−モノマー等、Ｐ−モ
ノマーやＰ−塩モノマーと共重合性を有するモノマーを
基材多孔質膜に担持させ、熱重合や光重合等、従来より
知られている適宜の方法によって、上記モノマーを重合
させればよい。しかし、重合法としては、なかでも、光
重合法が簡便で安全あり、しかも、短時間でＰ−ポリマ
ーの部分アミン塩を得ることができる。また、光重合を
行なった後、必要に応じて、残余のモノマーを重合させ
るために、より高温で更に光重合や熱重合を行なっても
よい。According to the invention, the proton-conducting membrane thus preferably comprises a partial amine salt of the P-monomer,
If necessary, the above-mentioned polyfunctional P-monomers, polyfunctional non-P-monomers, monofunctional non-P-monomers, and other P-monomers and monomers having copolymerizability with P-salt monomers are used as the base material porous. The above monomer may be polymerized by a suitable method conventionally known such as thermal polymerization or photopolymerization by supporting it on a polymer film. However, as the polymerization method, the photopolymerization method is simple and safe, and the partial amine salt of the P-polymer can be obtained in a short time. Further, after the photopolymerization, if necessary, in order to polymerize the remaining monomer, photopolymerization or thermal polymerization may be further performed at a higher temperature.

【００７２】上記光重合開始剤は、従来より知られてい
るものを適宜に用いればよい。例えば、２−ベンジル−
２−ジメチルアミノ−１−（４−モルホリノフェニル）
ブタノン−１（チバガイギー社製イルガキュア３６
９）、２−メチル−１−｛４−（メチルチオ）フェニ
ル｝−２−モルホリノプロパノン−１（チバガイギー社
製イルガキュア９０７）、１−ヒドロキシシクロヘキシ
ルフェニルケトン（チバガイギー社製イルガキュア１８
４）、ベンジルジメチルケタール（チバガイギー社製イ
ルガキュア６５１）等を用いることができる。３００ｎ
ｍ以上の波長の光を用いても重合が可能であるものが特
に好ましい。このような光重合開始剤は、通常、Ｐ−モ
ノマーの部分アミン塩を含むモノマー全体に対して０．
０１〜５重量％程度加えられる。As the photopolymerization initiator, those conventionally known may be appropriately used. For example, 2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl)
Butanone-1 (Irgacure 36 manufactured by Ciba Geigy)
9), 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropanone-1 (Irgacure 907 manufactured by Ciba Geigy), 1-hydroxycyclohexyl phenyl ketone (Irgacure 18 manufactured by Ciba Geigy)
4), benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba-Geigy) and the like can be used. 300n
Those that can be polymerized even using light having a wavelength of m or more are particularly preferable. Such a photopolymerization initiator is usually added to the total amount of the monomers including the partial amine salt of the P-monomer at 0.
About 01 to 5% by weight is added.

【００７３】Ｐ−モノマーの部分アミン塩や、必要に応
じて、前記その他の共重合性モノマーや、光重合開始剤
等を含む混合物を多孔質膜の空孔内に担持させるために
は、例えば、この混合物に多孔質膜を浸漬したり、ま
た、この混合物を基材多孔質膜に塗布すればよい。In order to support the partial amine salt of the P-monomer and, if necessary, the above-mentioned other copolymerizable monomer, a mixture containing a photopolymerization initiator and the like in the pores of the porous membrane, for example, The porous membrane may be dipped in this mixture, or this mixture may be applied to the substrate porous membrane.

【００７４】このように、Ｐ−モノマーの部分アミン塩
やそれを含む混合物を多孔質膜に担持させるに際して、
このＰ−モノマー部分アミン塩やそれを含む混合物の粘
度を適宜に調整してもよい。即ち、粘度を高めるために
Ｐ−モノマーの部分アミン塩の一部を予備重合させた
り、また、適宜のポリマーを少量、添加し、溶解させて
もよい。反対に、粘度を下げるために、適当な溶剤を加
えて、希釈してもよい。As described above, when the partial amine salt of P-monomer or the mixture containing the partial amine salt is supported on the porous membrane,
The viscosity of this P-monomer partial amine salt or the mixture containing it may be adjusted appropriately. That is, in order to increase the viscosity, a part of the partial amine salt of the P-monomer may be prepolymerized, or a small amount of an appropriate polymer may be added and dissolved. On the contrary, in order to reduce the viscosity, an appropriate solvent may be added and diluted.

【００７５】このようにして、多孔質膜にＰ−モノマー
の部分アミン塩やこれを含む混合物を担持させた後、例
えば、ポリエステル樹脂製離型フィルムで多孔質膜を挟
み、この交換膜を酸素（従って、例えば、空気）から遮
断して、高圧水銀ランプ等を用いてＰ−モノマーの部分
アミン塩やその他の共重合性モノマーに光照射し、光重
合させることによって、Ｐ−ポリマーの部分アミン塩を
多孔質膜の空孔内に担持させてなるプロトン伝導性膜を
得ることができる。In this way, the partial amine salt of P-monomer or a mixture containing the same is supported on the porous membrane, and then the porous membrane is sandwiched between release films made of polyester resin, and the exchange membrane is oxygenated. (Thus, for example, by shielding from the air), the partial amine salt of P-monomer or other copolymerizable monomer is irradiated with light using a high-pressure mercury lamp or the like, and photopolymerized to obtain a partial amine of P-polymer. It is possible to obtain a proton conductive membrane in which a salt is supported in the pores of the porous membrane.

【００７６】上記光重合に必要な光照射量は、系により
異なるが、通常は、０．１〜５Ｊ／ｃｍ2 程度で十分で
ある。光重合は、得られるＰ−ポリマーの部分アミン塩
の分子量を高くするために、通常、室温付近で行なう
が、しかし、重合率を高めるために、より高い温度で光
重合を行なってもよい。また、最初は低温で、次いで、
高温で光重合してもよい。The amount of light irradiation required for the above photopolymerization varies depending on the system, but normally 0.1 to 5 J / cm 2 is sufficient. The photopolymerization is usually carried out at around room temperature in order to increase the molecular weight of the partial amine salt of the P-polymer to be obtained, but the photopolymerization may be carried out at a higher temperature in order to increase the polymerization rate. Also, first at low temperature, then
You may photopolymerize at high temperature.

【００７７】また、別の方法として、本発明によるプロ
トン伝導性膜は、Ｐ−モノマーを多孔質膜の空孔内で前
述したと同様にして重合させて、Ｐ−ポリマーを生成さ
せ、次いで、このＰ−ポリマーにアミンを作用させて、
そのＰ−酸基の一部をアミン化することによっても得る
ことができる。本発明によれば、この場合、アミンのア
ミノ基／Ｐ−ポリマーの有するＰ−酸基の比率Ｒが０＜
Ｒ＜１となるように、アミンをＰ−ポリマーに作用さ
せ、好ましくは、アミンのアミノ基／Ｐ−ポリマーの有
するＰ−酸基の比率Ｒが０．１≦Ｒ≦０．９となるよう
に、アミンをＰ−ポリマーに作用させる。Alternatively, in the proton conductive membrane according to the present invention, the P-monomer is polymerized in the pores of the porous membrane in the same manner as described above to form the P-polymer, and then, By acting an amine on this P-polymer,
It can also be obtained by aminating part of the P-acid group. According to the invention, in this case the ratio R of the amine groups of the amine / P-acid groups of the P-polymer is 0 <
The amine is allowed to act on the P-polymer so that R <1, and the ratio R of the amine group of the amine / the P-acid group of the P-polymer is preferably 0.1 ≦ R ≦ 0.9. First, the amine is allowed to act on the P-polymer.

【００７８】このように、Ｐ−モノマーを多孔質膜の空
孔内で重合させて、Ｐ−ポリマーを生成させる場合に
も、Ｐ−モノマーの部分アミン塩を重合させる場合と同
様に、多官能性Ｐ−モノマーや多官能性非Ｐ−モノマー
を必要に応じて用いて、架橋構造を有するＰ−ポリマー
を架橋させ、また、単官能性Ｐ−モノマーを用いて、そ
れとの共重合体を生成させることができる。As described above, when the P-monomer is polymerized in the pores of the porous membrane to produce the P-polymer, the polyfunctional monomer is polyfunctional as in the case of polymerizing the partial amine salt of the P-monomer. A functional P-monomer or a polyfunctional non-P-monomer as necessary to crosslink a P-polymer having a crosslinked structure, and a monofunctional P-monomer to form a copolymer therewith. Can be made.

【００７９】本発明によれば、Ｐ−モノマーの部分アミ
ン塩又はＰ−モノマー、必要に応じて、これらに共重合
性を有する前記その他のモノマーとのモノマー混合物を
多孔質膜に含浸させる際、多孔質膜の空孔を上記モノマ
ー混合物が充填する比率（充填率）が低いときは、上記
モノマーの重合後も、基材多孔質膜は、通気性を有する
多孔質構造を有しており、かくして、（必要な場合に
は、生成したＰ−ポリマーのＰ−酸基をアミン塩化し
て、）通気性を有するプロトン伝導性多孔質膜を得るこ
とができる。他方、上記充填率が高いときは、上記モノ
マーの重合後、基材多孔質膜は、その空孔が実質的に閉
塞されて、（必要な場合には、生成したＰ−ポリマーの
Ｐ−酸基をアミン塩化して、）通気性のないプロトン伝
導性無孔膜を得ることができる。一応の目安として、モ
ノマーの充填率が８０％以上であれば、基材多孔質膜の
空孔が実質的に閉塞されてなる通気性のないプロトン伝
導性無孔膜を得ることができる。According to the present invention, when the porous membrane is impregnated with a partial amine salt of a P-monomer or a P-monomer, and optionally a monomer mixture with the other monomer having copolymerizability therewith, When the ratio of filling the pores of the porous membrane with the monomer mixture (filling rate) is low, the substrate porous membrane has a porous structure having air permeability even after the polymerization of the monomers. Thus, a proton-conducting porous membrane having air permeability can be obtained (if necessary, by subjecting the P-acid group of the produced P-polymer to amine chloride formation). On the other hand, when the filling rate is high, after the polymerization of the monomer, the substrate porous membrane has its pores substantially closed, and (when necessary, the P-acid of the produced P-polymer is The groups can be aminated with amines to obtain non-breathable, proton-conducting, nonporous membranes. As a tentative guideline, if the monomer filling rate is 80% or more, it is possible to obtain a non-permeable, proton-conducting non-porous membrane in which the pores of the porous substrate membrane are substantially closed.

【００８０】本発明においては、Ｐ−モノマーの部分ア
ミン塩やＰ−モノマー、これらに共重合性を有する上記
その他のモノマーとのモノマー混合物は、基材多孔質膜
の空孔を充填するのみならず、基材多孔質膜の少なくと
も一方の表面の少なくとも一部を被覆していてもよい。
この場合、上記モノマー混合物の充填率は１００％を越
える。このように、基材多孔質膜にモノマー混合物を１
００％を越える充填率で担持させ、これに光照射すれ
ば、多孔質膜は、その空孔が生成するポリマーで充填さ
れているのみならず、（必要な場合には、生成したＰ−
ポリマーのＰ−酸基をアミン塩化して、）少なくとも一
方の表面の少なくとも一部がそのポリマーで被覆された
プロトン伝導性膜を得ることができる。In the present invention, the partial amine salt of the P-monomer, the P-monomer, and the monomer mixture with the above-mentioned other monomer having copolymerizability therewith only need to fill the pores of the substrate porous membrane. Alternatively, at least a part of the surface of at least one of the base material porous membranes may be covered.
In this case, the filling rate of the monomer mixture exceeds 100%. In this way, 1% of the monomer mixture was added to the substrate porous membrane.
When loaded at a filling rate of more than 00% and irradiated with light, the porous film is not only filled with the polymer whose pores are generated, but (when necessary, the generated P-
The P-acid groups of the polymer can be aminized to obtain a proton conducting membrane in which at least a portion of at least one surface is coated with the polymer.

【００８１】更に、本発明によれば、このようにして得
られたプロトン伝導性膜の有する空孔の残余の空隙、即
ち、このようにして得られたプロトン伝導性膜に残存す
る空隙を加熱、収縮させ、又は加熱、溶融させる等の適
宜手段によって、プロトン伝導性膜に残存する上記空隙
の少なくとも一部を閉塞して、プロトン伝導性フィルム
とすることができ、特に、好ましくは、プロトン伝導性
膜に残存する空隙をすべて閉塞して、通気性のないプロ
トン伝導性無孔フィルムを得ることができる。また、必
要に応じて、プロトン伝導性膜に残存する空隙を一部閉
塞して、通気性のあるプロトン伝導性有孔フィルムを得
ることができる。Further, according to the present invention, the remaining voids of the pores of the proton conductive membrane thus obtained, that is, the voids remaining in the proton conductive membrane thus obtained are heated. At least a part of the voids remaining in the proton-conducting membrane can be closed by an appropriate means such as shrinking, shrinking, or heating or melting to give a proton-conducting film. It is possible to obtain a proton-permeable nonporous film having no air permeability by closing all the voids remaining in the permeable membrane. If necessary, the voids remaining in the proton conductive membrane can be partially closed to obtain a breathable proton conductive porous film.

【００８２】このように、Ｐ−ポリマーの部分アミン塩
を基材多孔質膜の空孔内に担持させてなるプロトン伝導
性膜やプロトン伝導性フィルムは、高いプロトン伝導性
を有する。本発明によれば、多孔質膜へのＰ−モノマー
の部分アミン塩やこれを含むモノマー混合物の充填率を
高くして、多孔質膜の有する空孔へのＰ−ポリマーの部
分アミン塩の充填率を高くするほど、高いプロトン伝導
性を有する膜やフィルムを得ることができる。As described above, the proton conductive membrane or the proton conductive film in which the partial amine salt of the P-polymer is carried in the pores of the base material porous membrane has high proton conductivity. According to the present invention, the filling rate of the partial amine salt of P-monomer or the monomer mixture containing the same is increased in the porous membrane so that the pores of the porous membrane are filled with the partial amine salt of P-polymer. The higher the ratio, the more the membrane or film having high proton conductivity can be obtained.

【００８３】本発明によれば、このように、多孔質構造
を有し、通気性を有するプロトン伝導性膜や、反対に、
無孔構造のプロトン伝導性膜を得ることができ、また、
多孔質構造を有し、通気性を有するプロトン伝導性フィ
ルムや、反対に、無孔構造のプロトン伝導性フィルムを
得ることができる。多孔質構造を有し、通気性を有する
プロトン伝導性膜やフィルムは、例えば、選択透過性荷
電膜等、その空隙を活かした用途に好ましく用いること
ができる。According to the present invention, as described above, a proton conductive membrane having a porous structure and having air permeability, or conversely,
It is possible to obtain a proton-conducting membrane having a non-porous structure, and
It is possible to obtain a proton conductive film having a porous structure and having air permeability, and conversely, a proton conductive film having a non-porous structure. A proton conductive membrane or film having a porous structure and having air permeability can be preferably used for applications making use of its voids, such as a selectively permeable charged membrane.

【００８４】しかし、多孔質構造を有し、通気性を有す
るプロトン伝導性膜やフィルムは、燃料電池用セパレー
ターとして用いれば、ガスのクロスリークが起こりやす
い等の問題がある。従って、このような用途には、上述
したように、多孔質膜の空孔を実質的にすべてＰ−ポリ
マーの部分アミン塩で充填したプロトン伝導性無孔膜を
用いたり、また、プロトン伝導性多孔質膜を前述したよ
うに加熱、溶融させる等の適宜の手段によって、プロト
ン伝導性膜に残存する空隙をすべて閉塞してなるプロト
ン伝導性無孔フィルムを用いることが好ましい。However, when a proton conductive membrane or film having a porous structure and air permeability is used as a separator for a fuel cell, there is a problem that a gas cross leak is likely to occur. Therefore, for such an application, as described above, a non-porous proton-conducting membrane in which substantially all pores of the porous membrane are filled with a partial amine salt of P-polymer, or a proton-conducting non-porous membrane is used. It is preferable to use a proton-conductive non-porous film obtained by closing all the voids remaining in the proton-conductive membrane by an appropriate means such as heating and melting the porous membrane as described above.

【００８５】本発明によるプロトン伝導性膜やプロトン
伝導性フィルムは、Ｐ−ポリマーの部分アミン塩からな
るプロトン伝導性ポリマーを多孔質膜に複合化したもの
であり、好ましくは、Ｐ−モノマーの部分アミン塩を多
孔質膜に含浸させ、この多孔質膜の空孔内で重合させ
て、Ｐ−ポリマーの部分アミン塩を生成させると共に、
このＰ−ポリマーの部分アミン塩を上記多孔質膜の空孔
内に担持させて、多孔質膜とＰ−ポリマーの部分アミン
塩とを一体化したものである。The proton-conducting membrane or the proton-conducting film according to the present invention is a composite of a proton-conducting polymer consisting of a partial amine salt of P-polymer in a porous membrane, preferably a P-monomer portion. The amine salt is impregnated into the porous membrane and polymerized in the pores of the porous membrane to generate a partial amine salt of the P-polymer, and
The partial amine salt of the P-polymer is supported in the pores of the porous membrane to integrate the porous membrane and the partial amine salt of the P-polymer.

【００８６】従って、本発明によれば、基材多孔質膜と
プロトン伝導性ポリマーとの複合化に由来して、種々の
点ですぐれたプロトン伝導性膜又はフィルムを得ること
ができる。例えば、超高分子量ポリエチレン等からなる
強靱な多孔質膜を基材として用いることによって、Ｐ−
ポリマーの部分アミン塩に由来する高いプロトン伝導性
に加えて、高い機械的強度とすぐれたハンドリング性を
有するプロトン伝導性膜又はフィルムを得ることができ
る。Therefore, according to the present invention, it is possible to obtain a proton-conducting membrane or film excellent in various points due to the composite of the porous substrate membrane and the proton-conducting polymer. For example, by using a tough porous membrane made of ultra-high molecular weight polyethylene or the like as a substrate, P-
In addition to high proton conductivity derived from the partial amine salt of the polymer, a proton conductive membrane or film having high mechanical strength and excellent handleability can be obtained.

【００８７】特に、本発明に従って、Ｐ−モノマーの部
分アミン塩を多孔質膜の空孔内に担持させ、重合させ
て、Ｐ−ポリマーの部分アミン塩を基材多孔質膜と一体
化することによって、Ｐ−ポリマーの部分アミン塩のポ
リマー鎖を多孔質膜の網目に高度に絡みつかせることが
でき、更には、Ｐ−モノマーの部分アミン塩と共に多官
能性Ｐ−モノマーや多官能性非Ｐ−モノマーを共重合さ
せれば、架橋したＰ−ポリマーの部分アミン塩と多孔質
膜を構成するポリマー鎖とが相互貫通したポリマーネッ
トワークによって物理的な結合が生じ、かくして、プロ
トン伝導性ポリマーと多孔質膜との密着性を一層強めた
プロトン伝導性膜やフィルムを得ることができる。In particular, according to the present invention, the partial amine salt of P-monomer is supported in the pores of the porous membrane and polymerized to integrate the partial amine salt of P-polymer with the substrate porous membrane. The polymer chain of the partial amine salt of the P-polymer can be highly entangled with the network of the porous membrane, and further, together with the partial amine salt of the P-monomer, a polyfunctional P-monomer or a polyfunctional non-functional non-functional polymer can be used. When the P-monomer is copolymerized, a physical network is formed by a polymer network in which the partial amine salt of the cross-linked P-polymer and the polymer chain forming the porous membrane are mutually penetrating, and thus, the proton-conducting polymer. It is possible to obtain a proton-conducting membrane or film having stronger adhesion to the porous membrane.

【００８８】[0088]

【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。また、以下において、用いた多孔質膜の特性や、得
られたプロトン伝導性膜又はフィルムの特性は、次のよ
うにして評価した。The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In the following, the properties of the porous membrane used and the properties of the obtained proton conductive membrane or film were evaluated as follows.

【００８９】（膜又はフィルムの厚み）１／１００００
シックネスゲージで測定した。 （多孔質膜の空孔率）多孔質膜の単位面積Ｓ（ｃｍ2 ）
あたりの重量Ｗ（ｇ）、平均厚みｔ（μｍ）及び密度ｄ
（ｇ／ｃｍ3 ）から下式にて算出した。(Thickness of film or film) 1/10000
Measured with a thickness gauge. (Porosity of Porous Membrane) Unit Area S (cm 2 ) of Porous Membrane
Weight W (g), average thickness t (μm) and density d
It was calculated from the following formula from (g / cm 3 ).

【００９０】空孔率（％）＝（１−（１０4 ・Ｗ／(Ｓ
・ｔ・ｄ））×１００Porosity (%) = (1- (10 4 · W / (S
・ T ・ d)) × 100

【００９１】（プロトン伝導度）プロトン伝導性膜又は
フィルムを温度２５℃、相対湿度５０％に調整した環境
下に４時間放置した後、ヒューレットパッカード社ＬＣ
ＲメーターＨＰ４２８４Ａを用いて、白金電極間に所定
厚みの１ｃｍ角の試料を挟み、温度２５℃、相対湿度５
０％の条件下で複素インピーダンス法にて測定し、虚数
部の抵抗値ゼロに外挿したときの実数部の抵抗値を用い
てプロトン伝導度を算出した。(Proton conductivity) The proton conductive membrane or film was allowed to stand in an environment adjusted to a temperature of 25 ° C. and a relative humidity of 50% for 4 hours, and then subjected to LC by Hewlett Packard.
Using a R meter HP4284A, a 1 cm square sample having a predetermined thickness is sandwiched between platinum electrodes, and the temperature is 25 ° C. and the relative humidity is 5
Proton conductivity was calculated using the resistance value of the real part when extrapolated to a resistance value of the imaginary part of zero by the complex impedance method under the condition of 0%.

【００９２】（基材多孔質膜の空孔へのＰ−ポリマーの
部分アミン塩の体積充填率）基材多孔質膜の体積Ｖ（ｃ
ｍ3 ）、基材多孔質膜の空孔率Φ（％）、Ｐ−ポリマー
の部分アミン塩の重量Ｍ（ｇ）及びＰ−ポリマーの部分
アミン塩の密度ｄ（ｇ／ｃｍ3 ）から下式にて算出し
た。(Volume Filling Ratio of Partial Amine Salt of P-Polymer in Voids of Porous Substrate Membrane) Volume V (c of porous substrate)
m 3 ), the porosity Φ (%) of the substrate porous membrane, the weight M (g) of the partial amine salt of the P-polymer, and the density d (g / cm 3 ) of the partial amine salt of the P-polymer. It was calculated by the formula.

【００９３】充填率（％) ＝１０4 ・Ｍ／（Ｖ・Φ・
ｄ）Filling rate (%) = 10 4 · M / (V · Φ ·
d)

【００９４】（引張強度）ダンベル型に打ち抜いた試験
片（ＪＩＳ Ｋ ７１１３、プラスチックの引張試験方
法における１号形試験片に準拠）について、引張試験機
（（株）島津製作所製オートグラフＡＧＳ−５０Ｄ）を
用いて測定した。(Tensile Strength) A test piece punched out in a dumbbell shape (JIS K 7113, conforming to the No. 1 test piece in the tensile test method for plastics) was used for a tensile tester (Autograph AGS-50D manufactured by Shimadzu Corporation). ) Was used for the measurement.

【００９５】実施例１ （Ｐ−モノマーの部分アミン塩の調製）２−メタクリロ
イルオキシエチルホスフェート／ビス（メタクリロイル
オキシエチル）ジホスフェート（６５／３５モル比）か
らなるＰ−モノマー（共栄社化学（株）製ライトエステ
ルＰ−１Ｍ）７０重量％とメトキシエチルアクリレート
３０重量％とからなるモノマー混合物１００重量部に攪
拌しながら、予め、計算した所要量のジエタノールアミ
ンを徐々に加えて、ジエタノールアミンのアミノ基／Ｐ
−モノマーのリン酸基の比率Ｒ＝１／２のＰ−モノマー
の部分アミン塩とメトキシエチルアクリレートとからな
るモノマー混合物を得た。Example 1 (Preparation of partial amine salt of P-monomer) P-monomer consisting of 2-methacryloyloxyethyl phosphate / bis (methacryloyloxyethyl) diphosphate (65/35 molar ratio) (Kyoeisha Chemical Co., Ltd.) (Light ester P-1M manufactured by K.K.) and 100 parts by weight of a monomer mixture consisting of 70% by weight of methoxyethyl acrylate and 30% by weight of methoxyethyl acrylate, while stirring, gradually adding the required amount of diethanolamine calculated in advance to obtain the amino group / P of diethanolamine.
A monomer mixture consisting of the partial amine salt of the P-monomer and the methoxyethyl acrylate with a ratio R = 1/2 of the phosphate groups of the monomer.

【００９６】（プロトン伝導性膜の製造）上記モノマー
混合物１００重量部にベンジルジメチルケタール（チバ
ガイギー社製イルガキュア６５１）０．２５重量部、１
−ヒドロキシシクロヘキシルフェニルケトン（チバガイ
ギー社製イルガキュア１８４）０．２５重量部を溶解さ
せた。(Production of Proton Conductive Membrane) 0.25 parts by weight of benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba-Geigy Co., Ltd.) was added to 100 parts by weight of the above monomer mixture.
-0.25 parts by weight of hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba-Geigy) was dissolved.

【００９７】これを希釈することなく、そのまま、重量
平均分子量１．０×１０6 の超高分子量ポリエチレン樹
脂からなる多孔質膜Ｔ１（膜厚２５μｍ、空孔率４０
％、平均孔径０．１０μｍ）の両面に塗布して、多孔質
膜の空孔に含浸させた。A porous membrane T1 (thickness: 25 μm, porosity: 40) made of an ultrahigh molecular weight polyethylene resin having a weight average molecular weight of 1.0 × 10 6 was used as it was without dilution.
%, Average pore diameter 0.10 μm) and applied to both sides to impregnate the pores of the porous membrane.

【００９８】このように処理した多孔質膜をポリエステ
ル樹脂製離型フィルムで挟んで、多孔質膜を空気から遮
断した後、高圧水銀ランプを備えた光照射装置（アイグ
ラフィック（株）製ＵＢ０２１−１Ｂ−１３）を用い
て、上記多孔質膜にエネルギー１．５Ｊ／ｃｍ2 にて光
照射して、その空孔内で上記モノマー混合物を光重合さ
せ、Ｐ−ポリマーの部分アミン塩とメトキシエチルアク
リレートとの共重合体を生成させると共に、これを上記
多孔質膜の空孔内に担持させて、厚み４０μｍのプロト
ン伝導性膜Ｆ１を得た。このプロトン伝導性膜において
は、多孔質膜の空孔は上記Ｐ−ポリマーの部分アミン塩
とメトキシエチルアクリレートとの共重合体にて完全に
充填されており、また、多孔質膜の両表面も、上記共重
合体の層で被覆されていた。The porous film thus treated was sandwiched between release films made of polyester resin to shield the porous film from air, and then a light irradiation device equipped with a high pressure mercury lamp (UB021-made by Eye Graphic Co., Ltd.) was used. 1B-13) was used to irradiate the porous membrane with light having an energy of 1.5 J / cm 2 , and the monomer mixture was photopolymerized in the pores thereof to form a partial amine salt of P-polymer and methoxyethyl. A copolymer with acrylate was produced and supported in the pores of the porous membrane to obtain a proton conductive membrane F1 having a thickness of 40 μm. In this proton conductive membrane, the pores of the porous membrane are completely filled with the copolymer of the partial amine salt of P-polymer and methoxyethyl acrylate, and both surfaces of the porous membrane are also filled. Was coated with a layer of the above copolymer.

【００９９】上記プロトン伝導性膜Ｆ１のプロトン伝導
度は２．３×１０-3Ｓ／ｃｍであり、引張強度は７５Ｍ
Ｐａであった。The proton conductivity of the proton conductive membrane F1 is 2.3 × 10 -3 S / cm, and the tensile strength is 75M.
It was Pa.

【０１００】（燃料電池）白金触媒を０．６ｍｇ／ｃｍ
2 の割合で表面に担持させたカーボンペーパー２枚の間
に上記プロトン伝導性膜Ｆ１を挟み、ホットプレスを用
いて接合して、膜−電極接合体（ＭＥＡ）を製作した。(Fuel cell) Platinum catalyst 0.6 mg / cm
The above-mentioned proton conductive membrane F1 was sandwiched between two sheets of carbon paper supported on the surface at a ratio of 2 and bonded by using a hot press to manufacture a membrane-electrode assembly (MEA).

【０１０１】（株）東陽テクニカ製燃料電池評価装置を
用いて、上記ＭＥＡの燃料電池特性を評価した。背圧弁
は絞らず、圧力は常圧にて行なった。加湿器温度は水素
側８０℃、酸素側７０℃とし、燃料電池セル温度は７０
℃とした。Ｔａｆｅｌ法にて電流−電圧（Ｉ−Ｖ）曲線
を得たところ、結果を図１に示すように、プロトン交換
膜として、ナフィオン（登録商標）１１７膜を用いた場
合とほぼ同等の電流−電圧（Ｉ−Ｖ）曲線を得た。即
ち、本発明によるプロトン伝導性膜は、ナフィオン１１
７膜と同等の燃料電池特性を有する。The fuel cell characteristics of the MEA were evaluated using a fuel cell evaluation device manufactured by Toyo Technica Co., Ltd. The back pressure valve was not throttled, and the pressure was normal pressure. The humidifier temperature was 80 ° C on the hydrogen side and 70 ° C on the oxygen side, and the fuel cell temperature was 70 ° C.
℃ was made. A current-voltage (IV) curve was obtained by the Tafel method. As a result, as shown in FIG. 1, the current-voltage was almost the same as when the Nafion (registered trademark) 117 membrane was used as the proton exchange membrane. An (IV) curve was obtained. That is, the proton conductive membrane according to the present invention is a Nafion 11
It has the same fuel cell characteristics as the 7-membrane.

【０１０２】実施例２ （Ｐ−モノマーの部分アミン塩の調製）実施例１と同じ
２−メタクリロイルオキシエチルホスフェートとビス
（メタクリロイルオキシエチル）ジホスフェートとから
なるＰ−モノマー１００重量部に攪拌しながら、予め、
計算した所要量のイミダゾールの粉末を徐々に加えて、
イミダゾールのアミノ基／Ｐ−モノマーのリン酸基の比
率Ｒ＝１／３のＰ−モノマーの部分アミン塩とした。Example 2 (Preparation of partial amine salt of P-monomer) 100 parts by weight of P-monomer consisting of the same 2-methacryloyloxyethyl phosphate and bis (methacryloyloxyethyl) diphosphate as in Example 1 was added with stirring. , In advance,
Gradually add the calculated amount of the required imidazole powder,
A partial amine salt of P-monomer having a ratio R = 1/3 of amino group of imidazole / phosphoric acid group of P-monomer was used.

【０１０３】（プロトン伝導性膜の製造）上記Ｐ−モノ
マーの部分アミン塩１００重量部にベンジルジメチルケ
タール（前記と同じ）０．２５重量部、１−ヒドロキシ
シクロヘキシルフェニルケトン（前記と同じ）０．２５
重量部を溶解させた。(Production of Proton-Conductive Membrane) 100 parts by weight of the partial amine salt of the above P-monomer, 0.25 parts by weight of benzyl dimethyl ketal (the same as above), and 0. 1-hydroxycyclohexyl phenyl ketone (the same as above). 25
Part by weight was dissolved.

【０１０４】実施例１と同じ超高分子量ポリエチレン樹
脂からなる多孔質膜Ｔ１をポリエステル樹脂製離型フィ
ルム上に載せ、多孔質膜の露出表面に、上記Ｐ−モノマ
ーの部分アミン塩を希釈することなく、そのまま、塗布
し、バーでしごいて余剰のモノマーを多孔質膜の表面か
ら除去して、多孔質膜の空孔中にのみ、上記Ｐ−モノマ
ーの部分アミン塩を含浸させた。The porous membrane T1 made of the same ultrahigh molecular weight polyethylene resin as in Example 1 was placed on a polyester resin release film, and the partial amine salt of the P-monomer was diluted on the exposed surface of the porous membrane. Instead, it was applied as it was, and the excess monomer was squeezed with a bar to remove the excess monomer from the surface of the porous membrane, and only the pores of the porous membrane were impregnated with the partial amine salt of the P-monomer.

【０１０５】このように処理した多孔質膜の露出表面に
もポリエステル樹脂製離型フィルムを被せて、多孔質膜
を空気から遮断し、実施例１と同じ光照射装置を用い
て、エネルギー１．５Ｊ／ｃｍ2 にて多孔質膜に光照射
して、その空孔内で上記Ｐ−モノマーの部分アミン塩を
光重合させ、Ｐ−ポリマーの部分アミン塩を生成させる
と共に、このＰ−ポリマーの部分アミン塩を上記空孔内
に担持させて、厚み２５μｍのプロトン伝導性膜Ｆ２を
得た。このプロトン伝導性膜においては、多孔質膜の空
孔はポリマーにて完全に充填されていた。このプロトン
伝導性膜Ｆ２のプロトン伝導度は１．２×１０-3Ｓ／ｃ
ｍであった。The exposed surface of the porous film thus treated was covered with a polyester resin release film to shield the porous film from air, and the same light irradiation apparatus as in Example 1 was used to obtain energy 1. The porous membrane is irradiated with light at 5 J / cm 2 , and the partial amine salt of the P-monomer is photopolymerized in the pores to generate the partial amine salt of the P-polymer, and the partial amine salt of the P-polymer is generated. A partial amine salt was supported in the pores to obtain a proton conductive membrane F2 having a thickness of 25 μm. In this proton conductive membrane, the pores of the porous membrane were completely filled with the polymer. The proton conductivity of this proton conductive membrane F2 is 1.2 × 10 −3 S / c.
It was m.

【０１０６】実施例３ （Ｐ−モノマーの部分アミン塩の調製）実施例１と同じ
２−メタクリロイルオキシエチルホスフェートとビス
（メタクリロイルオキシエチル）ジホスフェートとから
なるＰ−モノマー１００重量部に攪拌しながら、予め、
計算した所要量のアニリンを徐々に加えて、アニリンの
アミノ基／Ｐ−モノマーのリン酸基の比率Ｒ＝１／５の
Ｐ−モノマーの部分アミン塩とした。Example 3 (Preparation of partial amine salt of P-monomer) 100 parts by weight of P-monomer consisting of the same 2-methacryloyloxyethyl phosphate and bis (methacryloyloxyethyl) diphosphate as in Example 1 was added with stirring. , In advance,
The calculated required amount of aniline was gradually added to obtain a partial amine salt of P-monomer having an amino group ratio of aniline / phosphoric acid group of P-monomer R = 1/5.

【０１０７】（プロトン伝導性膜の製造）上記Ｐ−モノ
マーの部分アミン塩１００重量部にベンジルジメチルケ
タール（前記と同じ）０．２５重量部、１−ヒドロキシ
シクロヘキシルフェニルケトン（前記と同じ）０．５重
量部を溶解させ、これをＰ−モノマーの部分アミン塩濃
度が３０重量％となるようにメタノールにて希釈した。
希釈した。(Production of Proton-Conductive Membrane) 100 parts by weight of the partial amine salt of the above P-monomer, 0.25 parts by weight of benzyl dimethyl ketal (same as above), and 1-hydroxycyclohexyl phenyl ketone (same as above). 5 parts by weight was dissolved, and this was diluted with methanol so that the partial amine salt concentration of the P-monomer was 30% by weight.
Diluted.

【０１０８】重量平均分子量２．４×１０6 の超高分子
量ポリエチレン樹脂からなる多孔質膜Ｔ２（膜厚４０μ
ｍ、空孔率４４％、平均孔径0.１５μｍ）をポリエステ
ル樹脂製離型フィルム上に載せ、この多孔質膜の露出表
面に、上記Ｐ−モノマーの部分アミン塩混合物の希釈溶
液を塗布し、バーでしごいて余剰のモノマーを多孔質膜
の表面から除去して、風乾して、多孔質膜の空孔中にの
み、上記Ｐ−モノマーの部分アミン塩を含浸させた。A porous film T2 (having a thickness of 40 μm) made of an ultrahigh molecular weight polyethylene resin having a weight average molecular weight of 2.4 × 10 6.
m, porosity 44%, average pore diameter 0.15 μm) was placed on a polyester resin release film, and the exposed surface of this porous membrane was coated with a diluted solution of the partial amine salt mixture of the P-monomer, The excess monomer was squeezed from the surface of the porous membrane by squeezing with a bar and air-dried to impregnate the partial amine salt of the P-monomer only in the pores of the porous membrane.

【０１０９】このように処理した多孔質膜の露出表面に
もポリエステル樹脂製離型フィルムを被せて、多孔質膜
を空気から遮断し、実施例１と同じ光照射装置を用い
て、エネルギー１．５Ｊ／ｃｍ2 にて多孔質膜に光照射
して、その空孔内で上記モノマー混合物を光重合させ、
Ｐ−ポリマーの部分アミン塩を生成させると共に、この
Ｐ−ポリマーの部分アミン塩を上記空孔内に担持させ
て、厚み４０μｍのプロトン伝導性膜Ｆ３を得た。この
プロトン伝導性膜においては、多孔質膜の空孔はＰ−ポ
リマーの部分アミン塩にて部分的に充填されていた。こ
のプロトン伝導性膜Ｆ３のプロトン伝導度は８．５×１
０-5Ｓ／ｃｍであった。The exposed surface of the porous film thus treated was covered with a polyester resin release film to shield the porous film from the air, and the energy of 1. The porous membrane is irradiated with light at 5 J / cm 2 , and the monomer mixture is photopolymerized in the pores,
A partial amine salt of P-polymer was produced and the partial amine salt of P-polymer was supported in the pores to obtain a proton conductive membrane F3 having a thickness of 40 μm. In this proton conductive membrane, the pores of the porous membrane were partially filled with the partial amine salt of P-polymer. The proton conductivity of this proton conductive membrane F3 is 8.5 × 1.
It was 0 -5 S / cm.

【０１１０】比較例１ 実施例１において、基材多孔質膜を用いることなく、ポ
リエステル樹脂製離型フィルム上に実施例１と同じＰ−
モノマーの部分アミン塩を含むモノマー混合物を厚み４
０μｍの層に塗布した。Comparative Example 1 In Example 1, the same P-value as in Example 1 was applied on the polyester resin release film without using the porous substrate film.
A monomer mixture containing a partial amine salt of the monomer is formed to a thickness of 4
It was applied in a layer of 0 μm.

【０１１１】この塗布層の上にもポリエステル樹脂製離
型フィルムを載せて、上記モノマー混合物の部分アミン
塩の塗布層を空気から遮断し、実施例１と同じ光照射装
置を用いて、エネルギー１．５Ｊ／ｃｍ2 にて光照射し
て、Ｐ−ポリマーの部分アミン塩とメトキシエチルアク
リレートとの共重合体を生成させて、この共重合体のみ
からなる厚み４０μｍのプロトン伝導性膜Ｒ１を得た。
このプロトン伝導性膜のプロトン電導度は２．６×１０
-3Ｓ／ｃｍであり、また、引張強度は、９ＭＰａであっ
た。A polyester resin release film was also placed on this coating layer to shield the coating layer of the partial amine salt of the monomer mixture from the air, and the same light irradiation apparatus as in Example 1 was used to obtain energy 1 By irradiating with light at 0.5 J / cm 2 , a copolymer of a partial amine salt of P-polymer and methoxyethyl acrylate is produced, and a 40 μm-thick proton conductive membrane R1 consisting of this copolymer alone is obtained. It was
The proton conductivity of this proton conductive membrane is 2.6 × 10.
-3 S / cm, and the tensile strength was 9 MPa.

【０１１２】比較例２ ポリスチレンスルホン酸ナトリウムの水溶液（東ソー
（株）製ポリナスＰＳ−５）を強酸性カチオン交換樹脂
を用いてイオン交換し、ナトリウム塩を遊離酸に変換
し、これを濃縮した後、メタノールに溶解させて、２０
％濃度のポリスチレンスルホン酸のメタノール溶液を調
製した。Comparative Example 2 An aqueous solution of sodium polystyrene sulfonate (Polynas PS-5 manufactured by Tosoh Corporation) was subjected to ion exchange using a strongly acidic cation exchange resin to convert a sodium salt into a free acid, which was concentrated. , Dissolved in methanol, 20
A methanol solution of polystyrene sulphonic acid with a concentration of 1% was prepared.

【０１１３】実施例３と同じ超高分子量ポリエチレン樹
脂からなる多孔質膜Ｔ２をポリエステル樹脂製離型フィ
ルムに載せ、その露出表面に上記ポリスチレンスルホン
酸のメタノール溶液を塗布し、乾燥させて、厚み５８μ
ｍのプロトン伝導性膜Ｒ２を得た。The porous film T2 made of the same ultra high molecular weight polyethylene resin as in Example 3 was placed on a polyester resin release film, and the exposed surface thereof was coated with the above methanol solution of polystyrenesulfonic acid and dried to a thickness of 58 μm.
m proton-conducting membrane R2 was obtained.

【０１１４】このプロトン伝導性膜においては、多孔質
膜の空孔は上記ポリスチレンスルホン酸にて完全に充填
されており、また、多孔質膜の上記ポリスチレンスルホ
ン酸の塗布側の表面も、ポリスチレンスルホン酸の層で
被覆されていた。このプロトン伝導性膜Ｒ２のプロトン
伝導度は２．０×１０-5Ｓ／ｃｍであった。In this proton conductive membrane, the pores of the porous membrane were completely filled with the polystyrene sulfonic acid, and the surface of the porous membrane on which the polystyrene sulfonic acid was applied was also polystyrene sulfonate. It was covered with a layer of acid. The proton conductivity of this proton conductive membrane R2 was 2.0 × 10 −5 S / cm.

【０１１５】このプロトン伝導性膜を２４時間水に浸漬
したところ、ポリスチレンスルホン酸が一部、水中に溶
出した結果、この水への浸漬後に再び温度２５℃、相対
湿度５０％に調湿してプロトン伝導度を測定したとこ
ろ、３．７×１０-6Ｓ／ｃｍであった。When this proton conductive membrane was immersed in water for 24 hours, polystyrene sulfonic acid was partially eluted in the water. As a result, after the immersion in this water, the humidity was adjusted again to a temperature of 25 ° C. and a relative humidity of 50%. When the proton conductivity was measured, it was 3.7 × 10 −6 S / cm.

【０１１６】[0116]

【発明の効果】以上のように、本発明によるプロトン伝
導性膜は、側鎖のリン酸基、ホスホン酸基又はホスフィ
ン酸基の一部がアミン塩化されたＰ−ポリマーの部分ア
ミン塩を多孔質膜の空孔内に担持させてなるものであ
り、高いプロトン伝導性を有するのみならず、高い強度
を有し、更に、上記Ｐ−ポリマーの部分アミン塩は水不
溶性である。INDUSTRIAL APPLICABILITY As described above, the proton-conducting membrane according to the present invention contains a partial amine salt of P-polymer in which a part of the phosphoric acid group, phosphonic acid group or phosphinic acid group of the side chain is amine-chlorinated. It is supported in the pores of the membrane, has not only high proton conductivity but also high strength, and the partial amine salt of the P-polymer is water-insoluble.

【０１１７】特に、本発明に従って、Ｐ−モノマーの部
分アミン塩を多孔質膜の空孔内で重合させて、Ｐ−ポリ
マーの部分アミン塩を生成させると共に、このＰ−ポリ
マーの部分アミン塩を上記多孔質膜の空孔内に担持させ
てなるプロトン伝導性膜によれば、Ｐ−ポリマーの部分
アミン塩と多孔質膜が一体化され、Ｐ−ポリマーの部分
アミン塩は多孔質膜に対して高度の密着性を有する。し
かも、本発明によるプロトン伝導性膜は、従来のスルホ
ン酸基含有フッ素樹脂膜からなるプロトン伝導性膜に比
べて格段に低廉に得ることができる。In particular, in accordance with the present invention, the partial amine salt of the P-polymer is polymerized in the pores of the porous membrane to form the partial amine salt of the P-polymer and the partial amine salt of the P-polymer is formed. According to the proton conductive membrane supported in the pores of the porous membrane, the partial amine salt of the P-polymer and the porous membrane are integrated, and the partial amine salt of the P-polymer is added to the porous membrane. Has a high degree of adhesion. Moreover, the proton-conducting membrane according to the present invention can be obtained at a significantly lower cost than the conventional proton-conducting membrane made of a sulfonic acid group-containing fluororesin membrane.

【０１１８】かくして、本発明によるプロトン伝導性膜
は、燃料電池におけるイオン交換膜として好適に用いる
ことができ、ここに、低廉であることから、燃料電池シ
ステムのコストを大幅に低減せしめて、その実用化を速
めることができる。Thus, the proton conductive membrane according to the present invention can be suitably used as an ion exchange membrane in a fuel cell, and since it is inexpensive, the cost of the fuel cell system can be greatly reduced, and Practical application can be accelerated.

【図面の簡単な説明】[Brief description of drawings]

【図１】は、本発明によるプロトン伝導性膜を用いて調
製した膜−電極接合体（ＭＥＡ）の燃料電池特性を示す
Ｔａｆｅｌ法による電流−電圧（Ｉ−Ｖ）曲線である。FIG. 1 is a current-voltage (IV) curve by the Tafel method showing the fuel cell characteristics of a membrane-electrode assembly (MEA) prepared using a proton conducting membrane according to the present invention.

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） Ｈ０１Ｂ 13/00 Ｈ０１Ｂ 13/00 Ｚ Ｈ０１Ｍ 8/10 Ｈ０１Ｍ 8/10 // Ｃ０８Ｌ 101:00 Ｃ０８Ｌ 101:00 Ｆターム(参考） 4F074 AA16 AA17 AA32 AA38 AA48 AD13 AD16 CD04 CD20 DA24 DA49 4J100 AB07P AB07Q AL08P AL08Q BA02P BA02Q BA63P BA63Q BA64P BA64Q BC43P BC43Q CA04 CA05 CA31 FA00 HA55 HA61 HC43 HC47 JA45 5G301 CD01 CE01 5H026 AA06 BB03 BB10 CX04 CX05 EE18 EE19 Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01B 13/00 H01B 13/00 Z H01M 8/10 H01M 8/10 // C08L 101: 00 C08L 101: 00 F term ( (Reference) 4F074 AA16 AA17 AA32 AA38 AA48 AD13 AD16 CD04 CD20 DA24 DA49 4J100 AB07P AB07Q AL08P AL08Q BA02P BA02Q BA63P BA63Q BA64P BA64Q BC43P BC43Q CA04 CA05 CA31 FA00 HA55 HA61 HC43 HC47 JA45 5B018A19 501026A01

Claims (20)

【特許請求の範囲】[Claims] 【請求項１】側鎖のリン酸基、ホスホン酸基又はホスフ
ィン酸基が一部、アミン塩化されたポリマーを多孔質膜
の空孔内に担持させてなることを特徴とするプロトン伝
導性膜。1. A proton-conducting membrane, wherein a side chain of a phosphoric acid group, a phosphonic acid group or a phosphinic acid group is partially supported by an amine-chlorinated polymer in the pores of the porous membrane. . 【請求項２】多孔質膜が超高分子量ポリオレフィン樹脂
又はフッ素樹脂からなるものである請求項１に記載のプ
ロトン伝導性膜。2. The proton conductive membrane according to claim 1, wherein the porous membrane is made of an ultrahigh molecular weight polyolefin resin or a fluororesin. 【請求項３】ポリマーが架橋構造を有する請求項１に記
載のプロトン伝導性膜。3. The proton conductive membrane according to claim 1, wherein the polymer has a crosslinked structure. 【請求項４】請求項１から３のいずれかに記載のプロト
ン伝導性膜の空孔の残余の空隙の少なくとも一部が閉塞
されてなるプロトン伝導性フィルム。4. A proton-conducting film obtained by blocking at least a part of the remaining voids of the pores of the proton-conducting membrane according to claim 1. 【請求項５】側鎖にリン酸基、ホスホン酸基又はホスフ
ィン酸基を有する単官能性モノマーと側鎖のリン酸基、
ホスホン酸基又はホスフィン酸基がアミン塩化された単
官能性モノマーとを多孔質膜の空孔内で重合させて、側
鎖のリン酸基、ホスホン酸基又はホスフィン酸基が一
部、アミン塩化されたポリマーを生成させると共に、こ
のポリマーを上記多孔質膜の空孔内に担持させることを
特徴とするプロトン伝導性膜の製造方法。5. A monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group on the side chain and a phosphoric acid group on the side chain,
A phosphonic acid group or a phosphinic acid group is polymerized in the pores of the porous film with a monofunctional monomer in which the amine salt is amine-chlorinated, so that the side chain phosphoric acid group, phosphonic acid group or phosphinic acid group is partially amine-chlorinated. The method for producing a proton-conducting membrane, characterized in that the polymer is produced and the polymer is supported in the pores of the porous membrane. 【請求項６】請求項５に記載の方法において、側鎖にリ
ン酸基、ホスホン酸基又はホスフィン酸基を有する単官
能性モノマーと側鎖のリン酸基、ホスホン酸基又はホス
フィン酸基がアミン塩化された単官能性モノマーと共
に、リン酸基、ホスホン酸基及びホスフィン酸基のいず
れをも有しない単官能性モノマーを用いるプロトン伝導
性膜の製造方法。6. The method according to claim 5, wherein the monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group on the side chain and the phosphoric acid group, phosphonic acid group or phosphinic acid group on the side chain are used. A method for producing a proton-conducting membrane using a monofunctional monomer having neither a phosphoric acid group, a phosphonic acid group, nor a phosphinic acid group together with an aminized monofunctional monomer. 【請求項７】請求項５に記載の方法において、側鎖にリ
ン酸基、ホスホン酸基又はホスフィン酸基を有する単官
能性モノマーと側鎖のリン酸基、ホスホン酸基又はホス
フィン酸基がアミン塩化された単官能性モノマーと共
に、リン酸基、ホスホン酸基又はホスフィン酸基を有す
る多官能性モノマー及び／又はリン酸基、ホスホン酸基
及びホスフィン酸基のいずれをも有しない多官能性モノ
マーを用いて、一部、アミン塩化されたポリマーに架橋
構造を有せしめるプロトン伝導性膜の製造方法。7. The method according to claim 5, wherein the monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group on the side chain and the phosphoric acid group, phosphonic acid group or phosphinic acid group on the side chain are used. Polyfunctional monomer having phosphoric acid group, phosphonic acid group or phosphinic acid group together with amine chloride monofunctional monomer and / or polyfunctionality having neither phosphoric acid group, phosphonic acid group nor phosphinic acid group A method for producing a proton-conducting membrane in which a monomer is used to partially cross-link an amine-chlorinated polymer. 【請求項８】側鎖にリン酸基、ホスホン酸基又はホスフ
ィン酸基を有する単官能性モノマーを多孔質膜の空孔内
で重合させて、側鎖にリン酸基、ホスホン酸基又はホス
フィン酸基を有するポリマーを生成させると共に、この
ポリマーを上記多孔質膜の空孔内に担持させ、更に、こ
のポリマーの上記側鎖のリン酸基、ホスホン酸基又はホ
スフィン酸基を一部、アミン塩化することを特徴とする
プロトン伝導性膜の製造方法。8. A monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group on the side chain is polymerized in the pores of the porous membrane to give a phosphoric acid group, a phosphonic acid group or a phosphine on the side chain. While generating a polymer having an acid group, the polymer is supported in the pores of the porous membrane, and further, a phosphate group, a phosphonic acid group or a phosphinic acid group of the side chain of the polymer is partially converted into an amine. A method for producing a proton-conducting membrane, which comprises chlorinating. 【請求項９】請求項８に記載の方法において、側鎖にリ
ン酸基、ホスホン酸基又はホスフィン酸基を有する単官
能性モノマーと共に、リン酸基、ホスホン酸基及びホス
フィン酸基のいずれをも有しない単官能性モノマーを用
いるプロトン伝導性膜の製造方法。9. The method according to claim 8, wherein any one of a phosphoric acid group, a phosphonic acid group and a phosphinic acid group is used together with a monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain. A method for producing a proton-conducting membrane using a monofunctional monomer that does not have the above. 【請求項１０】請求項８に記載の方法において、側鎖に
リン酸基、ホスホン酸基又はホスフィン酸基を有する単
官能性モノマーと共に、リン酸基、ホスホン酸基又はホ
スフィン酸基を有する多官能性モノマー及び／又はリン
酸基、ホスホン酸基及びホスフィン酸基のいずれをも有
しない多官能性モノマーを用いて、ポリマーに架橋構造
を有せしめるプロトン伝導性膜の製造方法。10. The method according to claim 8, wherein a monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain is used together with a polyfunctional compound having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group. A method for producing a proton-conducting membrane in which a polymer has a crosslinked structure using a functional monomer and / or a polyfunctional monomer having neither a phosphoric acid group, a phosphonic acid group, nor a phosphinic acid group. 【請求項１１】多孔質膜が超高分子量ポリオレフィン樹
脂又はフッ素樹脂からなるものである請求項５から１０
のいずれか記載のプロトン伝導性膜の製造方法。11. The porous membrane comprises an ultra high molecular weight polyolefin resin or a fluororesin.
5. The method for producing a proton conductive membrane according to any one of 1. 【請求項１２】側鎖にリン酸基、ホスホン酸基又はホス
フィン酸基を有する単官能性モノマーと側鎖のリン酸
基、ホスホン酸基又はホスフィン酸基がアミン塩化され
た単官能性モノマーとを含むモノマー混合物を多孔質膜
の空孔内で重合させて、側鎖のリン酸基、ホスホン酸基
又はホスフィン酸基が一部、アミン塩化されたポリマー
を生成させると共に、このポリマーを上記多孔質膜の空
孔内に担持させて、プロトン伝導性膜を得、次いで、こ
のプロトン伝導性膜の空孔の残余の空隙の少なくとも一
部を閉塞することを特徴とするプロトン伝導性フィルム
の製造方法。12. A monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain and a monofunctional monomer having an amine salt of a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in the side chain. Is polymerized in the pores of the porous membrane to form a polymer in which a side chain phosphoric acid group, phosphonic acid group or phosphinic acid group is partly amine-chlorided, and the polymer is mixed with the above-mentioned porous polymer. Of a proton-conducting membrane by supporting in the pores of a porous membrane to obtain a proton-conducting membrane, and then closing at least a part of the remaining voids of the pores of the proton-conducting membrane. Method. 【請求項１３】請求項１２に記載の方法において、側鎖
にリン酸基、ホスホン酸基又はホスフィン酸基を有する
単官能性モノマーと側鎖のリン酸基、ホスホン酸基又は
ホスフィン酸基がアミン塩化された単官能性モノマーと
共に、リン酸基、ホスホン酸基及びホスフィン酸基のい
ずれをも有しない単官能性モノマーを用いるプロトン伝
導性フィルムの製造方法。13. The method according to claim 12, wherein the monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in the side chain and the phosphoric acid group, phosphonic acid group or phosphinic acid group in the side chain are used. A method for producing a proton conductive film using a monofunctional monomer having neither a phosphoric acid group, a phosphonic acid group, nor a phosphinic acid group together with an aminized monofunctional monomer. 【請求項１４】請求項１２に記載の方法において、側鎖
にリン酸基、ホスホン酸基又はホスフィン酸基を有する
単官能性モノマーと側鎖のリン酸基、ホスホン酸基又は
ホスフィン酸基がアミン塩化された単官能性モノマーと
共に、リン酸基、ホスホン酸基又はホスフィン酸基を有
する多官能性モノマー及び／又はリン酸基、ホスホン酸
基及びホスフィン酸基のいずれをも有しない多官能性モ
ノマーを用いて、一部、アミン塩化されたポリマーに架
橋構造を有せしめるプロトン伝導性フィルムの製造方
法。14. The method according to claim 12, wherein the monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in the side chain and the phosphoric acid group, phosphonic acid group or phosphinic acid group in the side chain are used. Polyfunctional monomer having phosphoric acid group, phosphonic acid group or phosphinic acid group and / or polyfunctionality having neither phosphoric acid group, phosphonic acid group nor phosphinic acid group together with amine-functionalized monofunctional monomer A method for producing a proton-conductive film, which comprises partially crosslinking an amine-chlorinated polymer with a monomer. 【請求項１５】側鎖にリン酸基、ホスホン酸基又はホス
フィン酸基を有する単官能性モノマーを多孔質膜の空孔
内で重合させて、側鎖にリン酸基、ホスホン酸基又はホ
スフィン酸基を有するポリマーを生成させると共に、こ
のポリマーを上記多孔質膜の空孔内に担持させ、更に、
このポリマーの上記側鎖のリン酸基、ホスホン酸基又は
ホスフィン酸基を一部、アミン塩化して、プロトン伝導
性膜を得、次いで、このプロトン伝導性膜の空孔の残余
の空隙の少なくとも一部を閉塞することを特徴とするプ
ロトン伝導性フィルムの製造方法。15. A monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group on the side chain is polymerized in the pores of the porous membrane to give a phosphoric acid group, a phosphonic acid group or a phosphine on the side chain. A polymer having an acid group is produced, and the polymer is supported in the pores of the porous membrane, and further,
A part of the phosphoric acid group, phosphonic acid group or phosphinic acid group of the side chain of this polymer is amine-chlorinated to obtain a proton conductive membrane, and then at least the remaining voids of the pores of the proton conductive membrane are obtained. A method for producing a proton conductive film, which comprises closing a part thereof. 【請求項１６】請求項１５に記載の方法において、側鎖
にリン酸基、ホスホン酸基又はホスフィン酸基を有する
単官能性モノマーと共に、リン酸基、ホスホン酸基及び
ホスフィン酸基のいずれをも有しない単官能性モノマー
を用いるプロトン伝導性フィルムの製造方法。16. The method according to claim 15, wherein a monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain is used together with any one of a phosphoric acid group, a phosphonic acid group and a phosphinic acid group. A method for producing a proton conductive film using a monofunctional monomer which does not have the above. 【請求項１７】請求項１５に記載の方法において、側鎖
にリン酸基、ホスホン酸基又はホスフィン酸基を有する
単官能性モノマーと共に、リン酸基、ホスホン酸基又は
ホスフィン酸基を有する多官能性モノマー及び／又はリ
ン酸基、ホスホン酸基及びホスフィン酸基のいずれをも
有しない多官能性モノマーを用いて、ポリマーに架橋構
造を有せしめるプロトン伝導性フィルムの製造方法。17. The method according to claim 15, wherein a monofunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in a side chain is used together with a polyfunctional monomer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group. A method for producing a proton conductive film, wherein a polymer has a crosslinked structure using a functional monomer and / or a polyfunctional monomer having no phosphoric acid group, phosphonic acid group or phosphinic acid group. 【請求項１８】多孔質膜が超高分子量ポリオレフィン樹
脂又はフッ素樹脂からなるものである請求項１２から１
７のいずれかに記載のプロトン伝導性フィルムの製造方
法。18. The porous membrane is made of an ultra high molecular weight polyolefin resin or fluororesin.
7. The method for producing the proton conductive film according to any one of 7. 【請求項１９】請求項１から３のいずれかに記載のプロ
トン伝導性膜をプロトン交換膜として用いてなる燃料電
池。19. A fuel cell comprising the proton conductive membrane according to any one of claims 1 to 3 as a proton exchange membrane. 【請求項２０】請求項４に記載のプロトン伝導性フィル
ムをプロトン交換膜として用いてなる燃料電池。20. A fuel cell comprising the proton conductive film according to claim 4 as a proton exchange membrane.
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JP2006160837A (en) * 2004-12-03 2006-06-22 Toagosei Co Ltd Method for preparation of electrolyte membrane
WO2006106726A1 (en) * 2005-03-31 2006-10-12 Ebara Corporation Polyelectrolyte membranes, electrodes, membrane electrode assemblies, and fuel cells
JP2008143920A (en) * 2006-12-05 2008-06-26 Canon Inc Proton electroconductive polymer, solid polymer electrolyte membrane, electrolyte membrane-electrode assembly and solid polymer type fuel cell

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