JP2006344587A - Solid electrolyte and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid electrolyte which has high ion conductivity and durability. <P>SOLUTION: This is the solid electrolyte which contains a polymer compound (1) -R1-X-, having a polymer on which a polymerizable monomer containing an acid residue as a side chain has been graft-polymerized. In (1), R1 is a structural unit containing 1 to 8 aromatic rings. X denotes -C(R5R6)-, -S-, -CO-, -SO-, -SO<SB>2</SB>-, as well as a structural unit selected from the group consisting of these combinations, and R5 and R6 respectively denote hydrogen, an alkyl group, an alkenyl group, an aryl group, and a halogen group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a solid electrolyte, particularly a solid electrolyte membrane having proton conductivity. The present invention also relates to a membrane / electrode assembly and a fuel cell using the solid electrolyte. Furthermore, it is related with the manufacturing method of a solid electrolyte.

  In recent years, lithium ion batteries and fuel cells that can be used as power sources for portable devices and the like have been actively researched, and active research has also been conducted on solid electrolytes such as lithium ion conductive materials and proton conductive materials.

In addition, it is extremely preferable that the portable device power supply is small if it has the same output. Direct methanol fuel cells, in particular, are easier to miniaturize because they do not require reformers in reforming fuel cells and high-pressure hydrogen tanks in hydrogen fuel fuel cells, making them more compact than lithium ion batteries. Because of this possibility, it is being actively studied.
In general, a sulfonic acid group-containing perfluorocarbon polymer represented by Nafion (registered trademark) is used as a proton conducting material. Because of the permeation, the direct methanol fuel cell has a low output. Also, in order to suppress the permeation of methanol, only a few percent methanol aqueous solution can be used as a fuel, resulting in a low energy density per unit weight or unit volume, which can be applied to small portable devices. There were issues such as being unable to do so.
In addition, there is a demand for strength suitable for the process of producing a membrane / electrode assembly and sufficient durability when used as a fuel cell.

  In recent years, there have been many development examples of solid electrolytes using high-rigidity polymer materials, and research on solid electrolytes using polymer materials with high solvent resistance has been conducted for many years. In Patent Document 1 and Patent Documents 1 to 5, solid electrolytes mainly composed of sulfonated polyether ether ketone, sulfonated polysulfone, and sulfonated polyether ketone have been developed. However, in any case, since the sulfonic acid group is directly bonded to the aromatic ring of the polymer main chain, there is a problem that the sulfonic acid group is gradually detached at a high operating temperature and the battery performance is lowered. In addition, since the sulfonic acid group is directly bonded to the polymer main chain, the distance between the hydrophobic main chain and the hydrophilic sulfonic acid group is short, and water molecules are absorbed more than necessary. The problem of being soluble in aqueous solvents by the amount arises.

  In Patent Document 6, a solid electrolyte is produced by bonding a sulfonic acid group to an aromatic ring of a polymer main chain synthesized by polycondensation via an alkyl group. In this method, the sulfonic acid group is bonded to the main chain via a methylene chain, thereby separating the hydrophobic portion of the main chain from the hydrophilic portion of the side chain with the sulfonic acid group at a relatively long distance. The aim is to improve proton conductivity and mechanical strength. However, in reality, since the reaction efficiency is very low, the amount of sulfonic acid groups introduced is small, and the hydrophobic part of the main chain and the hydrophilic part of the side chain with sulfonic acid groups are not sufficiently separated.

JP-A-6-49202 JP-A-6-93114 JP-A-8-20716 JP-A-9-245818 Japanese Patent Laid-Open No. 10-21944 Patent registration No. 3607862 Journal of Membrane Science, 197, 2002, p. 231-242

  An object of the present invention is to provide a solid electrolyte having high proton conduction performance while maintaining durability.

式（１）または式（４）中、Ｒ¹およびＲ⁴は、それぞれ、式（５）〜（２４）で表される構造単位であり、Ｘは、−Ｃ（Ｒ⁵Ｒ⁶）−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ−または−ＳＯ₂−、ならびにこれらの組み合わせからなる群より選ばれる構造単位を表し、Ｒ⁵およびＲ⁶は、それぞれ、水素原子、アルキル基、アルケニル基、アリール基またはハロゲン置換アルキル基を表す。
Ｓ¹〜Ｓ¹²は、それぞれ、水素原子または置換基を表す。
Ｑ¹は、−Ｏ−、−Ｓ−または−ＮＲ²¹−を表し、Ｑ²は、−Ｏ−、−ＣＲ²²Ｒ²³−、−ＣＯ−または−ＮＲ²⁴−を表す。ここで、Ｒ²¹〜Ｒ²⁴は、それぞれ、水素原子、アルキル基、アルケニル基、アリール基を表す。
式（２５）中、Ｂ¹は単結合または、連結基を表し、Ｄは重合性モノマーの重合物を含み、かつ、少なくとも１つの酸残基を有する原子団（Ｘ）を表す。
（５）式（２５）において、Ｄが少なくとも１つの酸素透過性の高い置換基を有している、（４）に記載の固体電解質。
（６）式（２５）においてＢ¹が、単結合、または、アルキレン基、ハロゲン置換アルキレン基、アルキル置換アルキレン基、アリーレン基、ハロゲン置換アリーレン基、アルキル置換アリーレン基、アルケニレン基、ハロゲン置換アルキニレン基、アルキル置換アルキニレン基、アルキニレン基、アミド基、エステル基、スルホアミド基、スルホン酸エステル基、ウレイド基、スルホニル基、スルフィニル基、チオエーテル基、エーテル基、カルボニル基、ヘテリレン基およびフェニレン基からなる群から選択される１または２以上を組み合わせて構成される炭素原子数０〜１００以下の連結基である、請求４または５に記載の固体電解質。
（７）前記高分子化合物（１）は、式（２６）で表される繰り返し単位および（２７）で表される繰り返し単位を含む、（１）〜（６）のいずれか１項に記載の固体電解質。

（式（２６）または（２７）中、Ｘ¹は単結合または−Ｃ（Ｒ⁵Ｒ⁶）−であり、Ｘ²およびＸ⁴は、それぞれ、−Ｏ−または−Ｓ−、ならびにこれらの組み合わせからなる基であり、Ｘ³は−ＣＯ−、−ＳＯ−、−ＳＯ₂−、ならびにこれらの組み合わせからなる基であり、ｎ₁およびｎ₂は、それぞれ、０または１であり、ｎ₁およびｎ₂の和は１以上である。Ｂ¹は単結合または、連結基を表し、Ｄは重合性モノマーの重合物を含み、かつ、少なくとも１つの酸残基を有する原子団（Ｘ）を表す。）
（８）前記高分子化合物（１）は、式（２８）で表される繰り返し単位および（２９）で表される繰り返し単位を含む、（１）〜（７）のいずれか１項に記載の固体電解質。

（式（２８）または（２９）中、Ｘ¹は単結合または−Ｃ（Ｒ₅Ｒ₆）−であり、Ｘ²およびＸ⁴は、それぞれ、−Ｏ−または−Ｓ−、ならびにこれらの組み合わせからなる基であり、Ｘ³は−ＣＯ−、−ＳＯ−、−ＳＯ₂−、ならびにこれらの組み合わせからなる基であり、ｎ₃およびｎ₄は、それぞれ、０または１であり、ｎ₃およびｎ₄の和は１以上である。Ｂ¹は単結合または、連結基を表し、Ｄは重合性モノマーの重合物を含み、かつ、少なくとも１つの酸残基を有する原子団（Ｘ）を表す。）
（９）式（２５）中のＤが、式（３０）で表される繰り返し単位を含み、かつ、式（３０）が有する芳香環に、少なくとも、式（３１）で表される基が結合している、（４）〜（８）のいずれか１項に記載の固体電解質。

（式(３０)中、Ｗ¹¹、Ｗ¹²およびＷ¹³はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表す。式(３１)中、Ｂ²は単結合または２〜６価の連結基を表し、Ａ¹は酸残基を表し、ｎ₅は１〜５の整数である。）
（１０）式（２５）中のＤが、式（３０）で表される繰り返し単位を含み、かつ、式（３０）中の芳香環に、少なくとも、式（３１）で表される基および式（３２）で表される基が結合している、（４）〜（８）のいずれか１項に記載の固体電解質。

（式(３０)中、Ｗ¹¹、Ｗ¹²およびＷ¹³はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表す。式(３１)中、Ｂ²は単結合または２〜６価の連結基を表し、Ａ¹は酸残基を表し、ｎ₅は１〜５の整数である。式(３２)中、Ｅ¹は酸素透過性の高い置換基を表す。）
（１１）膜状である、（１）〜（１０）のいずれか１項に記載の固体電解質。
（１２）固体電解質膜と、該固体電解質膜を介して両側に配置された一対の電極からなるガス拡散電極とを含む、膜／電極接合体であって、かつ、前記固体電解質膜および／または前記一対の電極が、（１）〜（１０）のいずれか１項に記載の固体電解質を含む、膜／電極接合体。
（１３）（１１）に記載の固体電解質と該固体電解質を介して両側に配置された一対の電極からなるガス拡散電極とを含む、膜／電極接合体。
（１４）前記ガス拡散電極が、触媒金属を炭素材からなる導電材の表面にバインダーによって担時された電極である、（１２）または（１３）に記載の膜／電極接合体。
（１５）前記バインダーが、（１）〜（１０）のいずれか１項に記載の固体電解質を含む、（１４）に記載の膜／電極接合体。
（１６）（１２）〜（１５）のいずれか１項に記載の膜／電極接合体を含む、燃料電池。
（１７）ガス拡散電極を挟むように設置されたガス不透過性の一対のセパレータをさらに有する、（１６）に記載の燃料電池。
（１８）膜／電極接合体とセパレータとの間に配置された一対の集電材をさらに有する、（１７）に記載の燃料電池。
（１９）高分子化合物の主鎖に酸残基を有する重合性モノマーをグラフト重合させることを含む、固体電解質の製造方法。
（２０）高分子化合物の主鎖が、芳香環を含み、該芳香環にハロゲノメチル基を導入した後、重合性モノマーを反応させることを含む、（１９）に記載の固体電解質の製造方法。
（２１）前記重合性モノマーが式（Ａ）で表される化合物または式（Ｂ）で表される化合物である、（１９）または（２０）に記載の固体電解質の製造方法。
式（Ａ）

（式（Ａ）中、ＥおよびＦは、それぞれ、単結合または２価の連結基を表し、Ｇはカルボン酸基、スルホン酸基またはリン酸基を表す。）
式（Ｂ）

（式（Ｂ）中、ｍ１は、０以上の整数であり、Ｇはカルボン酸基、スルホン酸基またはリン酸基を表す。）
（２２）前記重合性モノマーが式（３３）で表される化合物で表される化合物である、（１９）または（２０）に記載の固体電解質の製造方法。

（式（３３）中、Ｗ²¹、Ｗ²²およびＷ²³はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表し、Ｂ³は単結合または２〜６価の連結基を表し、Ａ²は酸残基を表し、ｎ６は１〜５の整数を表し、ｎ７は１〜５の整数を表す。）
（２３）前記重合性モノマーが式（３３）で表される化合物および式（３４）で表される化合物である、（１９）または（２０）に記載の固体電解質の製造方法。

（式（３３）および（３４）中、Ｗ²¹、Ｗ²²、Ｗ²³、Ｗ²⁴、Ｗ²⁵およびＷ²⁶はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表し、Ｂ³は単結合または２〜６価の連結基を表し、Ａ²は酸残基を表し、ｎ６は１〜５の整数を表し、ｎ７は１〜５の整数を表す。Ｅ²は酸素透過性の高い置換基を表し、ｎ８は１〜５の整数を表す。）
（２４）前記固体電解質が、（１）〜（１１）のいずれか１項に記載の固体電解質である、（１９）〜（２３）のいずれか１項に記載の固体電解質の製造方法。
（２５）側鎖として酸残基を含む重合性モノマーがグラフト重合された重合物を有する高分子化合物。 (1) A solid electrolyte comprising a polymer compound (1) having a polymer obtained by graft polymerization of a polymerizable monomer containing an acid residue as a side chain.
(2) The solid electrolyte according to (1), wherein the polymer has a molecular weight of 150 or more.
(3) The solid electrolyte according to (1) or (2), wherein the polymerizable monomer has a vinyl group.
(4) The polymer compound (1) is bonded to the main chain including a repeating unit represented by the formula (1) and / or a repeating unit represented by the formula (4), The solid electrolyte according to any one of (1) to (3), which has a side chain represented by the formula (25).

In Formula (1) or Formula (4), R ¹ and R ⁴ are structural units represented by Formulas (5) to (24), respectively, X is —C (R ⁵ R ⁶ ) —, Represents a structural unit selected from the group consisting of —O—, —S—, —CO—, —SO— or —SO ₂ —, and combinations thereof, and R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, respectively. Represents an alkenyl group, an aryl group or a halogen-substituted alkyl group.
S ^{1 to} S ¹² each represents a hydrogen atom or a substituent.
Q ¹ represents —O—, —S— or —NR ²¹ —, and Q ² represents —O—, —CR ²² R ²³ —, —CO— or —NR ²⁴ —. Here, R < ²¹ > -R < ²⁴ > represents a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, respectively.
In Formula (25), B ¹ represents a single bond or a linking group, D represents an atomic group (X) containing a polymer of a polymerizable monomer and having at least one acid residue.
(5) The solid electrolyte according to (4), wherein in formula (25), D has at least one substituent having high oxygen permeability.
(6) In the formula (25), B ¹ is a single bond or an alkylene group, a halogen-substituted alkylene group, an alkyl-substituted alkylene group, an arylene group, a halogen-substituted arylene group, an alkyl-substituted arylene group, an alkenylene group, or a halogen-substituted alkynylene group. An alkyl-substituted alkynylene group, an alkynylene group, an amide group, an ester group, a sulfoamide group, a sulfonic acid ester group, a ureido group, a sulfonyl group, a sulfinyl group, a thioether group, an ether group, a carbonyl group, a heterylene group, and a phenylene group. The solid electrolyte according to claim 4 or 5, which is a linking group having 0 to 100 carbon atoms, which is constituted by combining 1 or 2 selected.
(7) The polymer compound (1) according to any one of (1) to (6), comprising a repeating unit represented by the formula (26) and a repeating unit represented by (27). Solid electrolyte.

(In formula (26) or (27), X ¹ is a single bond or —C (R ⁵ R ⁶ ) —, and X ² and X ⁴ are —O— or —S—, and combinations thereof, respectively. X ³ is a group consisting of —CO—, —SO—, —SO ₂ —, and combinations thereof, and n ₁ and n ₂ are each 0 or 1, and n ₁ and The sum of n ₂ is at least 1. B ¹ represents a single bond or a linking group, D represents a polymer of a polymerizable monomer, and represents an atomic group (X) having at least one acid residue. .)
(8) The polymer compound (1) according to any one of (1) to (7), comprising a repeating unit represented by the formula (28) and a repeating unit represented by (29). Solid electrolyte.

(In formula (28) or (29), X ¹ is a single bond or —C (R ₅ R ₆ ) —, and X ² and X ⁴ are —O— or —S—, and combinations thereof, respectively. X ³ is a group consisting of —CO—, —SO—, —SO ₂ —, and combinations thereof, and n ₃ and n ₄ are each 0 or 1, and n ₃ and The sum of n ₄ is at least 1. B ¹ represents a single bond or a linking group, D represents a polymer of a polymerizable monomer, and represents an atomic group (X) having at least one acid residue. .)
(9) D in the formula (25) includes the repeating unit represented by the formula (30), and at least the group represented by the formula (31) is bonded to the aromatic ring of the formula (30). The solid electrolyte according to any one of (4) to (8).

(In Formula (30), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. In Formula (31), B ² is a single bond or 2-6. Represents a valent linking group, A ¹ represents an acid residue, and n ₅ is an integer of 1 to 5.)
(10) D in the formula (25) includes a repeating unit represented by the formula (30), and the aromatic ring in the formula (30) has at least a group and a formula represented by the formula (31) The solid electrolyte according to any one of (4) to (8), wherein the group represented by (32) is bonded.

(In Formula (30), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. In Formula (31), B ² is a single bond or 2-6. Represents a valent linking group, A ¹ represents an acid residue, and n ₅ represents an integer of 1 to 5. In formula (32), E ¹ represents a substituent having high oxygen permeability.
(11) The solid electrolyte according to any one of (1) to (10), which is in a film form.
(12) A membrane / electrode assembly including a solid electrolyte membrane and a gas diffusion electrode including a pair of electrodes disposed on both sides of the solid electrolyte membrane, and the solid electrolyte membrane and / or A membrane / electrode assembly, wherein the pair of electrodes includes the solid electrolyte according to any one of (1) to (10).
(13) A membrane / electrode assembly comprising the solid electrolyte according to (11) and a gas diffusion electrode comprising a pair of electrodes disposed on both sides of the solid electrolyte.
(14) The membrane / electrode assembly according to (12) or (13), wherein the gas diffusion electrode is an electrode in which a catalytic metal is supported on the surface of a conductive material made of a carbon material by a binder.
(15) The membrane / electrode assembly according to (14), wherein the binder includes the solid electrolyte according to any one of (1) to (10).
(16) A fuel cell comprising the membrane / electrode assembly according to any one of (12) to (15).
(17) The fuel cell according to (16), further comprising a pair of gas-impermeable separators disposed so as to sandwich the gas diffusion electrode.
(18) The fuel cell according to (17), further comprising a pair of current collectors disposed between the membrane / electrode assembly and the separator.
(19) A method for producing a solid electrolyte, comprising graft polymerization of a polymerizable monomer having an acid residue on the main chain of a polymer compound.
(20) The method for producing a solid electrolyte according to (19), wherein the main chain of the polymer compound includes an aromatic ring, and a polymerizable monomer is reacted after introducing a halogenomethyl group into the aromatic ring.
(21) The method for producing a solid electrolyte according to (19) or (20), wherein the polymerizable monomer is a compound represented by the formula (A) or a compound represented by the formula (B).
Formula (A)

(In the formula (A), E and F each represent a single bond or a divalent linking group, and G represents a carboxylic acid group, a sulfonic acid group or a phosphoric acid group.)
Formula (B)

(In formula (B), m1 is an integer of 0 or more, and G represents a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group.)
(22) The method for producing a solid electrolyte according to (19) or (20), wherein the polymerizable monomer is a compound represented by the compound represented by formula (33).

(In formula (33), W ²¹ , W ²² and W ²³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and B ³ represents a single bond or a divalent to hexavalent linking group. , a ² represents an acid residue, n6 represents an integer of 1 to 5, n7 is an integer of 1-5.)
(23) The method for producing a solid electrolyte according to (19) or (20), wherein the polymerizable monomer is a compound represented by formula (33) and a compound represented by formula (34).

(Expressed in the formula (33) and ^{(34), W 21, W} 22, W 23, W 24, W 25 and W ²⁶ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, B ³ Represents a single bond or a bivalent to hexavalent linking group, A ² represents an acid residue, n6 represents an integer of 1 to 5, n7 represents an integer of 1 to 5. E ² represents an oxygen-permeable substance. Represents a high substituent, and n8 represents an integer of 1 to 5.)
(24) The method for producing a solid electrolyte according to any one of (19) to (23), wherein the solid electrolyte is the solid electrolyte according to any one of (1) to (11).
(25) A polymer compound having a polymer obtained by graft polymerization of a polymerizable monomer containing an acid residue as a side chain.

 The solid electrolyte of the present invention was excellent in proton conductivity.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, the “A” -substituted “B” group means a B group substituted with A. For example, a halogen-substituted alkyl group refers to an alkyl group substituted with a halogen atom.

The solid electrolyte of the present invention contains a polymer compound (1), and the polymer compound (1) has a side chain that is a polymer obtained by graft polymerization of a polymerizable monomer containing an acid residue in its main chain. It is characterized by that.
In this specification, the graft polymerization refers to a polymerization reaction in which a monomer different from the main chain is introduced as a side chain so as to branch off the main chain of the polymer compound (1). Any polymerization method such as polymerization, suspension polymerization, solution polymerization or emulsion polymerization may be used. For the graft polymerization, a polymerization method described in 284-340, the Basics of Polymer Science, 2nd edition, Polymer Society, for example, cationic polymerization, radical polymerization, anionic polymerization, and redox polymerization can be used. Is preferred. Among radical polymerizations, Chem. Rev. When a living radical polymerization method such as atom transfer radical polymerization described in 2001, 101, 2921-2990 or stable free radical polymerization described in Macromolecules, 2004, 37, 1297-1303 is used, termination reaction such as radical recombination Is particularly preferable because the amount of grafting is suppressed and the amount of grafting can be controlled.

The solid electrolyte of the present invention is different from the polymer solid electrolyte containing an acid residue in the side chain, by graft polymerization of a polymerizable monomer containing an acid residue in the side chain, and adjusting the orientation order of the acid residue, A long proton transport channel is formed, which enables high proton conduction. That is, the conventional proton conducting membrane has a phase separation structure as shown in FIG. 1 (in the figure, the black line is the proton transport domain). On the other hand, the proton conducting membrane of the present invention has a phase separation structure as shown in FIG.
In addition, in the solid electrolyte of the present invention, as long as desired proton conduction can be achieved, the solid electrolyte as a whole may include a portion where a long proton transport channel is not formed.

The main chain of the polymer compound (1) used in the present invention preferably contains a repeating unit represented by the formula (1) and / or a repeating unit represented by the formula (4). Moreover, it is preferable that the side chain of the solid electrolyte of this invention is a side chain represented by Formula (25).
The side chain represented by the formula (25) can be obtained, for example, by grafting a polymerizable monomer having an acid residue.

First, the main chain containing the repeating unit represented by the formula (1) and / or the repeating unit represented by the formula (4) will be described.

In the formula, R ¹ and R ⁴ are structural units represented by the formulas (5) to (24), respectively, and the formulas (5) to (9) are preferable.
X represents a structural unit selected from the group consisting of —C (R ⁵ R ⁶ ) —, —O—, —S—, —CO—, —SO— or —SO ₂ —, and combinations thereof.
Here, R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen-substituted alkyl group, and each represents a hydrogen atom, an alkyl group (preferably a carbon atom number (hereinafter “C number”). 1-20 groups, for example, methyl group, ethyl group, propyl group, butyl group, isopropyl group, methoxyethyl group), alkenyl group (preferably C 2-20 group, for example, vinyl group) , An allyl group), an aryl group (preferably a group having 6 to 26 carbon atoms, such as a phenyl group, a pentafluorophenyl group, a 2-naphthyl group), a halogen-substituted alkyl group (preferably a group having 1 to 20 carbon atoms, such as Trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, difluoromethyl group, chloromethyl group).
X is preferably —C (R ⁵ R ⁶ ) —, —O—, —S—, —CO—, —SO— or —SO ₂ —, and more preferably —C (R ⁵ R ⁶ ) — (more It is more preferably —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —), —O—, —S—, —CO— or —SO ₂ —.

S ^{1 to} S ¹² each represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably a group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, a benzyl group, 3 -Sulfopropyl group, 4-sulfobutyl group, carboxymethyl group, 5-carboxypentyl group), alkenyl group (preferably a group having 2 to 20 carbon atoms such as vinyl group, allyl group, 2-butenyl group, 1,3 -Butadienyl group), a cycloalkyl group (preferably a group having 3 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group), an aryl group (preferably a group having 6 to 20 carbon atoms, such as a phenyl group, 2-chlorophenyl). Group, 4-methoxyphenyl group, 3-methylphenyl group, 1-naphthyl group, 2-nitrophenyl group), heterocyclic group (preferably having 1 to 20 carbon atoms) For example, pyridyl ring group, thienyl ring group, furyl ring group, thiazolyl ring group, imidazolyl ring group, pyrazolyl ring group, pyrrolidino ring group, piperidino ring group, morpholino ring group), alkynyl group (preferably C 2-20 Groups such as ethynyl group, 2-propynyl group, 1,3-butadiynyl group, 2-phenylethynyl group), halogen atoms (for example, F, Cl, Br, I), amino groups (preferably having a C number of 0 to 20 groups such as amino group, dimethylamino group, diethylamino group, dibutylamino group, anilino group), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, phosphonic acid group, acyl group (preferably Is a group having 1 to 20 carbon atoms, for example, acetyl group, benzoyl group, salicyloyl group, pivaloyl group, 3,5-dimethoxybenzo Group, 4-methoxybenzoyl group), an alkoxy group (preferably a group having 1 to 20 carbon atoms, for example, a methoxy group, a butoxy group, a cyclohexyloxy group), an aryloxy group (preferably a group having 6 to 26 carbon atoms, For example, phenoxy group, 1-naphthoxy group), alkylthio group (preferably a group having 1 to 20 carbon atoms, such as methylthio group, ethylthio group), arylthio group (preferably a group having 6 to 20 carbon atoms, such as phenylthio group) 4-chlorophenylthio group), an alkylsulfonyl group (preferably a group having 1 to 20 carbon atoms, such as a methanesulfonyl group or a butanesulfonyl group), an arylsulfonyl group (preferably a group having 6 to 20 carbon atoms, such as benzene) Sulfonyl group, paratoluenesulfonyl group), sulfamoyl group (preferably a group having 0 to 20 carbon atoms, for example, Rufamoyl group, N-methylsulfamoyl group, N-phenylsulfamoyl group), carbamoyl group (preferably a group having 1 to 20 carbon atoms, such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl) Group, N-phenylcarbamoyl group), acylamino group (preferably a group having 1 to 20 carbon atoms, such as acetylamino group, benzoylamino group), imino group (preferably a group having 2 to 20 carbon atoms, such as phthalimino group) ), An acyloxy group (preferably a group having 1 to 20 carbon atoms, such as an acetyloxy group or a benzoyloxy group), an alkoxycarbonyl group (preferably a group having 2 to 20 carbon atoms, such as a methoxycarbonyl group or a phenoxycarbonyl group) A carbamoylamino group (preferably a group having 1 to 20 carbon atoms such as a carbamoylamino group N-methylcarbamoylamino group, N-phenylcarbamoylamino group), more preferably alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, alkynyl group, halogen atom, nitro group, hydroxyl group, carboxyl Group, sulfo group, phosphonic acid group, acyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carbamoyl group, acylamino group, imino group.

Q ¹ represents —O—, —S— or —NR ²¹ —, preferably —O— or —S—.
Q ² represents —O—, —CR ²² R ²³ —, —CO— or —NR ²⁴ —, preferably —O—, —CH ₂ —, —CO— or —NH ₂ —.
Here, R < ²¹ > -R < ²⁴ > represents a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, respectively, and a hydrogen atom is preferable.

The main chain containing the repeating unit represented by the formula (1) and / or the repeating unit represented by the formula (4) is represented by any of the following (3-1) to (3-15), for example. However, the main chain of the polymer compound (1) used in the present invention is not limited to this.
In addition, n is a positive integer and is preferably in a range satisfying a preferable molecular weight of the polymer compound (1) used in the present invention described later. R ¹³ and R ¹⁴ are each an alkyl group having 1 to 10 carbon atoms or a phenyl group.

  As an example of a method for synthesizing the main chain of the polymer compound (1) used in the present invention, a known method as described in "4th edition Experimental Chemistry Course, Vol. 29, 4.1 Heat-resistant material" is used. Is preferred. Commercially available polymers can also be used as the main chain. More specifically, for example, when sulfone is contained in the main chain, a compound represented by formula (35) (sulfone compound) and a compound represented by formula (36) (aromatic diols) Examples of the production method include polycondensation.

In formula (35), Y ¹ represents a halogen atom (preferably F, Cl) or a nitro group.
In the formula (36), A represents a group consisting of a single bond, —C (R ⁵ R ⁶ ) —, —O—, —S—, —CO—, —SO— or —SO ₂ —, and combinations thereof. Represents a structural unit selected from
Here, R ⁵ and R ⁶ has the same meaning as R ⁵ and R ⁶ in the formula (1) or formula (4), respectively, a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, benzyl group, etc.) , An alkenyl group, an aryl group, and a halogen-substituted alkyl group (for example, a trifluoromethyl group and a pentafluoroethyl group) are preferable.
A represents —C (R ⁵ R ⁶ ) — (more preferably —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —), —O—, —S—, —CO—, —SO—. Or —SO ₂ —, preferably —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —O—, —S—, —CO— or —SO ₂ —. preferable.
m is 0, 1, or 2, R and R ⁱ are each an alkyl group having 1 to 10 carbon atoms, and s and s ⁱ are each an integer of 0 to 4.

Specific examples of the compound represented by the formula (35) include the compounds represented below.

  These sulfone compounds can be used alone or in admixture of two or more.

  Specific examples of the compound represented by formula (36) include hydroquinone, resorcin, 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-hexylhydroquinone, 2-octylhydroquinone, 2 -Decanyl hydroquinone, 2,3-dimethylhydroquinone, 2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 2,5-diethylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, 2 , 3,5,6-tetramethylhydroquinone, 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 3,3′-dimethyl-4,4′-dihydroxybiphenyl, 3,3 ′, 5,5 '-Tetramethyl-4,4'-dihi Droxybiphenyl, 3,3′-dichloro-4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetrachloro-4,4′-dihydroxybiphenyl, 3,3′-dibromo-4,4 '-Dihydroxybiphenyl, 3,3', 5,5'-tetrabromo-4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 3,3 ', 5,5'- Tetrafluoro-4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenylmethane, 3,3'-dimethyl-4,4'-dihydroxydiphenylmethane, 3,3 ', 5,5 '-Tetramethyl-4,4'-dihydroxydiphenylmethane, 3,3'-dichloro-4,4'-dihydroxydiphenylmethane, 3,3', 5,5'-tetrachloro-4 4'-dihydroxydiphenylmethane, 3,3'-dibromo-4,4'-dihydroxydiphenylmethane, 3,3 ', 5,5'-tetrabromo-4,4'-dihydroxydiphenylmethane, 3,3'-difluoro-4, 4'-dihydroxydiphenylmethane, 3,3'5,5'-tetrafluoro-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 3,3'-dimethyl-4 , 4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether, 3,3′-dichloro-4,4′-dihydroxydiphenyl ether, 3,3 ′, 5, 5′-tetrachloro-4,4′-dihydroxydiphenyl ether, 3,3′-dibromo-4,4′-di Droxydiphenyl ether, 3,3 ′, 5,5′-tetrabromo-4,4′-dihydroxydiphenyl ether, 3,3′-difluoro-4,4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-tetra Fluoro-4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 2,2′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5 , 5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dichloro-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetrachloro-4,4'- Dihydroxydiphenyl sulfide, 3,3′-dibromo-4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5, '-Tetrabromo-4,4'-dihydroxydiphenyl sulfide, 3,3'-difluoro-4,4'-dihydroxydiphenyl sulfide, 3,3', 5,5'-tetrafluoro-4,4'-dihydroxydiphenyl sulfide 4,4′-dihydroxydiphenylsulfone, 2,2′-dihydroxydiphenylsulfone, 3,3′-dimethyl-4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4, 4'-dihydroxydiphenylsulfone, 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone, 3,3 ', 5,5'-tetrachloro-4,4'-dihydroxydiphenylsulfone, 3,3'- Dibromo-4,4′-dihydroxydiphenyl sulfone, 3,3 ′, 5,5′-tetrabromo-4,4′-dihydroxydiphenyl Lufone, 3,3′-difluoro-4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetrafluoro-4,4′-dihydroxydiphenylsulfone, 2,2-bis (4-hydroxyphenyl) ) Propane, 2,2-bis (2-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-didibromo-4- Hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) Nyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-bis ( 2-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -1,3-diisopropylbenzene, α, α′-bis (2-hydroxyphenyl) -1,3- Diisopropylbenzene, α, α′-bis (3-methyl-4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-bis (3,5-dimethyl-4-hydroxyphenyl) -1,4- Diisopropylbenzene, α, α′-bis (3-methyl-4-hydroxyphenyl) -1,3-diisopropylbenzene, α, α′-bis (3,5-dimethyl-4-hydro Shifeniru) -1,3-diisopropyl benzene. These aromatic diols can be used alone or in admixture of two or more.

  Moreover, the preferable ratio of the compound represented by Formula (35) and the compound represented by Formula (36) is the ratio of the compound represented by (35) with respect to 1 mol of compounds represented by Formula (36). The molar ratio is preferably 0.9 to 1.1 mol, more preferably 0.93 to 1.07 mol, and even more preferably 0.95 to 1.05 mol.

  The main chain of the polymer compound (1) used in the present invention is synthesized by polycondensation of the compound represented by the formula (35) and one or more compounds selected from the compound represented by the formula (36). In this case, a method of polycondensation in the presence of a basic compound is preferably used.

  The kind of basic compound, reaction conditions, and the like are not particularly defined, and known basic compounds and reaction conditions can be applied. Examples of basic compounds include basic metal compounds such as alkali metals and alkaline earth metals, carbonates, acetates, hydroxides, quaternary ammonium salts, phosphonium salts and organic bases of various metals.

  The amount of these basic compounds used is preferably 0.05 to 10.0 moles and preferably 0.1 to 4.0 moles with respect to 1 mole of the compound represented by formula (36). More preferably, it is 0.5-2.5 mol.

The reaction for synthesizing the main chain of the polymer compound (1) used in the present invention is usually carried out in a solvent.
The following are mentioned as a preferable solvent.
1) ether solvent 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane and the like.
2) Aprotic amide solvents N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N -Methylcaprolactam, hexamethylphosphorotriamide and the like.
3) Amine solvents pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine etc.
4) Other solvents: dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole and the like.

These solvents may be used alone or in combination of two or more. Moreover, the 1 type (s) or 2 or more types of the solvent shown to the following 5) can also be mixed and used. When mixed and used, it is not always necessary to select a combination of solvents that are mutually soluble in an arbitrary ratio, and they may be mixed or non-uniform.
The concentration of the reaction carried out in these solvents (hereinafter referred to as polymerization concentration) is not limited.

  In the above solvent, the compound represented by the formula (36) and the compound represented by the formula (35) are reacted to obtain polysulfone (the main chain of the polymer compound (1)). Particularly preferred solvents for this reaction include the aprotic amide solvent described in 2) above and the dimethyl sulfoxide described in 4).

  The atmosphere is not particularly defined, but air, nitrogen, helium, neon, and argon are used, and nitrogen and argon which are inert gases are preferable.

Furthermore, in order to remove the water produced | generated by reaction out of the system, another solvent can also coexist. Examples of the solvent used here include the following 5).
5) benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p- Dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene and the like. Is mentioned. These solvents may be used alone or in combination of two or more.

  In addition, the solvents shown in the above items 1) to 5) can be used alone or in combination of two or more. When mixed and used, it is not always necessary to select a combination of solvents that are mutually soluble in an arbitrary ratio, and they may be mixed or non-uniform. There is no limit to the amount of these dehydrating agents used.

  The reaction temperature, reaction time, and reaction pressure are not particularly limited, and known conditions can be applied. That is, the reaction temperature is, for example, 50 ° C to 300 ° C, preferably 100 to 270 ° C, and more preferably 130 ° C to 250 ° C. Moreover, although reaction time changes with the kind of monomer to be used, the kind of solvent, and reaction temperature, 1 to 72 hours are preferable, 3 to 48 hours are more preferable, and 5 to 24 hours are more preferable. The reaction pressure may be under pressure or under reduced pressure, but may be normal pressure.

Ｂ¹は単結合または連結基を表し、Ｄは重合性モノマーの重合物を含み、かつ、少なくとも１つの酸残基を有する原子団（Ｘ）を表す。 Next, the side chain represented by Formula (25) is demonstrated.

B ¹ represents a single bond or a linking group, and D represents an atomic group (X) containing a polymer of a polymerizable monomer and having at least one acid residue.

In formula (25), B ¹ is preferably a single bond or a divalent to hexavalent linking group, and is a single bond or an alkylene group, a halogen-substituted alkylene group, an alkyl-substituted alkylene group, an arylene group, or a halogen-substituted arylene. Group, alkyl-substituted arylene group, alkenylene group, halogen-substituted alkynylene group, alkyl-substituted alkynylene group, alkynylene group, amide group, ester group, sulfoamide group, sulfonate group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether It is more preferably a linking group having 0 to 100 carbon atoms constituted by combining 1 or 2 or more selected from the group consisting of a group, a carbonyl group, a heterylene group and a phenylene group. The total number is preferably 0 to 100 carbon atoms constituting the B ^1, more preferably from 0 to 50, particularly preferably from 0 to 20.
More preferable examples of B ¹ include a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a decylene group, a phenylene (—Ph—) group, —CH ₂ —O— (CH ₂ ) _n - (n is an integer, preferably an integer of 1 to _{6), - CH 2 -Ph -,} - CH 2 CH 2 OCH 2 CH 2 -, - (CH 2 CH 2 O) 2 _{CH 2 CH 2 -, - CH} 2 CH = CH -, - CH 2 CH 2 CH = CH-, C ((CH 2) n -) 4 (n are each an integer of 0 or more, preferably 0 ), CH ((CH ₂ ) _n —) ₃ (n is an integer of 0 or more, preferably an integer of 0 to 6), CH ₃ C ((CH ₂ ) _n −) ₃ (n is an integer of 0 or more, preferably an integer of 0 to 6), EtC ((CH ₂ ) _n −) ₃ (n is an integer of 0 or more, preferably an integer of 0 to 6, respectively), —C ((CH ₂ ) _n —) ₃ (n is an integer of 0 or more, preferably Is an integer of 0 to 6), —CH ((CH ₂ ) _n —) ₂ (n is an integer of 0 or more, preferably an integer of 0 to 6), and these (the aforementioned groups and a comprising two or more combined group) -CO -, - SO -, - CS -, - SO 2 -,

の１つ以上との組み合わせが挙げられる。これらの中でも、単結合、メチレン基、−ＳＯ₂−、メチレン基と−ＳＯ₂−の組み合わせがさらに好ましく、単結合、メチレン基または−ＳＯ₂−が特に好ましい。

And a combination with one or more of the above. Among these, a single bond, a methylene group, —SO ₂ —, and a combination of a methylene group and —SO ₂ — are more preferable, and a single bond, a methylene group, or —SO ₂ — is particularly preferable.

D consists of a polymer of a polymerizable monomer and represents an atomic group (X) having at least one acid residue. Here, the atomic group (X) may have one or more substituents having high oxygen permeability.
The atomic group (X) is preferably a radical polymerizable polymer, a cationic polymerizable polymer, an anion polymerizable polymer or a redox polymerizable polymer, but is particularly preferably a radical polymerizable polymer. In addition, the atomic group (X) is a polystyrene derivative, polyacrylamide derivative, polymethacrylamide derivative, polyacrylic ester derivative, polymethacrylic ester derivative, polyacrylic acid derivative, polymethacrylic acid derivative, polyvinyl phosphoric acid derivative, polyvinyl ester derivative, polyvinyl A sulfonic acid derivative is preferable, and among them, a polystyrene derivative, a polyvinyl phosphoric acid derivative and a polyvinyl sulfonic acid derivative which are highly resistant to solvolysis are particularly preferably used. Hereinafter, polystyrene derivatives that are particularly preferably used will be described in detail.

Atomic group (X) (polystyrene derivative)
A compound containing a repeating unit represented by the formula (30) and having at least a group represented by the formula (31) bonded to the aromatic ring of the D is preferable, represented by the formula (31). Those having a group and / or a group represented by the formula (32) are more preferred.

In formula (30), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, each preferably a hydrogen atom, a halogen atom or an alkyl group.
When W ¹¹ , W ¹² and W ¹³ are halogen atoms, each is preferably a chlorine atom or a fluorine atom, more preferably a fluorine atom.
When W ¹¹ , W ¹² and W ¹³ are alkyl groups, each may be a straight chain, branched chain or cyclic alkyl group, and the number of carbon atoms thereof is preferably 1-20, more preferably 1-6. . Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, a decyl group, a cyclopropyl group, a cyclohexyl group, and a cyclododecyl group.
When W ¹¹ , W ¹² and W ¹³ are aryl groups, examples thereof include a substituted or unsubstituted phenyl group and naphthyl group having 6 to 20 carbon atoms.
When W ¹¹ , W ¹² and W ¹³ are heterocyclic groups, each is a substituted or unsubstituted hetero 6-membered ring (eg, pyridyl ring group, morpholino ring group, etc.), substituted or unsubstituted hetero 5-membered ring ( Preferred examples include a furyl ring group and a thiophene ring group.

In the formula (31), B ² represents a single bond or a linking group, and is preferably a single bond or a divalent to hexavalent linking group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group,

からなる群から選ばれる１つ以上の組み合わせからなる基がより好ましい。

A group consisting of one or more combinations selected from the group consisting of is more preferred.

  Here, the aliphatic hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon, and the hydrogen atom is a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) without departing from the spirit of the present invention. May be substituted. 1-12 are preferable and, as for the carbon atom number of an aliphatic hydrocarbon group, 1-6 are more preferable. The aromatic hydrocarbon group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) within the range in which the hydrogen atom on the ring does not depart from the spirit of the present invention. Group, naphthyl group, biphenyl group and phenyl group are preferred, naphthyl group, biphenyl group and phenyl group are more preferred, and phenyl group is most preferred. The heterocyclic group may be substituted with a substituent (for example, a halogen atom, preferably a fluorine atom, etc.) within the range in which the hydrogen atom on the ring does not depart from the spirit of the present invention, a pyridyl group, a furyl group, A thienyl group and a triazinyl group are preferable, and a triazinyl group is more preferable.

Preferred examples of B ² include methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, decylene group, phenylene (—Ph—) group, —CH ₂ —O— (CH ₂ ) _n — ( n is an integer of 0 or more, preferably an integer of 1 to 6), —CH ₂ —Ph—, —CH ₂ CH ₂ OCH ₂ CH ₂ —, — (CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ —, —CH ₂ CH═CH—, —CH ₂ CH ₂ CH═CH—, C ((CH ₂ ) _n —) ₄ (n is an integer of 0 or more, preferably 0 to 6), CH ((CH ₂ ) _n —) ₃ (n is an integer, preferably an integer of 0 to 6), CH ₃ C ((CH ₂ ) _n —) ₃ (n are each an integer of 0 or more, preferably an integer of _{0~6), EtC ((CH 2} ) n -) 3 (n is it An integer of 0 or more, preferably 0-6 _{integer), - C ((CH 2} ) n -) 3 (n are each an integer of 0 or more, preferably 0-6 integer ), —CH ((CH ₂ ) _n —) ₂ (where each n is an integer of 0 or more, preferably an integer of 0 to 6), and these (a combination of two or more of the above groups) and -CO containing group) -, - SO -, - CS -, - SO 2 -,

の１つ以上との組み合わせが挙げられる。

And a combination with one or more of the above.

A ¹ represents an acid residue, preferably a perfluorosulfo group, a sulfo group, a phosphonic acid group or a carboxylic acid group, more preferably a perfluorosulfo group, a sulfo group or a phosphonic acid group.
n ₅ is an integer of 1 to 5, and when n ₅ is 2 or more, 2 or more A ^{1 s} may be the same or different.

E ¹ represents a substituent having high oxygen permeability. Here, the substituent having a high oxygen permeability means a substituent having a negative permacol value. For permacall values of substituents, see M.M. By Salame, ACS Polymer Preprints 8, 137 (1967). The permacol value of E ¹ is preferably −10 / N or less, more preferably −20 / N or less, and particularly preferably −50 / N or less. Here, N represents the total number of structural units constituting the polymer main chain, and is synonymous with N described in the above document. More specifically, E ¹ is preferably composed of 3 or more carbon atoms. E ¹ is preferably a low-polarity substituent, and particularly preferably contains a silicon atom or a fluorine atom. Total number of carbon atoms in E ¹ is preferably 3 to 60, more preferably 3 to 40, particularly preferably from 3 to 30.
E ¹ is, for example, an alkyl group (n-propyl group, isopropyl group, n-butyl group, n-pentyl group, benzyl group, 3-sulfopropyl group, 4-sulfobutyl group, carboxymethyl group, carboxypentyl group), Alkoxy group (ethoxy group, n-propoxy group, n-butoxy group, tert-butoxy group, pentyloxy group, neopentyloxy group), alkenyl group (allyl group, 2-butenyl group, 1,3-butadienyl group), A cycloalkyl group (cyclopentyl group, cyclohexyl group), aryl group (phenyl group, 2-chlorophenyl group, 4-methoxyphenyl group, 3-methylphenyl group, 1-naphthyl group, 2-nitrophenyl group), heterocyclic group ( Pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, pyrazolyl group, pyrrolidino , Piperidino group, morpholino group), alkynyl group (2-propynyl group, 1,3-butadiynyl group, 2-phenylethynyl group), and combinations of these with one or more methylol groups, preferably alkyl groups, alkenyl groups Group, cycloalkyl group, methyloxyalkyl group, methyloxyalkenyl group, methyloxycycloalkyl group, alkyl group, cycloalkyl group, methyloxyalkyl group, and methyloxycycloalkyl group are particularly preferable. Compounds having an ether structure or silicon atom in the methylene chain (ethoxymethyl group, propoxymethyl group, butoxymethyl group, hexyloxymethyl group, trimethylsilyl group, triethylsilyl group, tributylsilyl group, 3-trimethylsilylpropyl group, 2- Trimethi Rusilylethyl group, 6-triethylsilylhexyl group, triethylsilylpropyl group) are particularly preferred.
These substituents may have a substituent without departing from the gist of the present invention. As a substituent, a halogen atom (for example, F, Cl, Br, I), an amino group (preferably having 0 to 20 carbon atoms, for example, an amino group, a dimethylamino group, a diethylamino group, a dibutylamino group, an anilino group) , A cyano group, a nitro group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group, a phosphonic acid group, an acyl group (preferably having 1 to 20 carbon atoms, such as an alkoxy group (preferably having 1 to 20 carbon atoms, such as , A methoxy group, a butoxy group, a cyclohexyloxy group), an aryloxy group (preferably having 6 to 26 carbon atoms, for example, a phenoxy group, 1-naphthoxy group), an alkylthio group (preferably having 1 to 20 carbon atoms, for example, Methylthio group, ethylthio group), arylthio group (preferably having 6 to 20 carbon atoms, such as phenylthio group) , 4-chlorophenylthio group), alkylsulfonyl group (preferably having 1 to 20 carbon atoms, such as methanesulfonyl group, butanesulfonyl group), arylsulfonyl group (preferably having 6 to 20 carbon atoms, such as benzenesulfonyl group) , Paratoluenesulfonyl group).

The repeating unit represented by the formula (30) may contain only one type or two or more types.
The number of repeating units of the formula (30) is preferably 1 to 100, more preferably 1 to 50, and particularly preferably 1 to 20.

（式（２５’）中、Ｂ¹はｎ１＋１価の連結基を表し、Ｍはイオン性基を表し、ｎ１は２以上の整数を表す。）
Ｂ¹は、好ましくは、アルキレン基、ハロゲン置換アルキレン基、アリーレン基、ハロゲン置換アリーレン基、アルケニレン基、ハロゲン置換アルキニレン基、アルキニレン基、アミド基、エステル基、スルホアミド基、スルホン酸エステル基、ウレイド基、スルホニル基、スルフィニル基、チオエーテル基、エーテル基、カルボニル基およびヘテリレン基からなる群から選択される１つの基または２つ以上を組み合わせて構成される基であって、炭素原子数０〜１００以下の基から、水素原子を（ｎ１−１）個除くことに得られる連結基である。
ｎ１は、２以上の整数であり、２または３が好ましい。
Ｍはイオン性基を表し、好ましくはアルカリ金属（例えば、リチウム、ナトリウム、カリウム）カチオン、アルカリ土類金属（例えば、カリウム、ストロンチウム、バリウム）カチオン、第四級アンモニウム（例えば、トリメチルアンモニウム、トリエチルアンモニウム、トリブチルアンモニウム、ベンジルトリメチルアンモニウム）カチオン、有機塩基（例えば、トリエチルアミン、ピリジン、メチルイミダゾール、モルホリン、トリブチルアンモニウム、トリス（例えば、２−ヒドロキシエチル）アミン）からなる群から選択される。
さらに、式（２５’）で表される基は本発明の趣旨を逸脱しない範囲内において置換基を有していてもよい。置換基としては、例えば、上記式（５）〜（７）で例示した置換基が挙げられる。
また、式（２５’）は、例えば、上記主鎖構造に直接結合していてもよいし、何らかの基を介して結合していてもよい。 Next, the side chain represented by Formula (25 ′) will be described.

(In the formula (25 ′), B ¹ represents an n1 + 1 valent linking group, M represents an ionic group, and n1 represents an integer of 2 or more.)
B ¹ is preferably an alkylene group, a halogen-substituted alkylene group, an arylene group, a halogen-substituted arylene group, an alkenylene group, a halogen-substituted alkynylene group, an alkynylene group, an amide group, an ester group, a sulfoamide group, a sulfonic acid ester group, or a ureido group. , A sulfonyl group, a sulfinyl group, a thioether group, an ether group, a carbonyl group and a heterylene group, one group selected from the group consisting of two or more, or a group having 0 to 100 carbon atoms This is a linking group obtained by removing (n1-1) hydrogen atoms from the group.
n1 is an integer of 2 or more, and 2 or 3 is preferable.
M represents an ionic group, preferably an alkali metal (eg, lithium, sodium, potassium) cation, alkaline earth metal (eg, potassium, strontium, barium) cation, quaternary ammonium (eg, trimethylammonium, triethylammonium) , Tributylammonium, benzyltrimethylammonium) cation, an organic base (eg, triethylamine, pyridine, methylimidazole, morpholine, tributylammonium, tris (eg, 2-hydroxyethyl) amine).
Furthermore, the group represented by the formula (25 ′) may have a substituent without departing from the spirit of the present invention. Examples of the substituent include the substituents exemplified in the above formulas (5) to (7).
In addition, for example, Formula (25 ′) may be directly bonded to the main chain structure or may be bonded via some group.

The polymer compound (1) used in the present invention preferably contains, for example, a repeating unit represented by the formula (26) and a repeating unit represented by (27).

In formula (26) or (27), X ¹ is a single bond or —C (R ⁵ R ⁶ ) —.
X ² and X ⁴ are each a group consisting of —O— or —S— and a combination thereof, and —O— or —S— is preferred respectively.
X ³ is -CO -, - SO -, - SO 2 -, and a group comprising a combination thereof, respectively, -CO -, - SO- or -SO ₂ - are preferred.
n ₁ and n ₂ are each 0 or 1, and the sum of n ₁ and n ₂ is 1 or more.
B ¹ represents a single bond or a linking group, D represents an atomic group (X) containing a polymer of a polymerizable monomer and having at least one acid residue, and has the same meaning as D in the above formula (25). The preferred range is also synonymous.

The polymer compound (1) used in the present invention preferably contains, for example, a repeating unit represented by the formula (28) and a repeating unit represented by (29).

In formula (28) or (29), X ¹ is a single bond or —C (R ₅ R ₆ ) —.
X ² and X ⁴ are each a group consisting of —O— or —S— and a combination thereof, and —O— or —S— is preferred.
X ³ is -CO -, - SO -, - SO 2 -, and a group comprising a combination thereof, -CO -, - SO- or -SO ₂ - are preferred.
n ₃ and n ₄ are each 0 or 1, and the sum of n ₃ and n ₄ is 1 or more.
B ¹ represents a single bond or a linking group, D represents an atomic group (X) containing a polymer of a polymerizable monomer and having at least one acid residue, and has the same meaning as D in the above formula (25). The preferred range is also synonymous.

(Graft polymerization method)
As a method for polymerizing the graft chain, any of cationic polymerization, anionic polymerization, radical polymerization, and redox polymerization can be preferably used, and radical polymerization is particularly preferably used. In particular, in the case of radical polymerization, it is preferable to form a radical polymerization starting point on the polymer main chain via a linking group and to polymerize the radical polymerization monomer using the starting point. Hereinafter, the polymerization method of the graft chain using radical polymerization will be described in detail.

 Examples of the radical polymerization monomer include a compound represented by the formula (33). In combination with the compound represented by the formula (33), the compound represented by the formula (34) may be graft polymerized. As for the compound represented by Formula (33) and the compound represented by Formula (34), only 1 type may be used, respectively, and 2 or more types may be used. Hereinafter, these compounds will be described.

（式（３３）および（３４）中、Ｗ²¹、Ｗ²²、Ｗ²³、Ｗ²⁴、Ｗ²⁵およびＷ²⁶はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表し、Ｂ³は単結合または２〜６価の連結基を表し、Ａ²はイオン性官能基を表し、ｎ₆は１〜５の整数を表し、ｎ₇は１〜５の整数を表す。Ｅ²は酸素透過性の高い置換基を表し、ｎ₈は１〜５の整数を表す。）

(Expressed in the formula (33) and ^{(34), W 21, W} 22, W 23, W 24, W 25 and W ²⁶ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, B ³ Represents a single bond or a divalent to hexavalent linking group, A ² represents an ionic functional group, n ₆ represents an integer of 1 to 5, n ₇ represents an integer of 1 to 5. E ² represents oxygen. Represents a highly permeable substituent, and n ₈ represents an integer of 1 to 5.)

In the formula (33) and the formula (34), W ²¹ , W ²² , W ²³ , W ²⁴ , W ²⁵ and W ²⁶ are respectively synonymous with W ¹¹ in the formula (30), and preferred ranges are also synonymous. .
B ³ has the same meaning as B ^{2 in} formula (31), and the preferred range is also the same.
A ² represents an acid residue and has the same meaning as A ¹ in formula (31), and the preferred range is also the same.
E ² represents a substituent having high oxygen permeability, and has the same meaning as E ¹ in formula (32), and the preferred range is also the same.
n ₆ is preferably an integer of 1 to 4. n ₇ and n ₈ are preferably each an integer of 1 to 3.
When n ₆ , n ₇ and n ₈ are 2 or more and A ² , B ³ and / or E ² are 2 or more, each A ² , B ³ and / or E ² may be the same Good or different,
Preferred examples of the compound represented by formula (33) and the compound represented by formula (34) are illustrated below, but the present invention is not limited thereto.

Compound represented by formula (33)

Compound represented by formula (34)

  For the polymerization of the compound represented by the formula (33) and the compound represented by the formula (34), radical polymerization, cationic polymerization, anionic polymerization, and coordination polymerization are preferably used, and radical polymerization or cationic polymerization is more preferable. Polymerization is more preferred. Among radical polymerizations, living radical polymerization such as atom transfer radical polymerization and stable free radical polymerization is most preferable. The polymerization is preferably used for random copolymerization or block copolymerization. The composition ratio X of the component derived from the compound represented by formula (34) with respect to the component derived from the compound represented by formula (33) contained in the produced polymer is preferably 0 to 10, and 0.1. Is more preferably ˜5, particularly preferably 0.2˜2.

  As the polymerizable monomer to be graft-polymerized, a compound represented by the formula (A) or a compound represented by the formula (B) is also preferable.

（式（Ａ）中、ＥおよびＦは、それぞれ、単結合または２価の連結基を表し、Ｇはカルボン酸基、スルホン酸基またはリン酸基を表す。）
ＥおよびＦは、それぞれ、好ましくは、アルキレン基（好ましくはＣ数１〜２０のアルキレン基、例えば、メチレン基、エチレン基、メチルエチレン基、プロピレン基、メチルプロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、オクチレン基）、ハロゲン置換アルキレン基（好ましくはＣ数１〜２０のハロゲン置換アルキレン基、例えば、ジフルオロメチレン基、テトラフルオロエチレン基、ヘキサフルオロヘキシレン基、テトラフルオロヘキシレン基、ジクロロンメチレン基）、アリーレン基（好ましくはＣ数６〜２６のアリーレン基、例えば、１，２−フェニレン基、１，３−フェニレン基、１，４−フェニレン基、４−フェニレンメチレン基、１，４−ナフチレン基）、ハロゲン置換アリーレン基（好ましくはＣ数６〜２６のハロゲン置換アリーレン基、例えば、２，３，５，６−テトラフルオロ−１，４−フェニレン基、２，６−ジフルオロ−１，４−フェニレン基、２，３，５，６−テトラクロロ−１，４−フェニレン基、３，４，５，６−テトラブロモフェニレン基）、アルケニレン基（好ましくはＣ数２〜２０のアルケニレン基、例えば、エテニレン基、プロペニレン基、ブタジエニレン基）、ハロゲン置換アルキニレン基（好ましくはＣ数２〜２０のアルケニレン基、例えば、ジフルオロエテニレン基、テトラフルオロプロペニレン基、ジクロロエテニレン基）、アルキニレン基（好ましくはＣ数２〜２０のアルキニレン基、例えば、エチニレン基、プロピニレン基）、アミド基、エステル基、スルホアミド基、スルホン酸エステル基、ウレイド基、スルホニル基、スルフィニル基、チオエーテル基、エーテル基、カルボニル基、ヘテリレン基（好ましくはＣ数１〜２６のヘテリレン基、例えば、６−クロロ−１，３，５−トリアジル−２，４−ジイル基、ピリミジン−２，４−ジイル基、キノキサリン−２，３−ジイル基）からなる群から選択される１つの基または２つ以上を組み合わせて構成される基、ならびに、これらと、−Ｓ−および／または−Ｏ−の組み合わせからなる基であってＣ数０〜１００以下の基（より好ましくはＣ数１〜２０）を表す。
式（Ａ）において、Ｇはカルボン酸基、スルホン酸基またはリン酸基を表すが、これらの官能基はイオン性基を有していてもよく、上記Ｍで例示したものが挙げられる。 Formula (A)

(In the formula (A), E and F each represent a single bond or a divalent linking group, and G represents a carboxylic acid group, a sulfonic acid group or a phosphoric acid group.)
E and F are each preferably an alkylene group (preferably an alkylene group having 1 to 20 carbon atoms, such as a methylene group, an ethylene group, a methylethylene group, a propylene group, a methylpropylene group, a butylene group, a pentylene group, or a hexylene group. Group, octylene group), halogen-substituted alkylene group (preferably C1-C20 halogen-substituted alkylene group, for example, difluoromethylene group, tetrafluoroethylene group, hexafluorohexylene group, tetrafluorohexylene group, dichloromethylene group) Group), an arylene group (preferably an arylene group having 6 to 26 carbon atoms such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4-phenylenemethylene group, 1,4- Naphthylene group), halogen-substituted arylene group (preferably having 6 to 26 carbon atoms) Logen-substituted arylene groups such as 2,3,5,6-tetrafluoro-1,4-phenylene group, 2,6-difluoro-1,4-phenylene group, 2,3,5,6-tetrachloro-1 , 4-phenylene group, 3,4,5,6-tetrabromophenylene group), alkenylene group (preferably an alkenylene group having 2 to 20 carbon atoms, for example, ethenylene group, propenylene group, butadienylene group), halogen-substituted alkynylene group (Preferably an alkenylene group having 2 to 20 carbon atoms, such as difluoroethenylene group, tetrafluoropropenylene group, dichloroethenylene group), an alkynylene group (preferably an alkynylene group having 2 to 20 carbon atoms such as ethynylene group, Propynylene group), amide group, ester group, sulfoamide group, sulfonic acid ester group, ureido group, sulfo group Nyl group, sulfinyl group, thioether group, ether group, carbonyl group, heterylene group (preferably a C1-C26 heterylene group, for example, 6-chloro-1,3,5-triazyl-2,4-diyl group, A group selected from the group consisting of one group selected from the group consisting of a pyrimidine-2,4-diyl group and a quinoxaline-2,3-diyl group) or a combination of two or more thereof, and —S— and / or Or, it is a group composed of a combination of —O— and represents a group having 0 to 100 carbon atoms (more preferably 1 to 20 carbon atoms).
In the formula (A), G represents a carboxylic acid group, a sulfonic acid group or a phosphoric acid group, and these functional groups may have an ionic group, and examples thereof include those exemplified for M above.

  In addition to the compound represented by the formula (A), those in which the benzene ring portion is replaced with a group composed of two or more aromatic rings in the formula (A) can also be employed. Furthermore, the thing of the structure where the benzene ring which a formula (A) has has 2 or more groups represented by -F-G is also employable. Further, the benzene ring in formula (A) may have a substituent without departing from the spirit of the present invention. Examples of the substituent include the substituents exemplified in the above formulas (5) to (7).

Examples of the compound represented by the formula (A) and other compounds that can be preferably used in the present invention are illustrated below, but the present invention is not limited thereto. In the following compounds, the sulfonic acid group may be in the form of a free acid or a salt of Na or K, but preferably in the form of an Li salt, or an ammonium salt such as tetramethylammonium salt or tetraethylammonium salt.

（式（Ｂ）中、ｍ１は、０以上の整数であり、Ｇはカルボン酸基、スルホン酸基またはリン酸を表す。）
式（Ｂ）中、ｍ１は、０〜２０の整数が好ましく、０〜１０の整数がより好ましく、０〜５の整数がさらに好ましい。
式（Ｂ）中、Ｇはカルボン酸基、スルホン酸基またはリン酸基を表し、式（Ａ）におけるＧと同義であり、好ましい範囲も同義である。 Formula (B)

(In formula (B), m1 is an integer of 0 or more, and G represents a carboxylic acid group, a sulfonic acid group, or phosphoric acid.)
In formula (B), m1 is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and still more preferably an integer of 0 to 5.
In the formula (B), G represents a carboxylic acid group, a sulfonic acid group or a phosphoric acid group, and has the same meaning as G in the formula (A), and the preferred range is also the same.

  Examples of the compound represented by formula (B) are shown below, but the present invention is not limited thereto. Here, the sulfonic acid group may be in the form of a free acid or a salt of Na or K, but is preferably an Li salt or an ammonium salt such as tetramethylammonium salt or tetraethylammonium salt.

In addition, a compound represented by the formula (B), in which a hydrogen atom in the alkylene chain portion is substituted with a substituent, can be preferably employed without departing from the gist of the present invention. Examples of the substituent include the substituents exemplified in the above formulas (5) to (7).
Moreover, what substituted some carbon atoms of the alkylene chain part by -O- and / or -S- can also be employ | adopted preferably.

  Examples of compounds composed of unsaturated carboxylic acids such as acrylic acid and methacrylic acid and derivatives thereof include crotonic acid, maleic acid, itaconic acid, and the like, and the carboxyl group is a free acid, Na, K or Li. It may be in a salt state or an ammonium salt state such as a tetramethylammonium salt or a tetraethylammonium salt.

  In order to introduce a graft chain into the main chain of the polymer compound (1) used in the present invention by radical polymerization, it is preferable to form a radical polymerization initiation point in the main chain. It is necessary to generate radicals at the radical polymerization initiation point, and therefore it is preferable to introduce a functional group capable of generating radicals into the main chain. Hereinafter, the functional group capable of generating a radical is described as a radical generating group. The radical generating group can be introduced at any position in the main chain by controlling the amount of introduction, that is, the radical generating position and amount in the main chain can be controlled. It is possible to control the position and number of graft chains introduced above. Hereinafter, the structure of the radical generating group and the introduction method thereof will be described.

Radical generating group The structure of a radical generating group and its introduction method are roughly as follows.
(1) Atom Transfer Radical Polymerization Initiator Structure The atom transfer radical polymerization initiator structure is a catalyst used for atom transfer radical polymerization such as a 2,2′-bipyridine complex of copper (I) halide (for example, Chem. Rev. 2001). , 101, 2921-2990), in the presence of a radical. Examples of the atom transfer radical polymerization initiator structure include a halogenoalkyl group, a halogenobenzyl group, an α-haloketone group, an α-halonitrile group, a sulfonyl halide group, and the like, and a sulfonyl halide group and a halogenobenzyl group are particularly preferable. Although the preferable example of an atom transfer radical polymerization initiator structure is illustrated below, this invention is not limited to these. Incidentally, L _p in compound represents a linking portion of the polymer backbone, does not represent a specific structure.

As a method for introducing the polymer compound (1) having an atom transfer radical polymerization initiator structure into the main chain, for example, in the case of halogenobenzyl, a halogenomethylating agent such as chloromethyl methyl ether is used to form the polymer main chain. Obtained by halogenomethylating the aromatic ring. In order to introduce a preferable halogenomethyl group in the present invention into the aromatic ring of the polymer main chain (halogenomethylation reaction of the aromatic ring), known reactions can be widely used. For example, chloromethyl methyl ether, 1,4-bis (chloromethoxy) butane, 1-chloromethoxy-4-chlorobutane, etc. are used as chloromethylating agents, and tin chloride, zinc chloride, aluminum chloride, titanium chloride, etc. are used as catalysts. A chloromethyl group can be introduced into an aromatic ring by carrying out a chloromethylation reaction using a Lewis acid or hydrofluoric acid. The solvent is preferably dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, nitrobenzene, etc., and the reaction is preferably carried out in a homogeneous system. Alternatively, the halogenomethylation reaction can be performed using paraformaldehyde and hydrogen chloride or hydrogen bromide.
For example, in the case of a sulfonyl halide, as shown in Scheme 1, a sulfonated compound represented by the following formula (37) and an aromatic diol represented by the above formula (36) are subjected to polycondensation. It is obtained by forming a polymer main chain having a sulfonate in the side chain and forming a sulfonyl chloride with thionyl chloride or phosphorus pentachloride.

（上式中、Ｘ³は−ＣＯ−、−ＳＯ−、−ＳＯ₂−より選ばれる構造単位を表す。Ｙ¹はハロゲンまたはニトロ基を表し、フッ素原子、塩素原子、ニトロ基が好ましい。Ｍは一価のカチオンを表し、Ｌｉ⁺、Ｎａ⁺、Ｋ⁺、ＮＨ₄ ⁺が好ましい。）

(In the above formula, X ³ represents a structural unit selected from —CO—, —SO—, and —SO ₂ —. Y ¹ represents a halogen or a nitro group, preferably a fluorine atom, a chlorine atom, or a nitro group. Represents a monovalent cation, and Li ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ are preferred.)

  As another method for introducing a sulfonyl halide, a sulfonyl chloride can be formed by reacting a polymer main chain with chlorosulfonic acid as shown in Scheme 2.

  As in the above schemes 1 and 2, the radical generating group introduction position on the polymer main chain can be changed by changing the introduction method. Note that both Scheme 1 and Scheme 2 can be preferably used.

When an atom transfer radical polymerization initiator structure is introduced into the polymer main chain and graft polymerization is performed using atom transfer radical polymerization, an etheric oxygen atom appears to be directly bonded to the para position of the aromatic ring as a monomer. Styrene derivatives (for example, (K-1) and (K-2) of the exemplary compound of the compound represented by the above formula (33), (L of the exemplary compound of the compound represented by the above formula (34) It is known that when -15), (L-16), etc.) are used, the chain transfer reaction has priority over the polymerization reaction, and a 1 to 3 mer is obtained as the main product. (For example, Macromolecules, 1997, 30, 5643-5648, etc.).
Therefore, when such a monomer is used, a short-chain graft polymer can be obtained regardless of the charged amount of the monomer, which is a preferable method for synthesizing the short-chain graft polymer.

(2) Stable free radical polymerization initiator structure The stable free radical polymerization initiator structure can generate carbon radicals by heating. Examples of the stable free radical polymerization initiator structure include those described in Chem. Rev. 2001, 101, 3661-3688, among which 2,2,6,6-tetramethylpiperidinyloxyalkyl, 4-oxo-2,2,6,6-tetramethylpiperidinyloxy Alkyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxyalkyl, 4-amino-2,2,6,6-tetramethylpiperidinyloxyalkyl, 2,2,5,5- Tetramethylpyrrolidinyloxyalkyl, N, N-di-tert-butylaminooxyalkyl, 1,1,3,3-tetramethylisoindoline-oxyalkyl, N-tert-butyl-N- (2-methyl- 1-phenylpropyl) aminooxyalkyl is preferred, 2,2,6,6-tetramethylpiperidinyloxyalkyl, 4-oxo-2,2,6,6-tetramethylpiperidinyloxy Alkyl is particularly preferred. Although the preferable example of a stable free radical polymerization initiator structure is illustrated below, this invention is not limited to these. Incidentally, L _p in compound represents a linking portion of the polymer backbone, does not represent a specific structure.

(3) Diazonium salt When a diazonium salt is formed from an aniline derivative introduced into the polymer main chain, the diazonium salt can be decomposed by heating to generate radicals. As a method for introducing a diazonium salt, the aromatic ring of the polymer main chain is halogenomethylated using a halogenomethylating agent such as chloromethylmethyl ether, and an aniline derivative is introduced by a nucleophilic substitution reaction, followed by reaction with sodium nitrite. Or a method of forming a polymer main chain using a monomer having a nitro group, reducing the nitro group to aniline with iron under acidic conditions, and reacting with sodium nitrite.

(4) Peracid ester When a peracid ester is heated, a carbon radical can be generated together with a decarboxylation reaction. Examples of the method for introducing a peracid ester include a method in which a carboxylic acid is introduced into a polymer main chain, an acid chloride is formed with thionyl chloride, and then reacted with a peroxide such as tert-butyl hydroperoxide.

(5) Azo compound derivative An azo compound can also be decomposed by heating to generate a carbon radical. Examples of the method for introducing the azo compound include a method in which the polymer main chain is halogenomethylated and reacted with an azo compound derivative such as 4,4′-azobis (4-cyanopentanol).

 The energy imparting treatment for generating radicals in the present invention is not particularly limited as long as the monomer having an acid residue or the like imparts energy for graft polymerization. For example, thermal polymerization, ultraviolet irradiation, far infrared irradiation, Examples include radiation irradiation and plasma treatment. Among these methods, thermal polymerization, ultraviolet irradiation, and radiation irradiation are preferable because the radical generation time of the reaction initiator is short and graft polymerization is possible in a short time.

Although it is reaction conditions which perform graft polymerization, there is no restriction | limiting in particular in reaction temperature, reaction time, and reaction pressure, Well-known conditions can be applied. In the case of thermal polymerization, the reaction temperature is preferably 30 ° C to 300 ° C, more preferably 40 to 200 ° C, and further preferably 50 ° C to 150 ° C. The reaction time varies depending on the type of monomer used, the type of solvent, and the reaction temperature. The reaction time varies depending on the type of monomer used, the type of solvent, and the reaction temperature. Time is preferable, 1 minute to 12 hours is more preferable, 5 minutes to 12 hours is further preferable, 5 minutes to 8 hours is further more preferable, and 10 minutes to 5 hours is particularly preferable. The reaction pressure may be under pressure, reduced pressure, or normal pressure.
In the case of ultraviolet irradiation, far-infrared irradiation, radiation irradiation, or plasma treatment, the reaction temperature is preferably -20 to 300 ° C as an approximate range, preferably 0 to 200 ° C, more preferably 10 to 160 ° C. Moreover, although reaction time changes with the kind of monomer to be used, the kind of solvent, and reaction temperature, 10 second-12 hours are preferable. More preferably, it is 30 seconds to 6 hours, and further preferably 1 minute to 3 hours. The reaction pressure may be under pressure or under reduced pressure, but may be normal pressure.

The reaction for producing the protonic acid group-containing polymer compound of the present invention is preferably carried out in a solvent or monomer.
As a preferred solvent, an aprotic amide solvent is preferred, and specific examples include the following.
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotri Amides etc.

  These solvents may be used alone or in combination of two or more. When mixing and using, it is not always necessary to select a combination of solvents that are mutually soluble in an arbitrary ratio, and they may be non-uniform.

  The concentration of the reaction carried out in these solvents (hereinafter referred to as polymerization concentration) is not limited.

  In addition, the solvents shown in the above items 1) to 5) can be used alone or in combination of two or more. When mixed and used, it is not always necessary to select a combination of solvents that are mutually soluble in an arbitrary ratio, and they may be mixed or non-uniform. There is no limit to the amount of these dehydrating agents used.

  Polymerization initiators include benzol peroxide, toluyl peroxide, aromatic alkyl peroxide compounds, dichlorobenzoyl peroxide, dichromyl peroxide, azobisisobutyronitrile, cumene hydroperoxide, ammonium persulfate, perbenzoic acid. Examples include acids and perbenzoic acid esters. In addition, the usage-amount of a polymerization initiator is about 0.01 to 5.0 weight% with respect to the high molecular compound used for graft polymerization.

  In the polymerization, examples of the emulsifier include sodium salts and potassium salts of weak acid carboxylic acids such as oleic acid, stearic acid, rosin acid, and alkyl succinic acid. The amount is preferably 3.0 parts by weight or less based on parts. It is also possible to use a small amount of an emulsifier other than a carboxylic acid such as an alkyl sulfate ester salt or an alkylbenzene sulfonate salt.

  In the present invention, the acid-based coagulant, that is, the coagulant mainly composed of an acid is not particularly limited, but strong acids such as sulfuric acid and hydrochloric acid are preferable. Also preferred are salts such as aluminum sulfate, which form sulfuric acid when dissolved in water. The amount of the coagulant used in the present invention is an amount necessary for rapidly agglomerating the graft copolymer, and cannot be generally specified by the type of emulsifier and the type of coagulant in the polymer compound. The amount that can lower the pH to 3.0 or less, more preferably 2.0 or less is preferable.

  In addition, the molecular weight of the precursor polymer before graft polymerization of the polymer compound of the present invention thus obtained is 1,000 to 1,000,000, preferably 1,500 to 1,000 in terms of polystyrene-equivalent weight average molecular weight. 200,000. If it is less than 1,000, the coating properties are insufficient, such as cracking in the molded film, and there is also a problem with the strength properties. On the other hand, when it exceeds 1,000,000, there are problems such as insufficient solubility, high solution viscosity, and poor processability.

The structure of the sulfonic group-containing polymer compound of the present invention, the infrared absorption spectrum, 1,030~1,045cm ^-1, S = O absorption at 1,160~1,190cm ^-1, 1,130~1 , C-O-C absorption at 250 cm ^-1, can be confirmed by such C = O absorption of 1,640～1,660Cm ^-1, these composition ratio, neutralization titration of sulfonic acid or be known by elemental analysis Can do. Moreover, the structure can be confirmed from the peak of the aromatic proton at 6.8 to 8.0 ppm by nuclear magnetic resonance spectrum ( ¹ H-NMR).

When the polymer compound obtained by the above method is used as a proton conducting material, it must be converted to a proton type. This step is performed by immersing the polymer compound in an acidic solution. As the acidic solution, a proton acid solution is preferable, and as the proton acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid, solid acid (tungstophosphoric acid, tungsten peroxo complex) Etc.) and sulfonic acids (for example, sulfonic acids having 1 to 15 carbon atoms such as benzenesulfonic acid, toluenesulfonic acid, hexafluorobenzenesulfonic acid, trifluoromethanesulfonic acid, dodecylsulfonic acid, etc.). Two or more of these may be used in combination. In particular, hydrochloric acid, sulfuric acid, and nitric acid are preferable. The temperature in this step is preferably from 10 to 100 ° C, particularly preferably from 20 to 80 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. The concentration of the acid solution is preferably 0.1 to 10 N, and more preferably 0.5 to 5 N.

  Next, in the solid electrolyte of the present invention, an inorganic acid such as sulfuric acid and phosphoric acid, an organic acid containing a carboxylic acid, an appropriate amount of water, and the like may be used in addition to the polymer compound converted to the proton type.

  In the film-forming process, a liquid obtained by maintaining a polymer compound as a raw material at a temperature higher than the melting point or a liquid dissolved with a solvent may be used to form a film by extrusion molding, or these liquids may be cast. Alternatively, the film may be formed by coating. These operations can be performed with a film forming machine using a roll such as a calendar roll or a cast roll or a T-die, and can also be a press forming using a press machine. Further, a stretching process may be added to control film thickness and improve film characteristics.

  Furthermore, surface treatment may be performed after the film forming step. As the surface treatment, rough surface treatment, surface cutting, removal, and coating treatment may be performed, which may improve the adhesion with the electrode.

  The shape of the solid electrolyte of the present invention is preferably a membrane, and the thickness is preferably 1 μm to 500 μm, preferably 10 to 300 μm, and particularly preferably 20 to 150 μm. It may be in the form of a film at the time of molding, or may be cut into a film after being formed into a bulk body.

  It is possible to form a film by impregnating the solid electrolyte of the present invention into the pores of the porous substrate. The reaction solution after completion of the second step of the present invention may be applied and impregnated on a substrate having pores, or the substrate may be immersed in the reaction solution to fill the pores with a solid electrolyte to form a film. . Preferable examples of the substrate having pores include porous polypropylene, porous polytetrafluoroethylene, porous cross-linked heat-resistant polyethylene, and porous polyimide.

Other components of solid electrolyte To improve the membrane characteristics, the solid electrolyte of the present invention may contain an antioxidant, fibers, fine particles, water-absorbing agent, plasticizer, compatibilizer, and the like, if necessary. The content of these additives is preferably in the range of 1 to 30% by mass with respect to the total amount of the solid electrolyte.

  Antioxidants include (hindered) phenol, mono- or divalent sulfur, trivalent and pentavalent phosphorus, benzophenone, benzotriazole, hindered amine, cyanoacrylate, salicylate, oxalic Acid anilide compounds are preferred examples. Specific examples thereof include compounds described in JP-A-8-53614, JP-A-10-101873, JP-A-11-114430, and JP-A-2003-151346.

  Preferred examples of the fibers include perfluorocarbon fibers, cellulose fibers, glass fibers, polyethylene fibers, and the like, and specifically, JP-A-10-31815, JP-A-2000-231828, JP-A-2001-307545. Examples thereof include fibers described in JP-A No. 2003-317748, JP-A No. 2004-63430, and JP-A No. 2004-107461.

  Examples of the fine particles include fine particles made of silica, alumina, titanium oxide, zirconium oxide, and the like. Specifically, Japanese Patent Application Laid-Open Nos. 6-1111834, 2003-178777, and 2004-217921. Fine particles described in the publication can be mentioned. Moreover, the ionic functional groups described in JP-T-2005-510828, JP-A-2004-22346, WO2004 / 017446, JP-A-2005-190724, and JP-A-2005-527687 have been introduced. Carbon materials can also be preferably used because they function as proton conduction aids or antioxidants.

  Water-absorbing agents (hydrophilic substances) include cross-linked polyacrylate, starch-acrylate, poval, polyacrylonitrile, carboxymethylcellulose, polyvinylpyrrolidone, polyglycol dialkyl ether, polyglycol dialkyl ester, silica gel, synthetic zeolite, alumina gel , Titania gel, zirconia gel, and yttria gel are preferable examples. Specific examples include water absorbing agents described in JP-A Nos. 7-13003, 8-20716, and 9-251857. .

  Plasticizers include phosphate ester compounds, phthalate ester compounds, aliphatic monobasic acid ester compounds, aliphatic dibasic acid ester compounds, dihydric alcohol ester compounds, oxyacid ester compounds, and chlorination. Paraffin, alkylnaphthalene compounds, sulfonalkylamide compounds, oligoethers, carbonates, and aromatic nitriles are preferable examples, and specifically, JP2003-970030A and JP2003-288916A. And plasticizers described in JP-A No. 2003-317539.

Further, the polymer electrolyte of the present invention may contain various polymer compounds for the purpose of (1) increasing the mechanical strength of the film and (2) increasing the acid concentration in the film.
(1) For the purpose of increasing mechanical strength, a polymer compound having a molecular weight of about 10,000 to 1,000,000 and having good compatibility with the solid electrolyte of the present invention is suitable. For example, perfluorinated polymer, polystyrene, polyethylene glycol, polyoxetane, poly (meth) acrylate, polyether ketone, polyether sulfone, and two or more polymers thereof are preferable, and the content is 1 to 30 based on the total. A range of mass% is preferred.
The compatibilizer preferably has a boiling point or sublimation point of 250 ° C. or higher, more preferably 300 ° C. or higher.
(2) For the purpose of increasing the acid concentration, perfluorocarbon sulfonic acid polymer represented by Nafion, poly (meth) acrylate having a phosphate group in the side chain, sulfonated polyetheretherketone, sulfonated polyethersulfone, sulfone Polymer compounds having a ptronic acid moiety such as sulfonated products of heat-resistant aromatic polymers such as sulfonated polysulfone and sulfonated polybenzimidazole are preferable, and the content is preferably in the range of 1 to 30% by mass.

As the characteristics of the solid electrolyte of the present invention, those having the following performances are preferred.
For example, the ionic conductivity is preferably 0.005 S / cm, particularly preferably 0.01 S / cm or more at 25 ° C. and 95% relative humidity.
The oxygen permeability coefficient is preferably 4 × 10 ⁻⁷ cm ² / s or less, and particularly preferably ² × 10 ⁻⁷ cm ² / s or less.
For example, the tensile strength is preferably 10 MPa or more, particularly preferably 20 MPa or more.
With respect to durability, the rate of change in weight, ion exchange capacity, and oxygen diffusion coefficient is preferably 20% or less, particularly preferably 10% or less, before and after aging at a constant temperature in boiling water. Further, the rate of change is preferably 20% or less, and particularly preferably 10% or less, before and after aging in hydrogen peroxide. Further, the volume swelling rate at a constant temperature in water is preferably 50% or less, and particularly preferably 30% or less.
The solid electrolyte of the present invention preferably has a stable water absorption and water content. Moreover, it is preferable that the solubility is substantially negligible with respect to alcohols, water, and mixed solvents thereof. Moreover, it is preferable that the weight reduction and the shape change when immersed in the solvent are substantially negligible.
When formed into a film, the ion conduction direction is preferably such that the direction from the front surface to the back surface is higher than the other directions.
The heat resistant temperature of the solid electrolyte of the present invention is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 200 ° C. or higher. The heat-resistant temperature can be defined as the time when the weight loss reaches 5% when the temperature is increased at a rate of 1 ° C./minute, for example. This weight loss is calculated excluding evaporation such as moisture.

Fuel Cell The solid electrolyte of the present invention can be used as a constituent material of a catalyst membrane (catalyst layer) as well as a solid electrolyte membrane (proton conductive membrane) of a fuel cell. In particular, it is preferably used for a catalyst membrane and / or a solid electrolyte membrane of a membrane / electrode assembly (hereinafter referred to as “MEA”).
FIG. 1 shows an example of a schematic cross-sectional view of the membrane / electrode assembly of the present invention. The MEA 10 includes a membrane-like solid electrolyte 11 and a gas diffusion electrode composed of an anode electrode 12 and a cathode electrode 13 that are opposed to each other with the membrane electrolyte 11 interposed therebetween.
The anode electrode 12 and the cathode electrode 13 are composed of conductive layers 12a and 13a and catalyst layers 12b and 13b.

The catalyst layers 12b and 13b include a conductive material carrying a catalyst metal. Here, the catalyst metal may be any metal that promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen, for example, platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, cobalt, Nickel, chromium, tungsten, manganese, vanadium, or an alloy thereof can be used. Of these catalysts, platinum is often used.
The particle size of the catalyst metal is preferably in the range of 2 to 10 nm. The smaller the particle size, the greater the surface area per unit mass, and the more active the activity tends to be. It tends to be difficult.

  Further, the active polarization in the hydrogen-oxygen fuel cell is larger in the cathode electrode (air electrode) than in the anode electrode (hydrogen electrode). This is because the cathode electrode reaction (oxygen reduction) is slower than the anode electrode. For the purpose of improving the activity of the oxygen electrode, various platinum-based binary metals such as Pt—Cr, Pt—Ni, Pt—Co, Pt—Cu, and Pt—Fe can be used. In a direct methanol fuel cell using an aqueous methanol solution as an anode fuel, it is important to suppress catalyst poisoning due to CO that occurs during the oxidation process of methanol. For this purpose, platinum-based binary metals such as Pt—Ru, Pt—Fe, Pt—Ni, Pt—Co, and Pt—Mo, Pt—Ru—Mo, Pt—Ru—W, Pt are used as catalyst metals. Platinum-based ternary metals such as —Ru—Co, Pt—Ru—Fe, Pt—Ru—Ni, Pt—Ru—Cu, Pt—Ru—Sn, and Pt—Ru—Au can also be used.

  The conductive material for supporting the catalyst metal is not particularly defined as long as it is an electron conductive substance, and examples thereof include various metals and carbon materials. Examples of the carbon material include carbon black, activated carbon, graphite and the like, but carbon particles are preferable, and acetylene black, Vulcan XC-72, ketjen black, carbon nanohorn (CNH), and carbon nanotube (CNT) are more preferable. Can be used alone or in combination. Also, ion functional groups described in JP-T 2005-510828, JP-A 2004-22346, WO 2004/017446, JP-A 2005-190724, JP-A 2005-527687, etc. are introduced. Carbon materials that have been used can also be used.

  The binder of the catalyst membrane is not limited as long as it is a solid (proton conductive material) having a proton donating group, but is a polymer compound having an acid residue used for a solid electrolyte (for example, perfluorocarbon sulfone represented by Nafion). Acid, side chain phosphate group poly (meth) acrylate, sulfonated polyetheretherketone, sulfonated products of heat-resistant aromatic polymers such as sulfonated polybenzimidazole, etc.) are preferably used. Further, a compound having water repellency, preferably a fluorine-containing resin, particularly those having excellent heat resistance and oxidation resistance, such as polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoro An ethylene-hexafluoropropylene copolymer or the like may be used by mixing with the solid having the proton donating group. Furthermore, from the viewpoint of adhesiveness, when the solid electrolyte of the present invention is used for a catalyst membrane, it becomes a material of the same kind as the solid electrolyte, so that the electrochemical adhesion between the solid electrolyte and the catalyst membrane is increased, which is more advantageous.

The amount of catalytic metal used is suitably in the range of 0.03 to 10 mg / cm ² from the viewpoint of battery output and economy. The amount of the conductive material supporting the catalyst metal is suitably 1 to 10 times the mass of the catalyst metal. The amount of the proton conductive material (binder) is suitably 0.1 to 0.7 times the mass of the catalyst metal-supported conductive material.

The conductive layer is not particularly defined as long as it is an electron conductive substance, and examples thereof include a carbon material. For example, a porous carbon non-woven fabric or carbon paper is used to efficiently transport a source gas to the catalyst layer. The porous conductive sheet is preferable.

There are no particular limitations on the electrolyte membrane and the electrode bonding method, and a known method can be used. For example,
In order to adhere the catalyst layers 12b and 13b to the solid electrolyte 11, the conductive layers 12a and 13a coated with the catalyst layers 12b and 13b are applied to the solid electrolyte 11 by a hot press method (preferably 120 to 130 ° C., 2 to 100 kg / cm ² ) or a method in which an appropriate support coated with catalyst layers 12b and 13b is bonded to a solid electrolyte 11 while being transferred and then sandwiched between conductive layers 12a and 13a. Use it.

  The function of the catalyst membrane was caused by (1) transporting fuel to the catalyst metal, (2) providing a field for fuel oxidation (anode electrode) and reduction (cathode electrode) reaction, and (3) redox. (4) transporting protons generated by the reaction to the solid electrolyte. For (1), the catalyst membrane needs to be porous so that liquid and gaseous fuel can permeate deeply. (2) is the catalyst metal described above, and (3) is the conductive material described above. In order to fulfill the function (4), a proton conductive material is mixed in the catalyst membrane as a binder.

The following four methods are preferable for the production of MEA.
(1) Proton conductive material coating method: A catalyst paste (ink) based on active metal-supported carbon, proton conductive material, and solvent is directly applied to both sides of the solid electrolyte membrane, and a porous conductive sheet is (thermally) pressed. A 5-layer MEA is manufactured.
(2) Porous conductive sheet coating method: After applying a catalyst paste to the surface of the porous conductive sheet to form a catalyst film, it is pressure-bonded to a solid electrolyte to produce a MEA having a five-layer structure.

(3) Decal method: After applying a catalyst paste on PTFE to form a catalyst film, only the catalyst film is transferred to the solid electrolyte film to form a three-layer MEA, and a porous conductive sheet is pressure-bonded. A MEA having a layer structure is manufactured.
(4) Post-catalyst support method: After coating and forming a solid electrolyte membrane, a porous conductive sheet or PTFE with an ink in which a platinum non-support carbon material is mixed with a proton conductive material, the solid electrolyte is impregnated with the solid electrolyte. Then, platinum particles are reduced and deposited in the film to form a catalyst film. After forming the catalyst film, the MEA is produced by the above methods (1) to (3).

FIG. 2 shows an example of a fuel cell structure. The fuel cell includes an MEA 10, a pair of separators 21 and 22 that sandwich the MEA 10, and a current collector 17 and a packing 14 attached to the separators 21 and 22. An anode pole side opening 15 is provided in the anode pole side separator 21, and a cathode pole side opening 16 is provided in the cathode pole side separator 22. Gas fuel such as hydrogen and alcohols (such as methanol) or liquid fuel such as an alcohol aqueous solution is supplied from the anode electrode side opening 15, and oxidant gas such as oxygen gas and air is supplied from the cathode electrode side opening 16. Is supplied.
Here, the separator has a high electron conductivity and is impermeable to gas, and a known material can be used. Specifically, a separator made of a carbon material or a metal material can be used.
In addition, as the current collector, carbon paper, carbon fiber, or the like can be used.

  The anode fuel that can be used as the fuel for the fuel cell using the solid electrolyte of the present invention is hydrogen, alcohols (methanol, isopropanol, ethylene glycol, etc.), ethers (dimethyl ether, dimethoxymethane, trimethoxymethane). Etc.), formic acid, borohydride complexes, ascorbic acid and the like. Examples of the cathode fuel include oxygen (including oxygen in the atmosphere) and hydrogen peroxide.

  The method for supplying the anode fuel and the cathode fuel to the respective catalyst membranes includes (1) a method of forced circulation using an auxiliary device such as a pump (active type), and (2) a method not using an auxiliary device ( For example, in the case of a liquid, there are two types, that is, a capillary type or a natural fall, and in the case of a gas, a passive type in which the catalyst film is exposed and supplied to the atmosphere, and these can be combined. An active type capable of obtaining high output is preferable.

  Since the single cell voltage of the fuel cell is generally 1 V or less, the single cells are used by stacking in series according to the required voltage of the load. As the stacking method, “planar stacking” in which the single cells are arranged on a plane and “bipolar stacking” in which the single cells are stacked via separators having fuel flow paths formed on both sides are used. The former is suitable for a small fuel cell because the cathode electrode (air electrode) comes out on the surface, so that air can be easily taken in and can be made thin. In addition to this, a method of applying MEMS technology, performing fine processing on a silicon wafer, and stacking has been proposed.

  Fuel cells are considered for various uses such as for automobiles, homes, and portable devices.In particular, direct methanol fuel cells are advantageous in that they can be reduced in size and weight and do not require charging. It is expected to be used as an energy source for various portable devices and portable devices. For example, mobile devices that can be preferably applied include mobile phones, mobile laptop computers, electronic still cameras, PDAs, video cameras, portable game machines, mobile servers, wearable personal computers, mobile displays, and the like. Examples of portable devices that can be preferably applied include portable generators, outdoor lighting devices, flashlights, and electric (assist) bicycles. Moreover, it can be preferably used as a power source for industrial or household robots or other toys. Furthermore, it is also useful as a power source for charging secondary batteries mounted on these devices.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1 Preparation of solid electrolyte
[Preparation of solid electrolyte M-1]
Performed according to Scheme 3. That is, according to a known method, 9.1 g of potassium carbonate, 120 mL of N-methyl-2-pyrrolidone, 25 mL of toluene, 10.0 g of bisphenol A and 8.4 g of 4,4′-dichlorodiphenylsulfone, 7 2 g of 3,3′-disulfo-4,4′-dichlorodiphenylsulfone disodium salt was added and stirred in an oil bath at 200 ° C. for 24 hours under a nitrogen stream. The reaction solution was filtered off and poured into a large excess of acetonitrile to obtain a precipitate. The supernatant was removed and the precipitate was washed with acetonitrile and then dried under reduced pressure to obtain 16.2 g of polysulfone p-1 having a sulfo group. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the methyl group of the main chain polysulfone was observed at δ1.7 ppm, and a signal based on the aromatic ring of the main chain was observed at δ6.8 to 8.4 ppm.
Next, 10.0 g of p-1, 30 mL of N, N-dimethylformamide and 100 mL of thionyl chloride were added, and the mixture was refluxed for 12 hours with stirring under a nitrogen stream. Thereafter, the pressure was reduced to remove unreacted thionyl chloride, and the resulting product was washed with acetonitrile to obtain 8.7 g of polysulfone p-2 having sulfonyl chloride.
Next, 3.0 g of p-2 was added to 780 mg of copper (I) chloride, 2.46 g of 2,2′-bipyridine, 5
0 mL of N-methyl-2-pyrrolidone, 3.90 g of 3- (3-sulfopropyloxy) styrene lithium salt (K-18) was added, and the mixture was stirred in a 160 ° C. oil bath for 26 hours under a nitrogen stream. Thereafter, 1.3 g of hydroquinone was added and the mixture was further stirred for 3 hours. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, precipitation occurred, the supernatant was removed, the precipitate was washed with water, and dried under reduced pressure to obtain 3.6 g of solid electrolyte M-1. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, signals based on propylene groups in the side chain were observed at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Further, from the ratio of the integral value of the signal based on the main chain of δ 1.7 ppm and the integral value of the signal based on the side chain of δ 4.0 ppm, the number of repeating units (x ₁ and x ₂ ) of the side chain polystyrene is It was found to be 3.7.

[Preparation of solid electrolyte M-2]
Performed according to Scheme 4. That is, according to a known method, 10.0 g of bisphenol A and 12.58 g of 4,4′-dichlorodiphenyl sulfone are added to 9.1 g of potassium carbonate, 100 mL of N-methyl-2-pyrrolidone, and 20 mL of toluene. In addition, the mixture was stirred in an oil bath at 200 ° C. for 24 hours under a nitrogen stream. The reaction solution was filtered off and poured into a large excess of acetonitrile to obtain a precipitate. The supernatant was removed, and the precipitate was washed with acetonitrile and then dried under reduced pressure to obtain 16.1 g of polysulfone p-3. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the methyl group of the main chain polysulfone was observed at δ 1.7 ppm, and a signal based on the aromatic ring of the main chain was observed at δ 6.8 to 8.1 ppm.
Next, 3.0 g of p-3 was dissolved in 60 mL of a dichloromethane solution of chlorosulfonic acid and stirred at room temperature for 12 hours. The reaction solution was distilled off under reduced pressure, and dried under reduced pressure to obtain 3.4 g of polysulfone p-4 having sulfonyl chloride. ^{From 1} H-NMR (DMSO-d ₆ solvent) measurement, it was confirmed that 0.7 sulfonyl chloride sites existed per repeating unit of polysulfone.
Next, to 2.0 g of p-4, 543 mg of copper (I) chloride, 1.71 g of 2,2′-bipyridine, 30
mL of N-methyl-2-pyrrolidone, 2.38 g of 3- (3-sulfopropyloxy) styrene lithium salt (K-18) was added, and the mixture was stirred in an oil bath at 160 ° C. for 24 hours under a nitrogen stream. Then, 905 mg of hydroquinone was added and further stirred for 3 hours. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, precipitation occurred, the supernatant was removed, the precipitate was washed with water, and dried under reduced pressure to obtain 3.53 g of a solid electrolyte M-2. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, signals based on propylene groups in the side chain were observed at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Further, from the ratio of the integral value of the signal based on the main chain of δ 1.7 ppm and the integral value of the signal based on the side chain of δ 4.0 ppm, the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is It was found to be 2.8.

[Preparation of solid electrolyte M-3]
The reaction was performed according to Scheme 5. That is, 5.0 g of the polymer p-3, 75 μL of tin chloride, 7.3 mL of chloromethyl methyl ether, 50 mL of 1,1,2,2-tetrachloroethane were added, and the mixture was stirred at 110 ° C. for 6 hours under a nitrogen stream. did. When the reaction solution was poured into a large amount of ethanol, a precipitate was obtained. The supernatant was removed, the precipitate was washed with ethanol, and dried under reduced pressure to obtain 4.8 g of polysulfone p-5 introduced with a chloromethyl group. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the chloromethyl group was confirmed at δ4.6 ppm, and from the ratio of the integrated intensity, the chloromethyl moiety was found to be 1. per polysulfone repeating unit. It was confirmed that two were present.
Next, 2.0 g of p-5 was added to 946 mg of copper (I) chloride, 2.99 g of 2,2′-bipyridine, 30 mL of N-methyl-2-pyrrolidone, 11.9 g of 4- (3- Sulfopropyloxy) styrene lithium salt (K-1) was added, and the mixture was stirred in a 140 ° C. oil bath for 28 hours under a nitrogen stream. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain 2.2 g of a solid electrolyte M-3. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on a vinylene group in a side chain at δ6.1 ppm, a propylene group in a side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is found to be 1.3 on average. It was.

[Preparation of solid electrolyte M-4]
The reaction was performed according to Scheme 6. That is, 5.0 g of the polymer p-3, 45 μL of tin chloride, 3.8 mL of chloromethyl methyl ether, 50 mL of 1,1,2,2-tetrachloroethane were added, and the mixture was stirred at 110 ° C. for 8 hours in a nitrogen stream. did. When the reaction solution was poured into a large amount of ethanol, a precipitate was obtained. The supernatant was removed, the precipitate was washed with ethanol, and dried under reduced pressure to obtain 4.9 g of polysulfone p-6 introduced with a chloromethyl group. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on a chloromethyl group was confirmed at δ4.6 ppm, and from the ratio of the integrated intensity, the chloromethyl moiety was 0. 0 per polysulfone repeating unit. It was confirmed that 5 existed.
Next, 2.0 g of p-6 was added to 424 mg of copper (I) chloride, 1.34 g of 2,2′-bipyridine, 50 mL of N-methyl-2-pyrrolidone, 520 mg of 3- (3-trimethylsilylpropyl). Oxy) styrene (L-24) was added and stirred in a 140 ° C. oil bath under a nitrogen stream. After confirming disappearance due to the reaction of L-24 by NMR, 3.19 g of 3- (3-sulfopropyloxy) styrene lithium salt (K-18) was subsequently added and reacted for another 24 hours. Thereafter, 710 mg of hydroquinone was added and the mixture was further stirred for 3 hours. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain 4.2 g of a solid electrolyte M-4. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, δ 4.0 ppm, δ 1.8 ppm, δ 0.6 ppm, δ 0.0 ppm, a signal based on a trimethylsilylpropyl group in a side chain, δ 4.0 ppm, δ 2.4- Signals based on the sulfopropyl group in the side chain were observed at 2.6 ppm and δ 2.0 ppm. From the integral value of the signal of δ4.0 ppm and the integral value of the signal of δ0.0 ppm, the ratio of y ₁ and y ₃ or the ratio of y ₂ and y _{4 in} the scheme (6) is 1: 5.6. I understood it. Further, from the ratio of the integral value of the signal based on the aromatic ring of δ8.1-6.6 ppm and the integral value of the signal based on the side chain of δ4.0 ppm, the number of repeating units of the side chain polystyrene (y ₁ + y ₃ and y ₂ + y ₄ ) was found to average 6.3.

[Preparation of solid electrolyte M-5]
The reaction was performed according to Scheme 7. That is, to 2.0 g of p-6, 424 mg of copper chloride (I
), 1.34 g of 2,2′-bipyridine, 55 mL of N-methyl-2-pyrrolidone, 5.34 g of 3- (1,1,2,2-tetrafluoro-3-sulfoethyloxy) styrene lithium salt (K-27) was added, and the mixture was stirred for 16 hours in an oil bath at 140 ° C. under a nitrogen stream. Thereafter, 720 mg of hydroquinone was added and the mixture was further stirred for 3 hours. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain 4.6 g of solid electrolyte M-5.

[Preparation of solid electrolyte M-6]
The reaction was performed according to Scheme 8. 15.1 g of polymer p-7 was obtained in the same manner except that 12.58 g of 4,4′-dichlorodiphenylsulfone was replaced with 9.56 g of 4,4′-difluorobenzophenone during the synthesis of polymer p-3. It was. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the methyl group of the main chain was confirmed at δ1.7 ppm, and a signal based on the aromatic ring of the main chain was observed at δ6.8 to 8.1 ppm.
Next, 9.8 g of a polymer p-8 into which a chloromethyl group was introduced was obtained using 10.0 g of the polymer p-7 in the same manner as in the synthesis method of the polymer p-6. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on a chloromethyl group was confirmed at δ4.6 ppm, and from the ratio of the integrated intensity, the chloromethyl moiety was 1. It was confirmed that there was one.
Next, 2.0 g of p-8 was added to 946 mg of copper (I) chloride, 2.99 g of 2,2′-bipyridine, 5
5 mL of N-methyl-2-pyrrolidone and 11.8 g of 4- (3-sulfopropyloxy) styrene lithium salt (K-1) were added, and the mixture was stirred in an oil bath at 140 ° C. for 26 hours under a nitrogen stream. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain 1.9 g of a solid electrolyte M-6. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on a vinylene group in a side chain at δ6.1 ppm, a propylene group in a side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is found to be 1.1 on average. It was.

[Preparation of solid electrolyte M-7]
The reaction was performed according to Scheme 9. That is, 12 g of commercially available polyethersulfone (manufactured by Sumitomo Chemical Co., PES-5200P) was dissolved in 100 mL of a dichloromethane solution of chlorosulfonic acid and stirred at room temperature for 6 hours. The reaction solution was distilled off under reduced pressure, and dried under reduced pressure to obtain 12.9 g of polysulfone p-9 having sulfonyl chloride. ^{From the 1} H-NMR (DMSO-d ₆ solvent) measurement, it was confirmed that the amount of introduced sulfonyl chloride groups was 0.2 per one repeating unit of polyethersulfone.
Next, 2.0 g of p-9 was added to 313 mg of copper (I) chloride, 990 mg of 2,2′-bipyridine, 4
5 mL of N-methyl-2-pyrrolidone, 1.96 g of 3- (3-sulfopropyloxy) styrene lithium salt (K-18) was added, and the mixture was stirred in an oil bath at 160 ° C. for 25 hours under a nitrogen stream. Thereafter, 522 mg of hydroquinone was added and the mixture was further stirred for 3 hours. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, precipitation occurred, the supernatant was removed, the precipitate was washed with water, and dried under reduced pressure to obtain 3.1 g of a solid electrolyte M-7. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, signals based on propylene groups in the side chain were observed at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Further, from the ratio of the integral value of the signal based on the aromatic ring of the main chain and the integral value of the signal based on the side chain of δ 4.0 ppm, the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 4 on average. .7.

[Preparation of solid electrolyte M-8]
The reaction was performed according to Scheme 10. That is, 6.0 g of the polymer p-3 was dissolved in anhydrous THF (400 ml), completely degassed, and then cooled to −40 ° C. in a state of flowing N ₂ gas. Thereafter, 10M n-butyllithium was added, and lithiation was carried out by reacting for about 20 minutes at -40 ° C.
Then, while stirring this solution with a stirrer, sulfuryl chloride (10 ml) was slowly added and stirred for about 3 hours. Thereafter, the precipitate was filtered, washed twice with isopropanol, and completely dried in vacuo at 50 ° C. to obtain polysulfone (4.1 g) having sulfonyl chloride. ^{From 1} H-NMR (DMSO-d ₆ solvent) measurement, it was confirmed that 1.1 sulfonyl chloride sites were present per repeating unit of polysulfone.
Next, the obtained polysulfone having sulfonyl chloride (1.3 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then iron (II) chloride (1.3 g), 2,2′-bipyridine ( 3 g), N-methyl-2-pyrrolidone and 3- (3-sulfopropyloxy) styrene lithium salt (K-1) (3.5 g) were added, and the mixture was stirred in an oil bath at 140 ° C. for 28 hours under a nitrogen stream. . The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain a solid electrolyte M-8 (1.0 g). ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, signals based on side chain propylene groups were observed at δ 4.0 ppm, δ 2.4-2.6 ppm, and δ 2.0 ppm. Further, from the ratio of the integral value of the signal based on the main chain of δ 1.7 ppm and the integral value of the signal based on the side chain of δ 4.0 ppm, the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is It was found to be 2.5.

Scheme (10)

[Preparation of solid electrolyte M-9]
The reaction was performed according to Scheme 11. That is, 5.0 g of the polymer p-3, 75 μL of tin chloride, 7.3 mL of chloromethyl methyl ether, 50 mL of 1,1,2,2-tetrachloroethane were added, and the mixture was stirred at 110 ° C. for 6 hours under a nitrogen stream. did. When the reaction solution was poured into a large amount of ethanol, a precipitate was obtained. The supernatant was removed, the precipitate was washed with ethanol, and dried under reduced pressure to obtain 4.8 g of polysulfone having a chloromethyl group introduced.
^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the chloromethyl group was confirmed at δ4.6 ppm, and from the ratio of the integrated intensity, the chloromethyl moiety was 1.2 per polysulfone repeating unit. It was confirmed that there were pieces.
Next, the obtained chloromethylated polysulfone (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then benzophenone (BP) (1.7 g), 4- (3-sulfopropyloxy) Styrene lithium salt (3.5 g) was added, heated to 60 ° C. under a nitrogen stream, and irradiated with long-wave ultraviolet light for 4 hours. After irradiation, the reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain a solid electrolyte M-9 (1.2 g).
^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group in the side chain at δ6.1 ppm, a propylene group at the side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 2.2 on average. It was.

Scheme (11)

[Preparation of solid electrolyte M-10]
The reaction was performed according to Scheme 12. That is, 5.0 g of the polymer p-3, 75 μL of tin chloride, 20.3 mL of bromomethyloctyl ether, 50 mL of 1,1,2,2-tetrachloroethane were added, and the mixture was stirred at 110 ° C. for 6 hours under a nitrogen stream. did. When the reaction solution was poured into a large amount of ethanol, a precipitate was obtained. The supernatant was removed, the precipitate was washed with ethanol, and dried under reduced pressure to obtain 4.8 g of polysulfone having a bromomethyl group introduced. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, it was confirmed that 1.0 bromomethyl moiety was present per repeating unit of polysulfone.
Next, the obtained bromomethylated polysulfone (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then benzophenone (BP) (1.7 g), 3- (3-sulfopropyloxy) styrene. Lithium salt (1.8 g) and 3- (3-trimethylsilylpropyloxy) styrene (1.8 g) were added, heated to 60 ° C. under a nitrogen stream, and irradiated with long-wave ultraviolet light for 4 hours. After irradiation, the reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain a solid electrolyte M-10 (1.3 g). ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, δ 4.0 ppm, δ 1.8 ppm, δ 0.6 ppm, δ 0.0 ppm, a signal based on a trimethylsilylpropyl group in the side chain, δ 4.0 ppm, δ 2.4- Signals based on the sulfopropyl group in the side chain were observed at 2.6 ppm and δ 2.0 ppm. From the integral value of the signal of δ4.0 ppm and the integral value of the signal of δ0.0 ppm, the ratio of y ₁ and y ₃ or the ratio of y ₂ and y _{4 in} the scheme (12) is 1: 3.7. I understood it. Further, from the ratio of the integral value of the signal based on the aromatic ring of δ8.1-6.6 ppm and the integral value of the signal based on the side chain of δ4.0 ppm, the number of repeating units of the side chain polystyrene (y ₁ + y ₃ and It was found that y ₂ + y ₄ ) averaged 4.6.

Scheme (12)

[Preparation of solid electrolyte M-11]
The reaction was performed according to Scheme 13. That is, 5.0 g of the polymer p-3, 75 μL of tin chloride, 21.4 mL of iodomethyl methyl ether, 50 mL of 1,1,2,2-tetrachloroethane were added, and the mixture was heated at 80 ° C. for 6 hours under a nitrogen stream. Stir. When the reaction solution was poured into a large amount of ethanol, a precipitate was obtained. The supernatant was removed, the precipitate was washed with ethanol, and dried under reduced pressure to obtain 4.8 g of polysulfone having an iodomethyl group introduced. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, it was confirmed that 1.3 iodomethyl sites were present per repeating unit of polysulfone.
Next, the obtained iodomethylated polysulfone (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then benzophenone (BP) (1.7 g) and styrene monomer (2.2 g) were added. In addition, it was heated to 40 ° C. under nitrogen substitution and irradiated with long-wavelength ultraviolet light for 4 hours. After irradiation, the reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to synthesize polysulfone into which a styrene monomer was introduced. ^{From 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group of the side chain was observed at δ6.1 ppm.
Next, the polysulfone (4.7 g) introduced with the styrene monomer obtained above was dissolved in dehydrated chloroform (300 ml), completely dissolved, and then cooled to about 0 ° C. in an ice bath. Thereafter, while maintaining the cooled state, propane sultone (7.0 g) and aluminum (III) chloride (7.5 g) were added, and the mixture was slowly heated to 60 ° C. and reacted at 60 ° C. for 6 hours. After the reaction, the mixture was cooled to room temperature, washed with 200 ml of water, and further washed with 200 ml of water. Thereafter, filtration was performed, and the chloroform layer was taken out and dried under reduced pressure to obtain a solid electrolyte M-11 (3.8 g) into which an alkylenesulfonic acid group was introduced. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group in the side chain at δ6.1 ppm, a propylene group at the side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 2.2 on average. It was.

Scheme (13)

[Preparation of solid electrolyte M-12]
Chloromethylated polysulfone was synthesized as in the case of the solid electrolyte M-9.
Next, the obtained chloromethylated polysulfone (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then iron (II) chloride (1.3 g), 2,2′-bipyridine. (3 g), N-methyl-2-pyrrolidone, and styrene monomer (2.2 g) were added, and the mixture was stirred in an oil bath at 140 ° C. for 26 hours under a nitrogen stream. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to synthesize polysulfone into which a styrene monomer was introduced. ^{From 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group of the side chain was observed at δ6.1 ppm.
Next, the polysulfone (4.7 g) introduced with the styrene monomer obtained above was dissolved in dehydrated chloroform (300 ml), completely dissolved, and then cooled to about 0 ° C. in an ice bath. Then, while maintaining the cooled state, propane sultone (7.0 g) and aluminum (III) chloride (7.5 g) were added, and the mixture was slowly heated to 60 ° C. and reacted at 60 ° C. for 6 hours. After the reaction, the mixture was cooled to room temperature, washed with 200 ml of water, and further washed with 200 ml of water. Thereafter, filtration was performed, and the chloroform layer was taken out and dried under reduced pressure to obtain a solid electrolyte M-12 (4.1 g) into which an alkylene sulfonic acid group was introduced. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group in the side chain at δ6.1 ppm, a propylene group at the side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Based signal was observed. Further, from the ratio of the integral value of the signal of δ6.1 ppm and the integral value of the signal of δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 2.9 on average. It was.

Scheme (14)

[Preparation of solid electrolyte M-13]
Iodomethylated polysulfone was synthesized as in the case of the solid electrolyte M11.
Next, the obtained iodomethylated polysulfone (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then benzoyl peroxide (BPO) (1.7 g), N-methyl-2- Pyrrolidone and 4- (3-sulfopropyloxy) styrene lithium salt (3.5 g) were added, and the mixture was stirred in a 120 ° C. oil bath for 8 hours under a nitrogen stream. Thereafter, the reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain a solid electrolyte M-13 (1.1 g). ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group in the side chain at δ6.1 ppm, a propylene group at the side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Based signal was observed. Further, from the ratio of the integral value of the signal of δ6.1 ppm and the integral value of the signal of δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 3.3 on average. It was.

Scheme (15)

[Preparation of solid electrolyte M-14]
Iodomethylated polysulfone was synthesized in the same manner as in the case of the solid electrolyte M-11.
Next, the obtained iodomethylated polysulfone (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then 2,2-azobisisobutyronitrile (AIBN) (1.5 g) N-methyl-2-pyrrolidone and styrene monomer (2.2 g) were added, and the mixture was stirred for 8 hours in an oil bath at 120 ° C. under a nitrogen stream. The reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to synthesize polysulfone into which a styrene monomer was introduced. ^{From 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group of the side chain was observed at δ6.1 ppm.
Next, the polysulfone (4.7 g) introduced with the styrene monomer obtained above was dissolved in dehydrated chloroform (300 ml), completely dissolved, and then cooled to about 0 ° C. in an ice bath. Thereafter, while maintaining the cooled state, propane sultone (7.0 g) and aluminum (III) chloride (7.5 g) were added, and the mixture was slowly heated to 60 ° C. and reacted at 60 ° C. for 6 hours. After the reaction, the mixture was cooled to room temperature, washed with 200 ml of water, and further washed with 200 ml of water. Thereafter, filtration was performed, and the chloroform layer was taken out and dried under reduced pressure to obtain a solid electrolyte M-14 (3.9 g) into which an alkylene sulfonic acid group was introduced. ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group in the side chain at δ6.1 ppm, a propylene group at the side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 2.6 on average. It was.

[Preparation of solid electrolyte M-15]
Bromomethylated polysulfone was synthesized in the same manner as in the case of the solid electrolyte M-10.
Next, the obtained bromomethylated polysulfone (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then sodium hydrosulfite (Na ₂ S ₂ O ₄ ) (1.3 g), N-methyl-2-pyrrolidone and 4- (3-sulfopropyloxy) styrene lithium salt (3.5 g) were added, and the mixture was stirred in an oil bath at 60 ° C. for 8 hours under a nitrogen stream. Thereafter, the reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain a solid electrolyte M-15 (1.0 g). ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on the vinylene group in the side chain at δ6.1 ppm, a propylene group at the side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm. Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 2.1 on average. It was.

[Preparation of solid electrolyte M-16]
A polysulfone having a sulfonyl chloride was synthesized as in the case of the solid electrolyte M-8.
Next, the obtained polysulfone having sulfonyl chloride (1.3 g) was dissolved in N-methyl-2-pyrrolidone (100 ml), and then sodium hydrosulfite (Na ₂ S ₂ O ₄ ) (1.3 g ), N-methyl-2-pyrrolidone and 3- (3-sulfopropyloxy) styrene lithium salt (3.5 g) were added, and the mixture was stirred in an oil bath at 60 ° C. for 8 hours under a nitrogen stream. Thereafter, the reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain a solid electrolyte M-16 (1.2 g). ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on a vinylene group in a side chain at δ6.1 ppm, a propylene group in a side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 4.1 on average. It was.

[Preparation of solid electrolyte M-17]
Bromomethylated polysulfone was synthesized in the same manner as in the case of the solid electrolyte M-10.
Next, the bromomethylated polysulfone obtained above (1.2 g) was dissolved in N-methyl-2-pyrrolidone (100 ml) and then 2,2,6,6-tetramethylpiperidinooxy free Radical (TEMPO) (1.6 g), cuprous bromide (CuBr) (1.6 g), 2,2′-bipyridine (3 g), N-methyl-2-pyrrolidone, 4- (3-sulfopropyloxy) ) Styrene lithium salt (3.5 g) was added, and the mixture was stirred in a 120 ° C. oil bath for 8 hours under a nitrogen stream. Thereafter, the reaction solution was cooled to room temperature and then poured into a large amount of acetonitrile, resulting in precipitation. The supernatant was removed and the precipitate was washed with acetonitrile and then dissolved in N-methyl-2-pyrrolidone. When this solution was poured into a large amount of water, a solid was precipitated, the supernatant was removed by centrifugal sedimentation, the precipitate was washed with water, and dried under reduced pressure to obtain a solid electrolyte M-17 (1.3 g). ^{As a result of 1} H-NMR (DMSO-d ₆ solvent) measurement, a signal based on a vinylene group in a side chain at δ6.1 ppm, a propylene group in a side chain at δ4.0 ppm, δ2.4-2.6 ppm, and δ2.0 ppm Based signal was observed. Further, from the ratio of the integral value of the signal at δ6.1 ppm and the integral value of the signal at δ4.0 ppm, it is found that the number of repeating units (y ₁ and y ₂ ) of the side chain polystyrene is 3.4 on average. It was.

(Example 2) Production of solid electrolyte membrane and measurement of ionic conductivity About 5 g of the polymer obtained in Example 3 was dissolved in 40 ml of DMF to prepare a dope solution. This dope solution was poured onto a glass plate and stretched using a bar coater. Then, after drying at 65 ° C. for 15 hours, the film is peeled off from the glass plate, immersed in 1 mol / l HCl overnight to perform salt exchange, washed with ion-exchanged water, air-dried overnight, and solid electrolyte. A membrane was obtained.
The ionic conductivity of the obtained membrane was measured according to Journal of the Electrochemical Society 143, No. 4, 1254-1259 (1996). The solid electrolyte membrane is cut out to a length of 2 cm and a width of 1 cm, and sandwiched in a conductivity cell described in Journal of Membrane Science, Vol. 219, pages 123-136 (2003). The measurement was performed by the AC impedance method under constant humidity or constant temperature water. Ionic conductivity was determined according to the following formula. Table 1 shows the measurement results of ionic conductivity. The ionic conductivity in Table 1 was measured at 25 ° C. and relative humidity 95%.

  It was confirmed that the solid electrolyte membrane of the present invention has high ionic conductivity. Such a solid electrolyte membrane can be preferably used as, for example, a proton conductive membrane of a fuel cell.

Example 3 Fabrication of MEA
[Production Method 1]
A fuel cell was fabricated using the solid electrolyte of Example 3. 2 g of platinum-supported carbon black (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) and 15 g of Nafion solution (5% alcohol aqueous solution) as a binder were mixed and dispersed with an ultrasonic disperser for 30 minutes. The obtained dispersion was coated on carbon paper (thickness 350 μm), dried, and then punched out into a circle with a diameter of 9 mm to produce an electrode.
The solid electrolyte membrane of Example 2 was used as the solid electrolyte membrane, the electrodes obtained above were bonded to both sides of the electrolyte membrane so that the coated surface was in contact with the solid electrolyte membrane, and thermocompression bonded by hot pressing, and the MEA was Produced.

[Production Method 2]
A fuel cell was produced using the solid electrolyte of Example 1. 2 g of platinum-supported carbon black (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) and 15 g of the solid electrolyte solution (5% solution) of Example 1 as a binder were mixed and dispersed with an ultrasonic disperser for 30 minutes. The obtained dispersion was coated on carbon paper (thickness 350 μm), dried, and then punched out into a circle with a diameter of 9 mm to produce an electrode.
A Nafion 117 membrane was used as the solid electrolyte membrane, and the electrodes obtained above were bonded to both sides of the Nafion 117 membrane so that the coated surface was in contact with the Nafion 117 membrane, and thermocompression bonded by hot pressing to produce an MEA.

[Production Method 3]
A fuel cell was produced using the solid electrolyte of Example 1. 2 g of platinum-supported carbon black (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Co., Ltd.) and 15 g of the solid electrolyte solution (5% solution) of Example 1 as a binder were mixed and dispersed with an ultrasonic disperser for 30 minutes. The obtained dispersion was coated on carbon paper (thickness 350 μm), dried, and then punched out into a circle with a diameter of 9 mm to produce an electrode.
The solid electrolyte membrane of Example 2 was used as the solid electrolyte membrane, the electrodes obtained above were bonded to both surfaces of the electrolyte membrane so that the coated surface was in contact with the solid electrolyte membrane, and thermocompression bonded by hot pressing, and the MEA Was made. The solid electrolyte used as the binder and the solid electrolyte used as the solid electrolyte membrane may be the same type of electrolyte or a combination of different types of electrolytes.

Comparative Example Fabrication of MEA
[Production Method 4]
An MEA was produced in the same manner as in Production Method 1, except that Nafion 117 was used as the solid electrolyte and a Nafion solution was used as the binder.

Example 4 Evaluation of Fuel Cell The MEA obtained in Example 5 was set in the fuel cell shown in FIG. 2, and hydrogen gas was allowed to flow through the anode side opening 15. At this time, the cathode side opening 16 flowed air. A potentiostat was connected between the anode electrode 12 and the cathode electrode 13, and the current value at 400 mV was recorded. The results are shown in Table 2.

  The solid electrolyte of the present invention has high ionic conductivity, and it has been confirmed that high output can be obtained even when used as a solid electrolyte membrane or as a binder for a catalyst membrane. In particular, when the solid electrolyte of the present invention having a substituent having high oxygen permeability was used as a binder, high output was obtained. In addition, it was confirmed that both the solid electrolyte membrane and the binder are more effective by adopting a solid electrolyte having the same main chain as the polymer main chain of the present invention.

It is the schematic which shows an example of the phase-separation structure of the conventional proton conductive membrane. It is the schematic which shows an example of the phase-separation structure of the proton conducting membrane of this invention. It is a schematic sectional drawing which shows an example of the structure of the membrane / electrode assembly of this invention. It is a schematic sectional drawing which shows an example of the structure of the fuel cell of this invention.

Explanation of symbols

10 ... Membrane / electrode assembly (MEA)
11 ... Solid electrolyte
12 ... Anode electrode
12a ... Anode electrode conductive layer
12b ... Anode electrode catalyst layer
13 ... Cathode electrode
13a ... Cathode electrode conductive layer
13b ... Cathode electrode catalyst layer
14 ... Packing
15 ... Anode pole side opening
16 ... Cathode pole side opening
17 ... current collector
21,22 ... Separator

Claims (25)

A solid electrolyte comprising a polymer compound (1) having a polymer obtained by graft polymerization of a polymerizable monomer containing an acid residue as a side chain. The solid electrolyte according to claim 1, wherein the polymer has a molecular weight of 150 or more. The solid electrolyte according to claim 1, wherein the polymerizable monomer has a vinyl group. The polymer compound (1) has a main chain containing a repeating unit represented by the formula (1) and / or a repeating unit represented by the formula (4), and the formula (25) bonded to the main chain. The solid electrolyte of any one of Claims 1-3 which has a side chain represented by this.

In Formula (1) or Formula (4), R ¹ and R ⁴ are structural units represented by Formulas (5) to (24), respectively, X is —C (R ⁵ R ⁶ ) —, Represents a structural unit selected from the group consisting of —O—, —S—, —CO—, —SO— or —SO ₂ —, and combinations thereof, and R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, respectively. Represents an alkenyl group, an aryl group or a halogen-substituted alkyl group.
S ^{1 to} S ¹² each represents a hydrogen atom or a substituent.
Q ¹ represents —O—, —S— or —NR ²¹ —, and Q ² represents —O—, —CR ²² R ²³ —, —CO— or —NR ²⁴ —. Here, R < ²¹ > -R < ²⁴ > represents a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, respectively.
In Formula (25), B ¹ represents a single bond or a linking group, D represents an atomic group (X) containing a polymer of a polymerizable monomer and having at least one acid residue. The solid electrolyte according to claim 4, wherein in formula (25), D has at least one oxygen-permeable substituent. In Formula (25), B ¹ is a single bond or an alkylene group, a halogen-substituted alkylene group, an alkyl-substituted alkylene group, an arylene group, a halogen-substituted arylene group, an alkyl-substituted arylene group, an alkenylene group, a halogen-substituted alkynylene group, or an alkyl-substituted group. Selected from the group consisting of alkynylene group, alkynylene group, amide group, ester group, sulfoamide group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, heterylene group and phenylene group The solid electrolyte according to claim 4 or 5, which is a linking group having 0 to 100 carbon atoms and formed by combining 1 or 2 or more. The said high molecular compound (1) is a solid electrolyte of any one of Claims 1-6 containing the repeating unit represented by the repeating unit represented by Formula (26), and (27).

(In formula (26) or (27), X ¹ is a single bond or —C (R ⁵ R ⁶ ) —, and X ² and X ⁴ are —O— or —S—, and combinations thereof, respectively. X ³ is a group consisting of —CO—, —SO—, —SO ₂ —, and combinations thereof, and n ₁ and n ₂ are each 0 or 1, and n ₁ and The sum of n ₂ is at least 1. B ¹ represents a single bond or a linking group, D represents a polymer of a polymerizable monomer, and represents an atomic group (X) having at least one acid residue. .) The said high molecular compound (1) is a solid electrolyte of any one of Claims 1-7 containing the repeating unit represented by the repeating unit represented by Formula (28), and (29).

(In formula (28) or (29), X ¹ is a single bond or —C (R ₅ R ₆ ) —, and X ² and X ⁴ are —O— or —S—, and combinations thereof, respectively. X ³ is a group consisting of —CO—, —SO—, —SO ₂ —, and combinations thereof, and n ₃ and n ₄ are each 0 or 1, and n ₃ and The sum of n ₄ is at least 1. B ¹ represents a single bond or a linking group, D represents a polymer of a polymerizable monomer, and represents an atomic group (X) having at least one acid residue. .) D in Formula (25) includes the repeating unit represented by Formula (30), and at least the group represented by Formula (31) is bonded to the aromatic ring of Formula (30). The solid electrolyte according to any one of claims 4 to 8.

(In Formula (30), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. In Formula (31), B ² is a single bond or 2-6. Represents a valent linking group, A ¹ represents an acid residue, and n ₅ is an integer of 1 to 5.) D in the formula (25) includes a repeating unit represented by the formula (30), and the aromatic ring in the formula (30) includes at least a group represented by the formula (31) and the formula (32). The solid electrolyte according to any one of claims 4 to 8, wherein a group represented by

(In Formula (30), W ¹¹ , W ¹² and W ¹³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. In Formula (31), B ² is a single bond or 2-6. Represents a valent linking group, A ¹ represents an acid residue, and n ₅ represents an integer of 1 to 5. In formula (32), E ¹ represents a substituent having high oxygen permeability. The solid electrolyte according to any one of claims 1 to 10, which is in a film form. A membrane / electrode assembly comprising a solid electrolyte membrane and a gas diffusion electrode comprising a pair of electrodes disposed on both sides of the solid electrolyte membrane, and the solid electrolyte membrane and / or the pair of pairs The membrane / electrode assembly in which an electrode contains the solid electrolyte of any one of Claims 1-10. 12. A membrane / electrode assembly comprising the solid electrolyte according to claim 11 and a gas diffusion electrode comprising a pair of electrodes disposed on both sides with the solid electrolyte interposed therebetween. The membrane / electrode assembly according to claim 12 or 13, wherein the gas diffusion electrode is an electrode in which a catalytic metal is supported on the surface of a conductive material made of a carbon material by a binder. The membrane / electrode assembly according to claim 14, wherein the binder comprises the solid electrolyte according to any one of claims 1 to 10. A fuel cell comprising the membrane / electrode assembly according to any one of claims 12 to 15. The fuel cell according to claim 16, further comprising a pair of gas-impermeable separators disposed so as to sandwich the gas diffusion electrode. The fuel cell according to claim 17, further comprising a pair of current collectors disposed between the membrane / electrode assembly and the separator. A method for producing a solid electrolyte, comprising graft polymerization of a polymerizable monomer having an acid residue on a main chain of a polymer compound. The method for producing a solid electrolyte according to claim 19, wherein the main chain of the polymer compound includes an aromatic ring, and a polymerizable monomer is reacted after introducing a halogenomethyl group into the aromatic ring. The method for producing a solid electrolyte according to claim 19 or 20, wherein the polymerizable monomer is a compound represented by the formula (A) or a compound represented by the formula (B).
Formula (A)

(In the formula (A), E and F each represent a single bond or a divalent linking group, and G represents a carboxylic acid group, a sulfonic acid group or a phosphoric acid group.)
Formula (B)

(In formula (B), m1 is an integer of 0 or more, and G represents a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group.) The method for producing a solid electrolyte according to claim 19 or 20, wherein the polymerizable monomer is a compound represented by a compound represented by formula (33).

(In formula (33), W ²¹ , W ²² and W ²³ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and B ³ represents a single bond or a divalent to hexavalent linking group. , a ² represents an acid residue, n6 represents an integer of 1 to 5, n7 is an integer of 1-5.) The method for producing a solid electrolyte according to claim 19 or 20, wherein the polymerizable monomer is a compound represented by formula (33) and a compound represented by formula (34).

(Expressed in the formula (33) and ^{(34), W 21, W} 22, W 23, W 24, W 25 and W ²⁶ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, B ³ Represents a single bond or a bivalent to hexavalent linking group, A ² represents an acid residue, n6 represents an integer of 1 to 5, n7 represents an integer of 1 to 5. E ² represents an oxygen-permeable substance. Represents a high substituent, and n8 represents an integer of 1 to 5.) The method for producing a solid electrolyte according to any one of claims 19 to 23, wherein the solid electrolyte is the solid electrolyte according to any one of claims 1 to 11. A polymer compound having a polymer obtained by graft polymerization of a polymerizable monomer having an acid residue as a side chain.

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