JP2008078128A - POLYMER ELECTROLYTE MEMBRANE, ITS LAMINATE, AND METHOD FOR PRODUCING THEM - Google Patents

Abstract

Provided is an electrolyte membrane having a small difference in wettability with respect to water on both surfaces of the electrolyte membrane so that it can be easily handled in a continuous process. Furthermore, in the step of attaching the electrode, a film having high wettability is provided on both surfaces of the electrolyte membrane so that the bondability at the membrane-electrode interface is enhanced.
An ion conductive polymer electrolyte membrane in which a difference between a water contact angle on one side of a polymer electrolyte membrane and a water contact angle on the other side is 30 ° or less is manufactured. The production method includes a polymer electrolyte solution in which a polymer electrolyte having an aromatic group in a main chain and / or a side chain and containing an ion conductive polymer having an ion exchange group in the aromatic group is dissolved in a solvent. And a step of casting the polymer electrolyte solution onto a support substrate to form a laminate in which a polymer electrolyte membrane is laminated on the support substrate. A polymer electrolyte membrane is obtained by removing the supporting substrate from the obtained laminate.
[Selection figure] None

Description

  The present invention relates to a polymer electrolyte membrane. More specifically, the present invention relates to a polymer electrolyte membrane used as an electrolyte membrane of a solid polymer fuel cell.

  BACKGROUND ART A polymer electrolyte fuel cell is a power generation device that generates power by a chemical reaction between hydrogen and oxygen, and is highly expected in fields such as the electric equipment industry and the automobile industry as one of the next generation energy. A hydrocarbon polymer excellent in heat resistance and gas barrier properties, instead of a fluorine polymer electrolyte represented by Nafion (registered trademark of DuPont), which has been conventionally used as a diaphragm in the solid polymer fuel cell In recent years, electrolytes have attracted attention (Patent Document 1).

  In order to industrially produce a hydrocarbon-based polymer electrolyte membrane, it is important to continuously form the membrane while maintaining high characteristics and high quality. For example, an aromatic polymer electrolyte is generally formed by a so-called solution casting method in which the polymer is dissolved in a solvent, casted, and dried (Patent Documents 2 to 5).

JP-A-6-93114 JP 2003-031232 A JP 2004-134225 A JP 2005-154710 A JP 2005-216525 A

  In the solution casting method relating to the production process (film formation) of a polymer electrolyte membrane for a polymer electrolyte fuel cell, the solution is applied onto a substrate in a solution state, dried with a solvent, and further subjected to solvent removal by immersion in water. The film is manufactured through a process of performing water drying. In the process of producing a membrane through such complicated processes, it is industrially required to continuously produce a polymer electrolyte membrane. Therefore, importance is attached to the ease of handling of the obtained polymer electrolyte membrane. For example, it is important that the properties of both surfaces of the polymer electrolyte membrane are almost the same, and both can be handled in the same manner.

  In addition, in the process of manufacturing a membrane-electrode assembly by attaching electrodes to both sides of the polymer electrolyte membrane obtained as described above, the bondability at the membrane-electrode interface is important. A polymer electrolyte membrane having a surface property with high affinity is important.

  Therefore, in the present invention, in view of industrially producing a polymer electrolyte membrane for a polymer electrolyte fuel cell, it is easy to handle on a continuous process, and moreover, in the process of producing a membrane-electrode assembly, Provided is a polymer electrolyte membrane having high bonding properties at the membrane-electrode interface.

  In order to achieve the above object, the present inventors have intensively studied, and as a result, completed the present invention. The present invention provides an ion conductive polymer electrolyte membrane described below, a laminate including the polymer electrolyte membrane, and methods for producing them. First, this invention provides the manufacturing method of the laminated body of following [1].

[1] An ion conductive polymer electrolyte membrane in which the difference between the contact angle with respect to water on one surface of the polymer electrolyte membrane and the contact angle with water on the other surface is 30 ° or less is any of the polymer electrolyte membranes. In a state where the surface is bonded to the support substrate, a method for producing a laminate laminated on the support substrate,
The following steps:
Includes an ion conductive polymer having an aromatic group in the main chain and / or side chain and having an ion exchange group directly bonded to the aromatic group or indirectly bonded through another atom or atomic group Preparing a polymer electrolyte solution in which the polymer electrolyte is dissolved in a solvent; and
A step of casting and applying the polymer electrolyte solution onto a supporting substrate, and laminating a polymer electrolyte membrane on the supporting substrate;
A process for producing a laminate comprising:

Furthermore, the present invention provides the following [2] and [3] as preferred embodiments according to the above [1].
[2] The method for producing a laminate according to [1], wherein a surface of the supporting substrate to be cast-coated is formed of a metal or a metal oxide.

  [3] The method for producing a laminate according to [1] or [2], wherein the support substrate is a continuous support substrate and is a film containing a metal or a metal oxide on the surface.

  As a support substrate that can easily reduce the contact angle difference between both surfaces of the polymer electrolyte membrane by casting, a support substrate in which the surface to be cast is formed of metal or metal oxide is suitable. From the viewpoint of industrial use, a film that is a continuous support substrate and contains a metal or metal oxide on the surface is used.

In addition, the present invention provides the following [4] to [15] in any one of the production methods.
[4] The ion-conducting polymer has an aromatic ring in the main chain, and an ion-exchange group bonded directly to the aromatic ring or indirectly through another atom or atomic group. The manufacturing method of the laminated body in any one of [1]-[3] characterized by the above-mentioned

[5] The method for producing a laminate according to [4], wherein the ion conductive polymer has a side chain. [6] The ion conductive polymer has an aromatic ring in the main chain. And may have an aromatic ring side chain, and at least one of the aromatic ring of the main chain or the aromatic ring of the side chain has an ion exchange group directly bonded to the aromatic ring [ [1] The method for producing a laminate according to any one of [3] [7] The laminate according to any one of [4] to [6], wherein the ion exchange group is a sulfonic acid group. Manufacturing method.
[8] The ion conductive polymer may have the following general formulas (1a) to (4a):

(In the formula, Ar ^{1 to} Ar ⁹ each independently represent a divalent aromatic group having an aromatic ring in the main chain and further having a side chain having an aromatic ring. At least one of the aromatic ring of the chain or the aromatic ring of the side chain has a proton exchange group directly bonded to the aromatic ring.
Z and Z ′ each independently represent one of CO and SO ₂ , and X, X ′ and X ″ each independently represent one of O and S. Y represents a direct bond or the following general formula (10) And p represents 0, 1 or 2, and q and r each independently represent 1, 2 or 3.
One or more repeating units having an ion exchange group selected from:
The following general formulas (1b) to (4b)

（式中、Ｒ¹及びＲ²は互いに独立に、水素原子、置換基を有していてもよい炭素数１〜１０のアルキル基、置換基を有していてもよい炭素数１〜１０のアルコキシ基、置換基を有していてもよい炭素数６〜１８のアリール基、置換基を有していてもよい炭素数６〜１８のアリールオキシ基又は置換基を有していてもよい炭素数２〜２０のアシル基を表し、Ｒ¹とＲ²が連結して環を形成していてもよい。） (In the formula, Ar ^{11 to} Ar ¹⁹ each independently represent a divalent aromatic group optionally having a substituent as a side chain. Z and Z ′ are each independently CO or SO ₂ . X, X ′, and X ″ each independently represent O or S. Y represents a direct bond or a group represented by the following general formula (10). P ′ is 0, 1 or 2 and q ′ and r ′ each independently represent 1, 2 or 3.)
The method for producing a laminate according to any one of [1] to [7], comprising at least one repeating unit substantially free of ion exchange groups selected from

(In the formula, R ¹ and R ² are independently of each other a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted substituent having 1 to 10 carbon atoms. An alkoxy group, an optionally substituted aryl group having 6 to 18 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted carbon Represents an acyl group of 2 to 20, and R ¹ and R ² may be linked to form a ring.)

[9] A copolymer in which the ion conductive polymer has at least one polymer segment (A) having an ion exchange group and at least one polymer segment (B) having substantially no ion exchange group. [10] The method for producing a laminate according to any one of [1] to [8] [10] The ion conductive polymer substantially has a block (A) having an ion exchange group and an ion exchange group. A method for producing a laminate according to any one of [1] to [9], wherein the laminate is a block copolymer comprising a block (B) that is not used.

[11] A method for producing a laminate according to any one of [1] to [10], wherein a polymer electrolyte membrane having a structure microphase-separated into at least two or more phases is obtained [12] The ion conductive polymer is a block copolymer comprising a block (A) having an ion exchange group and a block (B) having substantially no ion exchange group, and has an ion exchange group. A polymer electrolyte membrane having a microphase separation structure including a phase having a high density of the block (A) and a phase having a high density of the block (B) substantially not having an ion exchange group is obtained. The method for producing a laminate according to any one of [1] to [11]

（式中、ｍは５以上の整数を表し、Ａｒ⁹は２価の芳香族基を表し、ここで２価の芳香族基は、フッ素原子、置換基を有していてもよい炭素数１〜１０のアルキル基、置換基を有していてもよい炭素数１〜１０のアルコキシ基、置換基を有していてもよい炭素数６〜１８のアリール基、置換基を有していてもよい炭素数６〜１８のアリールオキシ基又は置換基を有していてもよい炭素数２〜２０のアシル基で置換されていてもよい。Ａｒ⁹は主鎖を構成する芳香環に直接又は側鎖を介してイオン交換基を有する。）
で表される繰返し構造を有し、且つ、
イオン交換基を実質的に有さないブロック（Ｂ）が下記一般式（１ｂ’）、（２ｂ’）、（３ｂ’）

（式中、ｎは５以上の整数を表す。Ａｒ¹¹〜Ａｒ¹⁸は互いに独立に２価の芳香族基を表し、ここでこれらの２価の芳香族基は、炭素数１〜１８のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基、炭素数６〜１８のアリールオキシ基又は炭素数２〜２０のアシル基で置換されていてもよい。その他の符号は、前記一般式（１ｂ）〜（３ｂ）のものと同じである。）
で表される繰返し構造から選ばれる１種以上を有することを特徴とする［１］〜［１２］のいずれかに記載の積層体の製造方法 [13] The ion-conducting polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and has an ion exchange group. Block (A) is represented by the following general formula (4a ′)

(In the formula, m represents an integer of 5 or more, Ar ⁹ represents a divalent aromatic group, wherein the divalent aromatic group has a fluorine atom and optionally has 1 carbon atom. Or an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, or a substituent. The aryloxy group having 6 to 18 carbon atoms or the optionally substituted acyl group having 2 to 20 carbon atoms may be substituted, Ar ⁹ may be directly or on the side of the aromatic ring constituting the main chain. It has an ion exchange group through the chain.)
And having a repeating structure represented by:
The block (B) having substantially no ion exchange group is represented by the following general formulas (1b ′), (2b ′), (3b ′)

(In the formula, n represents an integer of 5 or more. Ar ^{11 to} Ar ¹⁸ each independently represent a divalent aromatic group, and these divalent aromatic groups are alkyls having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or an acyl group having 2 to 20 carbon atoms. The same as those in the general formulas (1b) to (3b).
The method for producing a laminate according to any one of [1] to [12], comprising at least one selected from a repeating structure represented by

[14] The ion conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and the ion exchange group. In the block (A) having a structure, the ion-exchange group is directly bonded to the main chain aromatic ring. [15] The method for producing a laminate according to any one of [1] to [13] The ion conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and a block having an ion exchange group ( Any one of [1] to [14], wherein A) and the block (B) substantially not having an ion exchange group substantially have no substituent containing a halogen atom. Method for producing the laminate as described

In addition, the present invention provides the following [16] to [37] from any one of the above production methods.
[16] A method for producing a polymer electrolyte membrane, comprising a step of removing the support substrate from the laminate obtained by the production method according to any one of [1] to [15]. [17] The method for producing a polymer electrolyte membrane according to [16], which does not include a step of performing a surface treatment on both sides of the surface of the polymer electrolyte membrane after the support substrate is removed.

  [18] A laminate obtained by the production method described in any one of [1] to [15]

[19] Polymer electrolyte membrane obtained by the production method described in [16] or [17] [20] A polymer electrolyte membrane containing at least one ion-conductive polymer, the polymer The surface of at least one of the electrolyte membranes is not surface-treated, and the difference between the contact angle with water on one side of the polymer electrolyte membrane and the contact angle with water on the other side is 30 ° or less. [21] The ion conductive polymer electrolyte membrane according to [20], wherein both surfaces of the polymer electrolyte membrane are not subjected to surface treatment.

  [22] The polymer electrolyte membrane according to [20] or [21], wherein the contact angle with respect to water on one side and the other side of the membrane is 10 ° or more and 60 ° or less

[23] The ion-conducting polymer has an aromatic ring in the main chain, and an ion-exchange group bonded directly to the aromatic ring or indirectly through another atom or atomic group. [24] The polymer electrolyte membrane according to any one of [20] to [22] [24] The polymer according to [23], wherein the ion conductive polymer has a side chain. Electrolyte membrane [25] The ion conductive polymer may have an aromatic ring in the main chain, and may further have a side chain having an aromatic ring, and the main chain aromatic ring or the side chain aromatic ring. At least one of the polymer electrolyte membranes according to any one of [20] to [22], which has an ion exchange group directly bonded to the aromatic ring. [26] The ion exchange group is a sulfonic acid group. The high content according to any one of [23] to [25], Electrolyte membrane

（式中、Ａｒ¹〜Ａｒ⁹は、互いに独立に、主鎖に芳香族環を有し、さらに芳香族環を有する側鎖を有してもよい２価の芳香族基を表す。該主鎖の芳香族環か側鎖の芳香族環の少なくとも１つが該芳香族環に直接結合したイオン交換基を有する。
Ｚ、Ｚ’は互いに独立にＣＯ、ＳＯ₂のいずれかを表し、Ｘ、Ｘ’、Ｘ”は互いに独立にＯ、Ｓのいずれかを表す。Ｙは直接結合もしくは下記一般式（１０）で表される基を表す。ｐは０、１又は２を表し、ｑ、ｒは互いに独立に１、２又は３を表す。）
から選ばれるイオン交換基を有する繰り返し単位１種以上と、
下記一般式（１ｂ）〜（４ｂ）

（式中、Ａｒ¹¹〜Ａｒ¹⁹は、互いに独立に側鎖としての置換基を有していてもよい２価の芳香族炭素基を表す。Ｚ、Ｚ’は互いに独立にＣＯ、ＳＯ₂のいずれかを表し、Ｘ、Ｘ’、Ｘ”は互いに独立にＯ、Ｓのいずれかを表す。Ｙは直接もしくは下記一般式（１０）で表される基を表す。ｐ’は０、１又は２を表し、ｑ’、ｒ’は互いに独立に１、２又は３を表す。）
から選ばれるイオン交換基を実質的に有さない繰り返し単位１種以上とを有することを特徴とする［２０］〜［２６］のいずれかに記載の高分子電解質膜

（式中、Ｒ¹及びＲ²は互いに独立に、水素原子、置換基を有していてもよい炭素数１〜１０のアルキル基、置換基を有していてもよい炭素数１〜１０のアルコキシ基、置換基を有していてもよい炭素数６〜１８のアリール基、置換基を有していてもよい炭素数６〜１８のアリールオキシ基又は置換基を有していてもよい炭素数２〜２０のアシル基を表し、Ｒ¹とＲ²が連結して環を形成していてもよい。） [27] The ion conductive polymer may have the following general formulas (1a) to (4a):

(In the formula, Ar ^{1 to} Ar ⁹ each independently represent a divalent aromatic group having an aromatic ring in the main chain and further having a side chain having an aromatic ring. At least one of the aromatic ring of the chain or the aromatic ring of the side chain has an ion exchange group directly bonded to the aromatic ring.
Z and Z ′ each independently represent one of CO and SO ₂ , and X, X ′ and X ″ each independently represent one of O and S. Y represents a direct bond or the following general formula (10) And p represents 0, 1 or 2, and q and r each independently represent 1, 2 or 3.
One or more repeating units having an ion exchange group selected from:
The following general formulas (1b) to (4b)

(In the formula, Ar ^{11 to} Ar ¹⁹ each independently represent a divalent aromatic carbon group which may have a substituent as a side chain. Z and Z ′ are independently of each other CO and SO ₂ . X, X ′, and X ″ each independently represent O or S. Y represents a group represented directly or by the following general formula (10). P ′ is 0, 1 or 2 and q ′ and r ′ each independently represent 1, 2 or 3.)
The polymer electrolyte membrane according to any one of [20] to [26], comprising one or more repeating units substantially free of ion-exchange groups selected from

(In the formula, R ¹ and R ² are independently of each other a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted substituent having 1 to 10 carbon atoms. An alkoxy group, an optionally substituted aryl group having 6 to 18 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted carbon Represents an acyl group of 2 to 20, and R ¹ and R ² may be linked to form a ring.)

[28] The ion-conductive polymer is a copolymer comprising a polymer segment (A) having an ion exchange group and a polymer segment (B) having substantially no ion exchange group. The polymer electrolyte membrane according to any one of [20] to [27] [29] The ion-conductive polymer substantially does not have a block (A) having an ion exchange group and an ion exchange group. The polymer electrolyte membrane according to any one of [20] to [27], which is a block copolymer comprising the block (B)

[30] The polymer electrolyte membrane according to any one of [20] to [29], wherein the membrane has a microphase-separated structure into at least two or more phases. [31] The high ion conductivity A block is a block copolymer in which a molecule is composed of a block (A) having an ion exchange group and a block (B) substantially having no ion exchange group, and the membrane has a block having an ion exchange group ( Any one of [20] to [30], which has a microphase separation structure including a phase having a high density of A) and a phase having a high density of the block (B) having substantially no ion exchange group The polymer electrolyte membrane according to

（式中、ｍは５以上の整数を表し、Ａｒ⁹は２価の芳香族基を表し、ここで２価の芳香族基は、フッ素原子、置換基を有していてもよい炭素数１〜１０のアルキル基、置換基を有していてもよい炭素数１〜１０のアルコキシ基、置換基を有していてもよい炭素数６〜１８のアリール基、置換基を有していてもよい炭素数６〜１８のアリールオキシ基又は置換基を有していてもよい炭素数２〜２０のアシル基で置換されていてもよい。Ａｒ⁹は主鎖を構成する芳香環に直接又は側鎖を介してイオン交換基を有する。）
で表される繰返し構造を有し、且つ、
イオン交換基を実質的に有さないブロック（Ｂ）が下記一般式（１ｂ’）、（２ｂ’）、（３ｂ’）

（式中、ｎは５以上の整数を表す。Ａｒ¹¹〜Ａｒ¹⁸は互いに独立に２価の芳香族基を表し、ここでこれらの２価の芳香族基は、炭素数１〜１８のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基、炭素数６〜１８のアリールオキシ基又は炭素数２〜２０のアシル基で置換されていてもよい。その他の符号は、前記一般式（１ｂ）〜（３ｂ）のものと同じである。）
で表される繰返し構造から選ばれる１種以上とを有することを特徴とする［２０］〜［３１］のいずれかに記載の高分子電解質膜 [32] The ion-conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and has an ion exchange group. The block (A) is represented by the following general formula (4a ′).

(In the formula, m represents an integer of 5 or more, Ar ⁹ represents a divalent aromatic group, wherein the divalent aromatic group has a fluorine atom and optionally has 1 carbon atom. Or an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, or a substituent. The aryloxy group having 6 to 18 carbon atoms or the optionally substituted acyl group having 2 to 20 carbon atoms may be substituted, Ar ⁹ may be directly or on the side of the aromatic ring constituting the main chain. It has an ion exchange group through the chain.)
And having a repeating structure represented by:
The block (B) having substantially no ion exchange group is represented by the following general formulas (1b ′), (2b ′), (3b ′)

(In the formula, n represents an integer of 5 or more. Ar ^{11 to} Ar ¹⁸ each independently represent a divalent aromatic group, and these divalent aromatic groups are alkyls having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or an acyl group having 2 to 20 carbon atoms. The same as those in the general formulas (1b) to (3b).
The polymer electrolyte membrane according to any one of [20] to [31], having at least one selected from the repeating structure represented by

[33] The ion conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) substantially not having an ion exchange group, and the ion exchange group. The polymer electrolyte membrane according to any one of [20] to [32], wherein the ion-exchange group is directly bonded to the main chain aromatic ring in the block (A) having [34] The conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) substantially not having an ion exchange group, and a block having an ion exchange group (A ) And the block (B) substantially free of ion exchange groups both have substantially no substituent containing a halogen atom, according to any one of [20] to [33] Polymer electrolyte membrane

[35] A laminate in which the polymer electrolyte membrane according to any one of [20] to [34] is laminated on the support substrate. [36] The polymer electrolyte membrane of the support substrate is joined. The laminate according to [35], wherein the surface is formed of a metal or a metal oxide. [37] The support substrate is a continuous support substrate, and the surface includes a metal or a metal oxide. The laminate according to [35] or [36], which is a film

  According to the present invention, when a polymer electrolyte membrane is formed by a solution casting method, a polymer electrolyte solution is cast on the surface of an appropriate support substrate, whereby a polymer having substantially the same surface properties on both sides is obtained. It is possible to obtain an electrolyte membrane. Therefore, in the continuous production of the polymer electrolyte membrane, different treatments need not be performed in consideration of the properties of the front and back of the membrane. Therefore, it is possible to provide a polymer electrolyte membrane having extremely good handling properties in industrial production. In addition, when a membrane-electrode assembly is produced by attaching an electrode to the polymer electrolyte membrane without complicated post-processing such as surface treatment after film formation, the membrane-electrode assembly has good bondability. A membrane-electrode assembly can be obtained. Therefore, it is an industrially advantageous membrane as a polymer electrolyte membrane for a high-functional type solid polymer fuel cell.

Hereinafter, the polymer electrolyte membrane according to the present invention will be specifically described. The polymer electrolyte is an electrolyte resin containing at least one ion conductive polymer, and a film made of the polymer electrolyte is referred to as a polymer electrolyte film. The polymer electrolyte membrane preferably contains an ion conductive polymer in a proportion of 50% by weight or more, preferably 70% by weight or more, particularly preferably 90% by weight or more.
The ion conductive polymer is a polymer having an ion exchange group, and is a polymer having a group related to ion conduction, particularly proton conduction, when used as an electrolyte membrane of a solid polymer fuel cell. Means.

  In the polymer electrolyte membrane of the present invention, the amount of ion exchange groups responsible for ion conductivity is preferably 0.5 meq / g to 4.0 meq / g, more preferably 1.0 meq / g, expressed as ion exchange capacity. ~ 2.8 meq / g. When the ion exchange capacity indicating the amount of ion exchange groups introduced is 0.5 meq / g or more, the ion conductivity becomes higher and the function as a polymer electrolyte for a fuel cell is more preferable. On the other hand, when the ion exchange capacity indicating the amount of ion exchange groups introduced is 4.0 meq / g or less, the water resistance becomes better, which is preferable.

The polymer electrolyte membrane of the present invention is a polymer electrolyte membrane containing at least one ion-conducting polymer, and at least any surface of the polymer electrolyte membrane is not subjected to surface treatment, and The difference between the contact angle of water on one surface of the polymer electrolyte membrane and the contact angle of water on the other surface is 30 ° or less. The difference between the contact angles of both surfaces with respect to water is preferably 20 ° or less, and more preferably 10 ° or less.
If the difference in contact angle with water on both sides is within 30 °, the polymer electrolyte membrane is easy to process without special consideration of the surface properties of the front and back surfaces of the polymer electrolyte membrane. It becomes. For example, when a membrane-electrode assembly for a polymer electrolyte fuel cell is produced, the membrane-electrode assembly can be easily produced by performing the same treatment on the front and back of the polymer electrolyte membrane. Thus, in the processing of processing the polymer electrolyte membrane, it is desirable that the surface properties of the front and back sides of the membrane are more equal, and from this point of view, the difference in the contact angle with respect to water on both sides of the membrane is smaller. More preferred.
Further, the contact angle with respect to water on either one surface or the other surface of the membrane is preferably 10 ° or more and 60 ° or less, and more preferably 20 ° or more and 50 ° or less.
A contact angle of 10 ° or more with respect to water on both surfaces is preferable because the form stability of the polymer electrolyte membrane surface upon water absorption is excellent.
Moreover, if the contact angle with respect to the water of both surfaces is 60 degrees or less, since the joining property of the manufactured polymer electrolyte membrane and the electrode for fuel cells becomes strong, it is preferable.

The contact angle with respect to water of one surface and the other surface of the polymer electrolyte membrane is a value of the polymer electrolyte membrane that is not subjected to post-processing such as surface treatment on the polymer electrolyte membrane.
A film that is not subjected to post-processing treatment such as surface treatment can reduce the number of film forming steps, and is very useful industrially. Further, when surface treatment or the like is performed, the film surface may cause chemical or physical deterioration, and it is preferable not to perform the surface treatment or the like.
According to the present invention, when a polymer electrolyte membrane is formed by the solution casting method, the polymer electrolyte solution is cast on the surface of an appropriate support substrate, thereby performing post-processing such as surface treatment after film formation. Even if it does not perform, the contact angle difference of both surfaces of a polymer electrolyte membrane can be 30 degrees or less. That is, the difference in hydrophilicity between both surfaces of the film can be sufficiently reduced without performing special surface treatment on both surfaces after film formation by the solution casting method.

The fact that post-processing such as surface treatment is not performed means that the surface state of the film obtained in the film forming process including casting has not undergone additional changes after the casting process.
Examples of the surface treatment include hydrophilic treatment such as corona treatment and plasma treatment, and water repellency treatment such as fluorine treatment. The surface subjected to the hydrophilization treatment is usually a rough surface to which a hydrophilic group is added or has fine irregularities. Further, the surface subjected to the water repellent treatment is usually provided with a water repellent group.
Therefore, as a specific example of the state of the polymer electrolyte membrane that has not been surface-treated, a functional group other than the functional group originally possessed by the polymer electrolyte membrane is not provided on the surface, or The molecular electrolyte membrane has functional groups that are inherently present, but their abundance has not changed (the amount of functional groups has not increased or decreased), or is intentionally roughened after the film forming process. The state that it is not done is mentioned. Thus, the surface treatment represents a treatment that causes an irreversible change in the polymer electrolyte membrane. Therefore, in the polymer electrolyte constituting the polymer electrolyte membrane, the treatment related to the ion exchange reaction is not included in the category of the surface treatment because the ion exchange itself is a reversible reaction.

As a method for producing the polymer electrolyte membrane of the present invention, a method of forming a membrane from a solution state (so-called solution casting method) is particularly preferably used.
Specifically, at least one ion-conducting polymer is dissolved in a suitable solvent together with other components such as a polymer other than the ion-conducting polymer and additives as necessary, and the polymer electrolyte solution The film is preferably formed by casting (casting) on a specific base material and removing the solvent.
When preparing a polyelectrolyte solution, two or more types of ion-conducting polymers are separately added to the solvent, or the ion-conducting polymer and other components are separately added to the solvent. The polymer electrolyte solution may be prepared by separately adding and dissolving two or more components constituting the electrolyte in a solvent.

  The solvent used for film formation is not particularly limited as long as it can dissolve the ion-conductive polymer and other components added as necessary and can be removed thereafter. Dimethylformamide (DMF), Aprotic polar solvents such as dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), or chlorinated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene Alcohols such as methanol, ethanol and propanol, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Used to apply. These can be used singly, but two or more solvents can be mixed and used as necessary. Among these, DMSO, DMF, DMAc, NMP, and the like are preferable because of high polymer solubility.

（ｒ＝1〜2.5、ｓ＝0〜0.5、繰り返し単位の添え字数字は繰り返し単位のモル分率を示す。）

（ｒ＝1〜2.5、ｓ＝0〜0.5、繰り返し単位の添え字数字は繰り返し単位のモル分率を示す。）
で示されるホスホン酸基含有ポリマーを化学的安定化剤として含有することができる。なお、上式において「−（Ｐ（Ｏ）（ＯＨ）₂）_r」及び「−（Ｂｒ）_s」の表記は、ビフェニリレンオキシ単位当たりに、ホスホン酸基が平均ｒ個あり、ブロモ基が平均ｓ個あることを意味する。
添加する化学的安定剤含有量は全体の２０ｗｔ％以内が好ましく、それを超えて含有すると、高分子電解質膜の特性が低下する可能性がある。 In order to increase the chemical stability of the polymer electrolyte membrane produced by the present invention, such as oxidation resistance and radical resistance, a chemical stabilizer is added to the polymer electrolyte to the extent that the effects of the present invention are not hindered. Also good. Examples of the stabilizer to be added include antioxidants and the like, for example, additives as exemplified in JP2003-201403, JP2003-238678, and JP2003-282096. It is done. Alternatively, the following formulas described in JP-A-2005-38834 and JP-A-2006-66391

(R = 1 to 2.5, s = 0 to 0.5, the subscript number of the repeating unit indicates the mole fraction of the repeating unit.)

(R = 1 to 2.5, s = 0 to 0.5, the subscript number of the repeating unit indicates the mole fraction of the repeating unit.)
The phosphonic acid group-containing polymer represented by can be contained as a chemical stabilizer. In the above formula, “-(P (O) (OH) ₂ ) _r ” and “— (Br) _s ” are represented by an average of r phosphonic acid groups per biphenylyleneoxy unit, and bromo groups Means there are s on average.
The content of the chemical stabilizer to be added is preferably within 20 wt% of the whole, and if it exceeds this content, the properties of the polymer electrolyte membrane may be lowered.

In the present invention, it is preferable to use a base material that can be continuously formed as the support base material used for casting application. The base material that can be continuously formed refers to a base material that can be held as a scroll and can endure without cracking even under an external force such as a certain degree of curvature.
The base material that can be continuously formed refers to a base material that can be wound around a paper tube or a plastic tube to take a roll-like form, which is industrially advantageous because productivity is improved. A substrate having a width of 100 mm or more and a length of 10 m or more is preferable. More preferably, the substrate has a width of 150 mm or more and a length of 50 m or more. More preferably, the substrate has a width of 200 mm or more and a length of 100 m or more. Moreover, after fixing in the state of a roll, the base material which can be continuously drawn out or wound up is said. In general, a substrate that is inferior in flexibility or cracked when bent, such as a glass plate or a metal plate, is not preferable.

  As the substrate to be cast-coated, those having heat resistance and dimensional stability that can withstand the drying conditions during casting are preferable, and substrates having solvent resistance and water resistance to the above-mentioned solvents are preferable. Moreover, the base material which a polymer electrolyte membrane and a base material do not adhere | attach firmly but can peel after application | coating drying is preferable. Here, “having heat resistance and dimensional stability” means that the polymer electrolyte solution is not thermally deformed when the polymer electrolyte solution is cast and dried using a drying oven to remove the solvent. Further, “having solvent resistance” means that the substrate itself is not substantially dissolved by the solvent in the polymer electrolyte solution. Further, “having water resistance” means that the substrate itself does not substantially dissolve in an aqueous solution having a pH of 4.0 to 7.0. Further, “having solvent resistance” and “having water resistance” are concepts including not causing chemical deterioration with respect to a solvent and water, and having good dimensional stability without causing swelling or shrinkage.

  Control of the contact angle of the film surface with respect to water will be described. The wettability of the film surface is determined by the combination of the polymer electrolyte and the substrate, and is expressed as a difference in contact angle. Here, as the polymer electrolyte, a copolymer is preferable to a homopolymer, and it is more preferable to use a block copolymer among the copolymers. Among the block copolymers, it is particularly preferable when a microphase separation structure is expressed. The hypothesis is that, for example, the microphase-separated structure has microscopic aggregates, so that the contact angle is controlled by receiving strong interactions such as affinity and repulsive force between the polymer electrolyte and the substrate. Can be considered.

As a support substrate that can easily reduce the difference in water contact angle between both surfaces of a polymer electrolyte membrane by casting, a support substrate in which the surface to be cast is formed of a metal or metal oxide Is suitable.
Examples of the material of the substrate surface to be cast applied include a substrate made of a metal layer or a metal oxide layer. Specific examples of the metal layer include aluminum, copper, iron, stainless steel (SUS), gold, silver, platinum, and alloys thereof. Examples of the metal oxide layer include oxides of the above metals and silicon oxides.
These metals or metal oxides may be supported alone or may be formed on a resin film by lamination, vapor deposition or sputtering. Examples of the resin film include an olefin film, a polyester film, a polyamide film, a polyimide film, and a fluorine film. Of these, polyester films and polyimide films are preferable because they are excellent in heat resistance, dimensional stability, solvent resistance, and the like. Examples of the polyester film include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and aromatic polyester. Among them, polyethylene terephthalate is not limited to properties, and is industrially preferable from the viewpoint of versatility and cost.
Of the combination of the resin film layer and the metal thin film layer or metal oxide thin film layer, the resin film layer is made of polyethylene terephthalate, and the metal thin film layer or metal oxide thin film layer is an aluminum laminate layer, aluminum vapor deposition layer, alumina vapor deposition A combination comprising a layer, a silica vapor deposition layer, an alumina-silica binary vapor deposition layer, and the like is preferable. Examples of these laminated films include laminated films generally used for packaging materials.
Examples of the polyethylene terephthalate film subjected to alumina vapor deposition include Barrier Rocks (trade name) which is an alumina vapor deposition film manufactured by Toray Film Processing Co., Ltd., and examples of the polyethylene terephthalate film subjected to silica vapor deposition include Oike Kogyo Co., Ltd. Examples of the polyethylene terephthalate film subjected to alumina-silica binary vapor deposition include Ecosial (trade name) manufactured by Toyobo Co., Ltd. and the like.

  In addition, a film containing a metal or metal oxide on the surface can take the form of a long and continuous flexible base material, so that it can be held and used as a scroll, and a continuous production of a polymer electrolyte membrane is performed. Also preferably used.

  About a base material, you may give surface treatment which can change the wettability of the support base material surface according to a use. Examples of the treatment that can change the wettability of the supporting substrate surface include general techniques such as a hydrophilic treatment such as corona treatment and plasma treatment, and a water repellent treatment such as fluorine treatment.

Through the film forming process described above, a laminate in which a polymer electrolyte membrane is laminated on a support base material is obtained. In this laminate, the polymer electrolyte membrane constituting it has almost no difference in the hydrophilicity of the front and back surfaces, and both sides of the membrane of the polymer electrolyte membrane can be handled in the same manner. Excellent handling in the process of processing polymer electrolyte membranes.
The laminate may be stored and distributed as it is. When the support substrate is a flexible substrate, the laminate can also be handled in the form of a scroll.

A polymer electrolyte membrane is obtained by removing the supporting substrate from the laminate. What is necessary is just to remove a support base material by peeling from a laminated body normally.
Although there is no restriction | limiting in particular in the thickness of the polymer electrolyte membrane in this invention, 10-300 micrometers is preferable. A film having a film thickness of 10 μm or more is preferable because practical strength is more excellent, and a film having a film thickness of 300 μm or less is preferable because the film resistance is decreased and the characteristics of the electrochemical device tend to be further improved. The film thickness can be controlled by the concentration of the solution and the coating thickness on the substrate.

The polymer electrolyte membrane obtained by the present invention has a difference between the contact angle with water on one side of the membrane and the contact angle with water on the other side without performing post-processing such as surface treatment after film formation. , 30 ° or less.
This polymer electrolyte membrane has no front and back surfaces and can be handled in the same manner on both sides of the membrane of the polymer electrolyte membrane. Therefore, the polymer electrolyte membrane is excellent in handling property in the film forming process and is industrially advantageous.

The ion conductive polymer in the present invention has an aromatic ring in the main chain and an ion exchange group directly bonded to the aromatic ring or indirectly bonded through another atom or atomic group. Is preferred.
The ion conductive polymer in the present invention may have a side chain.
The ion conductive polymer in the present invention has an aromatic ring in the main chain and may further have a side chain having an aromatic ring, and at least one of the main chain aromatic ring or the side chain aromatic ring. It is preferable that one has an ion exchange group directly bonded to the aromatic ring.
The ion exchange group is preferably a cation exchange group.

The polymer electrolyte membrane of the present invention is preferably a hydrocarbon polymer electrolyte membrane, that is, a membrane made of a polymer electrolyte containing a hydrocarbon ion conductive polymer.
The hydrocarbon-based polymer electrolyte preferably contains 50% by weight or more of the hydrocarbon-based ion conductive polymer, preferably 70% by weight or more, particularly preferably 90% by weight or more. Is preferred. However, as long as the effect of the present invention is not hindered, other polymers, non-hydrocarbon ion conductive polymers, additives, and the like may be included.

The hydrocarbon-based ion conductive polymer typically does not contain any fluorine, but may be partially fluorine-substituted. Examples of the hydrocarbon ion conductive polymer include an aromatic main chain such as polyether ether ketone, polyether ketone, polyether sulfone, polyphenylene sulfide, polyphenylene ether, polyether ether sulfone, polyparaphenylene, and polyimide. Examples include engineering resins having a general-purpose resin such as polyethylene and polystyrene, or polymers obtained by introducing ion exchange groups into a copolymer having a combination of a plurality of repeating units forming these. In particular, since it is preferable to have an aromatic ring in the main chain, a polymer in which an ion exchange group is introduced into the engineering resin as described above or a resin having a combination of a plurality of repeating units constituting the engineering resin is provided. It is preferable because a polymer electrolyte membrane having more excellent heat resistance can be obtained.
Examples of the ion exchange group include a sulfonic acid group (—SO ₃ H), a carboxylic acid group (—COOH), a phosphoric acid group (—OP (O) (OH) ₂ ), and a phosphonic acid group (—P (O) (OH). ₂ ), a cation exchange group such as a sulfonylimide group (—SO ₂ —NH—SO ₂ —) is preferable, and a sulfonic acid group is particularly preferable.
Further, the hydrocarbon-based polymer electrolyte has an advantage that it is less expensive than the fluorine-based polymer electrolyte.

  As the polymer electrolyte used in the present invention, a copolymer comprising a repeating unit having an ion exchange group and a repeating unit having no ion exchange group is preferable because the contact angle with water can be easily controlled as described above. The copolymerization mode of the copolymer may be any of random copolymerization, block copolymerization, graft copolymerization, alternating copolymerization, or a copolymer obtained by combining such copolymerization modes. A block copolymer having at least one polymer segment (A) having an ion exchange group and a polymer segment (B) having substantially no ion exchange group, and a graft copolymer. A coalescence or the like is more preferable. More preferably, a block copolymer is mentioned.

In the present invention, the term “having an ion exchange group” means that the segment or block is a segment or block containing an average of 0.5 or more ion exchange groups per repeating unit. More preferably, an average of 1.0 or more per repeating unit is included.
On the other hand, these "substantially have no ion exchange group" mean that the ion exchange group is a segment or block having an average of less than 0.5 per repeating unit, and repeating unit 1 The average per piece is more preferably 0.1 or less, and the average is more preferably 0.05 or less.

  When the polymer electrolyte used in the present invention contains a block copolymer, the block copolymer has a block (A) having an ion exchange group and a block (B) having substantially no ion exchange group, What has 1 or more is preferable.

  When the polymer electrolyte used in the present invention contains a block copolymer, it is preferable that the polymer electrolyte membrane can form a microphase separation structure. The microphase separation structure here refers to the microscopic phase separation in the order of the molecular chain size by dissociating different polymer segments with chemical bonds in the block copolymer or graft copolymer. Refers to the resulting structure. For example, when viewed with a transmission electron microscope (TEM), the block (A) having an ion exchange group has a fine phase (microdomain) having a high density, and a block having substantially no ion exchange group (B ) And a fine phase (microdomain) having a high density, and the domain width of each microdomain structure, that is, the identity period is a few nm to a few hundred nm. Those having a microdomain structure of 5 nm to 100 nm are preferable.

  Examples of the ion conductive polymer used in the polymer electrolyte of the present invention include structures conforming to JP-A-2005-126684 and JP-A-2005-139432.

  More specifically, the ion conductive polymer of the present invention includes, as a repeating unit, any one or more of the above general formulas (1a), (2a), (3a), and (4a), and the above general It is preferable to include any one or more of formulas (1b), (2b), (3b), and (4b), and examples of the polymerization mode include block copolymerization, alternating copolymerization, and random copolymerization. .

  In the present invention, preferable block copolymers include one or more blocks composed of repeating units having an ion exchange group selected from the above general formulas (1a), (2a), (3a) and (4a), and the above general Although what has 1 or more types of blocks which consist of a repeating unit which does not have an ion exchange group substantially chosen from Formula (1b), (2b), (3b), (4b) is mentioned, More preferably, Examples include copolymers having the following blocks.

<A>. A block composed of the repeating unit (1a) and a block composed of the repeating unit (1b);
<I>. A block composed of the repeating unit (1a) and a block composed of the repeating unit (2b),
<U>. A block composed of the repeating unit (2a) and a block composed of the repeating unit (1b);
<D>. A block composed of the repeating unit (2a) and a block composed of the repeating unit (2b);

<O>. A block composed of the repeating unit (3a) and a block composed of the repeating unit (1b);
<F>. A block composed of the repeating unit (3a) and a block composed of the repeating unit (2b);
<Ki>. A block composed of the repeating unit (4a) and a block composed of the repeating unit (1b);
<K>. A block composed of the repeating unit (4a), a block composed of the repeating unit (2b), etc.

  More preferably, it has <i>, <c>, <d>, <d>, <d>, etc. described above. Particularly preferred are those having the above-mentioned <K>, <K> and the like.

  In the present invention, as a more preferable block copolymer, the number of repetitions of (4a), that is, m in the general formula (4a ′) represents an integer of 5 or more, preferably in the range of 5 to 1000, more preferably. 10-500. A value of m of 5 or more is preferable because proton conductivity is sufficient as a polymer electrolyte for a fuel cell. If the value of m is 1000 or less, it is preferable because production is easier.

Ar ⁹ in formula (4a ′) represents a divalent aromatic group. Examples of the divalent aromatic group include divalent monocyclic aromatic groups such as 1,3-phenylene and 1,4-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 1, Divalent condensed aromatic groups such as 5-naphthalenediyl, 1,6-naphthalenediyl, 1,7-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, pyridinediyl, quinoxalinediyl, Examples include heteroaromatic groups such as thiophenediyl. A divalent monocyclic aromatic group is preferred.

Ar ⁹ may have an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or a substituent. It is substituted with an aryl group having 6 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms which may have a substituent, or an acyl group having 2 to 20 carbon atoms which may have a substituent. May be.

Ar ⁹ has at least one ion exchange group in the aromatic ring constituting the main chain. As described above, as the ion exchange group, an acidic group (cation exchange group) is more preferable, and a sulfonic acid group is particularly preferable.

  These ion exchange groups may be partially or wholly exchanged with metal ions to form a salt, but when used as a polymer electrolyte membrane for a fuel cell, substantially all of them are exchanged. The free acid state is preferred.

  Preferable examples of the repeating structure represented by the formula (4a ′) include the following formula.

In the present invention, as a more preferable block copolymer, the number of repetitions of (1b) to (3b), that is, n in the above general formulas (1b ′) to (3b ′) represents an integer of 5 or more, The range of 5-1000 is preferable, More preferably, it is 10-500. A value of n of 5 or more is preferable because the ion conductivity is sufficient as a polymer electrolyte for a fuel cell. If the value of n is 1000 or less, it is preferable because production is easier.
Ar ^{11 to} Ar ¹⁸ in the formulas (1b ′) to (3b ′) represent divalent aromatic groups independent of each other. Examples of the divalent aromatic group include divalent monocyclic aromatic groups such as 1,3-phenylene and 1,4-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 1, Divalent condensed aromatic groups such as 5-naphthalenediyl, 1,6-naphthalenediyl, 1,7-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, pyridinediyl, quinoxalinediyl, Examples include heteroaromatic groups such as thiophenediyl. A divalent monocyclic aromatic group is preferred.
Ar ^{11 to} Ar ¹⁸ are each an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or 2 to 2 carbon atoms. It may be substituted with 20 acyl groups.

  Specific examples of the ion conductive polymer include, for example, the following structures.

  In addition, in said (1)-(26), the description of "Block" means that it is a block copolymer which has the block which consists of the repeating unit in a parenthesis. Further, such blocks may be in a directly connected form or may be connected in a suitable atom or atomic group.

  More preferable ion conductive polymers include, for example, the above (2), (7), (8), (16), (18), (22) to (25), and particularly preferably (16 ), (18), (22), (23), (25) and the like.

When the ion conductive polymer is the block copolymer, both the block (A) having an ion exchange group and the block (B) having substantially no ion exchange group both contain a halogen atom. It is particularly preferable that substantially no Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Here, “substantially not having a substituent containing a halogen atom” means having no more than 0.05 halogen atoms per repeating unit of the ion conductive polymer.
On the other hand, the following may be mentioned as examples that may be included as a substituent. For example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, etc. are mentioned, Preferably an alkyl group is mentioned. These substituents preferably have 1 to 20 carbon atoms, such as methyl group, ethyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, phenoxy group, naphthyloxy group, acetyl group, propionyl group, etc. Groups.
When the block copolymer contains a halogen atom, for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide or the like may be generated during operation of the fuel cell, which may corrode the fuel cell member, which is not preferable.

  In addition, the molecular weight of the proton conductive polymer is preferably 5000 to 1000000, and particularly preferably 15000 to 400000, expressed as a number average molecular weight in terms of polystyrene.

The polymer electrolyte membrane obtained by the present invention is expected to be used in various fields.
For example, the polymer electrolyte of the present invention can be used as a diaphragm for electrochemical devices such as fuel cells. Since this polymer electrolyte membrane has good compatibility with the electrode for fuel cells on both sides of the membrane, it is excellent in characteristics as an electrolyte membrane for fuel cells and has high utility value.
When used as an electrolyte membrane for a fuel cell, since there is almost no difference in hydrophilicity between both sides of the membrane, it can be used regardless of the front and back, and is industrially advantageous. In addition, since the affinity between the membrane and the electrode is high in the post-process for attaching the electrode, an effect of improving the bonding property at the membrane-electrode interface can be expected.
Therefore, the polymer electrolyte membrane produced by the production method of the present invention is an industrially advantageous membrane as a high-performance polymer electrolyte for solid polymer fuel cells.

Next, a fuel cell using the membrane of the present invention will be described.
The fuel cell of the present invention can be produced by bonding a catalyst and a conductive material as a current collector to both sides of a proton conductive polymer electrolyte membrane.
Here, the catalyst is not particularly limited as long as it can activate a redox reaction with hydrogen or oxygen, and a known catalyst can be used. However, it is preferable to use fine particles of platinum or a platinum-based alloy. The fine particles of platinum or a platinum-based alloy are often used by being supported on particulate or fibrous carbon such as activated carbon or graphite.
In addition, a gas diffusion layer and / or polymer electrolyte membrane and / or polymer electrolyte obtained by mixing platinum supported on carbon with an alcohol solution of a perfluoroalkylsulfonic acid resin as a polymer electrolyte into a paste. A catalyst layer is obtained by applying and drying the composite membrane. As a specific method, for example, J. et al. Electrochem. Soc. : Known methods such as those described in Electrochemical Science and Technology, 1988, 135 (9), 2209 can be used.
Here, instead of the perfluoroalkylsulfonic acid resin as the polymer electrolyte, the proton conductive polymer electrolyte of the present invention can be used as a catalyst composition.
A known material can be used for the conductive material as the current collector, but porous carbon woven fabric, carbon non-woven fabric or carbon paper is preferable for efficiently transporting the raw material gas to the catalyst.
The fuel cell of the present invention thus produced can be used in various forms using hydrogen gas, reformed hydrogen gas, and methanol as fuel.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes all modifications within the scope and meaning equivalent to the terms of the claims.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The physical property measuring method according to the present invention is shown below.

(Measurement of ion exchange capacity)
The dry weight of the polymer electrolyte membrane to be measured was determined using a halogen moisture meter set at a heating temperature of 105 ° C. Next, this polymer electrolyte membrane was immersed in 5 mL of a 0.1 mol / L sodium hydroxide aqueous solution, and then 50 mL of ion-exchanged water was further added and left for 2 hours. Thereafter, titration was performed by gradually adding 0.1 mol / L hydrochloric acid to the solution in which the polymer electrolyte membrane was immersed, and the neutralization point was determined. Then, the ion exchange capacity (unit: meq / g) of the polymer electrolyte membrane was calculated from the dry weight of the polymer electrolyte membrane and the amount of hydrochloric acid required for the neutralization.

(Measurement of GPC)
The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions. In addition, it measured using either of the following as a mobile phase (eluent).
[Mobile phase 1] DMAc (LiBr added to 10 mmol / dm ³ )
[Mobile phase 2] DMF (LiBr added to 10 mmol / dm ³ )

(Measurement of contact angle)
The polymer electrolyte membrane of each Example or Comparative Example was allowed to stand in a 23 ° C. 50% RH atmosphere for 24 hours in a state where it was peeled off from the support substrate, and then contact angle meter (CA-A type Kyowa Interface Science Co., Ltd.) The contact angle of the film surface with water droplets was determined by the droplet method. The contact angle 5 seconds after dropping a water droplet having a diameter of 2.0 mm on the polymer electrolyte membrane was used as a value.

(TEM observation method)
The polymer electrolyte membrane of each Example or Comparative Example was immersed in an aqueous dyeing solution (concentration potassium iodide 15%, iodine 5%) at room temperature for 30 minutes, and embedded with an epoxy resin that had been previously cured in advance. Further, a 60 nm thick section was cut out by a microtome under room temperature and dry conditions. The obtained sections were collected on a Cu mesh and observed with a transmission electron microscope (H9000NAR manufactured by Hitachi, Ltd.) at an acceleration voltage of 300 kV.

(Catalyst ink and transfer sheet manufacturing method)
0.83 g of platinum-supported carbon (SA50BK, manufactured by N.E. Chemcat) carrying 50% by weight of platinum in 6 mL of a commercially available 5% by weight Nafion solution (solvent: mixture of water and lower alcohol) was added, and ethanol was further added. 9 mL was added. The obtained mixture was subjected to ultrasonic treatment for 1 hour and then stirred for 5 hours with a stirrer to obtain a catalyst ink.
The catalyst ink was applied onto a Teflon (registered trademark) sheet using a doctor blade, dried in an oven at 80 ° C. for 1 hour to remove the solvent, and a transfer sheet was obtained.

(Jointness test between electrolyte membrane and electrode)
The polymer electrolyte membrane of each Example or Comparative Example was cut into a length of 5 cm × 5 cm, taken out by being immersed in water, the electrolyte membrane and the transfer sheet were overlapped, and sandwiched between two upper and lower SUS plates, and hot press (Press conditions: 100 kgf / cm ² , 100 ° C., 10 minutes). When the electrode was uniformly transferred within the electrolyte membrane surface, “◯” was given, and when the electrode was partially peeled or uneven, “x” was given.

(Synthesis Example 1)
Under an argon atmosphere, in a flask equipped with an azeotropic distillation apparatus, 142.2 parts by weight of DMSO, 55.6 parts by weight of toluene, 5.7 parts by weight of sodium 2,5-dichlorobenzenesulfonate, and the following polyether which is terminal chloro type Sulfone

(Sumitomo Chemical Sumika Excel PES5200P) 2.1 parts by weight and 2,2'-bipyridyl 9.3 parts by weight were added and stirred. Thereafter, the bath temperature was raised to 100 ° C., and the toluene in the system was azeotropically dehydrated by heating and distilling under reduced pressure. After cooling to 65 ° C., the pressure was returned to normal pressure. Next, 15.4 parts by weight of bis (1,5-cyclooctadiene) nickel (0) was added thereto, the temperature was raised to 70 ° C., and the mixture was stirred at the same temperature for 5 hours. After allowing to cool, the reaction solution is poured into a large amount of methanol to precipitate a polymer, which is filtered off. Thereafter, washing and filtration operations with 6 mol / L hydrochloric acid were repeated several times, followed by washing with water until the filtrate became neutral and drying under reduced pressure to obtain 3.0 parts by weight of the following polyarylene block copolymer ( IEC = 2.2 meq / g, Mn = 103000, Mw = 257000 [mobile phase 2]).

(Film forming condition 1)
Cast film formation was performed using a continuous drying furnace. That is, the polymer electrolyte solution is adjusted to a desired film thickness using a doctor blade with a variable film thickness, continuously cast on a support substrate, and continuously put into a drying furnace. Most of the solvent was removed. The drying conditions are described below.
Drying conditions: temperature 80 ° C, time 66 minutes
(Temperature refers to the set temperature of the drying furnace, time is cast film
It refers to the time from when the polymer electrolyte membrane enters the drying furnace until it exits. )
The polymer electrolyte membrane after drying was washed with ion exchange water to completely remove the solvent. This membrane was immersed in 2N hydrochloric acid for 2 hours, then washed again with ion-exchanged water, and further air-dried to produce a polymer electrolyte membrane.

Example 1
Polyarylene block copolymer obtained in Synthesis Example 1 (IEC = 2.2 meq / g, Mn = 103000, Mw = 257000 [mobile phase 2], where IEC is the ion exchange capacity, and Mn is the number in terms of polystyrene. The average molecular weight and Mw are polystyrene-equivalent weight average molecular weights, and the same applies to the following examples). BCP-1 was dissolved in DMSO to prepare a solution having a concentration of 10 wt%. A polymer electrolyte having a film thickness of about 30 μm was formed by the method of film forming condition 1 using a silica-deposited PET (manufactured by Oike Kogyo Co., Ltd., film thickness 12 μm) having a width of 300 mm and a length of 1000 m on the support substrate A membrane was prepared. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.

Example 2
Synthesized with reference to the polyarylene block copolymer (BCP-1) obtained in Synthesis Example 1 and the method described in Reference Example 3 of JP-A-2005-38834, containing phosphonic acid groups as shown in the following figure A mixture (weight ratio 90:10) with a polymer (referred to as AD-1) was dissolved in DMSO to prepare a solution having a concentration of 10 wt%. A polymer electrolyte membrane having a film thickness of about 30 μm was produced from the resulting solution by the method of Example 1 using an aluminum sheet (thickness: 200 μm) having a width of 300 mm and a length of 1000 m as a supporting substrate. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.

（ｒ＝1.9、ｓ＝0.0、繰り返し単位の添え字数字は繰り返し単位のモル分率を示す。）

(R = 1.9, s = 0.0, the subscript number of the repeating unit indicates the mole fraction of the repeating unit.)

Example 3
A block copolymer (IEC = 2.2 meq / g, Mn = 16000, Mw = 228000 [mobile phase 2]) synthesized according to the polymerization method of Synthesis Example 1 and having a different synthesis lot from BCP-1: BCP-2 ) And a phosphonic acid group-containing polymer (referred to as AD-2) as shown in the following figure, synthesized with reference to the method described in JP-A-2006-66391 ([0059]) (weight ratio of 90 pairs) 10) was dissolved in DMSO to prepare a solution having a concentration of 10 wt%. A polymer electrolyte membrane having a thickness of about 30 μm was produced from the obtained solution by the method of Example 1 using alumina-deposited PET (thickness: 100 μm) having a width of 300 mm and a length of 1000 m as a supporting substrate. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.

（ｒ＝1.6、ｓ＝0.0、繰り返し単位の添え字数字は繰り返し単位のモル分率を示す。）

(R = 1.6, s = 0.0, the subscript number of the repeating unit indicates the mole fraction of the repeating unit.)

Example 4
A sulfonic acid group-containing block copolymer (IEC = 1.8 meq / g, Mn = 60000, Mw) as shown in the following figure, synthesized with reference to the method described in JP-A-2005-206807 ([0059]) = 420,000 [mobile phase 1]) was synthesized (referred to as BCP-3) and dissolved in NMP to prepare a solution having a concentration of 13.5 wt%. A polymer electrolyte membrane having a film thickness of about 30 μm was produced from the obtained solution by the method of film formation condition 1 using alumina-deposited PET (film thickness: 100 μm) having a width of 300 mm and a length of 1000 m as a supporting substrate. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.

（繰り返し単位の添え字数字は繰り返し単位のモル分率を示す。）

(The subscript number of the repeating unit indicates the mole fraction of the repeating unit.)

Comparative Example 1
BCP-1 was dissolved in DMSO to prepare a solution having a concentration of 10 wt%. A polymer electrolyte membrane having a film thickness of about 30 μm was formed by the method of film formation condition 1 using a polyimide film (manufactured by DuPont Teijin Co., Ltd., trade name Kapton) having a width of 300 mm and a length of 30 m as a supporting substrate. Produced. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.

Comparative Example 2
A mixture of BCP-1 and a phosphonic acid group-containing polymer (AD-1) (weight ratio 90:10) was dissolved in DMSO to prepare a solution having a concentration of 10 wt%. Using the obtained solution as a supporting substrate, a polyethylene terephthalate (PET) film having a width of 300 mm and a length of 500 m (manufactured by Toyobo Co., Ltd., E5000 grade), a polymer having a film thickness of about 30 μm by the method of Film Formation Example An electrolyte membrane was produced. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.

Comparative Example 3
BCP-3 was dissolved in NMP to prepare a solution having a concentration of 13.5 wt%. Using the obtained solution as a supporting substrate, a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade) having a width of 300 mm and a length of 500 m, a polymer electrolyte having a film thickness of about 30 μm by the method of film forming condition 1 A membrane was prepared. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.

Comparative Example 4
BCP-1 was dissolved in DMSO to prepare a solution having a concentration of 10 wt%. Using the obtained solution as a supporting base material, a PET film (Toyobo Co., Ltd., E5000 grade) having a width of 300 mm and a length of 30 m is used to produce a polymer electrolyte membrane having a film thickness of about 10 μm by the method of film forming condition 1. did. As a result of TEM observation, it was found that the structure had a microphase separation structure, and the hydrophilic phase and the hydrophobic phase both formed a continuous phase.
Table 1 shows the polymer electrolyte compositions used in Examples 1 to 4 and Comparative Examples 1 to 4 and the types of supporting base materials at the time of film formation.

実施例１〜４、比較例１〜４の膜−電極間の接合試験について、下表に記す。

About the joining test between Examples 1-4 and Comparative Examples 1-4 and the membrane-electrode, it describes in the following table | surface.

Claims (37)

An ion conductive polymer electrolyte membrane in which the difference between the contact angle with respect to water on one surface of the polymer electrolyte membrane and the contact angle with water on the other surface is 30 ° or less is any surface of the polymer electrolyte membrane. Is a method of manufacturing a laminate laminated on the support base material in a state of being bonded to the support base material,
The following steps:
Includes an ion conductive polymer having an aromatic group in the main chain and / or side chain and having an ion exchange group directly bonded to the aromatic group or indirectly bonded through another atom or atomic group Preparing a polymer electrolyte solution in which the polymer electrolyte is dissolved in a solvent; and
A step of casting and applying the polymer electrolyte solution onto a supporting substrate, and laminating a polymer electrolyte membrane on the supporting substrate;
The manufacturing method of the laminated body characterized by including.   The method for producing a laminate according to claim 1, wherein a surface of the support substrate to be cast-coated is formed of a metal or a metal oxide.   The method for producing a laminate according to claim 1 or 2, wherein the support substrate is a continuous support substrate and is a film containing a metal or a metal oxide on the surface.   The ion conductive polymer has an aromatic ring in the main chain and an ion exchange group bonded directly to the aromatic ring or indirectly through another atom or atomic group. The manufacturing method of the laminated body in any one of Claims 1-3.   The method for producing a laminate according to claim 4, wherein the ion conductive polymer has a side chain.   The ion conductive polymer may have an aromatic ring in the main chain, and may further have a side chain having an aromatic ring, and at least one of the aromatic ring of the main chain or the aromatic ring of the side chain is It has an ion exchange group couple | bonded directly with this aromatic ring, The manufacturing method of the laminated body in any one of Claims 1-3 characterized by the above-mentioned.   The said ion exchange group is a sulfonic acid group, The manufacturing method of the laminated body in any one of Claims 4-6 characterized by the above-mentioned. The ion conductive polymer has the following general formulas (1a) to (4a):

(In the formula, Ar ^{1 to} Ar ⁹ each independently represent a divalent aromatic group having an aromatic ring in the main chain and further having a side chain having an aromatic ring. At least one of the aromatic ring of the chain or the aromatic ring of the side chain has an ion exchange group directly bonded to the aromatic ring.
Z and Z ′ each independently represent one of CO and SO ₂ , and X, X ′ and X ″ each independently represent one of O and S. Y represents a direct bond or the following general formula (10) And p represents 0, 1 or 2, and q and r each independently represent 1, 2 or 3.
One or more repeating units having an ion exchange group selected from:
The following general formulas (1b) to (4b)

(In the formula, Ar ^{11 to} Ar ¹⁹ each independently represent a divalent aromatic group optionally having a substituent as a side chain. Z and Z ′ are each independently CO or SO ₂ . X, X ′, and X ″ each independently represent O or S. Y represents a direct bond or a group represented by the following general formula (10). P ′ is 0, 1 or 2 and q ′ and r ′ each independently represent 1, 2 or 3.)
It has 1 or more types of repeating units which do not have substantially the ion exchange group chosen from these, The manufacturing method of the laminated body in any one of Claims 1-7 characterized by the above-mentioned.

(In the formula, R ¹ and R ² are independently of each other a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted substituent having 1 to 10 carbon atoms. An alkoxy group, an optionally substituted aryl group having 6 to 18 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted carbon Represents an acyl group of 2 to 20, and R ¹ and R ² may be linked to form a ring.)   The ion conductive polymer is a copolymer having at least one polymer segment (A) having an ion exchange group and at least one polymer segment (B) having substantially no ion exchange group. Item 9. A method for producing a laminate according to any one of Items 1 to 8.   The ion conductive polymer is a block copolymer comprising a block (A) having an ion exchange group and a block (B) having substantially no ion exchange group. The manufacturing method of the laminated body in any one of -9.   The method for producing a laminate according to any one of claims 1 to 10, wherein a polymer electrolyte membrane having a structure in which microphase separation into at least two or more phases is obtained.   The ion conductive polymer is a block copolymer comprising a block (A) having an ion exchange group and a block (B) having substantially no ion exchange group, and has an ion exchange group. A polymer electrolyte membrane having a microphase separation structure including a phase having a high density of the block (A) and a phase having a high density of the block (B) substantially not having an ion exchange group is obtained. The manufacturing method of the laminated body in any one of Claims 1-11 to do. The ion-conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and a block having an ion exchange group (A ) Is represented by the following general formula (4a ′)

(In the formula, m represents an integer of 5 or more, Ar ⁹ represents a divalent aromatic group, wherein the divalent aromatic group has a fluorine atom and optionally has 1 carbon atom. Or an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, or a substituent. The aryloxy group having 6 to 18 carbon atoms or the optionally substituted acyl group having 2 to 20 carbon atoms may be substituted, Ar ⁹ may be directly or on the side of the aromatic ring constituting the main chain. It has an ion exchange group through the chain.)
And having a repeating structure represented by:
The block (B) having substantially no ion exchange group is represented by the following general formulas (1b ′), (2b ′), (3b ′)

(In the formula, n represents an integer of 5 or more. Ar ^{11 to} Ar ¹⁸ each independently represent a divalent aromatic group, and these divalent aromatic groups are alkyls having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or an acyl group having 2 to 20 carbon atoms. The same as those in the general formulas (1b) to (3b).
It has 1 or more types chosen from the repeating structure represented by these. The manufacturing method of the laminated body in any one of Claims 1-12 characterized by the above-mentioned.   The ion conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and a block having an ion exchange group In (A), the ion exchange group is directly couple | bonded with the main chain aromatic ring, The manufacturing method of the laminated body in any one of Claims 1-13 characterized by the above-mentioned.   The ion conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and a block having an ion exchange group The block (B) substantially free of (A) and an ion-exchange group is substantially free of a substituent containing a halogen atom. The manufacturing method of the laminated body.   A method for producing a polymer electrolyte membrane, comprising a step of removing the support substrate from the laminate obtained by the production method according to any one of claims 1 to 15.   The method for producing a polymer electrolyte membrane according to claim 16, wherein the method does not include a step of performing a surface treatment on both sides of the surface of the polymer electrolyte membrane after removing the support substrate.   The laminated body obtained by the manufacturing method in any one of the said Claims 1-15.   A polymer electrolyte membrane obtained by the production method according to claim 16 or 17.   A polymer electrolyte membrane comprising at least one ion conductive polymer, wherein at least one surface of the polymer electrolyte membrane is not subjected to surface treatment, and one of the polymer electrolyte membranes An ion conductive polymer electrolyte membrane characterized in that a difference between a contact angle of one surface with water and a contact angle with water on the other surface is 30 ° or less.   21. The ion conductive polymer electrolyte membrane according to claim 20, wherein both surfaces of the polymer electrolyte membrane are not surface-treated.   The polymer electrolyte membrane according to claim 20 or 21, wherein a contact angle with respect to water on either one surface or the other surface of the membrane is 10 ° or more and 60 ° or less.   The ion conductive polymer has an aromatic ring in the main chain and an ion exchange group bonded directly to the aromatic ring or indirectly through another atom or atomic group. The polymer electrolyte membrane according to any one of claims 20 to 22.   The polymer electrolyte membrane according to claim 23, wherein the ion conductive polymer has a side chain.   The ion conductive polymer may have an aromatic ring in the main chain, and may further have a side chain having an aromatic ring, and at least one of the main ring aromatic ring or the side chain aromatic ring is The polymer electrolyte membrane according to any one of claims 20 to 22, wherein the polymer electrolyte membrane has an ion exchange group directly bonded to an aromatic ring.   26. The polymer electrolyte membrane according to claim 23, wherein the ion exchange group is a sulfonic acid group. The ion conductive polymer is
The following general formulas (1a) to (4a)

(In the formula, Ar ^{1 to} Ar ⁹ each independently represent a divalent aromatic group having an aromatic ring in the main chain and further having a side chain having an aromatic ring. At least one of the aromatic ring of the chain or the aromatic ring of the side chain has an ion exchange group directly bonded to the aromatic ring.
Z and Z ′ each independently represent one of CO and SO ₂ , and X, X ′ and X ″ each independently represent one of O and S. Y represents a direct bond or the following general formula (10) And p represents 0, 1 or 2, and q and r each independently represent 1, 2 or 3.
One or more repeating units having an ion exchange group selected from:
The following general formulas (1b) to (4b)

(In the formula, Ar ^{11 to} Ar ¹⁹ each independently represents a divalent aromatic group optionally having a substituent as a side chain. Z and Z ′ are each independently CO or SO ₂ . X, X ′, and X ″ each independently represent O or S. Y represents a direct bond or a group represented by the following general formula (10). P ′ is 0, 1 or 2 and q ′ and r ′ each independently represent 1, 2 or 3.)
27. The polymer electrolyte membrane according to any one of claims 20 to 26, comprising one or more repeating units substantially free of ion exchange groups selected from the group consisting of:

(In the formula, R ¹ and R ² are independently of each other a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted substituent having 1 to 10 carbon atoms. An alkoxy group, an optionally substituted aryl group having 6 to 18 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted carbon Represents an acyl group of 2 to 20, and R ¹ and R ² may be linked to form a ring.)   The ion conductive polymer is a copolymer comprising a polymer segment (A) having an ion exchange group and a polymer segment (B) having substantially no ion exchange group. The polymer electrolyte membrane according to any one of 20 to 27.   21. The block copolymer, wherein the ion conductive polymer is composed of a block (A) having an ion exchange group and a block (B) having substantially no ion exchange group. The polymer electrolyte membrane according to any one of -28.   30. The polymer electrolyte membrane according to any one of claims 20 to 29, wherein the membrane has a microphase-separated structure into at least two or more phases.   The ion conductive polymer is a block copolymer comprising a block (A) having an ion exchange group and a block (B) having substantially no ion exchange group, and the membrane is an ion exchange 21. A microphase-separated structure including a phase having a high density of the block (A) having a group and a phase having a high density of the block (B) having substantially no ion-exchange group. 30. The polymer electrolyte membrane according to any one of 30. The ion-conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and a block having an ion exchange group (A ) Is the following general formula (4a ′).

(In the formula, m represents an integer of 5 or more, Ar ⁹ represents a divalent aromatic group, wherein the divalent aromatic group has a fluorine atom and optionally has 1 carbon atom. Or an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 18 carbon atoms which may have a substituent, or a substituent. The aryloxy group having 6 to 18 carbon atoms or the optionally substituted acyl group having 2 to 20 carbon atoms may be substituted, Ar ⁹ may be directly or on the side of the aromatic ring constituting the main chain. It has an ion exchange group through the chain.)
And having a repeating structure represented by:
The block (B) having substantially no ion exchange group is represented by the following general formulas (1b ′), (2b ′), (3b ′)

(In the formula, n represents an integer of 5 or more. Ar ^{11 to} Ar ¹⁸ each independently represent a divalent aromatic group, and these divalent aromatic groups are alkyls having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or an acyl group having 2 to 20 carbon atoms. The same as those in the general formulas (1b) to (3b).
32. The polymer electrolyte membrane according to any one of claims 20 to 31, wherein the polymer electrolyte membrane has one or more selected from a repeating structure represented by the formula:   The ion conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and a block having an ion exchange group The polymer electrolyte membrane according to any one of claims 20 to 32, wherein in (A), the ion exchange group is directly bonded to the main chain aromatic ring.   The ion conductive polymer has at least one block (A) having an ion exchange group and one or more blocks (B) having substantially no ion exchange group, and a block having an ion exchange group Both (A) and the block (B) substantially free of ion-exchange groups are substantially free of a substituent containing a halogen atom. Polymer electrolyte membrane.   A laminate in which the ion conductive polymer electrolyte membrane according to any one of claims 20 to 34 is laminated on the support substrate.   36. The laminate according to claim 35, wherein a surface of the support base material bonded to the polymer electrolyte membrane is formed of a metal or a metal oxide.   37. The laminate according to claim 35 or 36, wherein the support substrate is a continuous support substrate and a film containing a metal or a metal oxide on the surface.