JP2002011787A - Manufacturing method of polyarylene base film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film excellent in a mechanical strength, an elasticity and dimensional stability upon heating from the composition of organic solvent of sulfonated polyarylene by a casting method. SOLUTION: The sulfonated polyarylene (A) and the composition (B) containing the organic solvent are applied on a substrate while the substrate is oriented uniaxially or biaxially, then, the substrate is heated under the oriented condition of the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyarylene film, and more particularly, to an electrolyte for a primary battery, an electrolyte for a secondary battery, a polymer solid electrolyte for a fuel cell, a display element, various sensors, The present invention relates to a method for producing a polyarylene-based film useful for a proton conductive membrane that can be used for a signal transmission medium, a solid capacitor, an ion exchange membrane, and the like.

[0002]

2. Description of the Related Art Electrolytes are often used as (water) solutions. However, in recent years, there has been an increasing tendency to replace this with a solid system. The first reason is, for example, the easiness of processing when applied to the above-mentioned electric and electronic materials, and the second reason is the shift to lighter, thinner, smaller and higher power. Conventionally, both proton conductive materials and inorganic materials are known. Examples of the inorganic substance include uranyl phosphate, which is a hydrated compound. However, these inorganic compounds have insufficient contact at the interface, and there are many problems in forming a conductive layer on a substrate or an electrode.

On the other hand, examples of organic compounds include polymers belonging to the so-called cation exchange resin, for example, sulfonated products of vinyl polymers such as polystyrene sulfonic acid,
Sulfonate and phosphate groups were introduced into perfluoroalkylsulfonic acid polymers and perfluoroalkylcarboxylic acid polymers represented by Nafion (manufactured by DuPont), and heat-resistant polymers such as polybenzimidazole and polyetheretherketone. Polymer [Polymer P
reprints, Japan, Vol. 42, no.
7, p. 2490-2492 (1993), Polym
er Preprints, Japan, Vol. 4
3, No. 3, p. 735-736 (1994), Po
lymer Preprints, Japan, Vo
l. 42, no. 3, p730 (1993)].

[0004] These organic polymers are usually used in the form of a film, but a conductive film can be bonded to an electrode by utilizing the fact that they are soluble in a solvent or thermoplastic. However, many of these organic polymers not only have insufficient proton conductivity, but also have poor durability, low proton conductivity at high temperatures (100 ° C. or higher), and are highly dependent on humidity conditions. In addition, there is a problem that the adhesion to the electrode is not sufficiently satisfactory, or the strength is reduced and the shape is collapsed due to excessive swelling during operation due to the structure of the water-containing polymer. Therefore, these organic polymers have various problems when applied to the above electric / electronic materials.

Further, US Pat. No. 5,403,675 proposes a solid polymer electrolyte composed of a sulfonated rigid polyphenylene (ie, a sulfonate having a polyarylene structure as a main component). This polymer has, as a main component, a polymer having a phenylene chain (structure described in column 9 in the same specification) obtained by polymerizing an aromatic compound, and reacts it with a sulfonating agent to introduce a sulfonic acid group. . However, an increase in the amount of sulfonic acid groups introduced leads to an increase in the proton conductivity, but the mechanical properties of the resulting sulfonated polymer are significantly impaired. Therefore, it is necessary to maintain an excellent mechanical property and to adjust an appropriate sulfonation concentration for exhibiting proton conductivity. In fact, in this polymer, sulfonation proceeds too much, and it is difficult to control an appropriate amount of sulfonic acid group introduced.

[0006] When the above-mentioned sulfonated polyarylene is used for an electric or electronic material such as a conductive film, it is usually formed into a film. For example, to form a conductive film using a sulfonated product of polyarylene, this polymer is usually dissolved in a solvent and formed into a film by a casting method. However, even if the sulfonated polyarylene is simply formed into a film by the casting method, the mechanical strength and elastic modulus of the film may be low due to the unstretched state. Is also possible). Further, a film of a sulfonated polyarylene film by a casting method has a large shrinkage ratio upon heating and is inferior in dimensional stability.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a film from an organic solvent-based composition of a sulfonated product of polyarylene by a casting method. An object is to obtain a polyarylene film having excellent stability.

[0008]

According to the present invention, a composition containing (A) a sulfonated product of polyarylene and (B) an organic solvent is applied to a substrate, and the substrate is stretched uniaxially or biaxially. And a method for producing a polyarylene film characterized by heating in a stretched state. Here, as the polyarylene constituting the component (A), a polyarylene composed of a structural unit represented by the following general formula (1) is preferable.

[0009]

Embedded image

[In the general formula (1), X is -CQQ'- (where Q and Q 'are the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) And R ^{1 to} R ³⁶ are the same or different and represent a hydrogen atom, a halogen atom or a monovalent organic group, and Y represents —O—, —CO—, -COO-, -CONH-
And -SO ₂ - is a group selected from the group of radicals, p is 0
-100 mol%, q is 0-100 mol%, r is 0-10
0 mol%, s is 0 to 100 mol% (provided that p + q + r
+ S = 100 mol%), and t is 0 or 1. The concentration (solid content) of the sulfonated polyarylene (A) in the composition is preferably from 3 to 40% by weight.
Further, the stretching ratio is preferably 1.05 to 1.75 times. Further, at the time of stretching, it is preferable to irradiate an electron beam while the substrate is stretched, because the dimensional stability is further improved.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in forming a film of a polyarylene sulfonate by a casting method, a polyarylene sulfonate applied on a substrate is stretched uniaxially or biaxially together with the substrate. Since the film is heated in the stretched state, the film itself is not damaged by stretching, and
The resulting film has improved mechanical strength and elastic modulus and excellent dimensional stability during heating.

(A) Sulfonated Polyarylene (A) The sulfonated polyarylene is preferably a sulfonated polyarylene represented by the above general formula (1) (hereinafter also referred to as “polymer (1)”). It is a sulfonate. Here, the polymer (1) is represented by the above general formula (1)
Having a repeating structural unit represented by Hereinafter, in the general formula (1), the structural unit enclosed by p is “structural unit p”, the structural unit enclosed by q is “structural unit q”, and the structural unit enclosed by r is “structural unit r”. , S is also referred to as a “structural unit s”.

In the above general formula (1), X is -CQQ'-
(Where Q and Q ′ are the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) and a group selected from the group consisting of a fluorenylene group. Here, of Q and Q ', the halogenated alkyl group includes a trifluoromethyl group and a pentafluoroethylene group, and the aryl group includes a phenyl group, a biphenyl group, a tolyl group, a pentafluorophenyl group and the like. No. In the above general formula (1), R ^{1 to} R ³⁶ are the same or different and each represent a hydrogen atom, an alkyl group, a halogen atom, a monovalent organic group (for example, a polymerization reaction for producing a halogenated alkyl group or polyarylene). (A monovalent organic group containing a non-functional group). In R ^{1 to} R ³⁶ , the alkyl group is a methyl group,
Examples include an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group. Examples of the halogen atom include fluorine. Examples of the halogenated alkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Furthermore, examples of the monovalent organic group containing a functional group that does not inhibit the polymerization reaction for producing polyarylene include aryloxy, aryloxo, arylthiocarbonyl, aryloxycarbonyl, arylthio, and arylsulfone. These also include monovalent organic groups containing two or more functional groups, for example, aryloxyaryloxo, aryloxyarylsulfone, arylthioaryloxo, and the like. Further, these may be used in place of the aryl group, instead of the alkyl group, the alkylaryl group, and the arylalkyl group. Further, in the general formula (1), Y represents -O-, -CO-,-.
At least one selected from the group consisting of COO—, —CONH—, and —SO ₂ — groups, p is 0 to 100 mol%, q is 0 to 100 mol%, r is 0 to 100 mol%, s
Is 0 to 100 mol% (however, p + q + r + s = 100
Mol%), t is 0 or 1. ]

In the formula (1), the monomers constituting the structural unit p (hereinafter also referred to as “monomer p”) include
2,2-bis (4-methylsulfonyloxyphenyl)
Hexafluoropropane, bis (4-methylsulfonyloxyphenyl) methane, bis (4-methylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4
-Methylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy- 3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxyphenyl) propane, 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) propane, 2,2 -Bis (4-methylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-
Bis (4-methylsulfonyloxy-3-fluorophenyl) propane, 2,2-bis (4-methylsulfonyloxy-3,5-difluorophenyl) propane, 2,
2-bis (4-trifluoromethylsulfonyloxyphenyl) propane, 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy) Phenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) propane, 2,2-
Bis (4-phenylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane,
2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, 2,2-bis (p
-Tolylsulfonyloxyphenyl) propane, 2,2
-Bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, bis (p-tolylsulfonyloxy-3-fluoro) Phenyl) propane, bis (p-tolylsulfonyloxy)
3,5-difluorophenyl) propane, 9,9-bis (4-methylsulfonyloxyphenyl) fluorene,
9,9-bis (4-methylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4- Methylsulfonyloxy-3-
Propenylphenyl) fluorene, 9,9-bis (4-
Methylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-methylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4- Methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-
Difluorophenyl) diphenylmethane, 9,9-bis (4-methylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4 -Methylsulfonyloxyphenyl) methane, bis (4-methylsulfonyloxy-3-methylphenyl) methane, bis (4-methylsulfonyloxy-3,
5-dimethylphenyl) methane, bis (4-methylsulfonyloxy-3-propenylphenyl) methane, bis (4-methylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-methylsulfonyloxyphenyl) phenyl Methane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane,
2,2-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) hexafluoropropane,
2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-trifluoromethylsulfonyloxyphenyl) fluorene, 9,9-bis (4-
Trifluoromethylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfone) Phonyloxy-3-propenylphenyl) fluorene,
9,9-bis (4-trifluoromethylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy) -3,5-dimethylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) diphenylmethane,
Bis (4-trifluoromethylsulfonyloxy-3-
(Fluorophenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) fluorene, 9,9 -Bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) ) Methane, bis (4-trifluoromethylsulfonyloxy-3,5-)
Dimethylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4
-Trifluoromethylsulfonyloxyphenyl),
2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane, bis (4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxyphenyl) diphenylmethane, 2,2-
Bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfur Phonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-phenylsulfonyloxyphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-
3,5-dimethylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-phenylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5)
-Difluorophenyl) diphenylmethane, 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3,5-difluorophenyl) fluorene, bis ( 4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxy-3-methylphenyl) methane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-
Phenylsulfonyloxy-3-propenylphenyl)
Methane, bis (4-phenylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-phenylsulfonyloxyphenyl) phenylmethane,
2,2-bis (p-tolylsulfonyloxyphenyl)
Hexafluoropropane, bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p
-Tolylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy- 3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (p-tolylsulfonyloxyphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-methylphenyl) fluorene, 9,9 -Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-propenylphenyl) fluorene,
9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene, bis (p-tolylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-dimethyl) Phenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-difluoro) Phenyl) diphenylmethane, 9,9-bis (p-tolylsulfonyloxy)
3-fluorophenyl) fluorene, 9,9-bis (p
-Tolylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (p-tolylsulfonyloxyphenyl) methane, bis (p-tolylsulfonyloxy-)
3-methylphenyl) methane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane, bis (p-tolylsulfonyloxy-3-propenylphenyl) methane, bis (p-tolylsulfonyloxyphenyl) ) Trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane and the like. The monomers p may be used alone or in combination of two or more.

In the formula (1), the monomers constituting the structural unit q (hereinafter also referred to as “monomer q”) include, for example, 4,4′-dimethylsulfonyloxybiphenyl, 4,4′-dimethylsulfone Phoniloxy-3,
3'-dipropenylbiphenyl, 4,4'-dibromobiphenyl, 4,4'-diiodobiphenyl, 4,4'-
Dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,4'-dimethylsulfonyloxy-3,3 '
-Difluorobiphenyl, 4,4'-dimethylsulfonyloxy-3,3 ', 5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl,
4,4-methylsulfonyloxyoctafluorobiphenyl, 3,3'-diallyl-4,4'-bis (4-fluorobenzenesulfonyloxy) biphenyl, 4,4 '
-Dichloro-2,2'-trifluoromethylbiphenyl, 4,4'-dibromo-2,2'-trifluoromethylbiphenyl, 4,4'-diiodo-2,2'-trifluoromethylbiphenyl, bis (4 -Chlorophenyl)
Sulfone, 4,4'-dichlorobenzophenone, 2,
4-dichlorobenzophenone and the like can be mentioned. The monomers q can be used alone or in combination of two or more.

Further, in the formula (1), the monomers constituting the structural unit r (hereinafter also referred to as “monomer r”) include, for example, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-diiodobenzene, Dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5
-Dibromotoluene, 2,5-diiodotoluene, 2,
5-dimethylsulfonyloxybenzene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene, 2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride, 2,5 -Dibromobenzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3,5,6-tetrafluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluoro Benzene, 1,4-diiodo-2,3
5,6-tetrafluorobenzene, 2,5-dichlorobenzoic acid, 2,5-dibromobenzoic acid, methyl 2,5-dichlorobenzoate, methyl 2,5-dibromobenzoate,
Examples include t-butyl 2,5-dichlorobenzoate, t-butyl 2,5-dibromobenzoate, and 3,6-dichlorophthalic anhydride, and preferably p-dichlorobenzene and p-dimethyl. Sulfonyloxybenzene,
2,5-dichlorotoluene, 2,5-dichlorobenzotrifluoride, 2,5-dichlorobenzophenone,
2,5-dichlorophenoxybenzene and the like.

The above-mentioned monomer r includes, for example,
m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene, 2,4-diiodotoluene, 3,5- Dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5
-Dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxy Phenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2, Methyl 4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, 3,
Methyl 5-dibromobenzoate, methyl 2,4-dibromobenzoate, t-butyl 2,4-dichlorobenzoate,
Examples thereof include t-butyl 3,5-dichlorobenzoate, t-butyl 2,4-dibromobenzoate, and t-butyl 3,5-dibromobenzoate.
Dichlorobenzene, 2,4-dichlorotoluene, 3,5
-Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dichlorobenzophenone, 2,4-dichlorophenoxybenzene and the like.

Further, in the formula (1), as a monomer constituting the structural unit s (hereinafter also referred to as “monomer s”), for example, 4,4′-bis (4-chlorobenzoyl) diphenyl ether, 4,4 ′ -Bis (3-chlorobenzoyl) diphenyl ether, 4,4'-bis (4
-Bromobenzoyl) diphenyl ether, 4,4'-
Bis (3-bromobenzoyl) diphenyl ether,
4,4'-bis (4-iodobenzoyl) diphenyl ether, 4,4'-bis (3-iodobenzoyl) diphenyl ether, 4,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether,
4,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-methylsulfonyloxyphenyl) ) Diphenyl ether and the like.

Examples of the monomer s include, for example, 4'-bis (4-chlorobenzoylamino) diphenyl ether, 3,4'-bis (4-chlorobenzoylami) diphenyl ether and 4,4'-bis (3-chloro Benzoylamino) diphenyl ether, 3,4'-bis (3-chlorobenzoyl) diphenyl ether, 4,
4'-bis (4-bromobenzoylamino) diphenyl ether, 3,4'-bis (4-bromobenzoylamino) diphenyl ether, 4,4'-bis (3-bromobenzoylamino) diphenyl ether, 3,4'-bis ( 3-bromobenzoylamino) diphenyl ether, 4,4'-bis (4-iodobenzoylamino) diphenyl ether, 3,4'-bis (4-iodobenzoylamino) diphenyl ether, 4,4'-bis (3
-Iodobenzoylamino) diphenyl ether, 3,
4'-bis (3-iodobenzoylamino) diphenyl ether, 4,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 3,
4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-
Trifluoromethylsulfonyloxyphenyl) diphenyl ether, 3,4′-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether,
4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 4,
Examples thereof include 4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether and 3,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether.

Further, as the monomer s, for example, 4,4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 4,4'-bis (3-chlorophenylsulfonyl) Diphenyl ether, 3,
4'-bis (3-chlorophenylsulfonyl) diphenyl ether, 4,4'-bis (4-bromophenylsulfonyl) diphenyl ether, 4'-bis (4-bromophenylsulfonyl) diphenyl ether, 4,4'-
Bis (3-bromophenylsulfonyl) diphenyl ether, 3,4'-bis (3-bromophenylsulfonyl) diphenyl ether, 4,4'-bis (4-iodophenylsulfonyl) diphenyl ether, 4'-bis (4-iodophenylsulfonyl) ) Diphenyl ether, 4,4'-bis (3-iodophenylsulfonyl)
Diphenyl ether, 3,4'-bis (3-iodophenylsulfonyl) diphenyl ether, 4,4'-bis (4-trifluoromethylsulfonyloxyphenisulfonyl) diphenyl ether, 4'-bis (4-trifluoromethylsulfonyloxy) Phenylsulfonyl) diphenyl ether, 4,4'-bis (3-trifluoromethylsulfonyloxyphenylisulfonyl) diphenyl ether, 3,4'-bis (3-trifluoromethylsulfonyloxyphenylsulfonyl) diphenyl ether, 4,4'- Bis (4-methylsulfonyloxyphenisulfonyl) diphenyl ether, 4'-bis (4-
Methylsulfonyloxyphenylsulfonyl) diphenyl ether, 4,4'-bis (3-methylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4 '
-Bis (3-methylsulfonyloxyphenylsulfonyl) diphenyl ether and the like.

Further, examples of the monomer s include 4,4'-bis (4-chlorophenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-chlorophenyl) diphenyl ether dicarboxylate,
4,4'-bis (3-chlorophenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-chlorophenyl) diphenyl ether dicarboxylate,
4,4'-bis (4-bromophenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-bromophenyl) diphenyl ether dicarboxylate,
4,4'-bis (3-bromophenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-bromophenyl) diphenyl ether dicarboxylate,
4'-bis (4-iodophenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-iodophenyl) diphenyl ether dicarboxylate, 4,
4'-bis (3-iodophenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-iodophenyl) diphenyl ether dicarboxylate, 4,
4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate,
3,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 4,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate,
3,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 4,4 '
-Bis (3-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (3
-Methylsulfonyloxyphenyl) diphenyl ether dicarboxylate.

Further, as the monomer s, for example, 4,4'-bis [(4-chlorophenyl) -1,1,1
1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-chlorophenyl)-
1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, , 4'-bis [(3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) -1,1,1,1 3,3,3-
Hexafluoropropyl] diphenyl ether, 3,
4'-bis [(4-bromophenyl) -1,1,1,1
3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) -1,
1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4′-bis [(3-bromophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4, 4'-bis [(4-iodophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-iodophenyl) -1,1,1,1 3,3,3-
Hexafluoropropyl] diphenyl ether, 4'-
Bis [(3-iodophenyl) -1,1,1,3,3
3-hexafluoropropyl] diphenyl ether,
3,4'-bis [(3-iodophenyl) -1,1,1
1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3
-Hexafluoropropyl] diphenyl ether, 3,
4'-bis [(4-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4'-bis [(3-
Trifluoromethylsulfonyloxyphenyl) -1,
1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4′-bis [(3-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3
3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'- Screw [(4-
Methylsulfonyloxyphenyl) -1,1,1,3,
3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-methylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'- Screw [(3-
Methylsulfonyloxyphenyl) -1,1,1,3,
3,3-hexafluoropropyl] diphenyl ether.

Further, examples of the monomer s include 4,4'-bis [(4-chlorophenyl) tetrafluoroethyl] diphenyl ether and 4,4'-bis [(3
-Chlorophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-chlorophenyl) hexafluoropropyl] diphenyl ether, 4,4 '
-Bis [(3-chlorophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-chlorophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-chlorophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4-chlorophenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3-chlorophenyl) decafluoropentyl] diphenyl ether,
4'-bis [(4-bromophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) hexa Fluoropropyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) hexafluoropropyl]
Diphenyl ether, 4,4'-bis [(4-bromophenyl) octafluorobutyl] diphenyl ether,
4,4'-bis [(3-bromophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4
-Bromophenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) decafluoropentyl] diphenyl ether, 4,4'-
Bis [(4-iodophenyl) tetrafluoroethyl]
Diphenyl ether, 4,4'-bis [(3-iodophenyl) tetrafluoroethyl] diphenyl ether,
4,4'-bis [(4-iodophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-iodophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) ) Octafluorobutyl] diphenyl ether,
4,4'-bis [(3-iodophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4
-Iodophenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3-iodophenyl) decafluoropentyl] diphenyl ether, 4,4'-
Bis [(4-trifluoromethylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether,
4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4'-bis [(3-trifluoromethylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-
Trifluoromethylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4′-bis [(3-trifluoromethylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether,
4'-bis [(4-trifluoromethylsulfonyloxyphenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxy) decafluoropentyl] diphenyl ether, 4,4'- Bis [(4-methylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether,
4,4'-bis [(3-methylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether;
4'-bis [(4-methylsulfonyloxyphenyl)
Hexafluoropropyl] diphenyl ether, 4,
4'-bis [(3-methylsulfonyloxyphenyl)
Hexafluoropropyl] diphenyl ether, 4,
4'-bis [(4-methylsulfonyloxyphenyl)
Octafluorobutyl] diphenyl ether, 4,4 '
-Bis [(3-methylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3- Methylsulfonyloxy) decafluoropentyl] diphenyl ether and the like.

In addition to the above-mentioned monomers p to s, for example, o-dichlorobenzene, o-dibromobenzene, o-dichlorobenzene,
-Diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3 2,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxybenzene,
3,4-dichlorobenzotrifluoride, 3,4-dibromobenzotrifluoride, 3,4-diiodobenzotrifluoride, 1,2-dibromo-3,4,5
6-Tetrafluorobenzene, 4,5-dichlorophthalic anhydride and the like can be copolymerized.

The proportion of repeating structural units in the polyarylene is such that in the above formula (1), p is 0 to 100 mol%,
q is 0 to 100 mol%, r is 0 to 100 mol%, and s is 0
-100 mol%, preferably p is 50-100 mol%, q is 0-50 mol%, r is 50-100 mol%, s
Is 0 to 50 mol% (however, p + q + r + s = 100 mol%).

The catalyst used for producing the polyarylene used in the present invention is preferably a catalyst system containing a transition metal compound. As the catalyst system, a transition metal salt and a ligand or a ligand are used. Transition metal (salt),
In addition, a reducing agent may be used as an essential component, and a “salt” may be added to increase the polymerization rate.

Here, the transition metal salt includes nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium chloride;
Examples include palladium compounds such as palladium bromide and palladium iodide, iron compounds such as iron chloride, iron bromide and iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferred.

Examples of the ligand include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, and 1,3-bis (diphenylphosphino) propane. Phenylphosphine and 2,2'-bipyridine are preferred. The ligand is
One type may be used alone, or two or more types may be used in combination.

Further, as the transition metal (salt) to which a ligand has been previously coordinated, for example, nickel chloride 2 triphenylphosphine, nickel bromide 2 triphenylphosphine, nickel iodide 2 triphenylphosphine, nickel nitrate 2 -Triphenylphosphine, nickel chloride 2,2 'bipyridine, nickel bromide 2,2' bipyridine, nickel iodide 2,2 'bipyridine, nickel nitrate 2,2' bipyridine, bis (1,5-cyclooctadiene) nickel , Tetrakis (triphenylphosphine)
Nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like can be mentioned, and nickel chloride2triphenylphosphine and nickel chloride2,2'bipyridine are preferable.

Examples of the above-mentioned reducing agent that can be used in such a catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, and calcium, and zinc and manganese are preferred. These reducing agents can be used after being activated by contact with an acid or an organic acid.

The "salt" which can be used in such a catalyst system includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide and sodium sulfate; potassium fluoride;
Potassium compounds such as potassium chloride, potassium bromide, potassium iodide, and potassium sulfate; and ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate can be given. But sodium bromide,
Preferred are sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide.

The use ratio of each component in such a catalyst system is usually such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is 0 to 1 mol of the total amount of the monomers p to s. 0.0001 to 10 mol, preferably 0.01 to
0.5 mole. When the amount is less than 0.0001 mol, the polymerization reaction does not sufficiently proceed.
The molecular weight may decrease.

When a transition metal salt and a ligand are used in such a catalyst system, the use ratio of the ligand is usually 0.1 to 100 mol, preferably 1 to 100 mol, per mol of the transition metal salt. 10 to 10 mol. If the amount is less than 0.1 mol, the catalytic activity becomes insufficient.
There is a problem that the molecular weight decreases.

The proportion of the reducing agent used in the catalyst system is usually 0.1 to 1 mol of the total amount of the monomers p to s.
１００100 mol, preferably 1-10 mol. 0.1
If it is less than 100 moles, the polymerization does not proceed sufficiently, and if it exceeds 100 moles, the resulting polyarylene may be difficult to purify.

Further, when a “salt” is used in the catalyst system,
The use ratio is usually 0.001 to 100 mol, preferably 0.0 to 1 mol based on 1 mol of the total amount of the monomers p to s.
1 to 1 mol. If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, and if it exceeds 100 mol, it may be difficult to purify the resulting polyarylene.

Examples of the polymerization solvent that can be used in the present invention include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2.
-Pyrrolidone, γ-butyrolactone, γ-butyrolactam, etc., and tetrahydrofuran, N,
N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone are preferred. These polymerization solvents are preferably used after being sufficiently dried.

The concentration of the total amount of the monomers p to s in the polymerization solvent is usually 1 to 100% by weight, preferably 5 to 100% by weight.
４０40% by weight.

The polymerization temperature for polymerizing the polyarylene of the present invention is usually from 0 to 200 ° C., preferably from 50 to 200 ° C.
８０80 ° C. The polymerization time is usually 0.5 to 1
00 hours, preferably 1 to 40 hours. The polyarylene used in the present invention generally has a weight average molecular weight in terms of polystyrene of 1,000 to 1,000,000.
0.

The sulfonated polyarylene used in the present invention can be obtained by introducing a sulfonic acid group into the above-mentioned polyarylene having no sulfonic acid group by a conventional method using a sulfonating agent. As a method for introducing a sulfonic acid group, for example, the above polyarylene is sulfonated under known conditions using a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, sodium hydrogen sulfite, or the like. [Pol
ymer Preprints, Japan, Vol.
42, no. 3, p. 730 (1993); Polym
er Preprints, Japan, Vol. 4
2, No. 3, p. 736 (1994); Polyme
r Preprints, Japan, Vol. 42,
No. 7, p. 2490-2492 (1993)].

That is, as the reaction conditions for this sulfonation, the above-mentioned polyarylene is reacted with the above-mentioned sulfonating agent in the absence or presence of a solvent. Examples of the solvent include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, N, N
Aprotic polar solvents such as -dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide, and halogenated hydrocarbons such as tetrachloroethane, dichloroethane, chloroform and methylene chloride. Can be The reaction temperature is not particularly limited, but is generally -50 to 200C, preferably -10 to 100C. The reaction time is usually 0.5 to 1,000 hours, preferably 1 to 200 hours.

The amount of sulfonic acid groups in the sulfonated polyarylene obtained as described above is usually 0.0 to 1 unit of the units p to r constituting the polymer.
It is 5 to 2, preferably 0.3 to 1.5. 0.0
When the number is less than 5, the proton conductivity does not increase. On the other hand, when the number is more than 2, the hydrophilicity is improved and the polymer becomes a water-soluble polymer.

The polyarylene sulfonate obtained in this manner has a base polymer before sulfonation having a molecular weight of 1,0 in terms of polystyrene equivalent weight average molecular weight.
00 to 1,000,000, preferably 1,500 to 3
00,000. If it is less than 1,000, cracks occur in the formed film, and the coating properties are insufficient,
There is also a problem in strength properties. On the other hand, 1,000,000
If it exceeds 00, there are problems such as insufficient solubility, high solution viscosity and poor processability.

The sulfonated polyarylene used in the present invention may be used in combination with an inorganic acid such as sulfuric acid or phosphoric acid, an organic acid containing a carboxylic acid, or an appropriate amount of water, in addition to the above sulfonated product.

(B) Organic Solvent The (B) organic solvent used in the present invention includes, for example,
N-methyl-2-pyrrolidone, methanol, tetrahydrofuran, cyclohexanone, dimethylsulfoxide,
N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether , Diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, toluene, xylene, methyl amyl ketone, 4-hydroxide Carboxymethyl-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid methyl, 2-hydroxy -
Ethyl 2-methylpropionate, ethyl ethoxyacetate,
Ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate,
Examples thereof include ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, methyl lactate, ethyl lactate, chloroform, and methylene chloride. Preferably, N-methyl-2-pyrrolidone, methanol, N, N-dimethylformamide,
Ethyl carbitol and methyl carbitol.

Polyarylene Composition The composition used in the present invention contains the above (A) sulfonated product of polyarylene and (B) an organic solvent, but has a solid content concentration in the composition [that is, the component (A) Percentage)
Is 3 to 40% by weight, preferably 5 to 35% by weight in the composition.
% By weight. When the amount is less than 3% by weight, a coating film having a sufficient thickness cannot be obtained.

In addition, the composition used in the present invention includes the above (A) to
Although the component (B) is a main component, an additive can be added as needed. As this additive,
Examples include a leveling agent and a silane coupling agent.

Film Forming For producing a film having excellent proton conductivity (proton conducting membrane) using the composition of the present invention, for example, the following (A)
A method in which a sulfonated product of polyarylene is dissolved in an organic solvent (B) to form a polyarylene composition, and then a film is produced by a casting method of forming the film on a substrate by casting or the like.

The substrate used in the present invention includes polyethylene terephthalate (PET) film,
Examples thereof include a polybutylene terephthalate (PBT) film, a nylon 6 film, a nylon 6,6 film, and a polypropylene film, and a PET film is preferable. The thickness of the film serving as the substrate is usually 25 to 250 μm, preferably 50 to 200 μm.

After film formation by the above-mentioned casting method, 30
-100 ° C, preferably 10-180 at 50-80 ° C
Minutes, preferably 15 to 60 minutes (preliminary drying step). The solid content in the film after the preliminary drying step is preferably 50 to 90% by weight, and more preferably 60 to 90% by weight. In the preliminary drying step, by allowing the organic solvent (B) to remain in the film, the stretching can be smoothly performed in the stretching step described below.

Next, after the preliminary drying, the film on the substrate is placed in a uniaxial or biaxial direction by 1.05 to 1.75 together with the substrate.
Draw, preferably 1.1 to 1.5 times (stretching step). When the stretching ratio is less than 1.05 times, the stretching is not sufficient, so that the mechanical strength and dimensional stability of the obtained film are not sufficiently improved. On the other hand, when the stretching ratio exceeds 1.75 times, uniform orientation becomes difficult. In this way, by stretching the film together with the substrate, there is no damage to the film at the time of stretching, and the molecular chain of the sulfonated polyarylene is stretched in the stretching direction, thereby improving the elastic modulus and improving the mechanical strength. , Heat shrinkage in the stretching direction becomes difficult.

In this stretching step, a high stretch is achieved by setting the solid content concentration in the film to the above-mentioned range, that is, by stretching the film while keeping the organic solvent (B) in the film. The achievement of the ratio and the arrangement of the molecular chains of the component (A) are uniformly arranged in the stretching direction, and the damage due to the stretching of the film is eliminated.

In this stretching step, the heating temperature of the substrate (film) is preferably 70 to 150 ° C., more preferably 80 to 120 ° C. In the stretching process,
By heating the substrate (film), stretching can be performed smoothly with a high stretching ratio.

In this stretching step, irradiation with an electron beam while stretching the substrate is also a preferable means.

In the present invention, the method of irradiating the film of the polyarylene sulfonated product formed on the substrate with an electron beam is not particularly limited, but is preferably performed, for example, under the following conditions. Atmosphere: nitrogen, argon or vacuum (particularly more preferably under nitrogen) Temperature: 20 to 450 ° C. (more preferably the glass transition temperature of the irradiated polymer from room temperature) Electron dose: 5 to 200 Mrad (10 to 150 Mra)
d is more preferred. )

In a nitrogen, argon or vacuum atmosphere,
When electron beam irradiation is performed, the film is not oxidized, and sufficient heat resistance and durability can be obtained. The temperature is 20-4
If the temperature is 50 ° C., there is no particular limitation. However, if the temperature is higher than the glass transition temperature of the polymer to be irradiated, or several tens of degrees Celsius, curing can be performed more efficiently. Electron dose is 5-2
When it is in the range of 00 Mrad, the curing reaction can proceed without causing decomposition of the sulfonated product of polyarylene. If it is less than 5 Mrad, irradiation energy required for crosslinking cannot be obtained, while if it exceeds 200 Mrad, a part of the polymer is decomposed, which is not preferable.

Further, after the above stretching, the substrate having the film formed on the surface thereof is usually stretched in a stretched state.
To 200 ° C., preferably 80 to 150 ° C., preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours,
Heat (post-heating treatment). By the post-heating treatment, the film is heat-set in a stretched state, (A) the molecular chain of the sulfonated product of polyarylene is heat-set, the mechanical properties (strength, elastic modulus) of the film are improved, and the dimensions at the time of heating are increased. Stability is improved. The atmospheric pressure during the post-heating treatment is in a range from normal pressure to vacuum, and is preferably 500 mmHg to 500 mmHg.
0.1 mmHg, more preferably 300 mmHg or more
0.1 mmHg. By performing the post-heating treatment under reduced pressure, the organic solvent (B) can be completely volatilized at a lower temperature and in a shorter time.

The dry thickness of the film (proton conductive membrane) obtained from the composition of the present invention is usually 10 to 150 μm.
m, preferably 20 to 80 μm.

The film (proton conductive membrane) obtained from the composition of the present invention has improved strength properties (strength and elastic modulus) of the film and excellent dimensional stability upon heating (shrinkage is suppressed). ). Therefore, the film (proton conductive membrane) obtained by the present invention includes, for example, an electrolyte for a primary battery, an electrolyte for a secondary battery, a polymer solid electrolyte for a fuel cell, a display element, various sensors, a signal transmission medium, a solid capacitor, It can be used for a proton-conductive conductive membrane that can be used for an exchange membrane or the like.

[0059]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In addition, various measurement items in the examples were obtained as follows.

Weight average molecular weight The weight average molecular weight of the polymer before sulfonation was determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and the molecular weight in terms of polystyrene was determined.

Sulfonation equivalent The obtained polymer was washed until the washing water became neutral. Except for the remaining free acid, the polymer was thoroughly washed with water, dried and weighed to a predetermined amount. Dissolved in a mixed solvent of
Using phenolphthalein as an indicator, titration was performed with a standard solution of NaOH, and the sulfonation equivalent was determined from the neutralization point.

Tensile Strength Tensile strength was measured by a tensile test at room temperature of the obtained film. The modulus of elasticity is the stress minus the tensile test at room temperature of the resulting film.
Calculated from the initial slope of the strain curve. Using a folding tester for film bending resistance , the number of bending times was 166 times / min, and the load was 200
g, the bending deformation angle was measured at 135 °.

Dimensional Stability (Dimensional Change) The dimensional change of the film after treating the obtained film in an oven at 100 ° C. for 3 hours is shown in%. Water absorption The film was immersed in distilled water at room temperature for 1 hour, and the weight was determined from the change in weight before and after.

Measurement of Proton Conductivity A film sample having a diameter of 13 mm placed under 100% relative humidity was sandwiched between platinum electrodes, sealed in a closed cell, and measured using an impedance analyzer (HYP4192A).
Frequency 5-13MHz, applied voltage 12mV, temperature 20
The absolute value of the impedance of the cell and the phase angle were measured at 50 ° C., 50 ° C., and 100 ° C. The obtained data was subjected to complex impedance measurement at an oscillation level of 12 mV using a computer to calculate proton conductivity.

Example 1 (4-Phenoxybenzoyl-1,4-phenylene) repeating unit (A) and (diphenylmethanone-4,4'-diyl) repeating unit (B) having a weight average molecular weight of 150,000 [Copolymer composition; (A) /
(B) = 90/10% by weight] and a sulfonate obtained by sulfonating with concentrated sulfuric acid [90 mol% of the unit (A) is sulfonated with respect to the repeating unit, and the unit (B) is not sulfonated. Was dissolved in a mixed solvent of 212 g of methanol and 638 g of NMP,
A solution having a concentration of 15% by weight was prepared. This solution was cast on a PET film using a die coater and preliminarily dried at 80 ° C. for 30 minutes to obtain a film containing 17% by weight of NMP. This is cut into a 20 cm square and 11 is drawn with a biaxial stretching machine.
The film was stretched by 0%. At this time, a heat treatment was performed at 150 ° C. for 60 minutes in a stretched state to prepare a film having a thickness of 50 μm. Measure the strength and elastic modulus of the obtained film with a tensile tester,
Film folding resistance, dimensional stability, water absorption, and proton conductivity were evaluated. Table 1 shows the results.

Comparative Example 1 The polymer solution used in Example 1 was cast on a PET film using a die coater, and was pre-dried at 80 ° C. in the same manner as in Example 1, but without stretching. Followed by 12
The film was dried at 0 ° C. for 30 minutes and further at 100 ° C. all day and night with a vacuum drier to prepare a film having a thickness of 50 μm. Table 1 shows the results
Shown in

Example 2 The 20 cm square film prepared in Example 1 was stretched by 105% with a biaxial stretching machine. At this time, in the stretched state, under nitrogen,
An electron beam was irradiated at 60 ° C. with a dose of 60 Mrad. Further, in a stretched state, heat treatment is performed at 150 ° C. for 60 minutes to form a film having a thickness of 50 ° C.
A μm film was prepared. The obtained film is measured for strength and elastic modulus with a tensile tester,
The dimensional stability, water absorption, and proton conductivity were evaluated. Table 1 shows the results.

Comparative Example 2 A film was treated in the same manner as in Example 2 except that the film was not cured by electron beam and was not stretched. Table 1 shows the results.

[0069]

[Table 1]

[0070]

According to the present invention, when a film is obtained by casting from a composition comprising an organic solvent system of a sulfonated polyarylene, the film containing the solvent is stretched and heat-treated. A polyarylene-based film having excellent mechanical strength, elastic modulus, and dimensional stability during heating can be obtained. Therefore, the polyarylene-based film (proton conductive membrane) obtained from the present invention has high proton conductivity over a wide temperature range as a conductive membrane, and has an electrolyte for a primary battery,
It can be used as an electrolyte for secondary batteries, polymer solid electrolytes for fuel cells, display elements, various sensors, signal transmission media, solid capacitors, and conductive membranes such as ion exchange membranes.
This industrial significance is extremely large.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29L 9:00 B29L 9:00 C08L 65:02 C08L 65:02 (72) Inventor: Fusumi Masaka Central Tokyo 2-11-11 Tsukiji-ku, Tokyo F-term (reference) 4J07 AA69 AH15 BA02 BB02 BB07 BB08 BC02 4F210 AA49J AG01 AG03 QC05 QD10 QG01 QG15 QG18 4J032 CA04 CA14

Claims (5)

[Claims] 1. A sulfonated polyarylene,
And (B) a method for producing a polyarylene film, comprising applying a composition containing an organic solvent to a substrate, stretching the substrate in a uniaxial or biaxial direction, and heating in a stretched state. 2. The polyarylene constituting the component (A) comprises a structural unit represented by the following general formula (1).
A method for producing the polyarylene-based film described in the above. Embedded image [In the general formula (1), X represents -CQQ '-(where Q,
Q ′ is the same or different and represents a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group) and a group selected from the group consisting of a fluorenylene group, and R ^{1 to} R ³⁶ are the same. Or differently, represents a hydrogen atom, a halogen atom or a monovalent organic group, and Y is -O
-, -CO-, -COO-, -CONH- and -SO
A group selected from the group consisting of _2- groups, p is 0 to 100 mol%, q is 0 to 100 mol%, r is 0 to 100 mol%, s
Is 0 to 100 mol% (however, p + q + r + s = 100
Mol%), t is 0 or 1. ] 3. The method for producing a polyarylene film according to claim 1, wherein the concentration of the sulfonated polyarylene (A) in the composition is 3 to 40% by weight. 4. The method for producing a polyarylene film according to claim 1, wherein the stretching ratio is 1.05 to 1.75. 5. The method for producing a polyarylene-based film according to claim 1, wherein the substrate is irradiated with an electron beam while being stretched.