JP2005120198A - Hydrophilic polymer composition - Google Patents

Abstract

Provided is a hydrophilic polymer composition that has sufficient water resistance while increasing the hydrophilic group content, and has improved functions such as low resistance and hydrophilicity.
(A) a polymer having a hydrophilic group in the molecule; (B) the following general formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² may be the same or different; n is an integer of 0 to 3), and the hydrophilic polymer composition comprising at least one silane compound selected from the group consisting of an organosilane represented by the following formula: To do.
[Selection figure] None

Description

The present invention relates to a hydrophilic polymer composition containing a polymer having a hydrophilic group in the molecule. More specifically, the present invention relates to a binder, a coating material, a film, a coating material for a battery separator, preferably a battery electrolyte. The present invention relates to a hydrophilic polymer composition useful as a conductive film usable for a solid polymer electrolyte for fuel cells, a solid capacitor, an ion exchange membrane, various sensors and the like.

Conventionally, polymers having hydrophilic groups such as sulfonic acid groups, carboxyl groups (carboxylic acid groups), and phosphoric acid groups are known. Surfactants, emulsifiers, dispersants, polymer solid electrolytes, ion exchange membranes It is used for such as. On the other hand, in recent years, binders have been utilized by taking advantage of such characteristics as dispersibility of hydrophilic groups, hydrophilicity, ion trapping properties, small volume resistance (hereinafter sometimes referred to as small resistance), and adhesion to substrates. Applications to resins, coating materials, surface treatment agents, and battery electrolytes are being studied. In particular, a sulfonic acid group-containing polymer has the strong ionic property of a sulfonic acid group, and thus easily exhibits the above characteristics, and its applicability has been attracting attention. For example, Patent Document 1 or Patent Document 2 proposes application of a polymer copolymerized with acrylamide sulfonic acid to an ion exchange membrane or a polymer electrolyte for a fuel cell.
Japanese Patent Laid-Open No. 11-302410 JP 2002-343381 A

However, a polar group-containing polymer such as a sulfonic acid group has a significantly reduced resistance to water when the content of the polar group is higher than a certain level due to the hydrophilicity of the hydrophilic group, in other words, water solubility. For example, when used as a film material, binder material, or coating material, the film expands significantly in the presence of water, resulting in a significant decrease in the mechanical strength of the film or the possibility of peeling from the substrate. Thus, there is a problem that durability is lowered. For this reason, the content of the hydrophilic group is limited, and the characteristics such as small resistance and hydrophilicity have not been sufficiently exhibited.

An object of the present invention is to provide a hydrophilic polymer composition that has a sufficient hydrophilic resistance while maintaining a sufficient water resistance and improved functions such as small resistance and hydrophilicity.

The present invention includes (A) a polymer having a hydrophilic group in the molecule, (B) the following general formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² may be the same or different; n is an integer of 0 to 3.) and at least one silane compound selected from the group consisting of derivatives thereof, and a hydrophilic polymer composition. .

Moreover, according to this invention, in addition to the above-mentioned (A) polymer and (B) silane compound, the hydrophilic polymer composition which contains (C) solvent further is provided.
In the hydrophilic polymer composition of the present invention, the hydrophilic group of the component (A) is preferably at least one of a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof. In addition, the polymer (A) having a hydrophilic group in the molecule is preferably obtained by copolymerizing a sulfonic acid group-containing acrylamide, and particularly preferably acrylamide-t-butylsulfonic acid. Furthermore, in the hydrophilic polymer composition of the present invention, the polymer (A) having a hydrophilic group in the molecule is 5% with respect to 100% by weight of the hydrophilic polymer composition [(A) + (B)]. It is preferable to contain -99weight%.
The volume resistance of the hydrophilic polymer composition according to the present invention is preferably 10 ⁻² to 10 ³ Ω · cm.

According to the hydrophilic polymer composition of the present invention, there is an excellent effect that the hydrophilic group content is increased to improve functions such as small resistance and hydrophilicity, and sufficient water resistance is provided.

Hereinafter, the hydrophilic polymer composition of the present invention will be described in detail.
<Hydrophilic polymer composition>
The hydrophilic polymer composition according to the present invention contains a polymer having a hydrophilic group in the molecule and at least one silane compound selected from the group consisting of organosilanes and derivatives thereof. Moreover, in this invention, you may contain other additives, such as a crosslinking agent, a solvent, particle | grains, as needed. Hereinafter, the components used in the present invention will be described.

(A) Polymer having a hydrophilic group in the molecule:
The “polymer having a hydrophilic group in the molecule” in the present invention (hereinafter simply referred to as “hydrophilic polymer (A)”) is not limited as long as it is a polymer having a hydrophilic group in the molecule. (A1) a structural unit derived from at least one monomer (a1) having a hydrophilic group such as a sulfonic acid group, a carboxyl group (carboxylic acid group), a phosphoric acid group, or a polyether group, and (A2) A co-polymer containing a structural unit derived from at least one monomer (a2) selected from vinyl compounds, (meth) acrylic acid esters, unsaturated carboxylic acid esters, (meth) acrylamides and unsaturated nitriles Coalescence is preferred.

(A1) Monomer:
The monomer (a1) used in the present invention is a compound having a polymerizable unsaturated double bond and at least one hydrophilic group, and includes, for example, (meth) acrylic acid, 2- (meth) acrylic. (Meth) such as leuoxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid, and acrylamide-t-butylsulfonic acid Examples thereof include phosphoric acid group-containing (meth) acrylic acid esters such as acrylamide sulfonic acids and 2- (meth) acryloyloxyethyl acid phosphate.
These compounds can be used alone or in admixture of two or more.

The structural unit (A1) derived from such a monomer (a1) is usually 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15 to 85% in the hydrophilic polymer (A). It is desirable to be included in an amount of% by weight. When the proportion of the structural unit (A1) is less than the lower limit, the hydrophilic group content in the obtained hydrophilic polymer (A) tends to be excessive, and the film obtained by drying the hydrophilic polymer composition is small. Resistance and hydrophilicity may not be sufficient. When the proportion of the structural unit (A1) exceeds the above upper limit, the water resistance of the resulting hydrophilic polymer (A) may be greatly reduced.

(A2) Monomer:
The monomer (a2) used in the present invention is not particularly limited as long as it is a monomer copolymerizable with the monomer (a1). For example, (meth) acrylic acid ester, (meth) acrylamide, Examples thereof include vinyl compounds, unsaturated carboxylic acid esters and unsaturated nitriles.

As (meth) acrylic acid ester, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl ) Acrylates, alkyl such isostearyl (meth) acrylate (meth) acrylates;

Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate;
Polyethylene glycol (meth) acrylates such as polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate;

Polypropylene glycol (meth) acrylates such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl ( Cycloalkyl (meth) acrylates such as (meth) acrylate and tricyclodecanyl (meth) acrylate;

Benzyl (meth) acrylate;
Tetrahydrofurfuryl (meth) acrylate is mentioned.
Examples of (meth) acrylamide include acryloylmorpholine, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and tert. -Octyl (meth) acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide are mentioned.

As a vinyl compound, for example,
Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, lauryl vinyl ether, Alkyl vinyl ethers or cycloalkyl vinyl ethers such as cetyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatic acid, vinyl stearate, benzoic acid;
Α-olefins such as ethylene, propylene and isobutene;
Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1 , 1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, vinylpyridine, vinylimidazole and the like.

Examples of the unsaturated carboxylic acid ester include methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, Examples include diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate and diethyl fumarate.

Examples of unsaturated nitriles include (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic nitrile, itaconic acid dinitrile, maleic acid dinitrile. And fumarate dinitrile.
These compounds can be used alone or in admixture of two or more.

Moreover, as a means for introducing a crosslinking site into the hydrophilic polymer, monomers having various functional groups such as a hydroxyl group-containing monomer and an epoxy group-containing monomer can be used.
Examples of the hydroxyl group-containing monomer include hydroxyl group-containing vinyl ethers such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether; hydroxyl group-containing (meth) acrylic acid esters such as hydroxyethyl (meth) acrylate; p-hydroxystyrene, m-hydroxy Examples thereof include phenolic hydroxyl group-containing monomers such as styrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol.

Examples of the epoxy group-containing monomer include epoxy group-containing vinyl ethers such as glycidyl vinyl ether; and epoxy group-containing (meth) acrylic esters such as glycidyl (meth) acrylate.
Furthermore, fluorine-containing compounds such as fluorine-containing (meth) acrylic acid esters, fluoroolefins and fluoroolefin derivatives can be used within a range that does not impair the properties of the hydrophilic polymer.

Examples of the fluorine-containing (meth) acrylic acid ester include trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate.
Examples of the fluoroolefin include tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene, and chlorotrifluoroethylene.

Examples of fluoroolefin derivatives include alkyl perfluorovinyl ethers such as methyl trifluorovinyl ether and ethyl trifluorovinyl ether; alkoxyalkyl perfluorovinyl ethers such as methoxyethyl trifluorovinyl ether and ethoxyethyl trifluorovinyl ether; perfluoro (methyl vinyl ether) Perfluoro (alkyl vinyl ethers) such as perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); and perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether). It is done.

The hydrophilic polymer (A) used in the present invention may contain a structural unit (A3) derived from a reactive emulsifier. It is preferable to use a nonionic reactive emulsifier as the reactive emulsifier. As a nonionic reactive emulsifier, the compound represented by following formula (2) is mentioned, for example.

In the present invention, as this nonionic reactive emulsifier, for example, “Adekalia Soap NE-5”, “Adekalia Soap NE-10”, “Adekalia Soap NE-20”, “Adekalia Soap NE-30”, Commercial products such as “ADEKA rear soap NE-40” (manufactured by Asahi Denka Kogyo Co., Ltd.) can be used.

The structural unit (A3) is usually contained in the hydrophilic polymer (A) in an amount of 0 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight. It is desirable. When the proportion of the structural unit (A3) is within the above range, good coating properties and leveling properties can be obtained when the hydrophilic polymer composition is used as a coating agent. If the proportion of the structural unit (A3) is less than the above lower limit, repelling or the like may occur when the coating material is applied, and if the upper limit is exceeded, the resulting hydrophilic polymer composition becomes sticky. Handling becomes difficult and moisture resistance decreases when used as a coating agent.

(Polymerization of hydrophilic polymer (A))
The hydrophilic polymer (A) used in the present invention can be synthesized using the monomers (a1) and (a2). Moreover, you may use a reactive emulsifier and the other copolymerizable monomer as needed.

The hydrophilic polymer (A) used in the present invention is polymerized by any polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method as long as it is a polymerization method using a radical polymerization initiator. be able to. The polymerization operation mode can be appropriately selected from batch, semi-continuous or continuous operation modes. The polymerization conditions are not particularly limited, but for example, it is preferable to perform polymerization at a temperature in the range of 50 to 200 ° C. for a polymerization time of 1 to 100 hours.

Examples of the radical polymerization initiator include:
Diacyl peroxides such as acetyl peroxide and benzoyl peroxide;
Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide;
Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide;
Dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide;
peroxy esters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate;
Azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile;
Examples thereof include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

The hydrophilic polymer (A) is preferably polymerized using a solvent. As a solvent that can be used at this time, for example,
Alcohols such as methanol, ethanol, isopropanol, n-butanol;
Esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Cyclic ethers such as tetrahydrofuran and dioxane;
Amides such as N, N-dimethylformamide and N, N-dimethylacetamide;
Aromatic hydrocarbons such as toluene and xylene are listed.
Moreover, you may mix and use water, aliphatic hydrocarbons, etc. as needed.

The reaction solution containing the hydrophilic polymer (A) obtained by the above polymerization method can be used as it is as a raw material of the hydrophilic polymer composition, but is used after appropriately post-treating this reaction solution. May be. As this post-treatment, for example, after carrying out a reprecipitation treatment, a treatment for dissolving the purified hydrophilic polymer (A) in a solvent can be carried out. Examples of the reprecipitation treatment include a purification treatment in which a reaction solution is dropped into an insolubilizing solvent for a hydrophilic polymer (A) such as an aliphatic hydrocarbon to solidify the hydrophilic polymer (A). Moreover, you may implement residual monomer removal from the obtained reaction solution as said post-process.

The molecular weight of the hydrophilic polymer (A) used in the present invention is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) method is usually 200,000 or less. Preferably it is 5,000-100,000. If the weight average molecular weight is too small, the physical properties such as strength and elongation of the cured product obtained by curing the hydrophilic polymer composition will decrease, and if it is too large, it will become a phase with other components in the hydrophilic polymer composition. The solubility may decrease, and the viscosity of the solution may increase and the applicability may decrease. In the present invention, the hydrophilic polymer (A) is preferably 5 to 99% by weight, more preferably 10 to 90% with respect to [(A) + (B)] 100% by weight of the hydrophilic polymer composition. It is used in an amount of% by weight, particularly preferably 15 to 85% by weight.

(B) Silane compound (organosilane and its derivatives):
The silane compound used in the present invention is represented by the following general formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² may be the same or different; n is an integer of 0 to 3.) and at least one silane compound selected from the group consisting of derivatives thereof.

Examples of the organosilane (1) derivative include hydrolyzate of organosilane (1) and condensate of organosilane (1). Of these three silane compounds, only one silane compound may be used, any two silane compounds may be mixed, or all three silane compounds may be mixed and used. Also good. Also, alkoxysilane compounds are preferred, but they may be completely hydrolyzed to silanols.

In the above formula (1), R ¹ is a monovalent organic group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group. Alkyl groups such as i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group;
Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

Furthermore, examples of R ¹ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acryloxy group. Ureido group, ammonium base and the like. However, the number of carbon atoms of R ¹ composed of these substituted derivatives is preferably 8 or less including the carbon atoms in the substituent.
When a plurality of R ¹ are present in the formula (1), they may be the same or different.

Examples of R ² which is an alkyl group having 1 to 5 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n -A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. are mentioned, for example.

Examples of R ² which is an acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, a benzoyl group, a trioyl group, and a caproyl group.
When a plurality of R ² are present in the formula (1), they may be the same or different.

Specific examples of such organosilane (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane;

Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxy Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Cypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- Trialkoxysilanes such as (meth) acrylicoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldi Ethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyl Diethoxysilane, diphenyl Silane, dialkoxy silanes such as diphenyl diethoxy silane;

Monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane;
Examples thereof include methyltriacetyloxysilane and dimethyldiacetyloxysilane.

Of these, trialkoxysilanes and dialkoxysilanes are preferable, and methyltrimethoxysilane and methyltriethoxysilane are more preferable as trialkoxysilanes, and dimethyldimethoxysilane and dimethyldisilane are preferable as dialkoxysilanes. Ethoxysilane is preferred.

As the silane compound used in the present invention, the organosilane (1) may be used singly or as a mixture of two or more. For example, trialkoxysilane alone or a mixture of trialkoxysilane 40 to 95 mol% and dialkoxysilane 60 to 5 mol% is particularly preferably used. By using dialkoxysilane and trialkoxysilane in combination, the resulting coating film can be softened and crack resistance can be improved.

In the present invention, organosilane (1) may be used as it is as the silane compound, but hydrolyzate and / or condensate of organosilane (1) can be used.
The hydrolyzate of organosilane (1) is sufficient if at least one of ² to 4 OR ² groups contained in organosilane (1) is hydrolyzed. For example, one OR ² group In which two or more OR ² groups are hydrolyzed, or a mixture thereof.

The organosilane (1) condensate is a product in which the silanol groups in the hydrolyzate produced by hydrolysis of the organosilane (1) are condensed to form Si—O—Si bonds. In the present invention, it is not necessary that all of the silanol groups are condensed, and the condensate may be one obtained by condensing a small part of silanol groups, one containing most (including all) silanol groups, And mixtures thereof.

Such hydrolyzate and / or condensate of organosilane (1) can be produced by hydrolyzing and condensing organosilane (1) in advance. As will be described later, when preparing the hydrophilic polymer composition, the hydrolyzate and / or condensate of organosilane (1) is obtained by hydrolyzing and condensing organosilane (1) and water. It can also be prepared. In addition, you may add this water independently, and you may use the water contained in a hydrophilic polymer (A1) or a solvent. The amount of water is usually 0.5-3 mol, preferably 0.7-2 mol, per 1 mol of organosilane (1).

Such a condensate of organosilane (1) has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”), preferably 300 to 100,000, more preferably 500 to 50,000. Used.

As the silane compound in the present invention, the above silane compound may be prepared, or a commercially available silane compound may be used. Commercially available silane compounds include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicon resin manufactured by Toray Dow Corning, silicon resin manufactured by Toshiba Silicone, and silicon resin manufactured by Shin-Etsu Chemical Co., Ltd. And hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia, silicone oligomer manufactured by Nihon Unicar, and ladder-type silicone oligomer manufactured by Showa Denko. These commercially available silane compounds may be used as they are, or may be used after being condensed.
Such silane compounds may be used alone or in combination of two or more.

In the present invention, the silane compound (B) is preferably 1% by weight or more, more preferably 5% by weight or more, particularly preferably 100% by weight of [(A) + (B)] in the hydrophilic polymer composition. It is preferably used in an amount of 15% by weight or more. Here, the completely hydrolyzed condensate is a product in which the OR ² group in formula (1) is 100% hydrolyzed to become a Si—OH group, and the Si—OH group is completely condensed to form a siloxane structure. Say. If the content of the silane compound is less than 1% by weight, sufficient water resistance may not be exhibited. On the other hand, the upper limit of the content of the silane compound is preferably 95% by weight. When it exceeds 95% by weight, for example, when a film or a coating film is formed, it may become brittle or cracks may occur.

(solvent)
The solvent used in the hydrophilic polymer composition of the present invention is added to improve the handleability of the hydrophilic polymer composition and to adjust the viscosity and storage stability. Although such a solvent is not specifically limited unless the objective of this invention is impaired, For example, water and an organic solvent are mentioned.

As an organic solvent,
Alcohols such as methanol, ethanol, isopropanol, n-butanol;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve;
Carbitols such as butyl carbitol;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate;
Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;

Aromatic hydrocarbons such as toluene and xylene;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun. Moreover, you may mix and use aliphatic hydrocarbons etc. as needed.
These solvents can be used alone or in combination of two or more.
These solvents are usually mixed in an amount of 2 to 99% by weight, preferably 5 to 95% by weight, based on 100% by weight of the hydrophilic polymer composition [(A) + (B) + (C)].

(Crosslinking agent)
In the present invention, a compound capable of reacting with the hydrophilic polymer (A) and / or organosilane and its derivative (B) to form a cured product can be used as a crosslinking agent.

Examples of such a cross-linking agent include all or part of an active methylol group such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea. Etherified nitrogen-containing compounds;
Phenolic resins such as novolak resins, polyhydroxystyrene and copolymers thereof, and low molecular weight phenol compounds;
Epoxy compounds such as phenol novolac epoxy resins, cresol novolac epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins;
Etc.

The crosslinking agent is usually used in an amount of 1 to 50% by weight, preferably 5 to 40% by weight, based on the hydrophilic polymer (A).

(Additive)
The hydrophilic polymer composition according to the present invention may contain additives such as inorganic or organic particles, adhesion aids, sensitizers, leveling agents, and colorants.

Examples of the inorganic particles include SrTiO ₃ , FeTiO ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , ZnO, Fe ₂ O ₃ , RuO ₂ , CdO, CdS, CdSe, GaP, GaAs, CdFeO. _{3, MoS 2, LaRhO 3,} GaN, CdP, ZnS, ZnSe, ZnTe, Nb 2 O 5, ZrO 2, InP, GaAsP, InGaAlP, AlGaAs, PbS, InAs, PbSe, InSb, SiO 2, Al 2 O 3, AlGaAs, Al (OH) ₃ , Sb ₂ O ₅ , Si ₃ N ₄ , Sn—In ₂ O ₃ , Sb—In ₂ O ₃ , MgF, CeF ₃ , CeO ₂ , 3Al ₂ O ₃ .2SiO ₂ , BeO, SiC, AlN, Fe, Co, Co-FeO x, CrO 2, Fe 4 N, BaTiO 3, BaO-Al 2 O 3 -SiO 2, Ba ferrite, SmC _{5, YCO 5, CeCO 5,} PrCO 5, Sm 2 CO 17, Nd 2 Fe 14 B, Al 4 O 3, α-Si, SiN 4, CoO, Sb-SnO 2, Sb 2 O 5, MnO 2, MnB , Co ₃ O ₄ , Co ₃ B, LiTaO ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂ O ₄ , ZrSiO ₄ , ZnSb, PbTe, GeSi, FeSi ₂ , CrSi ₂ , CoSi ₂ , MnSi _1.73 , Mg ₂ Si, β-B, BaC, BP, TiB ₂ , ZrB ₂ , HfB ₂ , Ru ₂ Si ₃ , TiO ₂ (rutile type, anatase type), TiO ₃ , PbTiO ₃ , Al ₂ TiO ₅ , Zn ₂ SiO ₄ , Zr _{2 SiO 4, 2MgO 2 -Al 2 O} 3 -5SiO 2, Nb 2 O 5, Li 2 O-Al 2 O 3 -4SiO 2, Mg ferrite, Ni ferrite, Ni-Zn ferrite, Li ferrite, S Ferrite, Pt, Au, Ag, Fe, Cu and the like.

By using such metal oxides or metal particles, optical property control such as refractive index of a cured film obtained by curing a hydrophilic polymer composition, and electrical properties such as dielectric constant, insulation, and conductivity. Can be controlled. These particles can be used alone, but may be supported on particles such as carbon black and calcium carbonate.

These particles preferably have a particle diameter of 10 nm to 100 μm. For example, when transparency is required, 10 to 200 nm is preferable, and 10 to 100 nm is particularly preferable. Moreover, although it is based on a use, Preferably it is 5-80 weight part with respect to 100 weight part of hydrophilic polymer compositions [(A) + (B)].

The hydrophilic polymer composition of the present invention has a small volume resistance, preferably 10 ⁻² to 10 ³ Ω · cm, more preferably 10 ⁻² to 10 ² Ω · cm. In the hydrophilic polymer composition of the present invention, the sulfonic acid group content is increased to a predetermined level or more, specifically, preferably 0.1 to 5 mmol / g, more preferably 0.3 to 4 mmol. / G sulfonic acid group content.

The hydrophilic polymer composition of the present invention can be applied to various uses such as a coating material, particularly a coating material for a nonwoven fabric for battery separator, a binder resin, and a polymer solid electrolyte membrane. Moreover, when applying to various uses, in order to improve physical properties etc., another polymer can also be used together. Examples of other polymers include known resins such as urethane resins, acrylic resins, polyester resins, polyamide resins, polyethers, polystyrenes, polyester amides, polycarbonates, polyvinyl chloride, and diene polymers such as SBR and NBR.

Moreover, the hydrophilic polymer composition of the present invention can obtain a film with high accuracy by using a molding method such as cast film molding, and can be suitably used for, for example, an ion exchange membrane.

The hydrophilic polymer composition of the present invention is usually used as a single product or a blend with various additives. When used as a coating material, the coating method is not particularly limited, and brush coating, spraying, roll coater, flow coater, bar coater, dip coater and the like can be used. Although a coating film thickness changes with uses, it is a dry film thickness, and is 0.01-1,000 micrometers normally, Preferably it is 0.05-500 micrometers.

Moreover, there is no restriction | limiting in particular in the base material used, For example, non-ferrous metals, such as polycarbonate resin, an acrylic resin, ABS resin, polyester resin, polyethylene, polypropylene, nylon, nonferrous metals, such as aluminum, copper, and duralumin, stainless steel Steel plates such as iron, glass, wood, paper, gypsum, alumina, and hardened inorganic materials. There is no restriction | limiting in particular in the shape of a base material, It can use for porous materials, such as a flat thing, a nonwoven fabric.

The hydrophilic polymer composition of the present invention can be used as a dry membrane for a solid polymer electrolyte such as a fuel cell, or a substrate surface modifier. For example, by coating on a hydrophobic surface, it becomes possible to develop or maintain hydrophilicity and hygroscopicity. In addition, it is possible to prevent dirt and dust due to static electricity. Further, when coated on a porous material such as a non-woven fabric, it exhibits an action of capturing weak bases such as ammonia and amines present in air or water, or ionic substances. In addition, by coating the surface of the battery separator, it is possible to expect an effect that the affinity with the battery electrolyte is improved and the battery characteristics such as self-discharge characteristics are improved. In addition, it is one of the characteristics that the various particles are highly dispersed, and the function of the particles can be sufficiently exhibited.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the following examples and comparative examples, “parts” and “%” mean parts by weight and% by weight unless otherwise specified. Various evaluations and measurements in the examples were performed by the following methods.

<Evaluation method>
(Sulphonic acid group content and acid value)
The synthesized sulfonated product was vacuum dried at 80 ° C. for 12 hours. The content of the sulfonic acid group was calculated from elemental sulfur analysis of the obtained dried product, an isopropyl alcohol (IPA) solution of the dried product was prepared, and the acid value was calculated from neutralization titration.

(Adhesion measurement)
Using a 100 mil applicator, the obtained hydrophilic polymer composition solution was evaluated for adhesion to a copper plate, a glass plate, and a PET film by a cross-cut adhesive tape (using cellophane tape) peeling test. The number of grids that did not peel was determined.

(Evaluation of hydrophilicity)
The solution of the obtained hydrophilic polymer composition was adjusted to a solid content concentration of 2% using the same solvent as used in the polymerization. A 10 cm square nonwoven fabric (made of polypropylene) was immersed in this solution. Then, it dried in oven at 100 degreeC for 1 hour, and was set as the evaluation sample. Distilled water and a 30% KOH aqueous solution were dropped on the coated nonwoven fabric, and the degree of penetration into the nonwoven fabric was qualitatively observed. The case where the penetration was considerably good was evaluated as ◎, the case where the penetration was relatively good was evaluated as ○, and the case where the penetration was poor was evaluated as ×.

(Evaluation of water resistance)
A solution of a hydrophilic polymer composition is prepared, poured into a frame made of a tetrafluoroethylene polymer (registered trademark: Teflon) so that the film thickness after drying is 200 μm, and left at 25 ° C. for 24 hours. The solvent was volatilized. Subsequently, after heat-treating at 150 ° C. for 1 hour, it was cured at a temperature of 25 ° C. and a relative humidity of 60% for 24 hours. The obtained film was immersed in water at 25 ° C. for 12 hours, dried, and the film remaining rate was measured from the weight change before and after immersion.

(Measurement of moisture content)
A film having a thickness of 200 μm was prepared in the same manner as the water resistance evaluation sample. The obtained membrane was immersed in water at 25 ° C. for 1 hour, and the water content was measured using the following formula.
Moisture content (%) = (film weight after immersion−film weight before immersion) / film weight before immersion × 100

(Measurement of volume resistance)
A film having a thickness of 200 μm was prepared in the same manner as the water resistance evaluation sample. The obtained film was sandwiched between two blocks made of a tetrafluoroethylene polymer (registered trademark: Teflon) with a platinum foil, and the four corners were stopped to prepare a measurement cell. At this time, the distance between the platinum foils was adjusted to 0.5 cm when viewed from the direction perpendicular to the film. An impedance meter was connected to the platinum electrode portion of this cell, and the alternating current impedance between the platinum electrodes was measured at a frequency of 60 Hz to calculate the volume resistance of the film.

<Synthesis of hydrophilic polymer (A)>
(Synthesis Example 1)
The inside of a glass reactor equipped with a stirrer with an internal volume of 0.5 liter was sufficiently replaced with nitrogen gas, and then charged with 150 g of methanol, 5 g of distilled water, and 30 g of acrylamide-t-butylsulfonic acid (ATBS: manufactured by Toagosei Co., Ltd.) and stirred. While starting the temperature rise. When the temperature in the reactor reached 60 ° C., 60 g of methoxyethyl acrylate (MEA) prepared in advance, 10 g of hydroxyethyl acrylate (HEA), azobisisobutyronitrile (AIBN) 0 as a polymerization initiator A homogeneous solution consisting of .5 g was charged. The reaction was continued at 60 ° C. for 8 hours as it was, and then the reactor was cooled with water to stop the reaction. As a result of measuring the polymer solution after drying the polymer solution on an aluminum dish at 200 ° C. for 10 minutes, the nonvolatile content concentration (active ingredient concentration) in the polymer solution was 32.4%. This polymer is designated as “A-1”. The sulfonic acid group content of A-1 was 1.43 mmol / g.

(Synthesis Example 2)
A polymer solution was obtained in the same manner as in Synthesis Example 1 except that ATBS 45 g, MEA 45 g, and HEA 10 g were used instead of ATBS 30 g, MEA 60 g, and HEA 10 g. The nonvolatile content concentration (active ingredient concentration) in this polymer solution was 33.1% as a result of measuring the polymer solution after drying it at 200 ° C. for 10 minutes on an aluminum dish. This polymer is designated as “A-2”. The sulfonic acid group content of A-2 was 2.15 mmol / g.

(Synthesis Example 3)
A polymer solution was obtained in the same manner as in Synthesis Example 1 except that ATBS 30 g, methyl methacrylate (MMA) 60 g, and HEA 10 g were used instead of ATBS 30 g, MEA 60 g, and HEA 10 g. The nonvolatile content concentration (active ingredient concentration) in this polymer solution was 38.9% as a result of measuring the polymer solution after drying it at 200 ° C. for 10 minutes on an aluminum dish. This polymer is designated as “A-3”. The sulfonic acid group content of A-3 was 1.45 mmol / g.

(Synthesis Example 4)
Synthetic Example 1 except that ATBS 45 g, 2- (perfluorooctyl) ethyl acrylate (FA-108: manufactured by Osaka Organic Chemical Industries) 45 g, and HEA 10 g were used instead of ATBS 30 g, MEA 60 g, and HEA 10 g. Similarly, a polymer solution was obtained. The nonvolatile content concentration (active ingredient concentration) in the polymer solution was 36.0% as a result of measuring the polymer solution after drying it at 200 ° C. for 10 minutes on an aluminum dish. This polymer is designated as “A-4”. The sulfonic acid group content of A-4 was 2.20 mmol / g.

(Synthesis Example 5)
A polymer solution was obtained in the same manner as in Synthesis Example 1 except that ATBS 45 g, isopropyl acrylamide (IPAA) 45 g, and hydroxyethyl acrylamide (HEAA) 10 g were used instead of ATBS 30 g, MEA 60 g, and HEA 10 g. As a result of measuring the polymer solution after drying the polymer solution on an aluminum dish at 200 ° C. for 10 minutes, the nonvolatile content concentration (active ingredient concentration) in the polymer solution was 36.8%. This polymer is designated as “A-5”. The sulfonic acid group content of A-5 was 2.13 mmol / g.

(Synthesis Example 6)
A polymer solution was prepared in the same manner as in Synthesis Example 1 except that ATBS 30 g, MEA 50 g, HEA 10 g, and diacetone acrylamide (DAAM: manufactured by Kyowa Hakko Kogyo Co., Ltd.) 10 g were used instead of ATBS 30 g, MEA 60 g, and HEA 10 g. Obtained. As a result of measuring the polymer solution after drying the polymer solution on an aluminum dish at 200 ° C. for 10 minutes, the concentration of the non-volatile content (active ingredient concentration) in the polymer solution was 33.3%. This polymer is designated as “A-6”. The sulfonic acid group content of A-6 was 1.46 mmol / g.

<Synthesis of organosilane derivative (B)>
(Synthesis Example 7)
In a glass reactor equipped with a stirrer having an internal volume of 0.5 liter, phenyltrimethoxysilane (76.9 g, 0.39 mol), methyltrimethoxysilane (101.7 g, 0.75 mol), and conductivity Was charged with 8 × 10 ⁻⁵ S · cm ⁻¹ ion-exchanged water (45.9 g, 2.55 mol) and oxalic acid (0.1 g, 1.1 mmol) at 60 ° C. for 6 hours. Hydrolysis and condensation reaction of phenyltrimethoxysilane and methyltrimethoxysilane were carried out by heating and stirring at. This organosilane condensate is designated as “B-1”.

(Synthesis Example 8)
In a glass reactor equipped with a stirrer with an internal volume of 0.5 liter, methyltrimethoxysilane (80.0 g, 0.59 mol) and ion-exchanged water with an electric conductivity of 8 × 10 ⁻⁵ S · cm ⁻¹ ( 23.8 g, 1.32 mol) and oxalic acid (0.039 g, 0.44 mmol) were added, and the mixture was heated and stirred at a temperature of 60 ° C. for 6 hours. Decomposition and condensation reactions were performed. This organosilane condensate is designated as “B-2”.

<Preparation and Evaluation of Hydrophilic Polymer Composition>
(Examples 1 to 10)
The hydrophilic polymer composition was prepared by dissolving the hydrophilic polymer (A), the organosilane derivative (B), the solvent (isopropanol) (C) and other additives as required in the proportions shown in Table 1. .
The properties of this composition were measured according to the above evaluation methods. The obtained results are shown in Table 2.

(Comparative Examples 1-7)
In the ratio shown in Table 1, the hydrophilic polymer (A), the solvent (isopropanol) (C), and other additives as necessary were dissolved to prepare a hydrophilic polymer composition.
The properties of this composition were measured according to the above evaluation methods. The obtained results are shown in Table 2.

The hydrophilic polymer composition of the present invention can be applied to various uses such as a coating material, particularly a non-woven fabric for battery separators, a binder resin, and a polymer solid electrolyte membrane. Moreover, it is applicable also to a film and can be used suitably for an ion exchange membrane etc., for example.
The hydrophilic polymer composition of the present invention can be used as a dry membrane for a solid polymer electrolyte such as a fuel cell, or a substrate surface modifier.

The hydrophilic polymer composition of the present invention can be further applied to various uses. When applied to porous materials, etc., for example, for removing cation dyeing aids for fibers, water-absorbing nonwoven fabrics, antifouling materials, ion exchange membranes, battery separator hydrophilizing agents, ammonia, ionic substances, etc. Filter applications such as air purification filters, water purification filters, leukocyte removal filters, hay fever allergen removal materials, water vapor permeable materials, antibacterial materials, deodorant fibers, deodorant paints, deodorant paper, antifogging materials, anti-condensation materials Humidity control materials such as antistatic materials, anticorrosion materials, oxygen absorbents, sanitary products, and surface modification of activated carbon. Further, it can be applied to photographic materials such as floor polish, masking material, paper size material, paper strength enhancing material, adhesive, and silver halide photographic light-sensitive material.

Moreover, the hydrophilic polymer composition of this invention is applicable to various uses by combining various functional particles. For example, battery materials such as general paint, circuit board paint, conductive material, solid electrolyte binder, or electrode material binder, electromagnetic shielding material, antistatic paint, sheet heating element, electrochemical reaction electrode plate, electric Contact materials, friction materials, antibacterial materials, sliding materials, polishing materials, magnetic recording media, thermal recording materials, electrochromic materials, light diffusion films, water shielding materials for communication cables, light shielding films, sound insulation sheets, plastic magnets, X-rays Examples include intensifying screens, printing inks, agricultural chemical granules, and electrophotographic toners. In addition, as a coating material for surface protection, for example, metals such as stainless steel, aluminum and copper, inorganic materials such as concrete and slate, polyolefin materials such as polyethylene and polypropylene, polymer materials such as polyester such as polyethylene terephthalate, wood and paper Application is also possible.

Claims (11)

(A) a polymer having a hydrophilic group in the molecule;
(B) The following general formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two or more exist, they may be the same or different, and R ² has 1 to 5 carbon atoms. Represents an alkyl group or an acyl group having 1 to 6 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ¹ and R ² may be the same or different; n is an integer of 0 to 3)), and at least one silane compound selected from the group consisting of derivatives thereof;
A hydrophilic polymer composition comprising: The hydrophilic polymer composition according to claim 1, further comprising (C) a solvent. The hydrophilic group according to claim 1 or 2, wherein the hydrophilic group of component (A) is at least one selected from the group consisting of a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof. Polymer composition. The hydrophilic polymer composition according to claim 1 or 2, wherein the polymer (A) having a hydrophilic group in the molecule is obtained by copolymerizing a sulfonic acid group-containing acrylamide. The hydrophilic polymer composition according to claim 1 or 2, wherein the polymer (A) having a hydrophilic group in the molecule is acrylamide-t-butylsulfonic acid. The polymer (A) having a hydrophilic group in the molecule is contained in an amount of 5 to 99% by weight based on 100% by weight of the hydrophilic polymer composition [(A) + (B)]. The hydrophilic polymer composition as described in any one of these. The hydrophilic polymer composition according to claim 1, which has a volume resistance of 10 ⁻² to 10 ³ Ω · cm. The coating material which consists of a hydrophilic polymer composition as described in any one of Claims 1-7. The film which consists of a hydrophilic polymer composition as described in any one of Claims 1-7. A polymer solid electrolyte comprising the hydrophilic polymer composition according to any one of claims 1 to 7. A filter comprising the hydrophilic polymer composition according to any one of claims 1 to 7.