JP2010065066A - Hydrophilic polymer, method for producing hydrophilic polymer, hydrophilic membrane composition, and hydrophilic member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic polymer capable of providing a hydrophilic member that has higher safety by reducing an amount of a monomer which remains in the hydrophilic polymer to be not more than a definite amount, and excels in hydrophilicity, water resistance, and adhesion to a surface of a base material, and to provide a method for producing the hydrophilic polymer, a hydrophilic membrane composition, and the hydrophilic member using it. <P>SOLUTION: This hydrophilic polymer has a structure represented by general formula (I-1) and (I-2), in which the amount of the residual monomer is ≤3.0 mass%. In general formula (I-1) and (I-2), R<SP>201</SP>to R<SP>205</SP>are each independently a hydrogen atom or a hydrocarbon group, q is an integer of 1-3, L<SP>201</SP>and L<SP>202</SP>are each independently a single bond or a polyvalent organic linking group, and A<SP>201</SP>is a specific substituent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  In general, a resin film generally used for the surface of an optical member or the like or an inorganic material such as glass or metal has a hydrophobic surface or a weak hydrophilic surface. When the surface of a substrate using a resin film or inorganic material is made hydrophilic, the attached water droplets spread uniformly on the surface of the substrate and form a uniform water film. It is useful for preventing devitrification due to moisture and ensuring visibility in rainy weather. In addition, combustion products such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oil and fat and sealant elution components are difficult to adhere. Therefore, it is useful for various applications. For this reason, studies are being made on hydrophilic members in which the surface of the substrate is made hydrophilic by a film formed from a hydrophilic polymer.

On the other hand, generally reducing the amount of residual monomer when synthesizing a compound leads to an improvement in productivity.
In addition, some compounds used as raw material monomers have been pointed out to be carcinogenic to humans, and it is preferable to reduce the residual amount in the product as much as possible.
Among hydrophilic polymers, it is particularly difficult to reduce residual monomers in water-absorbing polymers that require a crosslinked structure. However, in hydrophilic polymers used in sanitary materials, it is required that the required quality be low in residual monomers. There is an invention relating to a polymer in which the amount of residual monomer is reduced (Patent Document 1).
As a method of reducing the residual monomer, a method of once filtering and then reslurry is known among the contractors. However, the manufacturing cost increases because a large amount of solvent is used and the number of working days increases. It becomes high and is not preferable.
And as a compound for hydrophilizing the member, a hydrophilic polymer containing a hydrolyzable silyl group is known (Patent Document 2), but there is no description about the residual monomer in the patent, It is not known at all that the residual monomer in the hydrophilic polymer affects the hydrophilicity, water resistance and adhesion to the substrate surface of the hydrophilic member.

JP 2002-302513 A JP 2002-293824 A JP 2002-293824 A

  The object of the present invention is to make the amount of the monomer remaining in the hydrophilic polymer not more than a certain amount, so that the safety is high, and the hydrophilic property is excellent in hydrophilicity, water resistance and adhesion to the substrate surface. The object is to provide a hydrophilic polymer capable of providing a member, a method for producing a hydrophilic polymer, a hydrophilic film composition, and a hydrophilic member using the same.

That is, the present invention is as follows.
[1]
A hydrophilic polymer containing a structure represented by general formulas (I-1) and (I-2) and having a residual monomer amount of 3.0% by mass or less.

In the formula (I-1) and (I-2), each represent R ²⁰¹ to R ²⁰⁵ independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _{a, -OCON (R a) (} R b), - NHCON (R a) (R b), - SO 3 R e, -OSO 3 R e, -SO 2 R d, -NHSO 2 R d, -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.
[2]
The hydrophilic polymer as described in [1] or [2], wherein L ²⁰² in the general formula (I-1) is a single bond and R ²⁰⁵ is a hydrogen atom.
[3]
The hydrophilic polymer as described in [1], wherein the residual monomer amount is 1.0% by mass or less.
[4]
Residual monomer amount is 0.1 mass% or less, The hydrophilic polymer in any one of [1]-[3] characterized by the above-mentioned.
[5]
In [1] to [4], the residual monomer is acrylamide, and the hydrophilic polymer as described in any one of [1] to [4].
[6]
[1] A hydrophilic composition comprising the hydrophilic polymer according to any one of [5].
[7]
The hydrophilic member formed with the hydrophilic composition as described in [6].
[8]
A polymerization step of the monomer, and a step of adding an organic solvent having a solubility of the monomer at 20 ° C. of 10% by mass or more and an initiator after the polymerization step to the general formulas (I-1) and (I−) The manufacturing method of the hydrophilic polymer which contains the structure represented by 2) and whose residual monomer amount is 3.0 mass% or less.

In the formula (I-1) and (I-2), each represent R ²⁰¹ to R ²⁰⁵ independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _{a, -OCON (R a) (} R b), - NHCON (R a) (R b), - SO 3 R e, -OSO 3 R e, -SO 2 R d, -NHSO 2 R d, -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.
[9]
[7] or [8], wherein the monomer is acrylamide, and the organic solvent having a solubility of 10% by mass or more at 20 ° C. is methanol.
[10]
[9], wherein the solvent used in the polymerization step is an organic solvent having a solubility of the monomer at 20 ° C. of 10% by mass or more and an organic solvent having a solubility of the hydrophilic polymer of 10% by mass or less. The manufacturing method as described.

  ADVANTAGE OF THE INVENTION According to this invention, the hydrophilic member which has the surface where the safety | security was high on various board | substrate surfaces, and also was excellent in hydrophilicity, water resistance, and the adhesiveness with a base-material surface can be provided.

Hereinafter, the present invention will be described in detail.
The hydrophilic polymer of this invention contains the structure represented by general formula (I-1) and (I-2), and the amount of residual monomers is 3.0 mass% or less.

In the formula (I-1) and (I-2), each represent R ²⁰¹ to R ²⁰⁵ independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _{a, -OCON (R a) (} R b), - NHCON (R a) (R b), - SO 3 R e, -OSO 3 R e, -SO 2 R d, -NHSO 2 R d, -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

  The hydrophilic polymer (I) including the structures represented by the general formulas (I-1) and (I-2) has a structural unit represented by the above general formula (I-2) and has a polymer chain. It preferably has a partial structure represented by the above general formula (I-1) at the terminal thereof.

In the general formulas (I-1) and (I-2), R ^{201 to} R ²⁰⁵ each independently represents a hydrogen atom or a hydrocarbon group, and hydrocarbons in the case where R ^{201 to} R ²⁰⁵ represent a hydrocarbon group. Examples of the group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ^{201 to} R ²⁰⁵ are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability. R ²⁰⁵ is more preferably a hydrogen atom.

  These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is constituted by a bond between a substituent and an alkylene group, and a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent. Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, ア ル キ ル -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-reelcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N'- Rukyureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N— Arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureate group, N ′, N′-dialkyl-N -Arylureido group, N'-aryl-Ν-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N -Arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, Ryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino Group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group,

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfa Yl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group (-PO ₃ H ₂ ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), Oyo phosphonooxy group (-OPO ₃ H ₂₎ A conjugated base group thereof (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), diaryl phosphonooxy group (-OPO ₃ (aryl) _2), alkylaryl phosphonooxy aryloxy Group (—OPO (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, and alkynyl group.

Specific examples of the alkyl group in these substituents are the same as those of R ^{1 to} R ⁸ , and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl , Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoy Phenyl group include a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group. Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1-butenyl, A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoy Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group Group, phosphonooxy group, phosphonatooxy group, aryl group, and alkenyl group.

  On the other hand, the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Preferably, it is a straight chain having 1 to 12 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms, more preferably a branched structure having 3 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms, and More preferable examples include cyclic alkylene groups having 5 to 10 carbon atoms, and further preferably 5 to 8 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a hydroxymethyl group, a methoxymethyl group, and a methoxyethoxy group. Ethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonyl group Group, allyloxycarbonyl butyl group,

Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoyl Methyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Torilho Phonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.
Of these, a hydroxymethyl group is preferred from the viewpoint of hydrophilicity.

L ²⁰¹ and L ²⁰² each independently represents a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer is directly bonded to the A ²⁰¹ and Si atoms without a connecting chain. If L ^201, L ²⁰² represents an organic linking group, L ²⁰¹ ~L ¹⁰² represents a polyvalent linking group comprising non-metal atom, the carbon atoms of from 0 to 60, the nitrogen from 0 to 10 It consists of atoms, 0 to 50 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Specifically, it is preferably selected from -N <, an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof, -O-, -S-, -CO-, -NH-, or A combination containing -O- or -S- or -CO- or -NH- is preferably a divalent linking group.
More specific examples of the linking group include the following structural units or those formed by combining them.

L ²⁰¹ and L ²⁰² are more preferably a single bond, —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO. ₂ -, - CH ₂ - is.
More preferably, L ²⁰² is a single bond.

A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _{a, -OCON (R a) (} R b), - NHCON (R a) (R b), - SO 3 R e, -OSO 3 R e, -SO 2 R d, -NHSO 2 R d, -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R _d is a linear, branched or cyclic group. alkyl group (preferably having from 1 to 8 carbon atoms) represents, R _e and R _f each independently represents a hydrogen atom or a straight, branched or cyclic alkyl group (preferably having from 1 to 8 carbon atoms), an alkali metal, an alkaline earth metal or an onium,, R _g represents a halogen ion, an inorganic anion or an organic anion. In addition, —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) R _{a to} R _g may be bonded to each other to form a ring for (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ), The formed ring may be a heterocycle containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. R _{a to} R _g may further have a substituent, and the substituents that can be introduced here are the same as those exemplified as the substituents that can be introduced when R ^{1 to} R ⁸ are alkyl groups. Can be listed.

Specific examples of the linear, branched or cyclic alkyl group in R _{a to} R _f include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an isopropyl group. , Isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
In addition, in R _{a to} R _g , preferable examples of the alkali metal include lithium, sodium, and potassium, the alkaline earth metal includes barium, and the onium includes ammonium, iodonium, sulfonium, and the like.
Examples of the halogen ion include fluorine ion, chlorine ion, bromine ion, inorganic anion includes nitrate anion, sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion, etc., and organic anion includes methanesulfonate anion. Trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, p-toluenesulfonic acid anion, and the like.

The A ^201, _{specifically, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -COOH, -SO 3 - NMe 4 +, -SO 3 - K +, - (CH 2 CH 2 O) _n H, morpholyl group and the like are preferable. More _{preferably, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -SO 3 - K +, - (CH 2 CH 2 O) n H, is. In the above, n preferably represents an integer of 1 to 100.

  q represents an integer of 1 to 3. Preferably it is 2-3, More preferably, it is 3.

In the present invention, L ²⁰² in the general formula (I-1) is a single bond, it is preferred that R ²⁰⁵ is a hydrogen atom.
The structure represented by (I-2) is more preferably a structure derived from acrylamide. This is because a polymer obtained by polymerizing acrylamide can impart higher hydrophilicity.

  In the hydrophilic polymer (I) including the structures represented by the general formulas (I-1) and (I-2), the number of moles of the structural unit of the general formula (I-1) having a hydrolyzable silyl group amount. On the other hand, the number of moles of the structural unit of the general formula (I-2) is preferably in the range of 1000 to 5 times, more preferably in the range of 500 to 10 times, and most preferably in the range of 200 to 20 times. If it is 20 times or more, the hydrophilicity is not insufficient. On the other hand, if it is 200 times or less, the amount of hydrolyzable silyl groups is sufficient, sufficient curing is obtained, and the film strength is also sufficient.

  The weight average molecular weight of the hydrophilic polymer (I) including the structures represented by the general formulas (I-1) and (I-2) is preferably 1,000 to 1,000,000, and 1,000 to 500,000. 000 is more preferable, and 1,000 to 200,000 is most preferable.

  Specific examples of the hydrophilic polymer (I) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

  The hydrophilic polymer (I) may be a copolymer with another monomer. Examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. These known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.

  Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphene Chill acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxy E phenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.
Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

  The ratio of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but the function as a hydrophilic film is sufficient, and the specific hydrophilic polymer (I The ratio is preferably not too large in order to obtain the full advantage of adding the Accordingly, the preferred total proportion of other monomers in the specific hydrophilic polymer (I) is preferably 80% by mass or less, and more preferably 50% by mass or less.

  The copolymerization ratio of the hydrophilic polymer unit (I-2) and other monomers can be measured with an infrared spectrophotometer by creating a calibration curve using a nuclear magnetic resonance apparatus (NMR) or a standard substance. .

In the hydrophilic composition of the present invention, the hydrophilic polymer unit (I-2) may be used alone or in combination of two or more.
From the viewpoint of improving curability and imparting hydrophilicity, the hydrophilic polymer (I) is preferably used in an amount of 20 to 99.5% by mass with respect to the total solid content of the hydrophilic composition, and is preferably 30 to 99.5% by mass. More preferably it is used.

  The above-mentioned hydrophilic polymer forms a crosslinked film in a state where it is mixed with a hydrolysis and polycondensate of metal alkoxide. The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the hydrophilic polymer has a viscosity of 0.1 to 100 mPa · s (5% aqueous solution, measured at 20 ° C.), preferably When it is in the range of 0.5 to 70 mPa · s, more preferably 1 to 50 mPa · s, good film properties are provided.

[Residual monomer amount]
The amount of residual monomers in the hydrophilic polymer of the present invention is 3.0% by mass or less. The residual monomer is preferably 1.0% by mass or less, and more preferably 0.1% by mass or less. If the residual monomer amount is within this range, the adhesion is improved and water resistance can be imparted. The amount of residual monomer can be quantified by high performance liquid chromatography, gas chromatography or the like.
The residual monomer is preferably acrylamide. This is because a polymer obtained by polymerizing acrylamide can impart higher hydrophilicity.

[Method for producing hydrophilic polymer]
The method for producing a hydrophilic polymer in the present invention includes a monomer polymerization step and a step of adding an organic solvent having a solubility of the monomer of 10% by mass or more at 20 ° C. and an initiator after the polymerization step.

(Polymerization process)
The hydrophilic polymer containing the structure represented by the general formulas (I-1) and (I-2) is, for example, a chain transfer agent (described in the radical polymerization handbook (NTS, Mikiji Tsunoike, Go Endo)). And Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)) can be synthesized by radical polymerization of a hydrophilic monomer (eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate). Examples of chain transfer agents include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane. Alternatively, a hydrophilic monomer (eg, acrylamide) may be radically polymerized using a radical polymerization initiator having a reactive group without using a chain transfer agent.

  The hydrophilic polymer containing the structures represented by the general formulas (I-1) and (I-2) is represented by the following general formula (ii) and a radically polymerizable monomer represented by the following general formula (i). In the radical polymerization, it can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.

In the above formula (i) and ^{(ii), R 201 ~R 205} , L 201, L 202, A 201, q is the same as defined in the general formula (I-1). These compounds are commercially available and can also be easily synthesized. The radically polymerizable monomer represented by the general formula (i) has a hydrophilic group ^A201 , and this monomer becomes one structural unit in the hydrophilic polymer.
In the hydrophilic polymer including the structures represented by the general formulas (I-1) and (I-2), the number of moles of the structural unit of the general formula (I-1) having a hydrolyzable silyl group amount, The number of moles of the structural unit of the general formula (I-2) is preferably 1000 to 5 times, more preferably 500 to 10 times, and most preferably 200 to 20 times. If it is 20 times or more, the hydrophilicity is not insufficient. On the other hand, if it is 200 times or less, the amount of hydrolyzable silyl groups is sufficient, sufficient curing is obtained, and the film strength is also sufficient.

(Reaction format)
The reaction mode when the compound corresponding to the structural unit represented by the general formula (I-1) and the unsaturated compound corresponding to the structural unit represented by the general formula (I-2) are subjected to radical reaction is particularly limited. For example, a bulk reaction, a solution reaction, a suspension reaction (emulsification reaction), or the like is preferably performed in the presence of a radical initiator or irradiation with a high-pressure mercury lamp or the like. Also, the polymerization method can be appropriately selected according to the purpose, such as batch method (including divided addition method and sequential addition method), semi-continuous method or continuous method. In particular, the unsaturated compound split addition method (sometimes referred to as split charge) and the sequential addition method (also referred to as incremental method) include homopolymerization of the unsaturated compound represented by formula (I-2). Is a preferred polymerization method because it can be efficiently suppressed.

(Reaction ratio)
The reaction ratio when the compound corresponding to the structural unit represented by general formula (I-1) and the unsaturated compound corresponding to the structural unit represented by general formula (I-2) are reacted is also particularly limited. Although it is not a thing, For example, with respect to the compound corresponding to the structural unit represented by general formula (I-1), the reaction amount of the unsaturated compound corresponding to the structural unit represented by general formula (I-2) The ratio is preferably set to a value in the range of 0.5 to 200 mol times. The reason for this is that if the reaction ratio is outside these ranges, side reactions are likely to occur, and the yield of the hydrolyzable silane compound may be reduced. Therefore, the ratio of the reaction amount of the compound corresponding to the structural unit represented by the general formula (I-1) and the unsaturated compound corresponding to the structural unit represented by the general formula (I-2) is 1 to 100 mol times. It is more preferable to set it as the value within the range, and it is still more preferable to set it as the value within the range of 5-60 mol times.

(Reaction temperature)
The reaction temperature is particularly limited when the compound corresponding to the structural unit represented by formula (I-1) and the unsaturated compound corresponding to the structural unit represented by formula (I-2) are reacted. However, it is preferable to set the value within the range of −50 to 200 ° C., for example. The reason for this is that when the reaction temperature is less than −50 ° C., the reactivity may be significantly lowered. On the other hand, when the reaction temperature exceeds 200 ° C., the types of solvents that can be used are excessively limited. This is because there is a case where a side reaction is likely to occur. Accordingly, the reaction temperature is more preferably set to a value within the range of 0 to 100 ° C, and further preferably set to a value within the range of 30 to 100 ° C.

(Reaction time)
About reaction time, although depending on reaction temperature etc., it is usually preferable to set it as a value within the range of 0.5 to 100 hours from the relation between the certainty of reaction and productivity, and the range of 1 to 24 hours A value within the range is more preferable.

(Reaction atmosphere)
The reaction atmosphere is particularly limited when the compound corresponding to the structural unit represented by formula (I-1) and the unsaturated compound corresponding to the structural unit represented by formula (I-2) are reacted. Although it is not a thing, for example, it is preferable to carry out radical reaction of these compounds after carrying out nitrogen bubbling in the reaction system or performing deoxygenation treatment by ultrasonic waves. The reason for this is that when the radical reaction is performed in nitrogen or the like in this manner, the generation of a compound due to the coupling reaction between chain transfer agents can be efficiently suppressed. That is, when a coupling reaction of a mercapto group occurs, it is often colored, but this can be effectively prevented and a highly transparent hydrolyzable silane compound can be obtained. Further, with respect to the reaction atmosphere, if water is present in the reaction system, there is a problem that hydrolysis of the alkoxy group tends to spontaneously proceed at the radical reaction stage. Particularly, when a hydrolyzable silane containing a carboxy group is subjected to a radical reaction, hydrolysis of the alkoxy group easily proceeds even in the presence of a small amount of water. For this reason, when the raw material used is liquid, for example, dehydration treatment is performed using a dehydrating agent such as molecular sieve, calcium hydride, magnesium sulfate, or, if necessary, in the presence of these desiccants in nitrogen. More preferably, the distillation treatment is performed in advance.

(solvent)
When the compound corresponding to the structural unit represented by the general formula (I-1) and the unsaturated compound corresponding to the structural unit represented by the general formula (I-2) are reacted, these are reacted uniformly. Therefore, it is preferable to use a solvent. Examples of such solvents include alcohol solvents (for example, methanol, ethanol, 2-propanol, 1-methoxy-2-propanol, t-butanol, methylpropylene glycol, diacetone alcohol), amide solvents (for example, N, N- Dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3, dimethyl-2-imidazolidinone), sulfone solvents (eg sulfolane) sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents ( For example, tetramethyl urea), ether solvents (for example, tetrahydrofuran, dioxane, cyclopentyl methyl ether, diphenyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether Tate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, diethylene glycol dimethyl ether), ketone solvents (eg acetone, methyl ethyl ketone, 2-heptanone, cyclohexanone), hydrocarbon solvents (eg hexane, benzene, toluene, Xylene, n-decane), halogen-based solvents (for example, tetrachloroethane, chlorobenzene, methylene chloride), ester-based solvents (for example, ethyl acetate, butyl acetate, ethyl lactate), and nitrile-based solvents (for example, acetonitrile). These solvents may be used alone or in combination of two or more.
In addition, the usage-amount of a solvent is 1-10 when the total amount of the unsaturated compound corresponding to the structural unit represented by general formula (I-1) and general formula (I-2) is 100 weight part. The value is preferably in the range of 1,000 parts by weight, more preferably in the range of 50 to 1,000 parts by weight, and particularly preferably in the range of 50 to 800 parts by weight. It is.
The solvent used in the polymerization step is preferably an organic solvent having a solubility of the monomer at 20 ° C. of 10% by mass or more and a solubility of the hydrophilic polymer of 10% by mass or less.
This is to reduce the time required for dissolving the monomer at the time of charging and to allow easy removal by filtration after polymerization.

(Step of adding an organic solvent and an initiator)
After the polymerization process, the step of adding an organic solvent having a solubility of the monomer of 10% by mass or more at 20 ° C. and an initiator minimizes the time required for the synthesis, and a solvent having a high boiling point and an initiator having a high decomposition temperature. Since it is used, the safety during the polymerization reaction is increased, and the amount of residual monomer can be reduced at the same time.

Examples of the organic solvent having a monomer solubility of 20% by mass or more at 20 ° C. include ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone and 2-butanone, and amide solvents such as N, N-dimethylacetamide. , Alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether and tetrahydrofuran, and nitrile solvents such as acetonitrile.
The solubility of the 20 ° C. monomer includes the case where the monomer is liquid at 20 ° C.
By adding an organic solvent, the monomer remaining in the reaction system can be dissolved and removed from the polymer solid.
The addition amount of the organic solvent is preferably 0.05 to 20 equivalents, more preferably 0.5 to 5.0 equivalents, most preferably 1.0 to 3.0 equivalents with respect to the solvent used in the polymerization. preferable.
If the addition amount of the organic solvent is within the above range, a sufficient monomer removal effect can be obtained, and the amount of the solvent to be used is not increased, leading to cost reduction and improving productivity, which is preferable.

  The radical initiator is preferably an azo radical initiator or an organic peroxide, and more preferably an azo radical initiator. Specifically, preferred azo radical initiators include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1-[(1-cyano- 1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis [ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymes) L) ethyl] propionamide], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [2- (5-methyl-2-imidazoline-2) -Yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro -1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2, 2′-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- [1- (2- Hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (2-methyl-N) -Phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-hydroxyphenyl) -2- Methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine Dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride , 2,2'-azobis [N-(2-hydroxyethyl) -2-methyl - propionamidine] dihydrochloride, alone or in combinations of two or more such 2,2-dimethyl azobisisobutyrate and the like.

The initiator addition amount is 0 with respect to 100 mol parts of the total amount of the compound corresponding to the structural unit represented by the general formula (I-1) and the compound corresponding to the structural unit represented by the general formula (I-2). It is preferably within the range of .0005 to 20 mol parts, and more preferably within the range of 0.001 to 5 mol parts.
If the addition amount of the initiator is within the above range, the cost is not increased and the polymerization reaction proceeds sufficiently to obtain a desired molecular weight and yield.

In the production method of the present invention, the monomer is preferably acrylamide, and the organic solvent having a solubility of the monomer at 20 ° C. of 10% by mass or more is preferably methanol.
This is because methanol has the highest solubility of acrylamide at 20 ° C. and the solubility of the polymer is low.

[Hydrophilic composition]
The hydrophilic composition in the present invention contains the hydrophilic polymer. Preferably, it contains (A) a metal complex catalyst, (B) a metal alkoxide, and the like.

[(A) Catalyst]
In the hydrophilic composition and the composition for undercoat layer of this invention, it is preferable to contain (A) a catalyst. (A) The reaction of the hydrophilic polymer can be promoted by containing a catalyst. (A) As the catalyst, an acid or a basic compound is used as it is, or the acid or the basic compound is dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst inclusive) , Also referred to as a basic catalyst). The concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

  The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RCOOH. Examples thereof include substituted carboxylic acids in which R in the structural formula is substituted with other elements or substituents, sulfonic acids such as benzene sulfonic acid, etc., and basic catalysts include ammonia bases such as aqueous ammonia and amines such as ethylamine and aniline Etc.

The catalyst (A) is preferably a non-volatile catalyst. Nonvolatile catalysts are those other than those having a boiling point of less than 125 ° C., in other words, those having a boiling point of 125 ° C. or higher, or those having no boiling point in the first place (one that does not cause phase change such as thermal decomposition). Including).
The nonvolatile catalyst used in the present invention is not particularly limited, and examples thereof include metal chelate compounds and silane coupling agents.

The metal chelate compound (hereinafter also referred to as a metal complex) is not particularly limited, but a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketone, ketoester, hydroxycarboxylic acid or the like There are metal complexes composed of oxo or hydroxy oxygen-containing compounds selected from esters, amino alcohols, and enolic active hydrogen compounds.
Among constituent metal elements, 2A group elements such as Mg, Ca, Sr and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

  In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a β-diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetic acid Ketoesters such as ethyl and butyl acetoacetate, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and other hydroxycarboxylic acids and esters thereof, 4-hydroxy-4-methyl-2-pentanone, Ketoalcohols such as 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-heptanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl-mono Ethanolamine, diethanolamine , Amino alcohols such as triethanolamine, methylol melamine, methylol urea, methylol acrylamide, enol active compounds such as malonic acid diethyl ester, methyl group, methylene group or carbonyl carbon of acetylacetone (2,4-pentanedione) And compounds having a group.

  A preferred ligand is acetylacetone or an acetylacetone derivative. In the present invention, the acetylacetone derivative refers to a compound having a substituent on the methyl group, methylene group or carbonyl carbon of acetylacetone. As the substituents substituted on the methyl group of acetylacetone, all are linear or branched alkyl groups having 1 to 3 carbon atoms, acyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxy groups, alkoxyalkyl groups, and acetylacetone As a substituent for the methylene group, a carboxyl group, each of which is a linear or branched carboxyalkyl group and a hydroxyalkyl group having 1 to 3 carbon atoms, and a substituent for the carbonyl carbon of acetylacetone is a carbon number. Is an alkyl group of 1 to 3, and in this case, a hydrogen atom is added to the carbonyl oxygen to form a hydroxyl group.

  Specific examples of preferable acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid. , Acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol. Of these, acetylacetone and diacetylacetone are particularly preferred. The complex of the above acetylacetone derivative and the above metal element is a mononuclear complex in which one to four molecules of the acetylacetone derivative are coordinated per metal element, and the coordinateable bond of the acetylacetone derivative is a coordinateable bond of the acetylacetone derivative. When the number of hands is larger than the total number of hands, ligands commonly used for ordinary complexes such as water molecules, halogen ions, nitro groups, and ammonio groups may coordinate.

  Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aco complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, and among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

Although the description of the counter salt of the metal complex described above is omitted in this specification, the type of the counter salt is arbitrary as long as it is a water-soluble salt that maintains the neutrality of the charge as the complex compound, such as nitrate, Salt forms such as halogenates, sulfates, phosphates, etc., that ensure stoichiometric neutrality are used.
For the behavior of the metal complex in the silica sol-gel reaction, see J.A. Sol-Gel. Sci. and Tec. There is a detailed description in 16.209 (1999). The following scheme is estimated as the reaction mechanism. That is, in the coating solution, the metal complex has a coordinated structure and is stable, and in the dehydration condensation reaction that starts in the heat drying process after coating, it is considered that crosslinking is promoted by a mechanism similar to an acid catalyst. In any case, the use of this metal complex has led to the improvement of coating solution aging stability and film surface quality, as well as high hydrophilicity and high durability.

  The above metal complex catalyst can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.

  In the present invention, the silane coupling agent used as the non-volatile catalyst is not particularly limited, and examples thereof include those having a functional group exhibiting acidity or alkalinity, and more specifically, peroxo acids, carboxylic acids, carbohydrazones. Acid, carboxymido acid, sulfonic acid, sulfinic acid, sulfenic acid, selenonic acid, selenic acid, selenic acid, telluronic acid, and basic groups such as amino groups that show acidity such as the above alkali metal salts Examples thereof include silane coupling agents having the functional group shown.

  (A) The catalyst which concerns on this invention is used in the hydrophilic composition of this invention, Preferably it is 0-50 mass% with respect to a non-volatile component, More preferably, it is used in 5-25 mass%. Moreover, (A) a catalyst may be used independently or may be used together 2 or more types.

[(B) an alkoxide compound of an element selected from Si, Ti, Zi, and Al]
In the present invention, the hydrophilic composition preferably contains (B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al (hereinafter also referred to as (B) a specific alkoxide).
(B) In the hydrolysis and polycondensation in the system by including the specific alkoxide, the crosslinking is performed by the silane coupling group contained in the specific hydrophilic polymer and the polymerizable functional group (B) hydrolyzed by the specific alkoxide. Since the number of reaction sites to be formed increases and an organic-inorganic composite film with a denser and stronger cross-linked structure is formed, the resulting overcoat layer has even higher strength and exhibits excellent wear resistance. It is considered that high surface hydrophilicity can be maintained for a long time. Further, when water adheres to the surface having a very high hydrophilicity, the surface area with the air interface increases because the water spreads, the drying speed of water becomes very fast, and a coating film having excellent quick drying properties is obtained.
The alkoxide compound of an element selected from (B) specific alkoxide used in the present invention, Si, Ti, Zr, and Al, has a polymerizable functional group in its structure and is a hydrolyzate that functions as a crosslinking agent. It is a decomposition polymerizable compound, and forms a strong film having a crosslinked structure by condensation polymerization with a specific hydrophilic polymer.
(B) The specific alkoxide is preferably a compound represented by the following general formula (V). In forming a crosslinked structure in order to cure the hydrophilic film, the specific hydrophilic polymer general formula (V The specific alkoxide represented by (B) is mixed, coated on the substrate surface, heated and dried.

In the general formula (V), R ¹⁷ represents a hydrogen atom, an alkyl group or an aryl group, R ¹⁸ represents an alkyl group or an aryl group, Y represents Si, Al, Ti or Zr, and k is 0 to 2. Represents an integer. When R ¹⁷ and R ¹⁸ represent an alkyl group, the carbon number is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group. This compound is a low molecular compound and preferably has a molecular weight of 1000 or less.

  Although the specific example of (B) specific alkoxide represented by general formula (V) below is given, this invention is not limited to this. In the case where Y is Si, that is, those containing silicon in the specific alkoxide include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, Ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane Γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diph Alkenyl dimethoxysilane, mention may be made of diphenyl diethoxy silane. Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

In the case where Y is Al, that is, the specific alkoxide containing aluminum includes, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like.
When Y is Ti, i.e., including titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl triethoxy titanate. Examples thereof include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate.
In the case where Y is Zr, that is, those containing zirconium include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.
Among these, an alkoxide in which Y is Si is preferable from the viewpoint of film properties.

The (B) specific alkoxide according to the present invention may be used alone or in combination of two or more.
(B) The specific alkoxide is preferably used in the range of 5 to 80% by mass, more preferably 10 to 70% by mass with respect to the nonvolatile component in the hydrophilic composition of the present invention.
(B) The specific alkoxide can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.

The hydrophilic member of the present invention has a hydrophilic layer formed by coating a hydrophilic composition on a substrate, and the hydrophilic composition is the hydrophilic composition of the present invention described above. Thus, a hydrophilic member having sufficient hydrophilicity, abrasion resistance, antifouling property and adhesion and capable of maintaining excellent lubricity for a long period of time can be obtained.
The hydrophilic member of the present invention may further have an undercoat layer between the substrate and the hydrophilic layer in order to improve the adhesion between the substrate and the hydrophilic layer.
Here, the undercoat layer is preferably formed by applying the above-described composition containing the catalyst (A), thereby further improving the adhesion between the substrate and the hydrophilic layer. Can be made. Here, the catalyst (A) is preferably a non-volatile catalyst as described above.
(A) A catalyst is used in the composition for undercoat layers, Preferably it is 0-50 mass% with respect to a non-volatile component, More preferably, it is used in 1-25 mass%. Moreover, (A) a catalyst may be used independently or may be used together 2 or more types.

Further, the undercoat layer is preferably formed by applying a composition containing (B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al. In addition, the adhesion between the substrate and the hydrophilic layer can be improved.
(B) The specific alkoxide is preferably used in the hydrophilic composition of the present invention in the range of 5 to 99% by mass, more preferably 10 to 95% by mass with respect to the nonvolatile component. Moreover, (B) specific alkoxide may be used independently or may be used together 2 or more types.

[Other ingredients]
Various compounds can be used in combination with the hydrophilic composition and the composition for the undercoat layer according to the purpose as long as the effects of the present invention are not impaired. Hereinafter, components that can be used in combination will be described.

[Surfactant]
In the present invention, it is preferable to use a surfactant in order to improve the coating surface of the hydrophilic composition and the undercoat layer composition. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.

  The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, copolymers of polyethylene glycol and polypropylene glycol.

  The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters, and imidazolines.
Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.
The surfactant is preferably used in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the nonvolatile component in the hydrophilic composition of the present invention. Moreover, surfactant can be used individually or in combination of 2 or more types.

  Although the specific example of a preferable surfactant is shown below, this invention is not limited to these.

[Antimicrobial agent]
In order to impart antibacterial, antifungal and antialgal properties to the hydrophilic member of the present invention, an antibacterial agent can be contained in the hydrophilic composition and the undercoat layer composition. It is preferable to contain a hydrophilic or water-soluble antibacterial agent. By including a hydrophilic and water-soluble antibacterial agent, a surface hydrophilic member having excellent antibacterial, antifungal and antialgal properties can be obtained without impairing the surface hydrophilicity.
As the antibacterial agent, it is preferable to add a compound that does not lower the hydrophilicity of the hydrophilic member. Examples of such an antibacterial agent include inorganic antibacterial agents and water-soluble organic antibacterial agents. As the antibacterial agent, those exhibiting a bactericidal effect against fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, and fungi such as fungi and yeast are used.

Examples of organic antibacterial agents include phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, quaternary ammonium salts, pyridines, triazines, benzoisothiazolines, and isothiazolines. It is done.
For example, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyl Imido, copper 8-quinolinate, bis (tributyltin) oxide, 2- (4-thiazolyl) benzimidazole (hereinafter referred to as TBZ), methyl 2-benzimidazole carbamate (hereinafter referred to as BCM), 10,10 '-Oxybisphenoxyarsine (hereinafter referred to as OBPA) 2,3,5,6-tetrachloro-4- (methylsulfone) pyridine, bis (2-pyridylthio-1-oxide) zinc (hereinafter referred to as ZPT) >, N, N-dimethyl-N ′-(fluorodichloromethylthio) -N′-phenylsulfamide <dichloro Luanide>, poly- (hexamethylene biguanide) hydrochloride, dithio-2-2′-bis (benzmethylamide), 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-bromo-2 -Nitro-1,3-propanediol, hexahydro-1,3-tris- (2-hydroxyethyl) -S-triazine, p-chloro-m-xylenol, 1,2-benzisothiazolin-3-one, etc. However, it is not limited to these.
These organic antibacterial agents can be appropriately selected and used in consideration of hydrophilicity, water resistance, sublimation property, safety and the like. Among organic antibacterial agents, 2-bromo-2-nitro-1,3-propanediol, TBZ, BCM, OBPA, and ZPT are preferable from the viewpoint of hydrophilicity, antibacterial effect, and cost.

  Examples of inorganic antibacterial agents include mercury, silver, copper, zinc, iron, lead, bismuth and the like in descending order of bactericidal action. For example, the thing which carry | supported metals and metal ions, such as silver, copper, zinc, nickel, on the silicate type | system | group support | carrier, phosphate type | system | group support, an oxide, glass, potassium titanate, an amino acid, etc. is mentioned. For example, zeolite antibacterial, calcium silicate antibacterial, zirconium phosphate antibacterial, calcium phosphate antibacterial, zinc oxide antibacterial, soluble glass antibacterial, silica gel antibacterial, activated carbon antibacterial, titanium oxide Antibacterial agent, titania antibacterial agent, organometallic antibacterial agent, ion exchanger ceramic antibacterial agent, layered phosphate-quaternary ammonium salt antibacterial agent, antibacterial stainless steel, etc. Absent.

Natural antibacterial agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crabs and shrimp shells.
In the present invention, Nikko's “trade name Holon Killer Bees Sera” made of aminometal in which a metal is compounded on both sides of an amino acid is preferable.
These are not transpirationable, easily interact with the polymer and crosslinker component of the hydrophilic layer, can be stably molecularly dispersed or solid dispersed, the antibacterial agent is easily exposed to the surface of the topcoat layer, and Even if it is splashed with water, it does not elute, and the effect can be maintained for a long time without affecting the human body. Moreover, it can disperse | distribute stably with respect to a topcoat layer or a coating liquid, and deterioration of a topcoat layer or a coating liquid does not occur.
Among the antibacterial agents, silver-based inorganic antibacterial agents and water-soluble organic antibacterial agents are most preferable because of their great antibacterial effects. In particular, silver zeolite in which silver is supported on zeolite, which is a silicate carrier, antibacterial agent in which silver is supported on silica gel, 2-bromo-2-nitro-1,3-propanediol, TPN, TBZ, BCM, OBPA ZPT is preferred. Particularly preferred commercially available silver zeolite antibacterial agents include “Zeomic” from Shinagawa Fuel, “Sylwell” from Fuji Silysia Chemical, and “Bactenone” from JEOL. In addition, Toa Gosei's “Novalon” in which silver is supported on an inorganic ion exchanger ceramic, “Atomy Ball” from Catalytic Chemical Industry, and “Suneyeback P” as a triazine antibacterial agent are also preferred.

  The content of the antibacterial agent is generally 0.001 to 10% by mass with respect to the nonvolatile components in the hydrophilic composition and the composition for the undercoat layer, but is 0.005 to 5% by mass. Is preferable, 0.01-3 mass% is more preferable, 0.02-1.5 mass% is especially preferable, 0.05-1 mass% is the most preferable. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. Further, if the content is 10% by mass or less, the hydrophilicity is not lowered, the aging is not deteriorated, and the antifouling property and the antifogging property are not adversely affected.

[Inorganic fine particles]
The hydrophilic composition and the undercoat layer composition of the present invention may contain inorganic fine particles in order to improve the cured film strength and hydrophilicity of the film to be formed. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, more preferably 0.5 to 3 μm. Within the above range, it is possible to form a film that is stably dispersed in the layer, sufficiently retains the film strength, and is excellent in hydrophilicity. The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.

  The inorganic fine particles according to the present invention are used in the hydrophilic composition and the undercoat layer composition of the present invention in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, based on the nonvolatile components. The The inorganic fine particles can be used alone or in combination of two or more.

[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance and durability of the hydrophilic member.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
The addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5 to 15% by mass in terms of solid content.

〔Antioxidant〕
In order to improve the stability of the hydrophilic member of the present invention, an antioxidant can be added to the hydrophilic composition and the composition for the undercoat layer. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by mass in terms of solid content.

〔solvent〕
In forming the undercoat layer and the overcoat layer of the hydrophilic member of the present invention, an organic solvent may be appropriately added to the hydrophilic composition and the composition for the undercoat layer in order to ensure the formation of a uniform coating film on the substrate. It is valid.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
In this case, it is effective to add VOC (volatile organic solvent) in a range that does not cause a problem, and the amount thereof is preferably 0 to 50% by mass, more preferably based on the entire coating liquid when forming the hydrophilic member. Is in the range of 0-30% by weight.

[Polymer compound]
In order to adjust film physical properties, various polymer compounds can be added to the hydrophilic composition and the composition for the undercoat layer of the present invention as long as the hydrophilicity is not inhibited. High molecular compounds include acrylic polymer, polyvinyl alcohol resin, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.

[Other additives]
In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, and tackifiers within a range that does not impair hydrophilicity in order to improve adhesion to the substrate. Etc. can be contained. As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifying resin having a polymerizable unsaturated bond.

The hydrophilic composition and undercoat layer composition of the present invention may contain zirconia chlorides, nitrates, alkoxides and organic complexes from the viewpoints of wear resistance, acid resistance and alkali resistance. Examples of zirconia chloride include zirconium chloride, zirconium oxychloride (octahydrate), chlorine-containing zirconium alkoxide Zr (OC _m H _{2m + 1} ) _x Cl _y (m, x, y: integer, x + y = 4), etc. Examples of zirconium nitrate include zirconium oxynitrate (dihydrate). Examples of zirconium alkoxide include zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, zirconium butoxide, zirconium t-butoxide, and the like. Examples of the organic complex include acetylacetone derivatives. Specifically, tetrakis (acetylacetonato) zirconium, bis (acetylacetonato) zirconium dibutoxide, bis (acetylacetonato) zirconium dichloride, tetrakis 3,5-heptanedionate) zirconium, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate) zirconium, bis (2,2,6,6-tetramethyl-3,5- Heptanedionate) zirconium diisopropoxide and the like.
The zirconium compound is preferably used in the range of 0 to 50 mass%, more preferably 5 to 25 mass% as a nonvolatile component in the hydrophilic composition and the composition for undercoat layer of the present invention.

[Preparation of hydrophilic composition]
The hydrophilic composition can be prepared by stirring the hydrophilic polymer, if necessary, after dissolving (A) the catalyst and (B) the specific alkoxide in a solvent such as ethanol. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and organic inorganic A composite sol solution can be obtained.

  The solvent used in preparing the hydrophilic composition is not particularly limited as long as it can uniformly dissolve and disperse these, but for example, an aqueous solvent such as methanol, ethanol, water and the like is preferable.

  As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming a hydrophilic film with the hydrophilic composition of the present invention utilizes the sol-gel method. For the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the hydrophilic composition in the present invention.

[Preparation of composition for undercoat layer]
The undercoat layer composition can also be prepared by the same method as the hydrophilic composition.

The hydrophilic member in the present invention is formed of the above hydrophilic composition.
It is preferable to obtain the hydrophilic member of the present invention by coating a solution containing the composition for an undercoat layer of the present invention and a solution containing a hydrophilic composition on an appropriate substrate and drying. That is, preferably, the hydrophilic member of the present invention is formed by applying a composition for an undercoat layer on a substrate, heating and drying to form an undercoat layer, applying a hydrophilic composition thereon, heating, It is obtained by forming an overcoat layer by drying.
As heating and drying conditions, from the viewpoint of efficiently forming a high-density cross-linked structure, it is preferably performed in a temperature range of 50 to 200 ° C. for about 2 minutes to 1 hour, and in a temperature range of 80 to 160 ° C. It is more preferable to dry for 5 to 30 minutes. Moreover, as a heating means, it is preferable to use a well-known means, for example, the dryer etc. which have a temperature control function.

  In the hydrophilic member of the present invention, when the overcoat layer and the undercoat layer are coated on the substrate, the catalyst can be mixed immediately before coating on the substrate. Specifically, it is preferable to apply within 1 hour immediately after catalyst mixing. When the catalyst is mixed and left to stand for a long time, the composition of the undercoat layer or the hydrophilic composition increases in viscosity, and defects such as coating unevenness may occur. Other components are also preferably mixed immediately before coating, but may be stored for a long time after mixing.

〔substrate〕
The substrate used in the present invention is not particularly limited, but glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, tile, rubber, latex, combinations thereof, and lamination thereof Any body can be suitably used. A particularly preferable substrate is a flexible substrate having flexibility such as plastic or metal. By using a flexible substrate, the deformation of the article can be freely performed, and not only the degree of freedom of attachment work and the place of attachment is increased, but also the durability can be increased. Usually, when the trifunctional or bifunctional alkoxysilane (A) used in the present invention is used for the undercoat layer, the surface of the undercoat layer becomes hydrophobic, so that unevenness may occur when forming the hydrophilic layer thereafter. There is a concern of insufficient adhesion. For this reason, it was considered that there was a problem in using (A) trifunctional or bifunctional alkoxysilane for the undercoat layer of the hydrophilic member. However, in the present invention, a special effect can be exhibited due to the combination with the hydrophilic polymer having a silane coupling group.
The plastic substrate used in the present invention is not particularly limited, but a substrate used as an optical member is selected in consideration of optical characteristics such as transparency, refractive index, and dispersibility, and various types can be used depending on the purpose of use. It is selected in consideration of physical properties such as physical properties such as strength such as impact resistance and flexibility, heat resistance, weather resistance, and durability. Plastic substrates include polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, polysulfone. And films or sheets of polyether ketone, acrylic, nylon, fluororesin, polyimide, polyether imide, polyether sulfone and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use. The thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for the place where it is used for a plane or intensity | strength is requested | required.

  For the purpose of improving the adhesion between the substrate and the undercoat layer, one or both surfaces of the substrate can be subjected to a surface hydrophilization treatment by an oxidation method, a roughening method, or the like as desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

  As a plastic substrate, what formed the inorganic compound layer described in description of the following glass plate on the plastic plate can also be used. In this case, the inorganic compound layer can also act as an antireflection layer. Even when the inorganic compound layer is formed on the plastic plate, it can be formed by the same method as in the inorganic substrate described above.

  When an inorganic compound layer is formed on a transparent plastic substrate, a hard coat layer may be formed between both layers. By providing the hard coat layer, the hardness of the substrate surface is improved and the substrate surface is smoothed, so that the adhesion between the transparent plastic substrate and the inorganic compound layer is improved, the scratch resistance is improved, and the substrate is bent. It is possible to suppress the occurrence of cracks in the inorganic compound layer due to the above. By using such a substrate, the mechanical strength of the hydrophilic member can be improved. The material of the hard coat layer is not particularly limited as long as it has transparency, appropriate strength, and mechanical strength. For example, a curable resin or a thermosetting resin by irradiation with ionizing radiation or ultraviolet rays can be used, and an ultraviolet irradiation curable acrylic resin, an organosilicon resin, or a thermosetting polysiloxane resin is particularly preferable. The refractive index of these resins is more preferably equal to or close to the refractive index of the transparent plastic substrate.

  The coating method of such a hard coat layer is not particularly limited, and any method can be adopted as long as it is uniformly applied. In addition, the hard coat layer having a thickness of 3 μm or more provides sufficient strength, but is preferably in the range of 5 to 7 μm from the viewpoint of transparency, coating accuracy, and handling. Further, by mixing and dispersing inorganic or organic particles having an average particle size of 0.01 to 3 μm in the hard coat layer, a light diffusing treatment generally called anti-glare can be performed. These particles are not particularly limited as long as they are transparent, but a low refractive index material is preferable, and silicon oxide and magnesium fluoride are particularly preferable in terms of stability, heat resistance, and the like. The light diffusing treatment can also be achieved by providing irregularities on the surface of the hard coat layer. By providing these inorganic compound layers and hard coat layers between the substrate and the undercoat layer, adhesion between the substrate and the undercoat layer can be improved.

As the metal thin plate, an aluminum plate is particularly preferable.
The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of different elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

  The thickness of the substrate is preferably 0.05 to 0.6 mm, and more preferably 0.08 to 0.2 mm.

  Prior to using the aluminum plate, it is preferable to perform surface treatment such as roughening treatment or anodizing treatment. The surface treatment facilitates improving the hydrophilicity of the substrate and ensuring the adhesion between the undercoat layer and the substrate. Prior to the roughening treatment of the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired. The processing method of an aluminum substrate can be performed by a well-known method.

As the substrate used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is. However, in order to further improve the adhesion with the upper layer, JP-A-2001-253181 is necessary. Appropriately selected from the micropore enlargement treatment and sealing treatment of the anodized film and surface hydrophilization treatment immersed in an aqueous solution containing a hydrophilic compound, as described in Japanese Patent Laid-Open No. 2001-322365. Can do. Of course, the enlargement process and the sealing process are not limited to those described above, and any conventionally known method can be performed.
For example, as the sealing treatment, in addition to the vapor sealing, a single treatment with fluorinated zirconic acid, a treatment with sodium fluoride, or a vapor sealing with addition of lithium chloride is possible.

<Sealing treatment>
The sealing treatment used in the present invention is not particularly limited, and a conventionally known method can be used. Among them, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and sealing with hot water are particularly preferable. Hole treatment is preferred. Each will be described below.

<Sealing treatment with an aqueous solution containing an inorganic fluorine compound>
As the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.
Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluoride titanate, potassium fluoride titanate, zirconate fluoride, titanate fluoride, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphor fluoride, ammonium fluoride phosphate It is done. Of these, sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.

  The concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficiently sealing the micropores of the anodized film. Further, in terms of stain resistance, it is preferably 1% by mass or less, and more preferably 0.5% by mass or less.

It is preferable that the aqueous solution containing an inorganic fluorine compound further contains a phosphate compound. Suitable examples of the phosphate compound include phosphates of metals such as alkali metals and alkaline earth metals.
Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen phosphate Disodium, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite , Tripolyphosphate Potassium, and sodium pyrophosphate. Among these, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
The combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but the aqueous solution contains at least sodium zirconate fluoride as the inorganic fluorine compound and contains at least sodium dihydrogen phosphate as the phosphate compound. Is preferred.

  The concentration of the phosphate compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving stain resistance, and the solubility point. Therefore, it is preferably 20% by mass or less, and more preferably 5% by mass or less.

The ratio of each compound in the aqueous solution is not particularly limited, but the mass ratio of the inorganic fluorine compound and the phosphate compound is preferably 1/200 to 10/1, and preferably 1/30 to 2/1. Is more preferable.
Further, the temperature of the aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
Further, the aqueous solution preferably has a pH of 1 or more, more preferably has a pH of 2 or more, preferably has a pH of 11 or less, and more preferably has a pH of 5 or less.
A method for sealing with an aqueous solution containing an inorganic fluorine compound is not particularly limited, and examples thereof include an immersion method and a spray method. These may be used alone or in combination, or may be used in combination of two or more.
Of these, the dipping method is preferred. When the treatment is performed using the dipping method, the treatment time is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and 20 seconds or shorter. More preferred.

<Sealing treatment with water vapor>
Examples of the sealing treatment with water vapor include a method in which pressurized or normal-pressure water vapor is brought into contact with the anodized film continuously or discontinuously.
The temperature of the water vapor is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 105 ° C. or lower.
The water vapor pressure is preferably in the range (1.00 × 10 ^{5 to} 1.043 × 10 ⁵ Pa) from (atmospheric pressure−50 mmAq) to (atmospheric pressure + 300 mmAq).
Further, the time for which the water vapor is contacted is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, more preferably 20 seconds or shorter.

<Sealing treatment with hot water>
Examples of the sealing treatment with water vapor include a method of immersing an aluminum plate on which an anodized film is formed in hot water.
The hot water may contain an inorganic salt (for example, phosphate) or an organic salt.
The temperature of the hot water is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 100 ° C. or lower.
Further, the time of immersion in hot water is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and even more preferably 20 seconds or shorter.

<Hydrophilic treatment>
The hydrophilization treatment is described in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734, and 3,902,734. There are such alkali metal silicate methods. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.

  The substrate preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the undercoat layer and good stain resistance can be obtained.

  Examples of the glass plate used in the present invention include silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO A metal oxide such as (Indium Tin Oxide); a metal halide such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride; Glass plates can be mentioned. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do. In addition, the undercoat layer and the overcoat layer can be coated with the base glass as it is, but if necessary, for the purpose of improving the adhesion of the undercoat layer and the overcoat layer, on one side or both sides by an oxidation method or a roughening method, etc. Surface hydrophilization treatment can be performed. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

  The inorganic compound layer can have a single layer structure or a multilayer structure. Depending on the thickness of the inorganic compound layer, the light transmittance can be maintained, and the inorganic compound layer can also function as an antireflection layer. Examples of the inorganic compound layer forming method include dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure coating method, etc., vacuum deposition method, reactive deposition method, ion beam A known method such as a physical vapor deposition method (PVD) such as an assist method, a sputtering method, or an ion plating method, or a vapor phase method such as a chemical vapor deposition method (CVD) can be applied.

Examples of hydrophilic resins include polyvinyl alcohol (PVA), cellulose resins [methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.], chitins, chitosans, starch, and ether bonds. Examples thereof include resins [polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], resins having a carbamoyl group [polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), etc.], and the like. Moreover, the polyacrylic acid salt which has a carboxyl group, maleic acid resin, alginate, gelatins, etc. can also be mentioned.
Among these, at least one selected from polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.

Examples of the water-dispersible latex include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.
The above hydrophilic resin and water-dispersible latex may be used alone or in combination of two or more, or a hydrophilic resin and a water-dispersible latex may be used in combination.
Moreover, you may use the crosslinking agent which bridge | crosslinks the said hydrophilic resin and water-dispersible latex.
As a cross-linking agent applicable to the present invention, a cross-linking agent that forms a cross-link by known heat can be used. General thermal crosslinking agents include those described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981). The number of functional groups of the crosslinking agent used in the present invention is not particularly limited as long as it is 2 or more and can be effectively crosslinked with a hydrophilic resin or water-dispersible latex. Specific examples of the thermal crosslinking agent include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene ethylene glycol diglycidyl ether, polyethylene or Polyepoxy compounds such as polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyaldehyde compounds such as glyoxal and terephthalaldehyde, tri Range isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene Polyisocyanate compounds such as isocyanate, polymethylene polyphenyl isocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol / tolylene diisocyanate addition reaction product, block polyisocyanate Examples thereof include compounds, silane coupling agents such as tetraalkoxysilane, metal cross-linking agents such as acetylacetonate of aluminum, copper and iron (III), and polymethylol compounds such as trimethylolmelamine and pentaerythritol. Among these thermal cross-linking agents, a water-soluble cross-linking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic layer.
Wherein the hydrophilic resin and / or water-dispersible latex total amount in the undercoat layer is preferably from 0.01 to 20 g / m ^2, 0.1 to 10 g / m ² is more preferable.

[Layer structure when using hydrophilic members]
When the hydrophilic member of the present invention is used in anticipation of the appearance of antifouling and / or antifogging effects, it may be used by appropriately adding another layer depending on the purpose, form and place of use. it can. The layer structure added as needed is described below.

1) Adhesive layer When the hydrophilic member of the present invention is used by being affixed on another substrate, a pressure-sensitive adhesive that is a pressure-sensitive adhesive is preferably used as an adhesive layer on the back surface of the substrate. As an adhesive, what is generally used for an adhesive sheet, such as a rubber adhesive, an acrylic adhesive, a silicone adhesive, a vinyl ether adhesive, and a styrene adhesive, can be used.
When an optically transparent material is required, an adhesive for optical use is selected. When a pattern such as coloring, translucency, or matte tone is required, in addition to patterning on the substrate, a dye, organic or inorganic fine particles can be added to the adhesive to produce an effect.
When a tackifier is required, a resin, for example, a rosin-based resin, a terpene-based resin, a petroleum-based resin, a styrene-based resin, or an adhesion-imparting resin such as a hydrogenated product thereof can be used alone or in combination.
The adhesive strength of the pressure-sensitive adhesive used in the present invention is generally called strong adhesion, and is 200 g / 25 mm or more, preferably 300 g / 25 mm or more, more preferably 400 g / 25 mm or more. In addition, the adhesive force here is based on JIS Z 0237 and is a value measured by a 180 degree peel test.

2) Release layer When the hydrophilic member of the present invention has the adhesive layer, a release layer can be further added. The release layer preferably contains a release agent in order to give release properties. As the release agent, generally, a silicone release agent composed of polyorganosiloxane, a fluorine compound, a long-chain alkyl modified product of polyvinyl alcohol, a long-chain alkyl modified product of polyethyleneimine, and the like can be used. In addition, various release agents such as a hot melt type release agent, a monomer type release agent that cures a release monomer by radical polymerization, cationic polymerization, polycondensation reaction, etc., and other, acrylic-silicone copolymer Resin, acrylic-fluorine-based copolymer resin, and copolymer-based resin such as urethane-silicone-fluorine-based copolymer resin, and resin blends of silicone-based resin and acrylic-based resin, fluorine-based resin and acrylic-based resin A resin blend is used. Moreover, it is good also as a hard-coat release layer obtained by hardening | curing the curable composition containing either an atom of a fluorine atom and / or a silicon atom, and an active energy ray polymeric group containing compound.

3) Other layers A protective layer may be provided on the topcoat layer (hydrophilic layer). The protective layer has a function of preventing damage to the hydrophilic surface during handling, transportation, storage, and the like, and deterioration of hydrophilicity due to adhesion of dirt substances. As the protective layer, the hydrophilic polymer layer used in the release layer can be used. The protective layer is peeled off after the hydrophilic member is attached to a suitable substrate.

[Form of structure]
The structure having the hydrophilic layer of the present invention may be supplied in the form of a sheet, a roll, or a ribbon, or may be supplied as a pre-cut material for attaching to a suitable substrate.

When the hydrophilic member coated with the hydrophilic layer of the present invention is applied (used or attached) to a window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic layer of the present invention is excellent in transparency, and even when the film thickness is large, the transparency is not impaired and compatibility with durability is possible. The thickness of the hydrophilic layer of the present invention is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 20 μm. When the film thickness is 0.01 μm or more, it is preferable to obtain sufficient hydrophilicity and durability, and when the film thickness is 100 μm or less, there is no problem in film forming properties such as cracks, which is preferable.
The dry coating amount of the hydrophilic layer of the present invention is preferably 0.01 g / m ^{2 to} 100 g / m ² , more preferably 0.02 g / m ^{2 to} 80 g / m ² , and particularly preferably 0.05 g / m ² to. By setting it to 50 g / m ² , the above film thickness can be obtained.
The thickness of the undercoat layer is preferably 0.01 μm to 100 μm, more preferably 0.02 μm to 80 μm, and particularly preferably 0.05 μm to 50 μm.
Preferably the dry coating amount of the undercoat layer composition ^{0.01g / m 2 ~100g / m 2} , more preferably ^{0.02g / m 2 ~80g / m 2} , particularly preferably 0.05g / m ² ~50g / By setting m ² , the above film thickness can be obtained.
Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably 100% to 70%, more preferably 95% to 75%, and most preferably in the range of 95% to 80%. By being in this range, the hydrophilic member provided with a hydrophilic layer can be applied to various applications without obstructing the field of view.

As described above, the hydrophilic member of the present invention can be obtained by applying the composition for the undercoat layer and the hydrophilic composition on a suitable substrate, heating and drying to form a surface hydrophilic layer. it can.
As a method for applying the composition for the undercoat layer and the hydrophilic composition, a known coating method can be adopted, for example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method, screen printing. Methods such as coating, bar coating, brush coating, and sponge coating can be applied.

The hydrophilic member of the present invention can be applied to, for example, a transparent glass substrate or a transparent plastic substrate, a lens, a prism, a mirror or the like when an antifogging effect is expected.
As the glass, any glass such as soda glass, lead glass and borosilicate glass may be used. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do.
Applications that can be applied with anti-fogging effects include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, internal vision Lenses such as mirror lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; window glass for buildings and surveillance towers; other building glass; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, Ropeway gondola, amusement park gondola, various vehicle windows; automobiles, rail cars, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, various vehicle windshields Glass; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case Las; cover glass measuring instruments, and films to be attached to the article surface. The most preferred application is glass for automobiles and building materials.

When the surface hydrophilic member of the present invention is expected to have an antifouling effect, the substrate is made of, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper in addition to glass and plastic. , Combinations thereof, and laminates thereof can be suitably used.
Applications with antifouling components include building materials, building exteriors such as exterior walls and roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, bicycles, motorcycles Exterior and painting of such vehicles, machinery and equipment exteriors, dust covers and coatings, traffic signs, various display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors and coatings, tunnel interiors And paint, insulators, solar battery covers, solar water heater heat collector covers, greenhouses, vehicle lighting cover, housing equipment, toilets, bathtubs, sinks, lighting fixtures, lighting covers, kitchenware, dishes, dishwashers A dish dryer, a sink, a cooking range, a kitchen hood, a ventilation fan, and a film to be attached to the surface of the article.
Signs, traffic signs, noise barriers, plastic houses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors, solar battery covers, solar water heater and other heat collector covers, street lights, pavements, outdoor lighting, artificial Waterfalls / artificial fountain stones / tiles, bridges, greenhouses, exterior walls, sealers between walls and glass, guardrails, verandas, vending machines, air conditioner outdoor units, outdoor benches, various display devices, shutters, toll booths, price boxes , Roof lamps, vehicle lamp protection covers, dust covers and coatings, painting of machinery and equipment, exterior and coating of advertising towers, structural members, housing equipment, toilets, bathtubs, washstands, lighting equipment, kitchenware, tableware, Tableware dryer, sink, cooking range, kitchen hood, ventilation fan, window rail, window frame, tunnel inner wall, tunnel lighting, window sash, heat exchanger fins, pavement, bathroom toilet mirror, Neil House ceiling, including vanity, an automobile body, and the liquid to be attached for allowing the film to them the goods, the emblem and the like.
It can also be applied to snow country roofing materials, antennas, power transmission lines, and the like, and in that case, characteristics excellent in snow accretion prevention can be obtained.

In addition, when the surface hydrophilic member of the present invention is expected to have quick drying properties such as water, the base material may be, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric in addition to glass and plastic. , Paper, combinations thereof, and laminates thereof can be suitably used. Applications that can be applied to members that have a quick-drying effect such as water include building materials, building exteriors such as outer walls and roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, and bicycles. , Exteriors and paintings of vehicles such as motorcycles, exteriors of machinery and articles, dust covers and paintings, traffic signs, various display devices, advertising towers, noise barriers for roads, noise barriers for railways, bridges, guard rails and paintings , Tunnel interior and painting, insulator, solar battery cover, solar water heater heat collection cover, plastic house, vehicle lighting cover, housing equipment, toilet, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, It includes a dishwasher, a dish dryer, a sink, a cooking range, a kitchen hood, a ventilation fan, and a film for application to the surface of the article.
Signs, traffic signs, noise barriers, plastic houses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors, solar battery covers, solar water heater and other heat collector covers, street lights, pavements, outdoor lighting, artificial Waterfalls / artificial fountain stones / tiles, bridges, greenhouses, exterior walls, sealers between walls and glass, guardrails, verandas, vending machines, air conditioner outdoor units, outdoor benches, various display devices, shutters, toll booths, price boxes , Roof lamps, vehicle lamp protection covers, dust covers and coatings, painting of machinery and equipment, exterior and coating of advertising towers, structural members, housing equipment, toilets, bathtubs, washstands, lighting equipment, kitchenware, tableware, Tableware dryer, sink, cooking range, kitchen hood, ventilation fan, window rail, window frame, tunnel inner wall, tunnel lighting, window sash, heat exchanger fins, pavement, bathroom toilet mirror, Neil House ceiling, including vanity, an automobile body, and the liquid to be attached for allowing the film to them the goods, the emblem and the like. Further, in the case of having a drying process in the process of manufacturing products used for these applications, the drying time can be shortened and the productivity can be expected to be improved.

Among the above uses, the hydrophilic member according to the present invention is preferably a fin material, and is preferably a fin material having an aluminum fin main body. That is, the fin material of the present invention is a fin material comprising a fin main body (preferably an aluminum fin main body) and a hydrophilic layer provided on at least a part of the surface of the fin main body. Is formed by coating the composition for forming a hydrophilic film according to the present invention.
Aluminum fin material (aluminum fin body itself) used in heat exchangers such as indoor air conditioners and automobile air conditioners causes water droplets to form water droplets and stay between the fins, resulting in water bridges. Ability is reduced. In addition, the adhering of dust or the like between the fins similarly reduces the cooling capacity. To solve these problems, the fin material in which the composition for forming a hydrophilic film of the present invention is applied to the fin body provides a fin material excellent in hydrophilicity, antifouling property, and sustainability thereof. It is done.
The fin material according to the present invention preferably has a water contact angle of 40 ° or less after 5 cycles of 1-hour aeration, 30-minute water washing, and 30-minute drying of palmitic acid.

  Examples of the aluminum used for the fin body of the fin material include a degreased surface and an aluminum plate subjected to chemical conversion treatment as necessary. It is preferable that the surface of the fin body made of aluminum is subjected to a chemical conversion treatment in terms of adhesion of the hydrophilic treatment film, corrosion resistance, and the like. Examples of the chemical conversion treatment include chromate treatment, and typical examples thereof include alkali salt-chromate method (BV method, MBV method, EW method, Al And a treatment method such as a chromic acid method, a chromate method, and a chromic phosphate method, and an anhydrous washing coating type treatment with a composition mainly composed of chromium chromate.

  For example, as the aluminum thin plate used for the fin body of the heat exchanger fin material, according to JIS standard, pure aluminum plate such as 1100, 1050, 1200, 1N30, Al-Cu alloy plate such as 2017, 2014, 3003, Any of Al-Mn alloy plates such as 3004, Al-Mg alloy plates such as 5052 and 5083, and Al-Mg-Si alloy plates such as 6061 may be used. Any of the coils may be used.

Moreover, it is preferable to use the fin material which concerns on this invention for a heat exchanger. Since the heat exchanger using the fin material according to the present invention has excellent hydrophilicity, antifouling property and durability thereof, it is possible to prevent water droplets and dust from adhering between the fins. it can. Examples of the heat exchanger include heat exchangers used for indoor coolers, air conditioners, construction machine oil coolers, automobile radiators, capacitors, and the like.
Moreover, it is preferable to use the heat exchanger using the fin material according to the present invention for an air conditioner. Since the fin material according to the present invention has excellent hydrophilicity, antifouling property, and sustainability thereof, it is possible to provide an air conditioner in which problems such as a decrease in cooling capacity as described above are improved. . The air conditioner may be any one of a room air conditioner, a packaged air conditioner, a car air conditioner, and the like.
In addition, a well-known technique (for example, Unexamined-Japanese-Patent No. 2002-106882, Unexamined-Japanese-Patent No. 2002-156135 etc.) can be used for the heat exchanger and air conditioner of this invention, and it does not restrict | limit in particular.

〔Measuring method〕
¹³ C-NMR
The measurement was performed at a resonance frequency of 400 MHz using an AV400M manufactured by BRUKER. As a measurement solvent, deuterated dimethyl sulfoxide DMSO-d ₆ which is a deuterated solvent was used.

  Residual monomer quantification was analyzed by HPLC

HPLC apparatus Measuring instrument: Shimadzu LC-10ATvp
Column: Tsk-gel ODS100V (4.6 mmφ × 150 mm) particle size 3 μm
Eluent: acetonitrile: distilled water = 2: 98 (containing 0.1 vol% phosphoric acid)
Flow rate: 0.8 ml / min. Column temperature: 40 ° C. Measurement wavelength: UV 210 nm Injection amount: 20 μm

GPC device Measuring instrument: Tosoh HPLC-8220
Column: Tosoh α-guard column 6mm * 4cm
α-M 6mm * 30cm x 2 detectors: RI range 256
Eluent: Distilled water (containing 0.5 mmol / L sodium nitrate)
Flow rate: 1.0ml / min. Column temperature: 40 ° C

Adhesion test The surface of the substrate coated with a hydrophilic film is scratched with a cutter in accordance with JIS K-5400 to make 100 squares of 1 mm square, and cellophane adhesive tape (Sekisui Chemical, # 252, 25 mm width, SP adhesive) Force: 750 gf / 25 mm width). One end of this tape is kept at a right angle to the surface of the substrate, and represents the number of base meshes that have been peeled off instantaneously. The state in which all 100 bases are peeled is 0, and the state in which all 100 bases are not peeled is 100.

Water resistance test The water droplet contact angle after the formation of the hydrophilic member was measured and used as the initial contact angle. In addition, the contact angle of water droplets after the hydrophilic member was exposed to tap water with a flow rate of 5 L / hour for 240 hours was measured and set as the contact angle after the water resistance test. Those having a small difference in numerical value between the initial contact angle and the contact angle after the water resistance test are excellent in water resistance. The aerial water droplet contact angle was measured with a DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.

Example 1 Synthesis of hydrophilic polymer (II-1) (residual monomer amount 0.06% by mass)

A 500 ml four-necked flask was charged with 55 g of 1-methoxy-2-propanol and kept at 80 ° C. under a nitrogen stream. A solution obtained by stirring and dissolving 55 g of acrylamide, 3.7 g of 3-mercaptopropyltrimethoxysilane, and 0.52 g of dimethyl 2,2-azobisisobutyrate in 110 g of 1-methoxy-2-propanol was added dropwise over 3.5 hours with stirring. did. A white precipitate was observed about 10 minutes after the start of dropping, and became a slurry solution at the end of dropping. After maintaining the temperature as it was for 0.5 hour, a solution in which 0.26 g of dimethyl 2,2-azobisisobutyrate was dissolved in 100 ml of methanol was added, and the mixture was reacted at an internal temperature of 73 ° C. for 2 hours. After cooling, it was filtered under a nitrogen atmosphere to obtain a white solid. Drying at 60 ° C. overnight gave 54.6 g of a white solid.
The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 9000. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-1) having a trimethoxysilyl group (50.0 ppm) introduced at the terminal.
When the residual monomer of the obtained polymer was analyzed, it was determined that the residual monomer was acrylamide because the retention time coincided with that of acrylamide. The residual monomer amount determined by the absolute calibration curve method was 0.060% by mass.

[Coating method]
A glass coating solution (1) having the following composition is applied to a glass surface-treated with an ozone generator and oven-dried at 100 ° C. for 2 minutes. Hydrophilic glass was made by oven drying in minutes. The film thickness of the obtained hydrophilic layer was about 40 nm.
(Coating liquid 1)
19 g of distilled water, 6.1 g of ethanol, 0.23 g of acetylacetone, 0.31 g of tetraethyl orthotitanate and 3.12 g of tetramethyl orthosilicate were added in this order, and the mixture was stirred at room temperature for 2 hours.
196 g of distilled water, 225 g of ethanol, 0.86 g of a 5% aqueous solution of the following anionic surfactant, and 4.10 g of a 20% by mass aqueous solution of colloidal silica dispersion (Snowtex C) were added to the resulting liquid and stirred for 10 minutes.

(Coating solution 2)
88 g of distilled water and 3.5 g of the hydrophilic polymer (II-1) obtained above were stirred and dissolved. To this, 18.3 g of ethanol, 0.82 g of acetylacetone, 0.94 g of tetraethyl orthotitanate and 10.4 g of tetramethyl orthosilicate were sequentially added, and the mixture was stirred at room temperature for 2 hours.
To the obtained liquid was added 365 g of distilled water, 450 g of ethanol, 1.0 g of a 5% aqueous solution of the above anionic surfactant, and 17.29 g of a 20 mass% aqueous solution of colloidal silica dispersion (Snowtex C), and the mixture was stirred for 10 minutes. .

[Example 2]
A 500 ml four-necked flask was charged with 55 g of 1-methoxy-2-propanol and kept at 80 ° C. under a nitrogen stream. 53 g of acrylamide, 3.7 g of 3-mercaptopropyltrimethoxysilane and 0.52 g of dimethyl 2,2-azobisisobutyrate were added dropwise to 110 g of 1-methoxy-2-propanol while stirring over 3.5 hours. did. A white precipitate was observed about 10 minutes after the start of dropping, and became a slurry solution at the end of dropping. After the post-reaction was carried out for 0.5 hour, 0.26 g of dimethyl 2,2-azobisisobutyrate dissolved in 110 ml of 1-methoxy-2-propanol was added, and the post-reaction was carried out for 2 hours. After cooling, it was filtered under a nitrogen atmosphere and dried at 60 ° C. to obtain 54.1 g of a white solid. The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 9100. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-1).
When the residual monomer amount of the obtained polymer was analyzed, it was 0.124 mass%.
The obtained polymer was applied in the same manner as in Example 1, and an adhesion test and a water resistance test were conducted. The results are summarized in Table 1.

Example 3
In Example 1, Compound 1 was synthesized in the same manner as in Example 1 except that the solvent in the polymerization step was changed from 1-methoxy-2-propanol to ethanol. The obtained solid was 52.1 g.
The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 8900. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-1).
When the amount of residual monomers of the obtained polymer was analyzed, it was 0.289 mass%.
The obtained polymer was applied in the same manner as in Example 1, and an adhesion test and a water resistance test were conducted. The results are summarized in Table 1.

Example 4
Compound 1 was synthesized in the same manner as in Example 1 except that the reaction was carried out 0.5 hours after completion of the dropping in Example 1, followed by filtration and drying. The obtained solid was 53.3 g. The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 8900. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-1).
When the residual monomer amount of the obtained polymer was analyzed, it was 1.33 mass%.
The obtained polymer was applied in the same manner as in Example 1, and an adhesion test and a water resistance test were conducted. The results are summarized in Table 1.

Example 5
In Example 1, Compound 1 was synthesized in the same manner as in Example 4 except that the solvent in the polymerization step was changed to N, N′-dimethylacetamide. The obtained solid was 51.1 g. The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 12000. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-1).
When the residual monomer amount of the obtained polymer was analyzed, it was 0.91 mass%.
The obtained polymer was applied in the same manner as in Example 1, and an adhesion test and a water resistance test were conducted. The results are summarized in Table 1.

Example 6
A 500 ml four-necked flask was charged with 55 g of 1-methoxy-2-propanol and kept at 80 ° C. under a nitrogen stream. A solution obtained by stirring and dissolving 55 g of acrylamide, 3.7 g of 3-mercaptopropyltrimethoxysilane, and 0.52 g of dimethyl 2,2-azobisisobutyrate in 110 g of 1-methoxy-2-propanol was added dropwise over 3.5 hours with stirring. did. A white precipitate was observed about 10 minutes after the start of dropping, and became a slurry solution at the end of dropping. After maintaining the temperature as it was for 0.5 hour, a solution in which 0.26 g of dimethyl 2,2-azobisisobutyrate was dissolved in 100 ml of methanol was added and reacted at an internal temperature of 65 ° C. for 2 hours. After cooling, it was filtered under a nitrogen atmosphere to obtain a white solid. Drying at 60 ° C. overnight gave 54.7 g of a white solid.
The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 9300. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-1).
When the residual monomer amount of the obtained polymer was analyzed, it was 0.097 mass%.
The obtained polymer was applied in the same manner as in Example 1, and an adhesion test and a water resistance test were conducted. The results are summarized in Table 1.

[Example 7] (Reaction solvent at the time of initiator addition is changed from methanol to acetonitrile)
In Example 1, Compound 1 was synthesized in the same manner as in Example 1 except that the solvent when adding the initiator again after the polymerization was changed to acetonitrile. The obtained solid was 53.6 g. The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 9300. It was confirmed by 13C-NMR that it was a hydrophilic polymer (II-1).
When the residual monomer amount of the obtained polymer was analyzed, it was 1.31 mass%.
The obtained polymer was applied in the same manner as in Example 1, and an adhesion test and a water resistance test were conducted. The results are summarized in Table 1.

[Example 8] (Reaction solvent at the time of initiator addition was changed from methanol to ethyl acetate)
In Example 1, Compound 1 was synthesized in the same manner as in Example 1 except that the solvent for adding the initiator again after the polymerization was changed to ethyl acetate. The obtained solid was 52.5 g. The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 4000. ^It was confirmed by ¹³ C-NMR that it was (II-1).
When the residual monomer amount of the obtained polymer was analyzed, it was 2.11 mass%.
Using the obtained polymer, it apply | coated like Example 1 and the adhesiveness and the water resistance test were implemented. The results are summarized in Table 1.

[Example 9] Synthesis of hydrophilic polymer (II-114)

A 500 ml four-necked flask was charged with 55 g of 1-methoxy-2-propanol and kept at 80 ° C. under a nitrogen stream. 50 g of acrylamide, 18.2 g of N- (2-hydroxyethyl) acrylamide, 3.88 g of 3-mercaptopropyltrimethoxysilane, and 0.55 g of dimethyl 2,2-azobisisobutyrate are stirred and dissolved in 110 g of 1-methoxy-2-propanol. Was added dropwise over 3.5 hours with stirring. After maintaining the temperature as it was for 0.5 hours, 0.55 g of dimethyl 2,2-azobisisobutyrate dissolved in 100 ml of methanol was added and reacted at an internal temperature of 73 ° C. for 2 hours. After cooling, it was filtered under a nitrogen atmosphere to obtain a white solid. It was dried at 60 ° C. overnight to obtain 57.6 g of a white solid (yield 99.5%).
The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 19000. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-114) having a trimethoxysilyl group (50.0 ppm) introduced at the terminal.
When the residual monomer amount of the obtained polymer was analyzed, it was 0.094 mass%.
Using the obtained polymer, it apply | coated like Example 1 and the adhesiveness and the water resistance test were implemented. The results are summarized in Table 1.

[Comparative Example 1] (Synthesis of hydrophilic polymer (II-1) based on JP-A-2002-293824)
A 500 ml three-necked flask was charged with 50 g of acrylamide, 3.4 g of mercaptopropyltrimethoxysilane, and 220 g of dimethylformamide, and 0.5 g of 2,2-azobis (2,4-dimethylvaleronitrile) was added under a nitrogen stream at 65 ° C. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. When charged into 2 liters of ethyl acetate, a solid precipitated. The weight after drying was 52.4 g. It was confirmed by GPC (polyethylene oxide standard) that the polymer had a weight average molecular weight of 7500, and by ¹³ C-NMR, it was a polymer having a trimethoxysilyl group (50.0 ppm) introduced at the terminal.
When the residual monomer amount of the obtained polymer was analyzed, it was 3.88 mass%.
Using the obtained polymer, it apply | coated like Example 1 and the adhesiveness and the water resistance test were implemented. The results are summarized in Table 1.

[Comparative Example 2]
In Example 4, the hydrophilic polymer (II-1) was synthesized in the same manner as in Example 4 except that the initiator amount was changed to 0.052 g and 3-mercaptopropyltrimethoxysilane was 0.37 g. . The obtained solid was 50.1 g. The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 11,000. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-1).
When the residual monomer amount of the obtained polymer was analyzed, it was 3.23 mass%.
Using the obtained polymer, it apply | coated like Example 1 and the adhesiveness and the water resistance test were implemented. The results are summarized in Table 1.

[Comparative Example 3] (Reaction solvent at the time of initiator addition is changed from methanol to toluene)
In Example 1, Compound 1 was synthesized in the same manner as in Example 1 except that the solvent for adding the initiator again after the polymerization was changed to toluene. The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 8800. ^{By 13} C-NMR, it was confirmed that the polymer had a trimethoxysilyl group (50.0 ppm) introduced at the terminal. The obtained solid was 50.8 g.
When the residual monomer amount of the obtained polymer was analyzed, it was 3.11 mass%.
Using the obtained polymer, it apply | coated like Example 1 and the adhesiveness and the water resistance test were implemented. The results are summarized in Table 1.

[Comparative Example 4]
In the comparative example 1, it synthesize | combined like the comparative example 1 except having changed the hydrophilic polymer from (II-1) to (II-114). The resulting solid was analyzed by GPC. The weight average molecular weight of the polyethylene oxide standard was 18800. ^It was confirmed by ¹³ C-NMR that the polymer was a hydrophilic polymer (II-114) having a trimethoxysilyl group (50.0 ppm) introduced at the terminal. The obtained solid was 52.3 g. When the amount of residual monomers of the obtained polymer was analyzed, it was 4.18 mass%.
Using the obtained polymer, it apply | coated like Example 1 and the adhesiveness and the water resistance test were implemented. The results are summarized in Table 1.

The symbols in the table are as follows.
MP: 1-methoxy-2-propanol DMAc: N, N′-dimethylacetamide DMF: N, N′-dimethylformamide

  From Table 1, it is possible to provide a coating film excellent in adhesion and water resistance by setting the residual monomer amount of the hydrophilic polymer to 3.0% by mass or less.

  It shows below about the solubility (mass%) of the polymer in 20 degreeC with respect to the solvent used by the Example and the comparative example.

Claims (10)

A hydrophilic polymer containing a structure represented by general formulas (I-1) and (I-2) and having a residual monomer amount of 3.0% by mass or less.

In the formula (I-1) and (I-2), each represent R ²⁰¹ to R ²⁰⁵ independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _{a, -OCON (R a) (} R b), - NHCON (R a) (R b), - SO 3 R e, -OSO 3 R e, -SO 2 R d, -NHSO 2 R d, -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. The hydrophilic polymer according to claim 1 or 2, wherein L ²⁰² in the general formula (I-1) is a single bond, and R ²⁰⁵ is a hydrogen atom.   The hydrophilic polymer according to claim 1, wherein the residual monomer amount is 1.0% by mass or less.   The amount of residual monomers is 0.1 mass% or less, The hydrophilic polymer in any one of Claims 1-3 characterized by the above-mentioned.   The hydrophilic polymer according to any one of claims 1 to 4, wherein the residual monomer is acrylamide.   A hydrophilic composition comprising the hydrophilic polymer according to claim 1.   A hydrophilic member formed of the hydrophilic composition according to claim 6. A polymerization step of the monomer, and a step of adding an organic solvent having a solubility of the monomer at 20 ° C. of 10% by mass or more and an initiator after the polymerization step to the general formulas (I-1) and (I−) The manufacturing method of the hydrophilic polymer which contains the structure represented by 2) and whose residual monomer amount is 3.0 mass% or less.

In the formula (I-1) and (I-2), each represent R ²⁰¹ to R ²⁰⁵ independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _{a, -OCON (R a) (} R b), - NHCON (R a) (R b), - SO 3 R e, -OSO 3 R e, -SO 2 R d, -NHSO 2 R d, -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.   The method according to claim 7 or 8, wherein the monomer is acrylamide, and the organic solvent having a solubility of 10% by mass or more at 20 ° C is methanol.   The solvent used in the polymerization step is an organic solvent having a solubility of the monomer at 20 ° C of 10% by mass or more and an organic solvent having a solubility of the hydrophilic polymer of 10% by mass or less. The manufacturing method as described.