JP2009079076A - Hydrophilic polymer, composition for forming hydrophilic film, and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic polymer and a composition for forming a hydrophilic film used for forming, on the surface of various supports, a hydrophilic film that satisfies both an anti-fogging property and an antibacterial property and exhibits a better stainproof property, and to provide a hydrophilic member having a surface excellent in anti-fogging property, rub resistance, antibacterial property and stainproof property that is provided with a hydrophilic film formed of the composition for forming a hydrophilic film on the surface of an appropriate support. <P>SOLUTION: The specific hydrophilic polymer includes a constituting unit bearing a silane coupling group on its end, a polymer main chain-constituting unit containing no positively charged nitrogen atom, and a polymer main chain-constituting unit containing a positively charged nitrogen atom. The composition comprises the hydrophilic polymer and a metal complex catalyst. The hydrophilic member comprises a support having the composition applied thereon. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention provides a hydrophilic polymer and a composition for forming a hydrophilic film which are useful for forming a hydrophilic film having excellent anti-fogging properties, friction resistance and antibacterial properties and better antifouling properties on various substrate surfaces. And a hydrophilic member having an antifogging, antibacterial, and antifouling surface provided with a hydrophilic film made of the composition for forming a hydrophilic film.

Various techniques for preventing oily dirt from adhering to the member surface have been proposed. In particular, optical members such as antireflection films, optical filters, optical lenses, spectacle lenses, mirrors, etc., when used by humans, are contaminated with fingerprints, sebum, sweat, cosmetics, etc. Since removal of dirt is complicated, it is desired to perform effective dirt prevention treatment.
In recent years, with the spread of mobile devices, displays are often used outdoors, but when used in an environment where external light is incident, the incident light is regularly reflected on the display surface. As a result, the reflected light is mixed with the display light, causing problems such as difficulty in viewing the display image. For this reason, an antireflection optical member is often disposed on the display surface.
As such an antireflection optical member, for example, a transparent substrate with a high refractive index layer and a low refractive index layer made of a metal oxide or the like laminated thereon, an inorganic or organic fluoride compound or the like on the transparent substrate surface. Known are those in which a low refractive index layer is formed as a single layer, or those in which a coating layer containing transparent fine particles is formed on the surface of a transparent plastic film substrate and external light is irregularly reflected by the uneven surface. These anti-reflective optical member surfaces, like the above-mentioned optical members, are susceptible to dirt such as fingerprints and sebum when used by humans, but only the part where the dirt is attached becomes highly reflective and the dirt is more noticeable. In addition to the problem, the surface of the antireflection film usually has fine irregularities, and it is difficult to remove dirt.

Various techniques have been proposed for forming on the surface an anti-smudge function having performances such as making it difficult to get dirt on the surface of a solid member and making it easier to remove attached dirt. In particular, as a combination of an antireflection member and an antifouling member, for example, an antireflection film made mainly of silicon dioxide and an antifouling and friction resistant material treated with a compound containing an organosilicon substituent (for example, Patent Document 1), and an antifouling and friction-resistant CRT filter (for example, see Patent Document 2) in which the substrate surface is coated with a terminal silanol organopolysiloxane has been proposed. Further, an antireflection film containing a silane compound including a silane compound containing a polyfluoroalkyl group (see, for example, Patent Document 3), an optical thin film mainly composed of silicon dioxide, a perfluoroalkyl acrylate, and an alkoxysilane group. A combination with a copolymer with a monomer having a hydrogen atom (see, for example, Patent Document 4) has been proposed.
However, the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and the surface energy such as fluorine and silicon is low. The surface treatment with a material is concerned with a decrease in antifouling performance over time, and therefore, development of an antifouling member having excellent antifouling properties and durability is desired.

  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.

  Conventionally proposed surface treatment methods for hydrophilization, such as etching treatment and plasma treatment, are highly hydrophilized, but their effects are temporary and maintain the hydrophilized state for a long time. I can't. Further, a surface hydrophilic coating film using a hydrophilic graft polymer as one of hydrophilic resins has also been proposed (see, for example, Non-Patent Document 1), although this coating film has a certain degree of hydrophilicity, Affinity with the substrate is not sufficient, and higher durability is required.

  In addition, as a film having excellent surface hydrophilicity, a film using titanium oxide has been conventionally known. For example, a technique of forming a photocatalyst-containing layer on a substrate surface and making the surface highly hydrophilic according to photoexcitation of the photocatalyst. It is reported that if this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, water-circulating members, etc., excellent antifouling properties can be imparted to these composite materials ( For example, see Patent Document 5.) However, the hydrophilic film using titanium oxide does not have sufficient film strength, and since there is a problem that the use site is limited because the hydrophilization effect is not expressed unless photoexcited, and is durable, and There is a demand for antifouling members that can be used in any part.

  In order to achieve the above-mentioned problems, the anti-fogging and anti-fogging properties of the hydrophilic surface with a cross-linked structure by hydrolyzing and condensation-polymerizing the hydrophilic polymer and the alkoxide are focused on the characteristics of the sol-gel organic-inorganic hybrid film. It has been found that it exhibits fouling and has good friction resistance (see Patent Document 6). A hydrophilic surface layer having such a crosslinked structure can be easily obtained by combining a specific hydrophilic polymer having a reactive group at its terminal and a crosslinking agent.

However, the antifouling property against the positively charged soiling factor is low due to the influence of a large amount of silanol groups, and the antibacterial property, which is an essential performance for applications around water, is insufficient. Therefore, there is still room for improvement. Many polymer-containing members containing antibacterial agents have been known so far (see, for example, Patent Document 7), but many of them are not intended for use around water, and are directly between polymer fibers and antibacterial agents. There was no concern about the outflow of antibacterial agents due to contact with water for a long time because there was no mechanical bond.
JP-A 64-86101 JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 International Publication No. 96/29375 Pamphlet Japanese Patent Application No. 2006-256215 JP 2005-323953 A Newspaper "Chemical Industry Daily" article dated January 30, 1995

  The object of the present invention is to further solve the problems of the prior art by further researching sol-gel organic-inorganic hybrid films, and to have various anti-fogging properties, anti-friction properties and antibacterial properties on various substrate surfaces, and more It is an object of the present invention to provide a hydrophilic polymer and a hydrophilic film-forming composition used to form a hydrophilic film having good antifouling properties. Further, another object of the present invention is to provide a hydrophilic film formed of the hydrophilic film-forming composition on an appropriate support surface, and is excellent in antifogging property, friction resistance, antibacterial property and antifouling property. Another object is to provide a hydrophilic member having a curved surface.

As a result of advancing research on a sol-gel organic-inorganic hybrid film, the present inventors have found that a hydrophilic surface layer obtained by using a hydrophilic polymer containing a positively charged nitrogen atom has an antifogging equivalent to that of the prior art. The present invention has been completed by finding that it has excellent anti-fouling properties and has high antibacterial properties.
That is, the present invention is as follows.

[1]
(A) A hydrophilic polymer having a structure represented by the following general formula (1) or general formula (2).

In general formula (1) and (2), R < ¹ > -R < ⁸ > represents a hydrogen atom or a C1-C8 hydrocarbon group each independently. Of the hydrocarbon groups, R ⁴ , R ⁶ and R ⁸ may have a hydroxyl group and / or a silane coupling group at the side chain and / or terminal. m represents 0, 1 or 2, and x, y and z represent the composition ratio when x + z = 100 in the general formula (1) and x + y + z = 100 in the general formula (2), and 0 <x < 100, 0 <y <100, 0 <z <100. L ¹ , L ² , L ³ , L ⁴ and L ⁶ each independently represents a single bond or an organic linking group, and L ⁵ represents a single bond or CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, And a polyvalent organic linking group having one or more structures selected from the group consisting of —SO ₃ —. Y ¹ and Y ³ are each independently —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 represents an _{(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 having 1 to 8 carbon atoms, and R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion. Y ² and Y ⁴ each represents a functional group containing at least one nitrogen atom having a positive charge.
[2]
The hydrophilic polymer according to [1], wherein the functional group containing at least one positively charged nitrogen atom in Y ² and Y ⁴ is represented by any structure of the following general formula (3) .

In the general formula ^(3), at least one of R 11 ^{to R 14} may represent ^L 2, ^{L 6} is a connecting chain of the hydrophilic polymer backbone, ^R 11 ^{to R 14} except the linking chain, respectively Independently, it represents a hydrocarbon group which may be substituted with a hydroxyl group and / or a silane coupling group. X ⁻ represents an anion.
[3]
A composition for forming a hydrophilic film, comprising (A) the hydrophilic polymer according to [1] or [2] and (B) a metal complex catalyst.
[4]
The metal complex catalyst (B) is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and a β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, enolic active hydrogen compound. The composition for forming a hydrophilic film according to [3], which is composed of an oxo or hydroxy compound selected from the group consisting of:
[5]
Furthermore, the composition for forming a hydrophilic film according to [3] or [4], further comprising an alkoxide compound containing an element selected from Si, Ti, Al, and Zr.
[6]
Furthermore, the composition for hydrophilic film formation in any one of [3]-[5] containing colloidal silica.
[7]
[3] A hydrophilic member, wherein the hydrophilic forming composition according to any one of [6] to [6] is coated on a support.

The principle of the present invention is presumed as follows.
In the prior art hydrophilic film forming composition and hydrophilic member, the film has a negative charge due to the influence of alkoxide, silane coupling group, etc. It is done. In the present invention, by using the hydrophilic polymer, the hydrophilic film-forming composition is cationic, and the hydrophilic film on the surface of the hydrophilic member using the composition is also cationic. As a result, it is considered that an electrical repulsion occurs between a hydrophilic factor and a soiling factor such as a cationic surfactant, calcium ions, and magnesium ions, and adhesion becomes difficult. Furthermore, since the positively charged nitrogen atom is directly bonded to the polymer main chain, it is considered that the cationic property could be maintained for a long time. In addition, since cationic compounds are presumed to be adsorbed on the cell membrane of anionic bacteria and have effects such as cell membrane destruction and inactivation of enzyme function, antibacterial properties can be applied to hydrophilic membrane-forming compositions. It is thought that sex was given.

  According to the present invention, a hydrophilic polymer used for forming a hydrophilic film excellent in antifogging properties, abrasion resistance, antifouling properties, and antibacterial properties on various substrate surfaces, and a composition for forming a hydrophilic film And a hydrophilic member having an antifogging property, friction resistance, antibacterial property, and antifouling property having the hydrophilic film can be provided.

Hereinafter, the present invention will be described in detail.
[(A) hydrophilic polymer]
The hydrophilic polymer (A) that can be used in the present invention (hereinafter sometimes referred to as a specific hydrophilic polymer) has a structure represented by either general formula (1) or (2).

In general formula (1) and (2), R < ¹ > -R < ⁸ > represents a hydrogen atom or a C1-C8 hydrocarbon group each independently. Of the hydrocarbon groups, R ⁴ , R ⁶ and R ⁸ may have a hydroxyl group and / or a silane coupling group at the side chain and / or terminal. m represents 0, 1 or 2, and x, y and z represent the composition ratio when x + z = 100 in the general formula (1) and x + y + z = 100 in the general formula (2), and 0 <x < 100, 0 <y <100, 0 <z <100. L ¹ , L ² , L ³ , L ⁴ and L ⁶ each independently represents a single bond or an organic linking group, and L ⁵ represents a single bond or CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, And a polyvalent organic linking group having one or more structures selected from the group consisting of —SO ₃ —. Y ¹ and Y ³ are each independently —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 represents an _{(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 having 1 to 8 carbon atoms, and R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion. Y ² and Y ⁴ each represents a functional group containing at least one nitrogen atom having a positive charge.

Examples of the hydrocarbon group when R ^{1 to} R ⁸ represent a hydrocarbon 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 ^{1 to} R ⁸ are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability.

These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and the 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 conjugated base group (hereinafter referred to as sulfonate group), al Coxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N -Alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphine phono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group (- O 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 conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkylphosphono Oxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO (alkyl) (aryl)), monoalkyl phosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatoo A monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as an arylphosphonatooxy group), a morpholino group, a cyano group, a nitro group, an aryl group, Examples include alkenyl groups and alkynyl groups.

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-phenylcarbamo Butylphenyl group include a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- 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, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl 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, methoxycarbonylethyl group, allyloxy Rubonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) ) Caravamoylmethyl 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, tolylphosphono Xyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl Group, aryl 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.

L ¹ , L ² , L ^3, L ⁴ and L ⁶ represent a single bond or an organic linking group. Here, the single bond means that the main chain of the polymer and Y are directly bonded without a linking chain. Further, the organic linking group refers to a linking group composed of non-metallic atoms, specifically, 0 to 200 carbon atoms, 0 to 150 nitrogen atoms, 0 to 200 oxygen atoms. It consists of atoms, 0 to 400 hydrogen atoms, and 0 to 100 sulfur atoms. More specific examples of the linking group include the following structural units or those formed by combining them.

L ¹ , L ² , L ³ , L ⁴ and L ⁶ may be formed of a polymer or oligomer, specifically, polyacrylate, polymethacrylate, polyacrylonitrile, Polyvinyl, polystyrene, etc. are preferably included, and other preferred examples include poly (oxyalkylene), polyurethane, polyurea, polyester, polyamide, polyimide, polycarbonate, polyamino acid, polysiloxane, and the like, preferably polyacrylate, Examples thereof include polymethacrylate, polyacrylonitrile, polyvinyl, and polystyrene, and polyacrylate and polymethacrylate are more preferable. The structural unit used for these polymers and oligomers may be one type or two or more types. In addition, when L ¹ , L ² , L ³ , L ⁴ and L ⁶ are polymers or oligomers, the number of constituent elements is not particularly limited, and the molecular weight is preferably 1,000 to 1,000,000, and 1,000 ˜500,000 is more preferred, and 1,000 to 200,000 is most preferred.

L ⁵ represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. Here, the single bond represents that the polymer main chain and the Si atom are directly bonded without a linking group. In L ³ and L ⁵ , two or more structures may exist, and in that case, they may be the same as or different from each other. If one or more of the above structures are included, other structures can have the same structures as those listed for L ¹ , L ² , L ^3, L ⁴ and L ⁶ .

Y ¹ and Y ³ are hydrophilic groups, and are —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 represents an _{(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 having 1 to 8 carbon atoms, and R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion. _{Further, -CON (R a) (R} b), - OCON (R a) (R b), - NHCON (R a) (R b), - SO 2 N (R a) (R b) -PO 3 (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), —PO ₂ (R _d ) (R _e ), —N (R _a ) (R _b ) (R _c ) or N ( R _a ) (R _b ) (R _c ) (R _g ) R _{a to} R _g may be bonded to each other to form a ring, and the formed ring is an oxygen atom, sulfur atom, nitrogen atom Or a heterocycle containing a heteroatom such as R _{a to} R _g may further have a substituent, and the substituent that can be introduced here is the same as the substituent that can be introduced when R ^{1 to} R ⁶ are alkyl groups. Can be listed.

Specific examples of R _a , R _b or R _c include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, and s-butyl. Preferred examples include a group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
Specific examples of R _d include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, t-butyl, and isopentyl. Preferred examples include a group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
R _e, specifically as R _f, in addition to the alkyl groups mentioned R _a to R _d, a hydrogen atom; lithium, sodium, alkali metals such as potassium, calcium, alkaline earth such as barium metal, or, , Ammonium, iodonium, sulfonium and the like.
Specific examples of R _g include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a nitrate anion, a sulfate anion, or a tetrafluoroborate anion, in addition to the alkyl group represented by R _{a to} R _d Inorganic anions such as hexafluorophosphate anion, and organic anions such as methanesulfonate anion, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, and p-toluenesulfonate anion.
Further, as specifically such ^{_{Y, -CO 2 - Na +,}} -CONH 2, -SO 3 - Na +, -SO 2 NH 2, -PO 3 H 2 and the like are preferable.

Y ² and Y ⁴ preferably contain positively charged nitrogen atoms, and preferably contain 1 or 2 positively charged nitrogen atoms.
The hydrophilic film-forming composition of the present invention can form a hydrophilic member having high antibacterial properties when Y ² and Y ⁴ in the general formula (3) contain a positively charged nitrogen atom. .
Y ² and Y ⁴ in the general formula (3) are preferably selected from any structure shown in the following general formula (3).

In the general formula ^(3), at least one of R 11 ^{to R 14} may represent ^L 3, ^{L 6} is a connecting chain of the hydrophilic polymer backbone, ^R 11 ^{to R 14} except the linking chain, respectively Independently, it represents a hydrocarbon group which may be substituted with a hydroxyl group and / or a silane coupling group. X ⁻ represents an anion, and X preferably represents any one of halogen, BF ₄ , PF ₆ , and HCO ₃ , but is not limited thereto.

Examples of the hydrocarbon group in the case where R ^{11 to} R ¹⁴ excluding the connecting chains L ³ and L ⁶ represent a hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic group having 1 to 8 carbon atoms. Are preferred. 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.

These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and the 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, trialkoxysilyl groups, silane coupling groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyls. Dithio group, aryldithio group, amino group, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, Ν-alkylcarbamoyloxy group, N- Arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-reelcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group N-arylacylamino group, ureido group, N′-alkylureido 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- ア リ ー ル -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-ary Luureido group, alkoxycarbonylamino group, aryloxycarbonylamino 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 the like Conjugated base groups (hereinafter referred to as sulfonate groups), alkoxysulfonyl groups, aryloxysulfonyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group Group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkylphosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _(-PO 3 (ar yl) ₂ ), an alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), a monoalkyl phosphono group (—PO ₃ H (alkyl)) and a conjugate base group thereof (hereinafter referred to as an alkyl phosphonate group). ), Monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “aryl phosphonate group”). , Phosphonateoxy group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO (alkyl) ) (Aryl)), monoalkylphosphonooxy groups (—OPO ₃ H (alkyl)) and 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 arylphosphonatooxy group), morpholino group , A cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

Specific examples of the alkyl group in these substituents include the same alkyl groups listed in R ^{1 to} R ⁴ except for the linking chains L ³ and L ^6. Specific examples of the aryl group include a phenyl group, Biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, Benzyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl , Mention may be made of N- phenylcarbamoyl-phenyl group, a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- 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, alkoxysilyl groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N , N-dialkylamino 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, N- Lylsulfamoyl 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, Examples thereof include an aryl phosphonate group, a phosphonooxy group, a phosphonate oxy group, an aryl group, and an alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl 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, methoxycarbonylethyl group, allyloxy Rubonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) ) Caravamoylmethyl 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, tolylphosphono Xyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl Group, aryl 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.
In the present invention, R ^{1 to} R ⁴ are preferably an alkyl group which may be substituted with a hydroxyl group and / or a silane coupling group. R ^{1 to} R ⁴ are more preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group from the viewpoints of effects and availability.

x, y and z represent the composition ratio when x + z = 100 in the general formula (1) and x + y + z = 100 in the general formula (2), and 0 <x <100, 0 <y <100, 0 <Z <100 is represented.
The composition ratio x: z in the general formula (1) is preferably in the range of 70:30 to 99: 1, and more preferably in the range of 80:20 to 95: 5.
The composition ratio x: y: z in the general formula (2) is preferably in the range of 50:20:30 to 79: 20: 1, and in the range of 60:20:20 to 75: 20: 5. More preferably it is.
When z <1, antibacterial properties are not sufficient, and when z> 30, water resistance and friction resistance are impaired. Therefore, this range is preferable.

  (A) The molecular weight of the specific hydrophilic polymer is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 1,000 to 200,000.

  Specific examples of the cationic specific hydrophilic polymer having a silane coupling group at the terminal (A) represented by the general formula (1) are shown below. Structural examples of polymer terminal sites (1-1) to (1-12), structural examples of polymer main chain constituent units not containing a positively charged nitrogen atom (1-13) to (1-26) And (1-27) to (1-40) are structural examples of polymer main chain constitutional units containing a positively charged nitrogen atom, each of which constitutes a specific hydrophilic polymer in an arbitrary combination. To do. The present invention is not limited to these. In addition, the polymer of the specific example shown below means that it is a random copolymer containing each structural unit described.

  Similarly, specific examples of the cationic specific hydrophilic polymer having a silane coupling group in the side chain (A) represented by the general formula (2) are shown. Examples of polymer main chain structural units having a silane coupling group (2-1) to (2-12), and structural examples of polymer main chain structural units not containing a positively charged nitrogen atom (2-13) (2-26) Structural examples of polymer main chain constitutional units containing a positively charged nitrogen atom are shown in (2-27) to (2-40), and specific hydrophilic polymers are arbitrarily combined. It shall constitute. The present invention is not limited to these. In addition, the polymer of the specific example shown below means that it is a random copolymer in which each structural unit described is contained by the described molar ratio.

  Each of the compounds for synthesizing the specific hydrophilic polymer (A) of the present invention is commercially available, and can be easily synthesized. (A) As a radical polymerization method for synthesizing a specific hydrophilic polymer, any conventionally known method can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experimental Science 3, Polymer Synthesis and Reaction 1 (Edited by the Society of Polymer Science, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I) (Edited by Chemical Society of Japan, Maruzen), Materials Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

  Further, (A) the specific hydrophilic polymer may be a copolymer with another monomer as described later. 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 to improve various physical properties, but it has a sufficient function as a hydrophilic film. (A) Specific hydrophilic polymer In order to sufficiently obtain the advantage of adding, it is preferable that the ratio is not too large. Accordingly, the preferred total proportion of other monomers in the (A) specific hydrophilic polymer is preferably 80% by mass or less, and more preferably 50% by mass or less.

  The specific hydrophilic polymer (A) according to the present invention is preferably from 5 to 95% by mass, more preferably from the viewpoint of curability and hydrophilicity, with respect to the nonvolatile component of the hydrophilic film-forming composition of the present invention. Is contained in the range of 15 to 90% by mass, most preferably 20 to 85% by mass. These may be used alone or in combination of two or more. Here, the non-volatile component refers to a component excluding a volatile solvent.

[(B) metal complex catalyst]
The metal complex catalyst (B) that can be used in the present invention is preferably a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and a β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, It is composed of an oxo or hydroxy compound selected from amino alcohols and enolic active hydrogen compounds.

  Furthermore, among the constituent metal elements, 2A group elements such as Mg, Ca, St 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, and each form a complex having an 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, for example, acetylacetone, acetylacetone (2,4-pentanedione), β-diketones such as 2,4-heptanedione, methyl acetoacetate, Ketoesters such as ethyl acetoacetate and butylacetoacetate, hydroxycarboxylic acids and esters such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate, 4-hydroxy-4-methyl-2- Ketone alcohols such as pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl -Monoethanol Amino alcohols such as methyl, diethanolamine and triethanolamine, enol active compounds such as methylolmelamine, methylolurea, methylolacrylamide, malonic acid diethyl ester, methyl group, methylene group or carbonyl of acetylacetone (2,4-pentanedione) Examples include compounds having a substituent on carbon.

  A preferred ligand is 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. Substituents for substitution on the methyl group of acetylacetone are all 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 substituting the methylene group, a carboxyl group, each of which is a linear or branched carboxyalkyl group and hydroxyalkyl group having 1 to 3 carbon atoms, and as a substituent for substituting the carbonyl carbon of acetylacetone, 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 preferred acetylacetone derivatives include acetylacetone, ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, Examples include acetoacetic acid, acetopropionic acid, diacetoacetic acid, 3,3-diacetopropionic acid, 4,4-diacetobutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, and 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, but in particular, 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 takes a coordination 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 satisfying the improvement of coating solution aging stability and film surface quality, and high hydrophilicity and high durability.

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

  In the composition for forming a hydrophilic film of the present invention, in addition to the essential components (A) specific hydrophilic polymer and (B) metal complex catalyst, various compounds may be added according to the purpose to achieve the effects of the present invention. They can be used in combination as long as they are not impaired. Hereinafter, components that can be used in combination will be described.

[(C) Alkoxide Compound of Element Selected from Si, Ti, Al, Zr]
The alkoxide compound of an element selected from Si, Ti, Al, and Zr, which is (C) the specific alkoxide used in the present invention, 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 is preferably used because it forms a strong film having a cross-linked structure by condensation polymerization with the specific hydrophilic polymer (A).

  Furthermore, (C) the specific alkoxide is preferably a compound represented by the following general formula (7). In forming a crosslinked structure in order to cure the hydrophilic film, the (A) specific hydrophilic polymer is used. (C) The specific alkoxide is mixed and coated on the surface of the support, heated and dried.

In general formula (7), R ¹ represents a hydrogen atom, an alkyl group or an aryl group, R ² represents an alkyl group or an aryl group, Y represents Si, Ti, Al or Zr, and k is 0 to 2. Represents an integer. The number of carbon atoms when R ¹ and R ² represent an alkyl group 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 the specific alkoxide represented by (C) general formula (7) 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, Ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropylpyrethoxysilane, 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, those containing aluminum in the specific alkoxide include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like.
When Y is Ti, that is, those containing titanium include, 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 (C) specific alkoxide according to the present invention may be used alone or in combination of two or more.
(C) The specific alkoxide is preferably used in the composition for forming a hydrophilic film of the present invention as a nonvolatile component in an amount of preferably 5 to 80% by mass, more preferably 10 to 70% by mass. . 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.

[(D) Surfactant]
In the present invention, it is preferable to use a surfactant in order to improve the film surface of the hydrophilic film-forming 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 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 composition for forming a hydrophilic film of the present invention as a non-volatile component in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass. Moreover, surfactant can be used individually or in combination of 2 or more types.

[(E) Inorganic fine particles]
The composition for forming a hydrophilic film of the present invention may contain inorganic fine particles for improving the cured film strength and hydrophilicity of the hydrophilic 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 diameter 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 hydrophilic layer, sufficiently retains the film strength of the hydrophilic layer, and is excellent in hydrophilicity. The inorganic fine particles as described above are preferably colloidal silica, which 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 film forming composition of the present invention as a nonvolatile component, preferably in an amount of 20% by mass or less, more preferably 10% by mass or less. The inorganic fine particles can be used alone or in combination of two or more.

[(F) UV 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.

[(G) Antioxidant]
In order to improve the stability of the hydrophilic member of the present invention, an antioxidant can be added to the coating liquid for forming the hydrophilic 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.

[(H) polymer compound]
In order to adjust the film physical properties of the hydrophilic layer, various polymer compounds can be added to the coating liquid for forming the hydrophilic layer of the hydrophilic member of the present invention within a range not inhibiting the hydrophilicity. 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.

[(I) Other additives]
In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, tackifiers, etc. 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.

[Preparation of hydrophilic film-forming composition]
The composition for forming a hydrophilic film is prepared by (A) a specific hydrophilic polymer and (B) a metal complex catalyst, more preferably any one of (C) to (I) various additives (including two or more kinds). Good) is dissolved in a solvent such as ethanol and then stirred. The reaction temperature is room temperature to 80 ° C., and the reaction time, that is, the time for continuing the stirring is preferably in the range of 1 to 72 hours. By this stirring, the hydrolysis and polycondensation of the silane coupling group proceeds, An organic-inorganic composite sol solution can be obtained.

  The solvent used in preparing the hydrophilic film forming composition containing the (A) specific hydrophilic polymer and (B) the metal complex catalyst is not particularly limited as long as these can be uniformly dissolved and dispersed. Although there is no restriction | limiting, For example, aqueous solvents, such as methanol, ethanol, water, are preferable. Examples of the hydrophilic member forming method include dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure coating method and the like, vacuum deposition method, reactive deposition method, ion beam, etc. 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.

  As described above, the preparation of the organic-inorganic composite sol solution (hydrophilic film-forming composition) for forming the hydrophilic film by the hydrophilic film-forming composition of the present invention uses the sol-gel method. Yes. 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 a hydrophilic film-forming composition in the present invention.

  The hydrophilic member of the present invention can be obtained by coating a solution containing the composition for forming a hydrophilic film of the present invention on an appropriate support and drying it. That is, the hydrophilic member of the present invention has a hydrophilic film (hydrophilic layer) formed by coating the hydrophilic film-forming composition of the present invention on a support, heating and drying. It is. In the formation of the hydrophilic film, the heating and drying conditions after coating the solution containing the composition for forming a hydrophilic film are temperatures of 50 to 200 ° C. from the viewpoint of efficiently forming a high-density crosslinked structure. In the range, it is preferable to carry out for about 2 minutes to 1 hour, and more preferably in the temperature range of 80 to 160 ° C. 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.

〔substrate〕
As a substrate that can be used as the support of the hydrophilic member of the present invention, for example, in the case of a transparent substrate that is expected to have an antifouling and / or antifogging effect, the material contains glass or an undercoat layer. A substrate capable of transmitting visible light, such as an inorganic substrate such as glass, a transparent plastic, or a transparent plastic layer containing an undercoat layer, can be suitably used.

The details of the inorganic substrate include a normal glass plate, a laminated glass plate including a resin layer, a gas layer, and a vacuum layer, and various glass plates including a reinforcing component and a colorant.
The glass plate containing the primer layer includes 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, An undercoat layer formed of a metal oxide such as ITO (Indium Tin Oxide); a metal halide such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride; The glass plate provided can be mentioned.

  The undercoat layer can have a single layer or a multilayer structure between the substrate and the hydrophilic layer. 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. The undercoat layer is preferably obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound containing an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst. Here, the above-mentioned thing is mentioned as an alkoxide compound containing the element selected from Si, Ti, Zr, and Al. Among these, Si alkoxide compounds are preferable from the viewpoint of reactivity and availability, and specifically, compounds used for silane coupling agents can be suitably used.

Nonvolatile catalysts used in the undercoat layer are those other than those having a boiling point of less than 20 ° C., in other words, those having a boiling point of 20 ° C. or higher, or those having no boiling point in the first place (such as thermal decomposition, Including those that do not cause changes).
Although it does not specifically limit as a non-volatile catalyst used for this invention, A metal complex (it is also called a metal chelate compound) and a silane coupling agent are mentioned. In addition, although an acid or an alkali is suitably used as a catalyst in the industry, any of those having a boiling point of 20 ° C. or higher can be applied without particular limitation. For example, hydrochloric acid having a boiling point of −83 ° C. is excluded, but nitric acid having a boiling point of 121 ° C. or phosphoric acid having a decomposition temperature of 213 ° C. is applied as a nonvolatile catalyst in the present invention. Examples of the metal complex include those described above.

  The silane coupling agent used as the non-volatile catalyst is not particularly limited, and examples thereof include those having a functional group showing acidity or alkalinity, and more specifically, peroxo acid, carboxylic acid, carbohydrazone acid, carboximide Functional groups that exhibit acidity, such as acids, sulfonic acids, sulfinic acids, sulfenic acids, selenonic acid, selenic acid, selenic acid, telluronic acid, and the above alkali metal salts, or basic functional groups such as amino groups The silane coupling agent which has is mentioned.

  The undercoat layer is formed by applying a composition having at least the alkoxide compound and the non-volatile catalyst on the base material, heating and drying the base composition, thereby hydrolyzing and polycondensing the composition. Can be formed. The heating temperature and heating time for forming the undercoat layer are not particularly limited as long as the solvent in the sol solution is removed and a strong film can be formed. It is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour. The undercoat layer can be prepared by a known coating method, and is not particularly limited. 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 are applicable.

  The subbing layer thus obtained contains a non-volatile catalyst without losing its activity, and is also present on the surface of the subbing layer and the hydrophilic layer. The adhesion at the interface is extremely high.

  The undercoat layer can be further improved in adhesion at the interface between the undercoat layer and the hydrophilic layer by providing fine irregularities by mixing plasma etching or metal particles.

As the material for the undercoat layer, a hydrophilic resin or water-dispersible latex can be used.
Examples of hydrophilic resins include polyvinyl alcohol (PVA), cellulosic resins (methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.), chitins, chitosans, starch, and ether bonds. Examples 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 resins and water-dispersible latexes 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 thermal crosslinking agents include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, polyethylene or polypropylene Polyepoxy compounds such as 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, tolylene diene Isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene diiso Polyisocyanate compounds such as anate, 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 crosslinking agents, a water-soluble crosslinking 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, the total amount of 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 using the hydrophilic member of the present invention in anticipation of antifogging, friction resistance, antibacterial and antifouling effects, another layer is appropriately added depending on the purpose, form and place of use. Can be used. 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 onto 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, semi-transparency, or matte is required, in addition to the 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. In order to give mold release properties to the mold release layer, it is preferable to contain a mold release agent. 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 Resins, acrylic-fluorine-based copolymer resins, urethane-silicone-fluorine-based copolymer resins, and the like, as well as resin blends of silicone-based resins and acrylic resins, and fluorine-based resins and acrylic-based resins. 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 hydrophilic layer. The protective layer has a function of preventing damage to the hydrophilic surface during handling, transportation, storage, and the like, and a decrease in hydrophilicity due to adhesion of dirt substances. As the protective layer, the release layer or the hydrophilic polymer layer used for the undercoat layer can be used. The protective layer is peeled off after the hydrophilic member is attached to an appropriate 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, and can also be supplied as a pre-cut for pasting to an appropriate substrate. .

[Surface free energy]
The hydrophilicity of the hydrophilic layer surface is generally measured by the water droplet contact angle. However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and further 5 ° or less, and there is a limit to the mutual comparison of hydrophilicity. . On the other hand, as a method for evaluating the hydrophilicity of the solid surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, the surface free energy was measured using the Zisman plot method as an example. Specifically, using the property that an aqueous solution of an inorganic electrolyte such as magnesium chloride increases in surface tension with the concentration, after measuring the contact angle in the air at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship, and the surface tension when cos θ = 1, that is, the contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and it can be said that the higher the surface free energy value, the higher the hydrophilicity.
A hydrophilic layer whose surface free energy measured by such a method is in the range of 70 mN / m to 95 mN / m, preferably 72 mN / m to 93 mN / m, more preferably 75 mN / m to 90 mN / m is hydrophilic. Excellent performance and good performance.

When the hydrophilic member coated with the hydrophilic film 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 film 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 coating 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, sufficient hydrophilicity and durability can be obtained, and when the film thickness is 100 μm or less, there is no problem in film forming properties such as cracking, which is preferable.
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 film can be applied to various applications without obstructing the field of view.

  Among organic substrates such as plastic, examples of the transparent plastic substrate include substrates made of various plastic materials having visible light permeability. In particular, a substrate used as an optical member is selected in consideration of optical properties such as transparency, refractive index, and dispersibility, and has various physical properties such as impact resistance and flexibility depending on the purpose of use. It is selected in consideration of physical properties including heat resistance, weather resistance, durability and the like. From these viewpoints, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins, or polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, ethylene vinyl alcohol, and acrylic resins. Preferred examples include resins, cellulose resins such as triacetyl cellulose, diacetyl cellulose, and cellophane. 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.

  As the plastic substrate, a substrate in which the undercoat layer described in the description of the glass plate is formed on the plastic plate can also be used. In this case, the undercoat layer can also act as an antireflection layer. When the undercoat layer is formed on a plastic plate, it can be formed by the same method as that for the inorganic substrate described above.

  When an undercoat 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.

  Thus, the hydrophilic member of the present invention can be obtained by using a glass plate or plastic plate having an undercoat layer as a substrate and forming a hydrophilic surface. Since the hydrophilic member has a hydrophilic film excellent in hydrophilicity and durability on the surface, it is excellent in antifouling property on the surface of the support (substrate), in particular, antifouling property against oil and fat stains, antifogging property or Both can be granted.

  The antireflection layer applicable to the surface of the hydrophilic member of the present invention is not limited to the above-described inorganic compound layer. For example, an antireflection effect is obtained by laminating a plurality of thin layers having different reflectivities and refractive indexes. A known antireflection layer or the like can also be used as appropriate, and the material can be either an inorganic compound or an organic compound. In particular, a substrate having an inorganic compound layer as an antireflection film formed on the surface thereof has antifouling properties on the surface by applying the hydrophilic polymer chain according to the present invention to the surface on the side on which the antireflection film is formed. The antifouling and / or antifogging member of the present invention having excellent antifogging function and antireflection properties can be obtained. In addition, depending on the purpose, the hydrophilic member of the present invention can be used in various ways by bonding a functional optical member such as a polarizing plate to a member having the above-described structure by a bonding technique typified by a laminate. An antireflection / optical functional member having functions and characteristics can also be obtained.

  These anti-reflective members and anti-reflective / optical functional members can be used for the front plate of display devices of various displays (liquid crystal displays, CRT displays, projection displays, plasma displays, EL displays, etc.) using adhesives, adhesives, etc. By applying it to a glass plate, a plastic plate, a polarizing plate or the like, this antireflection member can be applied to a display device.

  Further, the hydrophilic member of the present invention can be applied to various uses that require antifouling and / or antifogging effects in addition to the display device described above. In addition, in the case of applying to a substrate that does not require transparency in the antifouling and / or antifogging member, in addition to the above transparent substrate, for example, metal, ceramics, wood, stone, cement, concrete, Fibers, fabrics, combinations thereof, and laminates thereof can be suitably used as the support substrate.

  If an example of the field | area which can apply the hydrophilic member of this invention is given, as a use which the board | substrate which can permeate | transmit visible light is applicable, as a vehicle rear-view mirror, bathroom mirror, toilet mirror, dental mirror, road Mirrors such as mirrors; glasses lenses, optical lenses, camera lenses, endoscope lenses, illumination lenses, semiconductor lenses, copier lenses; prisms; window glass for buildings and surveillance towers; Rail vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, vehicle window glass such as spacecraft; automobiles, rail vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, Windshields for motorcycles, ropeway gondola, amusement park gondola, spacecraft vehicles; protective goggles, sports goggles, protective mask shields, sports masks Field, helmet shield, glass frozen food display cases; cover glass measuring instruments, and the like films for attached to the article surface and the like.

  Other applicable applications include building materials, building exteriors, building interiors, window frames, window glass, structural members, vehicle exteriors and coatings, machinery and article exteriors, dust covers and coatings, traffic signs, and various display devices , Advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, solar cell covers, solar water heater heat collection covers, plastic houses, vehicle lighting cover, Housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking range, kitchen hood, ventilation fan, and film for application to the surface of the article, Housing, parts, exterior and paint for household electrical products, housing, parts, exterior and paint for OA equipment products, and for attaching to the surface of the article Films and the like, its application range is wide.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Example 1]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic layer coating solution (1) having the following composition is added to the bar. This was coated and dried in an oven at 100 ° C. for 10 minutes to form a hydrophilic layer having a dry coating amount of 1.0 g / m ² to prepare a hydrophilic member. The surface free energy of this hydrophilic member was 82 mN / m, which was a highly hydrophilic surface. The visible light transmittance of the hydrophilic layer was 87% (measured with a Hitachi spectrophotometer U3000).

<Hydrophilic layer coating solution (1)>
・ 500g of the following sol-gel preparation (1)
・ Purified water 450g

<Sol-gel preparation liquid (1)>
200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate, 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), a cationic specific hydrophilic polymer having a silane coupling group in the side chain (structure) 4 g of units (2-2), (2-13) and (2-27) were mixed and stirred at room temperature for 2 hours to prepare.

<Synthesis of cationic specific hydrophilic polymer (copolymer of structural units (2-2), (2-13) and (2-27)) having a silane coupling group in the side chain>
A 500 ml three-necked flask was charged with 83 g of acrylamide, 93 g of acrylamide- (triethoxysilyl) propyl, 50 g of acrylamide- (tetramethylammonium) propyl iodide, and 1100 g of dimethyl sulfoxide, and 2,2′-azobis (2 -4.6 g of methyl propionate) dimethyl were added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The mixture was put into 15 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with hexane, a copolymer (copolymerization ratio 70:20:10) of structural units (2-2), (2-13) and (2-27) in Table 2 was obtained. It was. The mass after drying was 210 g. It was a polymer having a weight average molecular weight of 6,000 according to GPC (polyethylene oxide standard).

[Example 2]
In Example 1, instead of the cationic specific hydrophilic polymer having a silane coupling group in the side chain (copolymer of structural units (2-2), (2-13) and (2-27)), The same procedure was carried out except that a cationic specific hydrophilic polymer (a copolymer of structural units (2-2), (2-13) and (2-28)) having a silane coupling group in the side chain was used. The hydrophilic member of Example 2 was produced.

Example 3
In Example 1, instead of the cationic specific hydrophilic polymer having a silane coupling group in the side chain (copolymer of structural units (2-2), (2-13) and (2-27)), The same procedure was carried out except that a cationic specific hydrophilic polymer (copolymer of structural units (2-2), (2-13) and (2-29)) having a silane coupling group in the side chain was used. The hydrophilic member of Example 3 was produced.

Example 4
In Example 1, instead of the cationic specific hydrophilic polymer having a silane coupling group in the side chain (copolymer of structural units (2-2), (2-13) and (2-27)), The same procedure was carried out except that a cationic specific hydrophilic polymer (copolymer of structural units (2-2), (2-13) and (2-30)) having a silane coupling group in the side chain was used. The hydrophilic member of Example 4 was produced.

Example 5
<Synthesis of a cationic polymer having a silane coupling group at the terminal (copolymer of structural units (1-1), (1-13) and (1-27))>
A 500 ml three-necked flask was charged with 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, 13 g of acrylamide- (tetramethylammonium) propyl iodide, and 51.3 g of dimethylformamide, and the 2,2′- 0.25 g of azobis (2-methylpropionic acid) dimethyl was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The solution was put into 1.5 liters of ethyl acetate, and the precipitated solid was collected by filtration. After the obtained solid was washed with ethyl acetate, a copolymer (copolymerization ratio 90:10) of structural units (1-1), (1-13) and (1-27) in Table 1 was obtained. . The mass after drying was 32 g. It was a polymer having a weight average molecular weight of 4,000 according to GPC (polyethylene oxide standard).

  In Example 1, instead of the cationic specific hydrophilic polymer having a silane coupling group in the side chain (copolymer of structural units (2-2), (2-13) and (2-27)), Other than using a cationic specific hydrophilic polymer having a silane coupling group at the terminal (copolymer of structural units (1-1), (1-13) and (1-27) in Table 1 above) Thus, a hydrophilic member of Example 5 was produced.

Example 6
In Example 5, the cationic specific hydrophilic polymer having a silane coupling group at the terminal (copolymer of structural units (1-1), (1-13) and (1-27) in Table 1). Instead, a cationic specific hydrophilic polymer having a silane coupling group at the terminal (a copolymer of structural units (1-1), (1-13) and (1-28) in Table 1 above) was used. In the same manner, a hydrophilic member of Example 6 was produced.

Example 7
In Example 5, the cationic specific hydrophilic polymer having a silane coupling group at the terminal (copolymer of structural units (1-1), (1-13) and (1-27) in Table 1). Instead, a cationic specific hydrophilic polymer having a silane coupling group at the terminal (a copolymer of structural units (1-1), (1-13) and (1-29) in Table 1 above) was used. Produced a hydrophilic member of Example 7 in the same manner.

Example 8
In Example 5, the cationic specific hydrophilic polymer having a silane coupling group at the terminal (copolymer of structural units (1-1), (1-13) and (1-27) in Table 1). Instead, a cationic specific hydrophilic polymer having a silane coupling group at the terminal (a copolymer of structural units (1-1), (1-13) and (1-30) in Table 1 above) was used. Produced a hydrophilic member of Example 8 in the same manner.

[Comparative Example 1]
In Example 1, instead of the cationic specific hydrophilic polymer having a silane coupling group in the side chain (copolymer of structural units (2-2), (2-13) and (2-27)), A hydrophilic member of Comparative Example 1 was prepared in the same manner except that the comparative compound (i) outside the scope of the present invention having the following structure was used.

[Comparative Example 2]
In Example 1, instead of the cationic specific hydrophilic polymer having a silane coupling group in the side chain (copolymer of structural units (2-2), (2-13) and (2-27)), A hydrophilic member of Comparative Example 2 was prepared in the same manner except that the comparative compound (ii) outside the scope of the present invention having the following structure was used.

[Comparative Example 3]
In Example 5, instead of the cationic specific hydrophilic polymer having a silane coupling group at the terminal (copolymer of structural units (1-1), (1-13) and (1-27)), A hydrophilic member of Comparative Example 3 was prepared in the same manner except that the comparative compound (iii) outside the scope of the present invention having a structure was used.

[Comparative Example 4]
In Example 5, instead of the cationic specific hydrophilic polymer having a silane coupling group at the terminal (copolymer of structural units (1-1), (1-13) and (1-27)), A hydrophilic member of Comparative Example 4 was prepared in the same manner except that the comparative compound (iv) outside the scope of the present invention having a structure was used.

[Comparative Example 5]
In Example 1, the copolymerization ratio of the cationic specific hydrophilic polymer (copolymer of the structural units (2-2), (2-13) and (2-27)) having a silane coupling group in the side chain The hydrophilic member of Comparative Example 5 was produced in the same manner except that the ratio was set to 79.5: 20: 0.5.

[Comparative Example 6]
In Example 1, the copolymerization ratio of the cationic specific hydrophilic polymer (copolymer of the structural units (2-2), (2-13) and (2-27)) having a silane coupling group in the side chain The hydrophilic member of Comparative Example 6 was produced in the same manner except that the ratio was 45:20:35.

(Evaluation) The following evaluation was performed on the hydrophilic member.
Surface free energy: The hydrophilicity of the surface of the hydrophilic layer is generally measured by a water droplet contact angle (Kyowa Interface Science Co., Ltd., DropMaster 500). However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and further 5 ° or less, and there is a limit to the mutual comparison of hydrophilicity. . On the other hand, as a method for evaluating the hydrophilicity of the solid surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, as an example, the surface free energy was measured using the Zisman plot method. Specifically, using the property that an aqueous solution of an inorganic electrolyte such as magnesium chloride increases in surface tension with the concentration, after measuring the contact angle in the air at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship, and the surface tension when cos θ = 1, that is, the contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and it can be said that the higher the surface free energy value, the higher the hydrophilicity.

  Transparency: When the hydrophilic member coated with the hydrophilic film of the present invention is used for window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic film 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. Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer (Hitachi spectrophotometer U3000).

Anti-fogging: Applying water vapor for 1 minute in the daytime under an indoor fluorescent lamp, separating it from the water vapor, placing it in an environment of 25 ° C. and RH 10%, and clouding under a fluorescent lamp under the same irradiation conditions as above And the change was sensory-evaluated in three steps according to the following criteria.
○: No cloudiness is observed Δ: Cloudy, but recovers within 10 seconds, no cloudiness is seen ×: Cloudy, no cloudiness recovers even after 10 seconds

Ink resistance: A line was drawn with oil-based ink (Mitsubishi Pencil Co., Ltd. oil-based marker), water was continuously applied, and the sensor was evaluated in three stages to determine whether it would flow down.
◎: Ink can be taken within 30 seconds. ○: Ink can be taken within 1 minute. △: Ink can be taken after 1 minute. ×: Ink cannot be removed even after 10 minutes.

Rinsing resistance: After immersing in a 5% by weight rinsing aqueous solution (Shiseido Super Mild) for 5 minutes, it was washed with running water for 1 minute. The above antifogging property evaluation was performed on the treated member, and sensory evaluation was similarly performed in three stages.
○: No cloudiness is observed Δ: Cloudy, but recovers within 10 seconds, no cloudiness is seen ×: Cloudy, no cloudiness recovers even after 10 seconds

Adhesion: The member was stored in 60 ° C. warm water and tested in 10 days and 1 month. The test method was a peel test with a 2 mm grid according to JISK5400.
◎: Grid board peeling 5% or less ○: Grid board peeling 5-10%
Δ: 10-50% peeling of the grid
X: 50% or more peeling of the grid

  Scratch test: Starting from 5 g on a 0.1 mm diameter sapphire needle, the surface of the member was scanned by applying a weight to 5 g increments, and the weight at which scratching occurred was evaluated (measured with a scratch strength tester Type 18S manufactured by Shinto Kagaku Co., Ltd.). Durability is better when there is no damage even if the load is large.

Weather resistance: A hydrophilic member is exposed to a sunshine carbon arc lamp type accelerated weathering tester for 500 hours, and the hydrophilicity, antifogging property, antifouling property, visible light transmittance, adhesion, and scratch strength are as described above. evaluated. Judgment was made according to the following criteria.
○: Performance equivalent to that before exposure in all items Δ: One item is inferior before exposure ×: Two or more items are inferior before exposure

Water resistance: Sponge reciprocation 1 by applying a weight of 1kg to a 120cm ² size hydrophilic member in water
Rubbing was performed 0 times, and the remaining film ratio was measured from the weight change before and after that. The water resistance was represented by the remaining film ratio.

Antibacterial activity: confirmed against two strains of Escherichia coli (IFO 3301) and Staphylococcus aureus (IFO 12732). Moreover, the evaluation test was implemented by the film contact | adherence method. The test method is shown below.
(1) Each test strain is cultured in a normal agar medium at 37 ° C. for 20 hours and suspended in a solution of 1/500 normal medium to adjust the number of bacteria to 2.0 × 10 ⁵ cells / ml.
(2) A sample is prepared by cutting each hydrophilic member so that the surface area is 25 cm ² .
(3) Put the sample in separate sterilization dishes, add 0.5 ml of the fungus test solution prepared in (1) to cover each film. At this time, care should be taken so that the bacterial test solution does not adhere to the inner surface of the film.
(4) Store each sterile petri dish containing the sample at 35 ° C. for 24 hours.
(5) After storing for 24 hours, the test bacterial solution is washed away with sterile buffered physiological saline, and the number of viable bacteria in the washed-out solution is measured by the pour plate culture method. Antibacterial properties are better if there are no viable bacteria.

  The results of the evaluation are shown in Table 3. In any of the examples, all of the antifogging properties, ink proofing properties, rinsing proofing properties, adhesion properties, weather resistance, water resistance and antibacterial properties were good. In the scratch test, no damage was found up to 55 g, and the durability was excellent. In the antibacterial test, the number of viable bacteria was zero, and no bacterial growth was observed. Also, in the antibacterial test of the hydrophilic member after the water resistance test, the number of viable bacteria was zero, and a good antibacterial action was shown. On the other hand, all of the comparative examples had problems with rinsing properties, and viable bacteria were observed in the antibacterial test. In comparison between these examples and comparative examples, it is apparent that the present invention can impart antifouling properties and antibacterial properties to the hydrophilic members of the prior art.

Claims (7)

(A) A hydrophilic polymer having a structure represented by the following general formula (1) or general formula (2).

In general formula (1) and (2), R < ¹ > -R < ⁸ > represents a hydrogen atom or a C1-C8 hydrocarbon group each independently. Of the hydrocarbon groups, R ⁴ , R ⁶ and R ⁸ may have a hydroxyl group and / or a silane coupling group at the side chain and / or terminal. m represents 0, 1 or 2, and x, y and z represent the composition ratio when x + z = 100 in the general formula (1) and x + y + z = 100 in the general formula (2), and 0 <x < 100, 0 <y <100, 0 <z <100. L ¹ , L ² , L ³ , L ⁴ and L ⁶ each independently represents a single bond or an organic linking group, and L ⁵ represents a single bond or CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, And a polyvalent organic linking group having one or more structures selected from the group consisting of —SO ₃ —. Y ¹ and Y ³ are each independently —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 represents an _{(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 having 1 to 8 carbon atoms, and R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion. Y ² and Y ⁴ each represent a functional group containing at least one nitrogen atom having a positive charge. ^2. The hydrophilic polymer according to claim 1, wherein the functional group containing at least one positively charged nitrogen atom in Y ² and Y ⁴ is represented by any structure of the following general formula (3). .

In the general formula ^(3), at least one of R 11 ^{to R 14} may represent ^L 2, ^{L 6} is a connecting chain of the hydrophilic polymer backbone, ^R 11 ^{to R 14} except the linking chain, respectively Independently, it represents a hydrocarbon group which may be substituted with a hydroxyl group and / or a silane coupling group. X ⁻ represents an anion.   A composition for forming a hydrophilic film comprising (A) a hydrophilic polymer according to claim 1 or 2 and (B) a metal complex catalyst.   The metal complex catalyst (B) is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and a β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, enolic active hydrogen compound. The composition for forming a hydrophilic film according to claim 3, which is composed of an oxo or hydroxy compound selected from the group consisting of:   Furthermore, the composition for hydrophilic film formation of Claim 3 or 4 containing the alkoxide compound containing the element selected from Si, Ti, Al, and Zr.   Furthermore, the composition for hydrophilic film formation in any one of Claims 3-5 containing colloidal silica.   A hydrophilic member, wherein the hydrophilic forming composition according to claim 3 is coated on a support.