JP2009185088A - Hydrophilic polymer, composition for forming hydrophilic membrane and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic polymer for forming a hydrophilic membrane maintaining adequate antifogging and antifouling properties even under severe conditions on various support surfaces. <P>SOLUTION: The hydrophilic polymer has a structure, e.g. represented by general formula (1), wherein R<SP>1</SP>represents a hydrogen atom or a 1-8C hydrocarbon group; m represents 0-2; x and y represent a composition ratio; L<SP>1</SP>and L<SP>2</SP>each represents a single bond or an organic linking group; and Y<SP>1</SP>-Y<SP>4</SP>each represents a group forming a crosslinking spot. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrophilic polymer useful for forming a hydrophilic film having antifouling properties, antifogging properties, and durability (particularly abrasion resistance) on various support surfaces, and a composition for forming a hydrophilic film. And a hydrophilic member 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 that makes it difficult to get dirt on the surface of a solid member or that makes it easier to remove the attached dirt. In particular, as a combination of the antireflection member and the antifouling member, for example, an antireflection and abrasion resistant material (for example, an antireflection film mainly composed of silicon dioxide and a compound containing an organosilicon substituent) Patent Document 1), and an antifouling and wear-resistant CRT filter (for example, see Patent Document 2) in which a 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 (for example, see 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 having good wear resistance.

In order to achieve the above-mentioned problems, the hydrophilic surface with a crosslinked structure exhibits excellent antifouling properties by hydrolyzing and condensing a hydrophilic polymer and an alkoxide by focusing on the characteristics of the sol-gel organic-inorganic hybrid film. And it has been found to have good wear 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 and a crosslinking agent.
However, the conventional hydrophilic membrane as described above cannot be said to have a sufficient level when it is used under severe conditions such as around the water in a kitchen or a car body coat, and its application is limited. This is the current situation. In order to develop these applications, a member that has sufficient durability to withstand detergent, sponge rubbing, heat, light, etc., and that maintains high hydrophilicity is required.
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 JP 2002-361800 A Newspaper "Chemical Industry Daily" article dated January 30, 1995

  An object of the present invention is to solve the problems of the prior art by further research on hydrophilic membranes. That is, as a first problem, a hydrophilic polymer for forming a hydrophilic film capable of maintaining sufficient antifogging property and antifouling property even under severe conditions on various support surfaces and a polymer containing the same are included. A hydrophilic film-forming composition, and as a second problem, by forming a hydrophilic film using the hydrophilic film-forming composition on an appropriate support surface, An object of the present invention is to provide a hydrophilic member having a surface excellent in durability (particularly abrasion resistance) and having excellent antifogging and antifouling properties.

  As a cause of insufficient durability (especially abrasion resistance) of conventional hydrophilic membranes, lack of crosslinking points in the membrane can be considered. Thus, as a result of research on hydrophilic membranes, the present inventors have introduced a new crosslinking point into the polymer structure, so that the basic performances of antifogging and antifouling properties are not impaired, and more advanced We have succeeded in developing a hydrophilic polymer capable of imparting abrasion resistance, a hydrophilic film forming composition containing the hydrophilic polymer, and a hydrophilic member.

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 < ⁵ > represents a hydrogen atom or a C1-C8 hydrocarbon group each independently. m represents 0, 1 or 2, x and y represent a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and x + y = 100. L ¹ and L ² each independently represents a single bond or an organic linking group, and L ³ represents a single bond or —COO—, —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, —SO ₃ —. A polyvalent organic linking group having one or more structures selected from the group consisting of: Y ^{1 to} Y ⁴ are each independently —H, —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —NHC (NH) N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SR _a , —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 ), —N (R _a ) (R _b ) ( _{R g), - PO 3 (} R e) (R f), - OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . However, Y ^{2 to} Y ⁴ are not all hydrogen atoms. 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.
2. 2. A hydrophilic film-forming composition comprising (A) the hydrophilic polymer according to 1 and (B) a metal complex catalyst.
3. 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. 3. The hydrophilic film forming composition as described in 2 above, which is composed of an oxo or hydroxy compound selected from the group consisting of:
4). 4. The composition for forming a hydrophilic film as described in 2 or 3 above, further comprising an alkoxide compound containing an element selected from Si, Ti, Al, and Zr.
5. Furthermore, the composition for hydrophilic film formation in any one of said 2-4 containing colloidal silica.
6). A hydrophilic member, wherein the hydrophilic film forming composition according to any one of 2 to 5 is coated on a support.

The principle of the present invention is presumed as follows.
The hydrophilic polymer of the present invention has many crosslinking points due to covalent bonds such as hydroxyl groups, amino groups, and amide groups, as well as hydrogen bonds, as indicated by Y ^{1 to} Y ⁴ in the above general formula (1) or (2). Since it introduced, the hydrophilic film | membrane bridge | crosslinked more densely can be obtained compared with bridge | crosslinking of silane coupling groups of a hydrophilic polymer, or only a hydrogen bond. Thereby, it is thought that durability improved. In addition, these cross-linking points are introduced at the α-position of the methacrylamide derivative monomer, which is located away from the functional group (including the silane coupling group) on the side chain, for example, so that the basic performance is antifogging and antifouling. It is thought that sex etc. could be maintained.

  According to the present invention, hydrophilic polymer and hydrophilic film formation useful for forming hydrophilic films having antifouling properties, antifogging properties, and durability (particularly abrasion resistance) on the surfaces of various supports And a hydrophilic member provided with a hydrophilic film made of the composition for forming a hydrophilic film. The hydrophilic member of the present invention can withstand use under more severe conditions such as around the water in a kitchen and body coat of a car. Further, when the functional group introduced as a crosslinking point is a hydrophilic group, the antifogging property can be greatly improved.

Hereinafter, the present invention will be described in detail.
[(A) hydrophilic polymer]
The hydrophilic polymer (A) of 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 < ⁵ > represents a hydrogen atom or a C1-C8 hydrocarbon group each independently. m represents 0, 1 or 2, x and y represent a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and x + y = 100. L ¹ , L ² and L ³ each independently represents a single bond or an organic linking group, and L ³ represents a single bond or COO—, CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, —SO _3. -Represents a polyvalent organic linking group having at least one structure selected from the group consisting of-. Y ^{1 to} Y ⁴ are each independently —H, —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —NHC (NH) N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SR _a , —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 ), —N (R _a ) (R _b ) ( _{R g), - PO 3 (} R e) (R f), - OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . However, Y ^{2 to} Y ⁴ are not all hydrogen atoms. 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.

  It is preferable to have the silane coupling group in General formula (1) at the terminal of (A) specific hydrophilic polymer.

Examples of the hydrocarbon group when R ^{1 to} R ⁵ 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 ⁵ 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 ′ 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-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, 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 its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfur group Sulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H) (Aryl)) and conjugated base groups thereof (hereinafter referred to as aryl phosphonate groups), phosphonooxy groups (-OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonatooxy group”), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugate base group thereof (hereinafter referred to as an alkylphosphonatooxy group), mono Arylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group It is done.

Specific examples of the alkyl group in these substituents include the alkyl groups mentioned in R ^{1 to} R ⁵ , 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 Rubonirubuchiru group,

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

L ¹ and L ^{2 each} represents a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer and Y ¹ or Si atom are directly bonded without a connecting 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 and L ² may be formed of a polymer or oligomer, and specifically, preferably include polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene, and the like made of an unsaturated double bond monomer. Other preferred examples include poly (oxyalkylene), polyurethane, polyurea, polyester, polyamide, polyimide, polycarbonate, polyamino acid, polysiloxane, etc., preferably polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene More preferred are polyacrylates and polymethacrylates.
The structural unit used for these polymers and oligomers may be one type or two or more types. Further, when L ¹ and L ² 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, more preferably 1,000 to 500,000. 000 to 200,000 is most preferred.

L ³ is a single bond or a polyvalent organic linkage having one or more structures selected from the group consisting of —COO—, —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, —SO ₃ —. Represents a group. Here, the single bond represents that the polymer main chain and the Si atom are directly bonded without a linking group. In L ³ , two or more of the structures may be present, 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, the other structures can have the same structure as that described for L ¹ .

Y ^{1 to} Y ⁴ are each independently —H, —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R. _a , -NHC (NH) N (R _a ) (R _b ), -OCON (R _a ) (R _b ), -NHCON (R _a ) (R _b ), -SR _a , -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 ), —N (R _a ) (R _b ) _{) (R g), - PO} 3 (R e) (R f), - OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . However, Y ^{2 to} Y ⁴ are not all hydrogen atoms. 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, 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. In addition, —CON (R _a ) (R _b ), —NHC (NH) N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _g ), —PO ₃ (R _e ) (R _f ) , —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ), R _{a to} R _g may be bonded to each other to form a ring. The ring may be a heterocycle containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. R _{a to} R _g may further have a substituent, and the substituent that can be introduced here is the same as the substituent that can be introduced when R ^{1 to} R ⁵ 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 1 ~Y 4, -CO 2 -}} Na +, -CONH 2, -SO 3 - Na +, -SO 2 NH 2, -PO 3 H 2 and the like are preferable.

In the general formula (2), x and y are composition ratios of the structural unit represented by the general formula (Ia) and the structural unit represented by the general formula (Ib) in the specific hydrophilic polymer (A). Represents. x is 0 <x <100, y is 0 <y <100, and represents a number such that x + y = 100. x is preferably in the range of 40 <x <99, and more preferably in the range of 45 <x <98. y is preferably in the range of 1 <y <40, and more preferably in the range of 2 <y <35.
Here, the structural units constituting the polymer chain (Ia) and (Ib) may all be the same or may include a plurality of different structural units, In that case, the composition ratio of the structural unit corresponding to the general formula (Ia) and the structural unit corresponding to the general formula (Ib) is preferably in the above range.

  (A) The molecular weight (mass average) 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 specific hydrophilic polymer (A) having a silane coupling group at the terminal are shown below. Examples of the structure of the polymer terminal site are shown in (1-1) to (1-12), and examples of the structure of the polymer main chain structural unit are shown in (1-13) to (1-34). It shall constitute a hydrophilic polymer. 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 specific hydrophilic polymer (A) having a silane coupling group in the side chain are shown below. The polymer main chain constituent units having a silane coupling group are shown in (2-1) to (2-12), and other structural examples of the polymer main chain constituent units are shown in (2-13) to (2-34). Each specific hydrophilic polymer is composed of an arbitrary combination. 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. For example, (2-13) described in the specific example of the specific hydrophilic polymer having a silane coupling group in the side chain (A) can be synthesized from acrylamide and formaldehyde. Further, (2-13) is used as a substrate, (2-14) is ammonia, (2-15) is hydrogen disulfide, (2-17) is dimethylamine, (2-29) is trimethyl phosphate, (2- 30) can be synthesized by reaction with dimethylcarbamoyl chloride, respectively. Further, with (2-14) as a substrate, (2-23) is isothiourea, (2-26) is methanesulfonyl chloride, (2-31) is methyl iodide, and (2-33) is a reaction with acetyl chloride. Respectively. (2-19) can be synthesized from itaconic anhydride and ammonia. Furthermore, (2-19) is used as a substrate, (2-20) is ammonia, (2-22) is dimethylamine, and (2-32) is synthesized by reaction with methylmagnesium bromide. (A) (1-13) to (1-34) described in specific examples of the specific hydrophilic polymer having a silane coupling group at the terminal can also be synthesized in the same manner.
(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.

  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 proportion of these other monomers used in the synthesis of the copolymer needs to be an amount sufficient to improve various physical properties, but the function as a hydrophilic film is sufficient. (A) Specific hydrophilicity In order to obtain the full advantage of adding the polymer, it is preferred that the proportion 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 composition for forming a hydrophilic film of the present invention comprises (A) a specific hydrophilic polymer and (B) a metal complex catalyst.

  As the (B) metal complex catalyst used in the present invention, for example, a catalyst that promotes a reaction of hydrolyzing and polycondensing an alkoxide compound described below and causing a bond with a specific hydrophilic polymer is selected. The acid or basic compound is used as it is, or the acid or basic compound is dissolved in a solvent such as water or alcohol (hereinafter collectively referred to as acidic catalyst and basic catalyst, respectively) ) Is used. The concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

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

A Lewis acid catalyst comprising a metal complex can also be preferably used. Particularly preferred catalysts are metal complex catalysts, metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or their esters, amino alcohols, enolic active hydrogen compounds It is a metal complex comprised from the oxo or hydroxy oxygen containing compound chosen from these.
Among 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. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

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

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

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

  Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aco complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, 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. et al. 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 the improvement of coating solution aging stability and film surface quality, as well as high hydrophilicity and high durability.

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

  The (B) metal complex catalyst according to the present invention is preferably in the range of 1 to 30% by mass, more preferably 5 to 25% by mass with respect to the nonvolatile component in the hydrophilic film forming composition of the present invention. Used in. Moreover, (B) a metal complex catalyst may be used independently or may be used together 2 or more types.

The composition for forming a hydrophilic film of the present invention preferably contains an alkoxide compound (also referred to as a specific alkoxide compound) containing an element selected from Si, Ti, Zr, and Al. The specific alkoxide compound is a hydrolyzable polymerizable compound that has a polymerizable functional group in its structure and functions as a crosslinking agent. (A) A cross-linked structure is formed by condensation polymerization with a specific hydrophilic polymer. A strong film is formed.
The specific alkoxide compound is preferably a compound represented by the following general formula (3). In forming a crosslinked structure in order to cure the hydrophilic film, the (A) specific hydrophilic polymer, the general formula The specific alkoxide compound represented by (3) is mixed, coated on the substrate surface, heated and dried.

In the general formula (3), R ⁹ represents a hydrogen atom, an alkyl group or an aryl group, R ¹⁰ represents an alkyl group or an aryl group, Y represents Si, Al, Ti or Zr, and k is 0 to 2. Represents an integer. The number of carbon atoms when R ⁹ and R ¹⁰ 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.

  Specific examples of the specific alkoxide compound represented by the general formula (3) are given below, but the present invention is not limited thereto. When Y is Si, that is, as silicon containing specific alkoxide, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, Ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane Γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diph Alkenyl dimethoxysilane, mention may be made of diphenyl diethoxy silane. Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

In the case where Y is Al, that is, those containing aluminum in the specific alkoxide compound 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 specific alkoxide compound according to the present invention may be used alone or in combination of two or more.
The specific alkoxide compound is used in the hydrophilic film-forming composition of the present invention in an amount of preferably 5 to 80% by mass, more preferably 10 to 70% by mass with respect to the nonvolatile component.
The specific alkoxide compound can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.
In the composition for forming a hydrophilic film of the present invention, in addition to the essential components (A) and (B) and a specific alkoxide compound used in combination as desired, various compounds may be used according to the purpose. As long as the effect of is not impaired, it can be used in combination. Hereinafter, components that can be used in combination will be described.

[Surfactant]
In the present invention, it is preferable to use a surfactant in order to improve the 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.
In the composition for forming a hydrophilic film of the present invention, the surfactant is preferably used in a range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the nonvolatile component. The Moreover, surfactant can be used individually or in combination of 2 or more types.

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

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

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

Natural antibacterial agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crabs and shrimp shells.
In the present invention, Nikko's “trade name Holon Killer Bees Sera” made of aminometal in which a metal is compounded on both sides of an amino acid is preferable.
These are not transpirationable, easily interact with the polymer and crosslinker component of the hydrophilic film, can be stably dispersed in a molecule or solid, and the antibacterial agent is easily exposed to the hydrophilic film surface effectively. And even if it splashes with water, it does not elute, the effect can be maintained for a long time, and it does not affect the human body. Moreover, it can disperse | distribute stably with respect to a hydrophilic film | membrane and a coating liquid, and deterioration of a hydrophilic film | membrane and a coating liquid does not occur.
Among the antibacterial agents, silver-based inorganic antibacterial agents and water-soluble organic antibacterial agents are most preferable because of their great antibacterial effects. In particular, silver zeolite in which silver is supported on zeolite, which is a silicate carrier, antibacterial agent in which silver is supported on silica gel, 2-bromo-2-nitro-1,3-propanediol, TPN, TBZ, BCM, OBPA ZPT is preferred. Particularly preferred commercially available silver zeolite antibacterial agents include “Zeomic” by Shinagawa Fuel, “Sylwell” by Fuji Silysia Chemical, and “Bactenone” by JEOL. In addition, Toa Gosei's “Novalon” in which silver is supported on an inorganic ion exchanger ceramic, “Atomy Ball” from Catalytic Chemical Industry, and “Suneyeback P” as a triazine antibacterial agent are also preferred.

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

[Inorganic fine particles]
The 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 film, sufficiently retains the film strength of the hydrophilic film, and has excellent 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 in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, based on the nonvolatile components. The inorganic fine particles can be used alone or in combination of two or more.

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

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

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

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

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

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

[Hydrophilic member]
The hydrophilic member of the present invention was formed by coating a hydrophilic film-forming composition containing (A) a specific hydrophilic polymer and (B) a metal complex catalyst on a support, and heating and drying. It has a hydrophilic film formation. Furthermore, it is more preferable to have an undercoat layer between the support and the hydrophilic film.

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

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

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

  The undercoat layer is preferably obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound of an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst. Examples of the alkoxide compound of the element selected from Si, Ti, Zr, and Al include the same as those shown for the specific alkoxide compound.

  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 in particular because it is present on the surface of the subbing layer. When a film is provided, the adhesion at the interface between the undercoat layer and the hydrophilic film is extremely high.

  In addition, the undercoat layer of the hydrophilic member of the present invention is further improved in adhesion at the interface between the undercoat layer and the hydrophilic film by providing fine irregularities by mixing plasma etching or metal particles. Can do.

[Preparation of hydrophilic film-forming composition]
The composition for forming a hydrophilic film can be prepared by dissolving (A) the specific hydrophilic polymer and (B) the metal complex catalyst, more preferably the specific alkoxide compound in a solvent such as ethanol, and then stirring. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time during which stirring is continued, is preferably in the range of 1 to 72 hours. A composite sol solution can be obtained.

  The solvent used in preparing the hydrophilic film-forming composition is not particularly limited as long as it can uniformly dissolve and disperse these, and examples thereof include aqueous solvents such as methanol, ethanol, and water. preferable.

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 such a composition for forming a hydrophilic film of the present invention on an appropriate support (substrate) and drying. That is, the hydrophilic member of the present invention has a hydrophilic film formed by coating the hydrophilic film-forming composition of the present invention on a substrate, heating and drying.
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.

  Moreover, the hydrophilic member of this invention can be mixed just before coating a catalyst on a board | substrate, when coating a hydrophilic film | membrane and undercoat on a board | substrate. Specifically, it is preferable to apply within 1 hour immediately after catalyst mixing. When the catalyst is mixed and left to stand for a long period of time, the composition of the hydrophilic film-forming composition increases in viscosity, and defects such as coating unevenness may occur. Other components are also preferably mixed immediately before coating, but may be stored for a long time after mixing.

〔substrate〕
The substrate used in the present invention is not particularly limited, but glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, combinations thereof, and laminates thereof are all suitable. Available to: Particularly preferred substrates are glass substrates or plastic substrates.
As the glass plate, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO (Indium Tin Oxide) A metal plate such as magnesium oxide, magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride, etc .; be able to. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do. In addition, the hydrophilic film can be applied as it is with the base glass, but for the purpose of improving the adhesion of the hydrophilic film, if necessary, the surface is hydrophilized by oxidation or roughening on one or both sides. Can be applied. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

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

  The plastic substrate used in the present invention is not particularly limited, but the substrate used as the optical member is selected in consideration of optical characteristics such as transparency, refractive index, and dispersibility, and various types are used depending on the purpose of use. It is selected in consideration of physical properties such as physical properties such as strength such as impact resistance and flexibility, heat resistance, weather resistance and durability. Plastic substrates include polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, polysulfone. And films or sheets of polyether ketone, acrylic, nylon, fluororesin, polyimide, polyether imide, polyether sulfone and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use. The thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for a plane or the place where intensity | strength is requested | required.

For the purpose of improving the adhesion between the substrate and the hydrophilic film, one or both surfaces of the substrate can be subjected to a surface hydrophilization treatment by an oxidation method, a roughening method, or the like as desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.
Furthermore, one or more undercoat layers can be provided. 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 a polyvinyl alcohol resin, a cellulose resin, a resin having an ether bond, a resin having a carbamoyl group, a resin having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.

Examples of the water-dispersible latex include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.
The above hydrophilic resin and water-dispersible latex may be used alone or in combination of two or more, or a hydrophilic resin and a water-dispersible latex may be used in combination.
Moreover, you may use the crosslinking agent which bridge | crosslinks the said hydrophilic resin and water-dispersible latex.
As a cross-linking agent applicable to the present invention, a cross-linking agent that forms a cross-link by known heat can be used. General thermal crosslinking agents include those described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981). The number of functional groups of the crosslinking agent used in the present invention is not particularly limited as long as it is 2 or more and can be effectively crosslinked with a hydrophilic resin or water-dispersible latex. Specific examples of the thermal crosslinking agent include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene ethylene glycol diglycidyl ether, polyethylene or Polyepoxy compounds such as polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyaldehyde compounds such as glyoxal and terephthalaldehyde, tri Range isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene Polyisocyanate compounds such as socyanate, 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 film.
Wherein the hydrophilic resin and / or water-dispersible latex 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.

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

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

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

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

2) Release layer When the hydrophilic member of the present invention has the adhesive layer, a release layer can be further added. 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, and 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 film. 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 hydrophilic polymer layer used in the release 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 film of the present invention may be supplied in the form of a sheet, a roll, or a ribbon, and may be supplied as a pre-cut material for attaching to a suitable substrate.

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 film of the present invention is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 20 μm. When the film thickness is 0.01 μm or more, it is preferable to obtain sufficient hydrophilicity and durability, and when the film thickness is 100 μm or less, there is no problem in film forming properties such as cracks, which is preferable.
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.

The hydrophilic member of the present invention can be obtained by applying a coating solution composition for forming a hydrophilic film on an appropriate substrate, heating and drying to form a surface hydrophilic film. The heating temperature and heating time for forming the hydrophilic film are not particularly limited as long as the solvent and the time in which the solvent in the sol solution is removed and a strong film can be formed. The heating time is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour.
The hydrophilic member of the present invention 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 Methods such as screen printing, bar coater, brush coating and sponge coating can be applied.

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

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

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

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

<Method for forming hydrophilic film>
Float plate glass (thickness 2 mm) which is the most common transparent plate glass is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 5 minutes, and then a coating liquid (A) having the following composition is applied to the bar, It was oven dried at 100 ° C. for 10 minutes to form a hydrophilic layer having a dry coating amount of 1.0 g / m ² .
Subsequently, a coating solution B having the following composition was applied by a bar and oven dried at 150 ° C. for 15 minutes to form a hydrophilic layer having a dry coating amount of 30.0 g / m ² . The surface free energy of this hydrophilic member was 84 mN / m, which was a highly hydrophilic surface. The visible light transmittance of the hydrophilic layer was 90% (measured with a Hitachi spectrophotometer U3000).

<Coating liquid (A) preparation method>
In 180 g of purified water, 3 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6 g of a catalyst solution having the following composition were added and stirred at room temperature for 2 hours.
<Coating liquid (B) preparation method>
In 210 g of purified water, 15 g of a specific hydrophilic polymer and 6 g of a catalyst solution having the following composition were added and stirred for 2 hours at room temperature.
<Catalyst liquid preparation method>
300 g of ethyl alcohol, 14 g of acetylacetone, and 16 g of tetraethyl orthotitanate were stirred at room temperature for 10 minutes, 2.5 g of purified water was added, and the mixture was further stirred for 2 hours.

  The hydrophilic films in the following Examples 1 to 8 and Comparative Examples 1 to 6 were all prepared based on the above prescription and evaluated. That is, the hydrophilic member compositions produced in Examples 1 to 8 and Comparative Examples 1 to 6 differ only in the specific hydrophilic polymer in the coating liquid (B).

Example 1
Using a specific hydrophilic polymer having a silane coupling group at the terminal (combination of exemplary compounds (1-2) and (1-13)), a hydrophilic member was prepared and evaluated by the above method.
<Method for synthesizing specific polymer (combination of exemplary compounds (1-2) and (1-13))>
A 500 ml three-necked flask was charged with 25 g of α-hydroxymethacrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethyl sulfide, and 2,2′-azobis (2-methylpropionic acid) under a nitrogen stream at 65 ° C. 0.25 g of dimethyl was 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 1.5 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with acetone, a specific hydrophilic polymer (combination of exemplary compounds (1-2) and (1-13)) was obtained. The mass after drying was 20 g. It was a polymer having a mass average molecular weight of 3000 according to GPC (polyethylene oxide standard).

Example 2
Using a specific hydrophilic polymer having a silane coupling group at the terminal (combination of exemplary compounds (1-2) and (1-14)), a hydrophilic member was prepared and evaluated by the above method.
<Method for synthesizing specific polymer (combination of exemplary compounds (1-2) and (1-14))>
A 500 ml three-necked flask was charged with 25 g of α-aminomethacrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethyl sulfide, and 2,2′-azobis (2-methylpropionic acid) in a nitrogen stream at 65 ° C. 0.25 g of dimethyl was 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 1.5 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with acetone, a specific polymer (combination of exemplary compounds (1-2) and (1-14)) was obtained. The mass after drying was 18 g. It was a polymer having a mass average molecular weight of 4000 according to GPC (polyethylene oxide standard).

Example 3
Using a specific hydrophilic polymer having a silane coupling group at the terminal (combination of exemplary compounds (1-2) and (1-19)), a hydrophilic member was prepared and evaluated by the above method.
<Method for synthesizing specific polymer (combination of exemplary compounds (1-2) and (1-19))>
A 500 ml three-necked flask was charged with 25 g of itacon monoamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethyl sulfide, and 2,2′-azobis (2-methylpropionic acid) dimethyl was added in a nitrogen stream at 65 ° C. 25 g was 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 1.5 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with acetone, a specific polymer (combination of exemplary compounds (1-2) and (1-19)) was obtained. The mass after drying was 22 g. It was a polymer having a mass average molecular weight of 7000 according to GPC (polyethylene oxide standard).

Example 4
Using a specific hydrophilic polymer having a silane coupling group at the end (combination of exemplary compounds (1-2) and (1-20)), a hydrophilic member was prepared and evaluated by the above method.
<Method for synthesizing specific polymer (combination of exemplary compounds (1-2) and (1-20))>
A 500 ml three-necked flask was charged with 25 g of itacondiamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethyl sulfide, and 2,2′-azobis (2-methylpropionic acid) dimethyl was added in a nitrogen stream at 65 ° C. 25 g was 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 1.5 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with acetone, a specific polymer (combination of exemplary compounds (1-2) and (1-20)) was obtained. The mass after drying was 20 g. It was a polymer having a mass average molecular weight of 6000 according to GPC (polyethylene oxide standard).

Example 5
Using a specific hydrophilic polymer having a silane coupling group in the side chain (combination of exemplary compounds (2-2) and (2-13)), a hydrophilic member was prepared and evaluated by the above method.
<Method of synthesizing specific polymer (combination of exemplary compounds (2-2) and (2-13))>
A 500 ml three-necked flask was charged with 71 g of α-hydroxymethacrylamide, 83 g of acrylamide- (triethoxysilyl) propyl and 150 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methylpropion) under a nitrogen stream at 80 ° C. Acid) 2.2 g of dimethyl was 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 1.5 liters of hexane, and the precipitated solid was collected by filtration. After the obtained solid was washed with hexane, a specific polymer (combination of exemplary compounds (2-2) and (2-13)) was obtained. The mass after drying was 150 g. It was a polymer having a mass average molecular weight of 50,000 by GPC (polyethylene oxide standard) (composition ratio x: y = 70: 30).

Example 6
Using a specific hydrophilic polymer (combination of exemplary compounds (2-2) and (2-14)) having a silane coupling group in the side chain, a hydrophilic member was prepared and evaluated by the above method.
<Synthesis Method of Specific Polymer (Combination of Exemplary Compounds (2-2) and (2-14))>
A 500 ml three-necked flask was charged with 70 g of α-aminomethacrylamide, 83 g of acrylamide- (triethoxysilyl) propyl, and 150 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methylpropion) in a nitrogen stream at 80 ° C. Acid) 2.2 g of dimethyl was 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 1.5 liters of hexane, and the precipitated solid was collected by filtration. After the obtained solid was washed with hexane, a specific polymer (combination of exemplary compounds (2-2) and (2-14)) was obtained. The mass after drying was 145 g. The polymer had a mass average molecular weight of 60,000 according to GPC (polyethylene oxide standard) (composition ratio x: y = 70: 30).

Example 7
Using a specific hydrophilic polymer having a silane coupling group in the side chain (combination of exemplary compounds (2-2) and (2-19)), a hydrophilic member was prepared and evaluated by the above method.
<Method for synthesizing specific polymer (combination of exemplary compounds (2-2) and (2-19))>
A 500 ml three-necked flask is charged with 90 g of itacon monoamide, 83 g of acrylamide- (triethoxysilyl) propyl and 150 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methylpropionic acid) dimethyl under a nitrogen stream at 80 ° C. 2.2g was 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 1.5 liters of hexane, and the precipitated solid was collected by filtration. After the obtained solid was washed with hexane, a specific polymer (combination of exemplary compounds (2-2) and (2-19)) was obtained. The mass after drying was 140 g. It was a polymer having a mass average molecular weight of 40,000 according to GPC (polyethylene oxide standard) (composition ratio x: y = 70: 30).

Example 8
Using a specific hydrophilic polymer having a silane coupling group in the side chain (combination of exemplary compounds (2-2) and (2-20)), a hydrophilic member was prepared and evaluated by the above method.
<Method for synthesizing specific polymer (combination of exemplary compounds (2-2) and (2-20))>
In a 500 ml three-necked flask, 90 g of itacondiamide, 83 g of acrylamide- (triethoxysilyl) propyl, and 150 g of 1-methoxy-2-propanol were added, and 2,2′-azobis (2-methylpropionic acid) dimethyl under a nitrogen stream at 80 ° C. 2.2g was 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 1.5 liters of hexane, and the precipitated solid was collected by filtration. The obtained solid was washed with hexane to obtain a specific polymer (combination of exemplary compounds (2-2) and (2-20)). The mass after drying was 160 g. It was a polymer having a mass average molecular weight of 70,000 according to GPC (polyethylene oxide standard) (composition ratio x: y = 70: 30).

Comparative Example 1
Using the polymer (3-1) shown below, a hydrophilic member was prepared and evaluated by the above method.

Comparative Example 2
Using the polymer (3-2) shown below, a hydrophilic member was prepared and evaluated by the above method.

Comparative Example 3
Using the polymer (3-3) shown below, a hydrophilic member was prepared and evaluated by the above method.

Comparative Example 4
Using the polymer (3-4) shown below, a hydrophilic member was prepared and evaluated by the above method.

Comparative Example 5
Using the polymer (3-5) shown below, a hydrophilic member was prepared and evaluated by the above method.

Comparative Example 6
Using the specific polymer (3-6) shown below, a hydrophilic member was prepared and evaluated by the above method.

<Evaluation>
The following evaluation was performed about the said hydrophilic member.
(1) Surface free energy The hydrophilicity of the surface of the hydrophilic layer is generally measured with 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 degree of 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, 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 the higher the surface free energy value, the higher the hydrophilicity.

(2) Transparency When the hydrophilic member coated with the hydrophilic film of the present invention is used for 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. Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer (Hitachi spectrophotometer U3000).

(3) Anti-fogging In the daytime under indoor fluorescent lamps, after being exposed to water vapor for 3 minutes, separated from the water vapor, placed in an environment of 25 ° C. and RH 10%, under fluorescent lamps with the same irradiation conditions as above The degree of haze and its change were sensory evaluated in three stages 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

(4) Ink-proofing property A line was written with oil-based ink (oil-based marker manufactured by Mitsubishi Pencil Co., Ltd.), water was poured on, and sensory evaluation was performed in three stages to determine whether or not 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.

(5) Adhesiveness 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 JIS K5400.
◎: 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

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

(7) Weather resistance The hydrophilic member is exposed to the 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. Evaluation was made according to the method. 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

(8) Water resistance A 120 cm ² size hydrophilic member was rubbed 10 times with a sponge in a load under a load of 1 kg, and the remaining film ratio was measured from the mass change before and after that. The water resistance was represented by the remaining film ratio.

(9) Abrasion resistance After applying a weight of 1 kg to a 120 cm ² size hydrophilic member and rubbing the nell cloth (wet cloth) 2000 times, the above antifogging evaluation is performed, and sensory evaluation is performed in three stages according to the following criteria. did.
◎: Cloudiness is not observed ○: Cloudy, but it recovers within 10 seconds, and no cloudiness is seen △: It is cloudy and does not recover even after 10 seconds

  The results of the evaluation are shown in Table 1. In any of the examples, the adhesion, weather resistance, water resistance, antifouling property, and scratch test were all good. In particular, both the antifogging property and the abrasion resistance gave good results. On the other hand, in Comparative Examples 1, 2, 4, and 5, deterioration in wear resistance was observed, and in Comparative Examples 3 and 6, deterioration in antifogging was observed. By comparing these Examples and Comparative Examples, the advantage of introducing a group that forms a crosslinking point at a specific position is clear.

Claims (6)

(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 < ⁵ > represents a hydrogen atom or a C1-C8 hydrocarbon group each independently. m represents 0, 1 or 2, x and y represent a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and x + y = 100. L ¹ and L ² each independently represents a single bond or an organic linking group, and L ³ represents a single bond or —COO—, —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, —SO ₃ —. A polyvalent organic linking group having one or more structures selected from the group consisting of: Y ^{1 to} Y ⁴ are each independently —H, —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —NHC (NH) N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SR _a , —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 ), —N (R _a ) (R _b ) ( _{R g), - PO 3 (} R e) (R f), - OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . However, Y ^{2 to} Y ⁴ are not all hydrogen atoms. 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.   A composition for forming a hydrophilic film comprising (A) a hydrophilic polymer according to claim 1 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 2, which comprises an oxo or hydroxy compound selected from the group consisting of:   Furthermore, the composition for hydrophilic film formation of Claim 2 or 3 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 2-4 containing colloidal silica.   A hydrophilic member, wherein the hydrophilic film-forming composition according to any one of claims 2 to 5 is coated on a support.