JP2008239949A - Composition for forming hydrophilic membrane and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic composition to be used for forming a hydrophilic film having excellent stainproofness, antifoggingness, further good frictional resistance, and to provide a stainproof and antifogging hydrophilic member bearing such hydrophilic film. <P>SOLUTION: The composition for forming hydrophilic membrane comprising (A) an amphoteric low molecular compound; (B) a hydrophilic polymer; (C) an alkoxide compound including an element selected from Si, Ti, Zr, and Al; (D) a metal complex catalyst is used. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrophilic film forming composition and a surface hydrophilic member. Specifically, the present invention relates to a hydrophilic film-forming composition that provides a hydrophilic surface layer excellent in hydrophilicity, durability, transparency, and storage stability, and a surface hydrophilic member including the surface hydrophilic layer.

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. 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 to cause 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 surface of a transparent substrate in which a high refractive index layer and a low refractive index layer made of a metal oxide or the like are laminated, and a surface of a transparent substrate such as an inorganic or organic fluoride compound is used. 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 optical members described above, can easily be contaminated with fingerprints, sebum, and other dirt when used by humans. In addition to the problem, the surface of the antireflection film usually has fine irregularities, and there is a problem that 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 an antireflection member and an antifouling member, for example, an antifouling and antifriction material (for example, an antireflection film mainly composed of silicon dioxide and an antisilicon antifouling material treated with a compound containing an organosilicon substituent (for example, , See Patent Document 1), and an antifouling and friction-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 (see, for example, Patent Document 4) has been proposed.
However, the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and 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.

  Further, as a film having excellent surface hydrophilicity, a film using titanium oxide has been conventionally known. For example, a photocatalyst-containing layer is formed on the substrate surface, and the surface is highly hydrophilized according to photoexcitation of the photocatalyst. Technology has been disclosed, and it has been 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 need for an antifouling member having good wear resistance.

In order to achieve the above-mentioned problems, the anti-fogging and anti-fogging properties of the hydrophilic surface with a cross-linked structure by hydrolyzing and condensation-polymerizing the hydrophilic polymer and the alkoxide are focused on the characteristics of the sol-gel organic-inorganic hybrid film. It has been found that it exhibits fouling and has good wear resistance (see Patent Document 6).
However, if the substrate is a window glass, a mirror or the like, if dust or dirt in the air adheres, it must be wiped with a dry cloth. In this case, when static electricity is generated due to friction, further dirt adheres, the dirt accumulates, and it becomes difficult to wash away even if water is applied. For this reason, further improvement of antifouling property and film | membrane intensity | strength is calculated | 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

  The object of the present invention is to further advance research on sol-gel organic-inorganic hybrid films to develop the above-mentioned prior art, and to provide excellent anti-fouling and anti-fogging properties on various substrate surfaces and better friction resistance. An object of the present invention is to provide a hydrophilic composition used for forming a hydrophilic film. Further, another object of the present invention is to provide a hydrophilic film having a surface excellent in antifouling property, antifogging property and anti-friction property provided with a hydrophilic film formed of the hydrophilic composition on the surface of an appropriate support. It is to provide a member.

The present inventors paid attention to zwitterionic low molecular weight compounds, particularly compounds having a betaine structure, and by adding this to the composition for forming a hydrophilic film, not only the antifouling property of the hydrophilic film but also hydrophilicity, The present invention was completed by finding that the coating strength and durability were further improved.
That is, the present invention is as follows.

(1) (A) a zwitterionic low molecular compound, (B) a hydrophilic polymer, (C) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al, and (D) a hydrophilic containing a metal complex catalyst Composition for conductive film formation.
(2) The metal complex catalyst (D) 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 The composition for forming a hydrophilic film according to the above (1), which is composed of an oxo or hydroxy oxygen compound selected from the compounds.
(3) The hydrophilic film-forming composition as described in (1) or (2) above, wherein the (A) zwitterionic low molecular weight compound has a betaine structure.
(4) The hydrophilic film-forming composition according to any one of (1) to (3), wherein the hydrophilic polymer (B) is a hydrophilic polymer having a silane coupling group at a polymer terminal or a side chain. .
(5) For forming a hydrophilic film as described in (4) above, wherein the hydrophilic polymer having a silane coupling group at the polymer end (B) is a compound having a structure represented by the following general formula (1): Composition.

The hydrophilic polymer having the structure represented by the general formula (1) is a silane represented by the structural unit (iii) at least one terminal of the polymer unit represented by the structural units (i) and (ii). Has a coupling group.
In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and m is 0, 1 Or, 2 is represented, x and y represent a composition ratio when x + y = 100, and x: y represents a range of 100: 0 to 1:99. L ¹ , L ² and L ³ each independently represents a single bond or an organic linking group, and Y ¹ and Y ² each independently represent —N (R ⁷ ) (R ⁸ ), —OH, —NHCOR. ⁷ , —CONH ₂ , —CON (R ⁷ ) (R ⁸ ), —COR ⁷ , —CO ₂ M or —SO ₃ M, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or An alkyl group having 1 to 8 carbon atoms is represented, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or onium.

(6) Hydrophilic film formation as described in said (4) whose said (B) hydrophilic polymer which has a silane coupling group in a polymer side chain is a compound which has a structure at least represented by following General formula (2). Composition.

In the general formula (2), R ¹ ~R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹¹ represents a single bond or a polyvalent organic linking group. L ¹² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. n represents an integer of 1 to 3. p and q represent a composition ratio when p + q = 100, and p: q represents a range of 99: 1 to 0: 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group 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.

(7) The composition for forming a hydrophilic film according to any one of (1) to (6), further comprising (E) colloidal silica.
(8) A hydrophilic member provided with the hydrophilic film forming composition according to any one of (1) to (7).

(9) A hydrophilic film-forming composition containing (A) an amphoteric ion low-molecular compound, (B) a hydrophilic polymer, and (D) a metal complex catalyst.
(10) The metal complex catalyst (D) is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table, and β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, enolic active hydrogen The composition for forming a hydrophilic film according to (9), which is composed of an oxo or hydroxy oxygen compound selected from the compounds.
(11) The composition for forming a hydrophilic film according to (9) or (10), wherein the (A) zwitterionic low-molecular compound has a betaine structure.
(12) The composition for forming a hydrophilic film according to any one of (9) to (11), wherein the hydrophilic polymer (B) is a hydrophilic polymer having a silane coupling group in a polymer side chain.
(13) The hydrophilic film-forming composition according to (12), wherein the hydrophilic polymer having a silane coupling group in the polymer side chain is a compound having at least a structure represented by the following general formula (2).

In the general formula (2), R ¹ ~R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹¹ represents a single bond or a polyvalent organic linking group. L ¹² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. n represents an integer of 1 to 3. p and q represent a composition ratio when p + q = 100, and p: q represents a range of 99: 1 to 0: 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group 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.
(14) The hydrophilic film-forming composition according to any one of (9) to (13), further comprising (E) colloidal silica.
(15) A hydrophilic member provided with the hydrophilic film forming composition according to any one of (9) to (14).

  In the present invention, a zwitterionic low molecular weight compound, particularly a compound having a specific betaine structure is added to the hydrophilic film forming composition. Addition of betaine makes it difficult for dirt to adhere. This is probably because the addition of betaine lowered the electrical resistance of the hydrophilic film and made it difficult to be charged. Furthermore, since betaine is also highly hydrophilic, the hydrophilic film improves not only antifouling properties but also hydrophilicity. Further, when the betaine compound has an amphoteric ion part, when the composition of the present invention is hydrolyzed and polycondensed to form an organic-inorganic composite sol solution, a specific alkoxide in which the betaine compound as an organic component is an inorganic component is formed. It becomes easy to interact with the hydrolysis-condensation polymer by ionic bond, and after curing, a coating film in which organic and inorganic are uniformly dispersed is formed, and exhibits excellent strength and durability.

Hereinafter, the present invention will be described in detail.
The hydrophilic film-forming composition of the present invention comprises (A) an amphoteric ion low-molecular compound, (B) a hydrophilic polymer, (C) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al; D) It contains a metal complex catalyst.
Below, each component contained in the hydrophilic composition of this invention is demonstrated.

[(A) Zwitterionic low molecular weight compound]
The zwitterionic low molecular weight compound of the present invention is not particularly limited, and examples thereof include a compound having a cation and an anion in the same molecule, and a compound having an acidic group and a basic group. An example of a compound having a cation and an anion in the same molecule is a compound having a betaine structure, and an example of a compound having an acidic group and a basic group in the same molecule is an amino acid. Particularly preferred in the present invention is a compound having a betaine structure having no charge as a whole molecule, a cation such as quaternary ammonium, sulfonium or phosphonium as a cation, and —CO ₂ ⁻ or —SO ₃ as an anion. ^-, -PO ₃ H ^- is preferably an anion such.

The betaine compound preferably has at least one hydroxyl group in the molecule for immobilization in the hydrophilic member, and more preferably has at least one silane coupling group in the molecule.
Specific examples of the specific betaine compound used in the present invention include the following compounds, but the present invention is not limited thereto.

  The content of the betaine compound in the composition for forming a hydrophilic film is preferably 5 to 80% by mass, more preferably 10 to 50% by mass. Within this range, good antistatic ability, hydrophilicity and film strength can be obtained, and there is no concern of cracks in the film, which is preferable.

[(B) hydrophilic polymer]
The composition for forming a hydrophilic film of the present invention contains a hydrophilic polymer, and particularly has a hydrophilic polymer having a silane coupling group at the polymer terminal and a silane coupling group in the side chain from the viewpoint of improving the crosslinking density. It is preferable to contain at least one of the hydrophilic polymers. Below, the hydrophilic polymer (B1) which has a polymer terminal silane coupling group, and the hydrophilic polymer (B2) which has a silane coupling group in a side chain are demonstrated.

<(B1) hydrophilic polymer having a silane coupling group at the polymer terminal>
As the hydrophilic polymer having a silane coupling group at the polymer terminal of the present invention, the logP of the monomer as the structural unit is preferably −3 to 2, and more preferably −2 to 0. In this range, good hydrophilicity can be obtained.
Here, log P is the logarithm of the value of the octanol / water partition coefficient (P) of a compound calculated using the software PCModels developed by Medicinal Chemistry Project, Pomona College, Claremont, California and available from Daylight Chemical Information System Inc. It is.

By using such a hydrophilic polymer having a silane coupling group at the terminal, the interaction between the silane coupling group of the hydrophilic polymer and the crosslinking component, and further, between the silane coupling groups of the hydrophilic polymer The cross-linking structure formed by Si (OR) _{4 is} formed by the interaction of the above, the strength and durability of the hydrophilic film are improved by the strong cross-linking structure, and the terminal has a silane coupling group Thus, it is presumed that the portion having a hydrophilic group becomes free and the hydrophilicity is further improved.

  In the present invention, from the viewpoint of further improving the properties of the hydrophilic film, (B1) a specific hydrophilic polymer having a structure represented by the following general formula (1) as the terminal silane-modified hydrophilic polymer [hereinafter, It is preferable to contain “(B1-1) specific hydrophilic polymer” as appropriate.

The hydrophilic polymer compound having the structure represented by the general formula (1) is represented by the structural unit (iii) at at least one of both ends of the polymer unit represented by the structural units (i) and (ii). As long as it has a silane coupling group, the other terminal may have this functional group, and may have a hydrogen atom or a functional group having a polymerization initiating ability.
In the general formula (1), m represents 0, 1 or 2, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a C 1-8 carbon atom. Represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less 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 ⁶ 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 constituted by a bond between a substituent and an alkylene group, and here, 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, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy 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-N-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- Alkoxycarbonyl amino group, N- aryl -N- aryloxycarbonylamino group, a formyl group, an acyl group, a 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-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonate group”), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkyl An arylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugate base group thereof (hereinafter referred to as an alkylphosphonate group), a monoarylphosphono group (-PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (- PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), diaryl phosphonooxy group (-OPO ₃ (aryl) ₂₎ , An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as an alkylphosphonatooxy group), A monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group Can be mentioned.

Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophene Group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, and 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 be a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkylene group 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) carbamoylmethyl group , Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phos Phonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphos Onatohexyl 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 can be mentioned.

L ¹ and L ² represent a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a nonmetallic atom, and specifically includes 0 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 carbon atoms. It consists of up to 0 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More specific examples of the linking group include the following structural units or those formed by combining them.

L ³ represents a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a nonmetallic atom, and specific examples thereof include those similar to the above L ¹ and L ² . Among them, a particularly preferable structure is — (CH ₂ ) _n —S— (n is an integer of 1 to 8).

Y ¹ and Y ² represent —NHCOR ⁷ , —CONH ₂ , —CON (R ⁷ ) (R ⁸ ), —COR ⁷ , —OH, —CO ₂ M or —SO ₃ M, R ⁷ and R ⁸ each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. In addition, with respect to —CON (R ⁷ ) (R ⁸ ), R ⁷ and R ⁸ may be bonded to each other to form a ring, and the formed ring is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may be a heterocycle containing an atom. R ⁷ and R ⁸ may further have a substituent, and the substituents that can be introduced here are the same as the substituents that can be introduced when R ^{1 to} R ⁶ are alkyl groups. Can be listed.

Specific examples of R ⁷ and R ⁸ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, and t-butyl. Preferred examples include a group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
Examples of M include a hydrogen atom; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as calcium and barium; or an onium such as ammonium, iodonium and sulfonium.
Further, specifically as _{^{Y 1, Y 2, -NHCOCH 3}} , -CONH 2, -COOH, -SO 3 - NMe 4 +, a morpholino group, etc. are preferable.

  x and y represent a composition ratio (molar ratio) when x + y = 100, x: y represents a range of 100: 0 to 1:99, and a range of 100: 0 to 5:95 is more preferable.

  (B1-1) The molecular weight of the specific hydrophilic polymer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and most preferably 1,000 to 30,000.

  Specific examples (1-1) to (1-23) of the specific hydrophilic polymer (B1-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

<Synthesis method>
As the (B1) terminal silane-modified hydrophilic polymer in the present invention, for example, the (B1-1) specific hydrophilic polymer includes a radical polymerizable monomer represented by the following structural units (i) and (ii), and the following structural unit: In the radical polymerization represented by (iii), it can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability. Since the silane coupling agent has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.
Although this reaction mode is not particularly limited, bulk reaction, solution reaction, suspension reaction and the like may be performed in the presence of a radical polymerization initiator or irradiation with a high-pressure mercury lamp.

Further, in the polymerization reaction, the amount of the structural unit represented by (iii) is controlled, and in order to effectively suppress the homopolymerization of the structural unit with the structural unit (i) or (ii), A polymerization method using an addition method, a sequential addition method, or the like is preferably performed.
The reaction ratio of the structural units (i) and (ii) with respect to the structural unit (iii) is not particularly limited, but the structural units (i) and (ii) are 0 with respect to 1 mol of the structural unit (iii). From the viewpoint of suppressing side reactions and improving the yield of the hydrolyzable silane compound, the range of 1 to 45 mol is more preferable, and the range of 5 to 40 mol is preferable. Most preferred.

In the structural units (i), (ii), and (iii), R ^{1 to} R ⁶ , L ^{1 to} L ³ , Y ¹ , Y ² , and m are the same as those in the general formula (1). These compounds are commercially available and can be easily synthesized.

[(B2) hydrophilic polymer containing silane coupling group in side chain]
The hydrophilic polymer containing a silane coupling group in the side chain (B2) that can be used in the present invention has structural units represented by the following general formulas (2-a) and (2-b). preferable.

Formula (2-a) and in (2-b), R ¹ to R ⁸ are the same as R ¹ to R ⁶ in the general formula (1) each independently represent a hydrogen atom or not more than 8 carbon atoms Represents a hydrocarbon group. L ¹¹ represents a single bond or a polyvalent organic linking group. L ¹² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. n represents an integer of 1 to 3. p and q represent a composition ratio when p + q = 100, and p: q represents a range of 99: 1 to 0: 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group 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 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.
The preferable range of R ^{1 to} R ^8, the substituent that may be included, and the like are the same as those in R ^{1 to} R ⁶ in the general formula (1).

L ¹¹ represents a single bond or a polyvalent organic linking group. Here, the single bond means that the polymer main chain and X are directly bonded without a linking chain. Further, the organic linking group refers to a linking group composed of non-metallic atoms, specifically, 0 to 200 carbon atoms, 0 to 150 nitrogen atoms, 0 to 200 oxygen atoms. It consists of atoms, 0 to 400 hydrogen atoms, and 0 to 100 sulfur atoms. More specific examples of the linking group include the following structural units or those formed by combining them.

L ¹¹ may be formed from a polymer or oligomer, and specifically includes polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene, and the like made of an unsaturated double bond monomer, Preferred examples include poly (oxyalkylene), polyurethane, polyurea, polyester, polyamide, polyimide, polycarbonate, polyamino acid, polysiloxane, and the like, and preferably polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, and 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 ¹¹ is a polymer or oligomer, 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, and 1,000 to 200,000 is most preferred.

L ¹² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. Here, the single bond means that the polymer main chain and the Si atom are directly bonded without a linking group. In L ¹² , 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 ¹¹ .

X is a hydrophilic group, and is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), — NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , — NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ) ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group 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. _{Further, -CON (R a) (R} b), - OCON (R a) (R b), - NHCON (R a) (R b), - SO 2 N (R a) (R b) -PO 3 (R _e ) (R _f ), -OPO ₃ (R _e ) (R _f ), -PO ₂ (R _d ) (R _e ), -N (R _a ) (R _b ) (R _c ) or -N Regarding (R _a ) (R _b ) (R _c ) (R _g ), R _{a to} R _g may be bonded to each other to form a ring, and the formed ring is an oxygen atom, sulfur atom, nitrogen It may be a heterocycle containing a heteroatom such as an atom. R _{a to} R _g may further have a substituent. Examples of the substituent that can be introduced here include those that can be introduced when R ^{1 to} R ⁶ in formula (1) are alkyl groups. The ones listed can be cited as well.

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 ^{_{X, -CO 2 - Na +,}} -CONH 2, -SO 3 - Na +, -SO 2 NH 2, -PO 3 H 2 and the like are preferable.

p and q are the structural unit represented by the general formula (2-a) and the structural unit represented by the general formula (2-b) in the hydrophilic polymer (B2) containing a silane coupling group in the side chain. The polymerization molar ratio when p + q = 100 is represented, and p: q represents a range of 99: 1 to 0: 100. The polymerization molar ratio p: q is more preferably in the range of 99: 1 to 10:90, and further preferably in the range of 99: 1 to 50:50.
Here, the structural units constituting the polymer chain (2-a) and (2-b) may all be the same or may include a plurality of different structural units, In that case, the polymerization molar ratio of the structural unit corresponding to the general formula (2-a) and the structural unit corresponding to the general formula (2-b) is preferably in the above range.

  (B2) The molecular weight of the hydrophilic polymer containing a silane coupling group in the side chain is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and 1,000 to 200,000. 000 is most preferred.

  Specific examples [Example compounds (1) to (50)] of the hydrophilic polymer containing a silane coupling group in the side chain (B2) are shown below together with their mass average molecular weight (MW). 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 hydrophilic polymers (B1) and (B2) of the present invention is commercially available, and can also be easily synthesized.
As the radical polymerization method for synthesizing the hydrophilic polymers of (B1) and (B2), 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) (The Chemical Society of Japan, Maruzen), Materials Engineering, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., can be applied.

  The specific hydrophilic polymers (B1) and (B2) may be copolymers with other monomers 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, dihydroxy phen Chill acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

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

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

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

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

  The ratio of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but the function as a hydrophilic film is sufficient, and (B1) and (B2) In order to sufficiently obtain the advantage of adding the hydrophilic polymer (1), it is preferable that the ratio is not too large. Accordingly, the preferred total proportion of other monomers in the total hydrophilic polymer of (B1) and (B2) is preferably 80% by mass or less, and more preferably 50% by mass or less.

  One of the hydrophilic polymers (B1) and (B2) may be used alone, or both may be used in combination. Further, for example, a plurality of types of hydrophilic polymers belonging to (B1) may be mixed and used.

In the composition, the hydrophilic polymer (B1) or / and (B2) can be used in combination with the following hydrophilic polymer.
Acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyls or hydrolysates thereof, styrenes, acrylic acid or salts thereof, methacrylic acid or salts thereof, acrylonitrile, maleic anhydrides, maleic imides And polymers made from monomers such as
Among these monomers, monomers having an amino group, an ammonium group, a hydroxyl group, a sulfonamide group, a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an ether group, particularly an ethyleneoxy group are preferable.
In addition to the above, hydrophilic polymers having a urethane bond, an amide bond, or a urea bond in the main chain can also be used.

  Specific examples of acrylic esters include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, hydroxybenzyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate , Tetrahydrofurfuryl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl acrylate, diethylene glycol ethyl ether acrylate, 2-ethoxyethyl acrylate and the like.

  Specific examples of methacrylic acid esters include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl. Examples include methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate, diethylene glycol ethyl ether methacrylate, 2-ethoxyethyl methacrylate, and methoxytetraethylene glycol monomethacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N, N-dimethylacrylamide, N- Examples include 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-hydroxyethylmethacrylamide, N- (sulfamoylphenyl). ) Methacrylamide, N- (phenylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N
-Methyl methacrylamide etc. are mentioned.

Specific examples of vinyls include vinyl acetate and vinyl pyrrolidone.
Specific examples of styrenes include trimethoxystyrene, carboxystyrene, styrene sulfone or a salt thereof.

  The total amount of the specific hydrophilic polymer belonging to (B1) and (B2) according to the present invention is preferably 5 to 95 from the viewpoint of curability and hydrophilicity with respect to the nonvolatile components of the hydrophilic composition of the present invention. It is contained in the range of mass%, more preferably 15 to 90 mass%, most preferably 20 to 85 mass%. Here, the non-volatile component refers to a component excluding a volatile solvent.

[(C) Alkoxide Compound Containing Element Selected from Si, Ti, Zr, Al]
The (C) alkoxide compound of an element selected from Si, Ti, Zr, and Al (also referred to as a specific alkoxide) used in the present invention has a polymerizable functional group in its structure and functions as a crosslinking agent. It is a hydrolyzable polymerizable compound that performs (B) a condensation polymerization with a hydrophilic polymer, thereby forming a strong film having a crosslinked structure.
(C) The specific alkoxide is preferably a compound represented by the following general formula (3). In forming a crosslinked structure in order to cure the hydrophilic film, the (B) hydrophilic polymer, ( C) The specific alkoxide represented by the general formula (3) is mixed, coated on the surface of the support, 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.

  Although the specific example of the specific alkoxide represented by (C) general formula (3) below is given, this invention is not limited to this. 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, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

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

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

[(D) metal complex catalyst]
In the hydrophilic composition of the present invention, (A) a zwitterionic low molecular compound, (B) a hydrophilic polymer, and (C) a crosslinking component such as a specific alkoxide are dissolved in a solvent, and these are mixed well, The components are hydrolyzed and polycondensed to form an organic-inorganic composite sol solution, and a hydrophilic film having high hydrophilicity and high film strength is formed by this sol solution. In preparing the organic-inorganic composite sol solution, a metal complex catalyst is used to promote hydrolysis and polycondensation reactions.

As the (D) metal complex catalyst used in the present invention, a catalyst that promotes the reaction of hydrolyzing and polycondensing the (C) alkoxide compound and causing a bond with the hydrophilic polymer (B) is selected. A Lewis acid catalyst comprising a metal complex can also be preferably used. Particularly preferred catalysts are metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, and oxo compounds selected from enolic active hydrogen compounds. Or it is a metal complex comprised from a hydroxy oxygen containing compound.
Among constituent metal elements, 2A group elements such as Mg, Ca, Sr and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

  In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a β-diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetic acid Ketoesters such as ethyl and butyl acetoacetate, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and other hydroxycarboxylic acids and esters thereof, 4-hydroxy-4-methyl-2-pentanone, Ketoalcohols such as 4-hydroxy-2-heptanone, 4-hydroxy-4-methyl-2-pentanone, 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, and among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

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

  The (D) metal complex catalyst according to the present invention is used in the hydrophilic composition of the present invention as a non-volatile component, preferably in the range of 0 to 50 mass%, more preferably 5 to 25 mass%. Moreover, (D) a catalyst may be used independently or may be used together 2 or more types.

  The hydrophilic composition of the present invention includes an alkoxide compound containing an element selected from (A) a zwitterionic low-molecular compound, (B) a hydrophilic polymer, and (C) Si, Ti, Zr, and Al as the essential components. In addition to the metal complex catalyst, and (D), various compounds can be used in accordance with the purpose as long as the effects of the present invention are not impaired. Hereinafter, components that can be used in combination will be described.

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

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

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

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

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

[Inorganic fine particles]
The hydrophilic composition of the present invention may contain inorganic fine particles in order to improve 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 is preferably exemplified.
The inorganic fine particles preferably have an average particle diameter of 5 nm to 10 μm, more preferably 0.5 to 3 μm. Within the above range, it is possible to form a film that is stably dispersed in the hydrophilic layer, sufficiently retains the film strength of the hydrophilic layer, and is excellent in hydrophilicity. The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.

  The inorganic fine particles according to the present invention are used in the hydrophilic composition of the present invention as a non-volatile component, preferably 20% by mass or less, more preferably 10% by mass or less. The inorganic fine particles can be used alone or in combination of two or more.

[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 coating liquid for forming the hydrophilic layer. Examples of the antioxidant include European Published Patent Nos. 223739, 309401, 309402, 310551, 310552, 457416, and German Patent No. 3435443. JP-A-54-48535, JP-A-62-262047, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, and JP-A-3 No. 112449, 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.

[Polymer compound]
In order to adjust the film physical properties of the hydrophilic layer, various polymer compounds can be added to the coating liquid for forming the hydrophilic layer of the hydrophilic member of the present invention 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.

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

[Preparation of hydrophilic composition]
Preparation of the hydrophilic composition includes (A) a zwitterionic low molecular compound, (B) a hydrophilic polymer, (C) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al, and (D) a metal complex. It can be carried out by stirring the catalyst after dissolving it in a solvent such as ethanol. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and organic inorganic A composite sol solution can be obtained.

  (A) a zwitterionic low molecular weight compound, (B) a hydrophilic polymer, (C) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al, and (D) a hydrophilic film containing a metal complex catalyst The solvent used in preparing the forming composition is not particularly limited as long as it can uniformly dissolve and disperse these, but for example, an aqueous solvent such as methanol, ethanol, water and the like is preferable.

As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming a hydrophilic film with the hydrophilic composition of the present invention utilizes the sol-gel method. Regarding the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the hydrophilic composition in the present invention.
The hydrophilic member of the present invention can be obtained by coating a solution containing such a hydrophilic composition of the present invention on an appropriate support and drying. That is, the hydrophilic member of the present invention has a hydrophilic film formed by coating the hydrophilic composition of the present invention on a support, heating and drying.
In the formation of the hydrophilic film, as the heating and drying conditions after coating the solution containing the hydrophilic composition, from the viewpoint of efficiently forming a high-density crosslinked structure, in the temperature range of 50 to 200 ° C., It is preferable to carry out for about 2 minutes to 1 hour, and it is more preferable to dry in the temperature range of 80 to 160 ° C. for 5 to 30 minutes. Moreover, as a heating means, it is preferable to use a well-known means, for example, the dryer etc. which have a temperature control function.

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

The details of the inorganic substrate include a normal glass plate, a laminated glass plate including a resin layer, a gas layer, and a vacuum layer, and various glass plates including a reinforcing component and a colorant.
Examples of the glass plate containing the inorganic compound layer include silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, An inorganic compound layer formed of a metal oxide such as ITO (Indium Tin Oxide); a metal halide such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride; The glass plate provided can be mentioned.

  The 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.

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

  As 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.

Thus, the hydrophilic member of the present invention can be obtained by using a glass plate or plastic plate having an inorganic compound layer as a substrate and forming a hydrophilic surface. Since the hydrophilic member has a hydrophilic film excellent in hydrophilicity and durability on the surface, it is excellent in antifouling property on the surface of the support (substrate), in particular, antifouling property against oil and fat stains, antifogging property or Both can be granted.
The antireflection layer applicable to the surface of the hydrophilic member of the present invention is not limited to the above-described inorganic compound layer. For example, an antireflection effect is obtained by laminating a plurality of thin layers having different reflectivities and refractive indexes. A known antireflection layer or the like can also be used as appropriate, and the material can be either an inorganic compound or an organic compound. In particular, the substrate on which the inorganic compound layer as the antireflection film is formed on the surface is applied with the hydrophilic polymer chain according to the present invention on the surface on the side where the antireflection film is formed. The antifouling and / or antifogging member of the present invention having excellent antifogging function and antireflection properties can be obtained. In addition, depending on the purpose, the hydrophilic member of the present invention can be used in various ways by bonding a functional optical member such as a polarizing plate to a member having the above-described structure by a bonding technique typified by a laminate. An antireflection / optical functional member having functions and characteristics can also be obtained.

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

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

In the present invention, one or more undercoat layers can be provided between the substrate and the hydrophilic layer.
The undercoat layer is preferably obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound containing an element selected from Si, Ti, Zr and Al and a nonvolatile catalyst.
An undercoat layer obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound containing an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst has a crosslinked structure. In the present invention, a crosslinked structure formed by hydrolysis and condensation polymerization of a compound is appropriately referred to as a sol-gel crosslinked structure.

  Examples of the alkoxide compound containing an element selected from Si, Ti, Zr and Al include those described above. Among these, Si alkoxides are preferable from the viewpoint of reactivity and availability, and specifically, compounds used for silane coupling agents can be suitably used.

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

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

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

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

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

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

Examples of the water-dispersible latex include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.
The above hydrophilic 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 thermal crosslinking agents include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, polyethylene or polypropylene Polyepoxy compounds such as glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyaldehyde compounds such as glyoxal and terephthalaldehyde, tolylene diene Isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene diiso Polyisocyanate compounds such as anate, polymethylene polyphenyl isocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol / tolylene diisocyanate addition reaction product, block polyisocyanate Examples thereof include compounds, silane coupling agents such as tetraalkoxysilane, metal cross-linking agents such as acetylacetonate of aluminum, copper and iron (III), and polymethylol compounds such as trimethylolmelamine and pentaerythritol. Among these thermal cross-linking agents, a water-soluble cross-linking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic layer.
Wherein the hydrophilic resin and / or water-dispersible latex total amount in the undercoat layer is preferably from 0.01 to 20 g / m ^2, 0.1 to 10 g / m ² is more preferable.

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

[Example 1]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by glow treatment, and then a hydrophilic layer coating solution (1) having the following composition is applied by bar coating at 100 ° C. It was oven dried in 10 minutes to form a hydrophilic layer having a dry coating amount of 1.0 g / m ² to form a hydrophilic member. The surface free energy of this hydrophilic member was 83 mN / m, which was a highly hydrophilic surface. The visible light transmittance of the hydrophilic layer was 95% (measured with a Hitachi spectrophotometer U3000).

<Hydrophilic layer coating solution (1)>
・ 500g of the following sol-gel preparation
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

<Sol-gel preparation solution>
In 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate, and 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4 g of a hydrophilic polymer having a silane coupling group at the following terminal, specific betaine 1 g of the compound (Exemplary Compound 1) was mixed and stirred at room temperature for 2 hours to prepare.

<Synthesis of hydrophilic polymer having a silane coupling group at the terminal>
A three-necked flask was charged with 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethylformamide and heated to 65 ° C. under a nitrogen stream to produce 2,2′-azobis (2,4-dimethylvaleronitrile). 0.25 g was added to start the reaction. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of ethyl acetate, and a solid precipitated. Thereafter, filtration was performed, and the product was sufficiently washed with ethyl acetate and dried (yield 21 g). It was confirmed by GPC (polyethylene oxide standard) that the polymer had a mass average molecular weight of 4000 (Exemplary Compound (1-1)). The viscosity of the 5% aqueous solution was 2.5 cPs, and the functional group density of the hydrophilic group was 13.4 meq / g.

(Evaluation) The following evaluation was performed on the hydrophilic member.
Surface resistance value: measured using a trade name “Hiresta HT-210” (manufactured by Mitsubishi Yuka Co., Ltd.) at 25 ° C. and 60% RH.

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

  Antifouling property: Apply with air spray containing carbon black suspension (10% aqueous solution) until the surface of the hydrophilic member is uniformly covered, dry at 60 ° C for 1 hour, and then let cool to room temperature . Thereafter, the surface of the hydrophilic member was washed with carbon black under running water, dried at room temperature for 1 h, and the contact angle was measured. If the water droplet contact angle shows a low value even after the carbon black (CB) treatment (after coating, drying, washing and drying at room temperature for 1 h), the antifouling property is considered good.

Water resistance: A hydrophilic member having a size of 120 cm ^{2 was} rubbed with a sponge 10 times in water, and the remaining film ratio was measured from the weight change before and after that. The higher the remaining film ratio, the higher the water resistance.

  Durability Abrasion test: 100 times of rubbing with a non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.), and the contact angle before and after that was measured. Durability was good when the water droplet contact angle showed a low value even after rubbing.

  Scratch test: Starting from 5 g on a 0.1 mm diameter sapphire needle and applying 5 g increments to scan the hydrophilic layer surface to evaluate the weight at which scratches occurred (measured with a scratch strength tester Type 18S manufactured by Shinto Kagaku Co., Ltd.) . The durability is better when there is no damage even if the load is large.

  Storage stability (backside adhesion): 50 sheets of 5 cm square hydrophilic members are stacked, pressure-bonded using a vise with a torque of 300 kg, and evaluated for backside adhesion after aging in a 45 ° C 75% humidity environment for 1 day. did. If the back side is not bonded, it means that the storage stability is excellent.

The results are shown in Table 1. The surface resistance is 4.5 × 10 ⁹ Ω, the antifouling property is good (the contact angle does not change before and after the carbon black treatment), and the antifogging property is good. There was no problem with water resistance at a residual film ratio of 95%. There was no decrease in hydrophilicity due to the abrasion test, and in the scratch test, there was no damage up to 50 g, and the durability was excellent. In the storage stability evaluation, the hydrophilic layer did not adhere to the back surface and was excellent in storage stability.

[Comparative Example 1]
A hydrophilic film was formed in the same manner as in Example 1 except that the specific betaine compound (Exemplary Compound 1) was not added. The results are shown in Table 1. The hydrophilic property was a surface energy of 79 mN / m and the antifogging property was good (◯), but the surface resistance value was 5.2 × 10 ¹¹ Ω, and the antifouling property was a contact angle of 10 after treatment with carbon black. The scratch strength was 10 g, which was inferior in antifouling property and film strength as compared with Example 1.

[Examples 2 to 5]
A hydrophilic film was formed and evaluated in the same manner as in Example 1 except that the specific betaine compound (Exemplary Compound 1) was changed to the specific betaine compound shown in Table 2. The results are shown in Table 1.

Example 6
A polyethylene terephthalate substrate (thickness 50 μm) whose surface has been hydrophilized by bar coating is applied with a hydrophilic layer coating solution having the following composition, oven-dried at 100 ° C. for 10 minutes, and a dry coating amount of 1.0 g / m ^2. A hydrophilic member was prepared by forming a hydrophilic layer. The results are shown in Table 1.

<Hydrophilic layer coating solution (2)>
-Colloidal silica dispersion 20% by weight aqueous solution (Snowtech C) 100g
・ 500g of the following sol-gel preparation
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

<Sol-gel preparation solution>
In 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate, and 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4 g of a hydrophilic polymer having a run coupling group in the following side chain, specific betaine 1 g of compound (Exemplary Compound 2) was mixed and stirred at room temperature for 2 hours to prepare.

<Synthesis of hydrophilic polymer having a silane coupling group in the side chain>
A 500 ml three-necked flask is charged with 56.9 g of acrylamide, 11.6 g of acrylamide-3- (ethoxysilyl) propyl, and 280 g of 1-methoxy-2-propanol. 2.3 g of dimethyl propionate) 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 2 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with acetone, the specific hydrophilic polymer (1) as the exemplified compound (1) was obtained. The mass after drying was 65.6 g. It was a polymer having a mass average molecular weight of 8,500 by GPC (polyethylene oxide standard).

[Examples 7 to 10, Comparative Example 2]
A hydrophilic film was formed in the same manner as in Example 6 except that the specific betaine compound (Exemplary Compound 2) was changed to the specific betaine compound shown in Table 3. The evaluation results are shown in Table 1.

[Examples 11 to 15]
The specific betaine compound (1) is changed to the specific betaine compound shown in Table 4, the hydrophilic polymer having a silane coupling group at the terminal is changed to the hydrophilic polymer shown in Table 4, the plate glass is washed with UV ozone, and the hydrophilic layer coating solution A hydrophilic film was formed in the same manner as in Example 1 except that a hydrophilic film was formed by spin coating. The evaluation results are shown in Table 1.

[Comparative Example 3]
A hydrophilic film was formed in the same manner as in Example 11 except that the specific betaine compound (3) was changed to the following comparative compound (1). As can be seen from the evaluation results shown in Table 1, compared with Example 11, the hydrophilicity and the film strength were inferior.

Example 16
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the first layer coating solution (1) having the following composition is spun. The coating was applied and oven-dried at 100 ° C. for 10 minutes to form a first layer having a dry coating amount of 1.0 g / m ² . After sufficiently cooling at room temperature, the hydrophilic layer coating solution (1) used in Example 1 was spin-coated as the second layer on the first layer coating surface, oven dried at 100 ° C. for 10 minutes, and dried coating amount A second layer of 1.0 g / m ² was formed.
The evaluation results are shown in Table 1.

<First layer coating solution (1)>
-Colloidal silica dispersion 20% by weight aqueous solution (Snowtex C) 100g
・ 500g of the following sol-gel preparation (2)
・ 30 g of 5% by weight aqueous solution of the anionic surfactant
・ Purified water 450g

<Sol-gel preparation liquid (2)>
Into 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate and 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at room temperature for 2 hours to prepare.

Example 17
A hydrophilic member was produced in the same manner as in Example 16 except that the hydrophilic layer coating solution (1) was changed to the hydrophilic layer coating solution (2) used in Example 6.
The evaluation results are shown in Table 1.

Example 18
A polyethylene terephthalate (PET) substrate (thickness: 50 μm) whose surface has been hydrophilized by glow treatment is prepared, and the first layer coating solution (2) having the following composition is spin-coated (1000 rpm for 30 seconds) and oven-dried at 100 ° C. for 2 minutes. A first layer having a dry coating amount of 0.5 g / m ² was formed. The water droplet contact angle of the first layer was 80 °. Subsequently, the hydrophilic layer coating solution (2) used in Example 6 was spin-coated on the first layer (100 rpm for 2 minutes, then 50 rpm for 5 minutes, 200 rpm for 2 minutes), and 100 ° C. for 10 minutes. It was oven dried to form a hydrophilic layer having a dry coating amount of 2.0 g / m ² to produce a hydrophilic member.
The evaluation results are shown in Table 1.

<First layer coating solution (2)>
・ Epicoat 1009 (manufactured by Shell Chemicals Japan) 100g
・ Takenate D110N (manufactured by Takeda Pharmaceutical, solid content 10%) 100g
・ Methyl ethyl ketone 1200g

Example 19
The first layer described in Example 11 was provided on a SUS substrate (thickness 1.1 mm) whose surface was hydrophilized by UV / O ₃ treatment for 10 minutes, and the first layer coating liquid (with the following composition) was further formed on the first layer ( 3) was spin-coated (1000 rpm for 60 seconds) and oven-dried at 100 ° C. for 10 minutes to form a layer having a dry coating amount of 0.5 g / m ² to form a first layer having a two-layer structure. The water droplet contact angle of the layer formed from the first layer coating solution (3) was 10 °. Subsequently, a hydrophilic layer was formed on the first layer having the two-layer structure by using the hydrophilic layer coating solution (2) used in Example 6 to produce a hydrophilic member.
The evaluation results are shown in Table 1.

<First layer coating solution (3)>
-PVA105 aqueous solution (Kuraray, solid content 6%) 130g
・ Glyoxal aqueous solution (Tokyo Kasei, solid content 40%) 50g
・ Ethylene glycol diglycidyl ether (Tokyo Kasei) 10g
・ Methanol silica (Nissan Chemical, solid content 30%) 30g
・ 20 g of 5% by weight aqueous solution of the anionic surfactant (1)
・ Purified water 7600g

Example 20
A hydrophilic member was produced by forming a hydrophilic layer in the same manner as in Example 17 except that the substrate was changed to an alkali degreased aluminum substrate (thickness: 100 μm).
The evaluation results are shown in Table 1.

Example 21
A hydrophilic polymer (exemplary compound (1)) having a silane coupling group in the side chain and a specific betaine compound (exemplary compound 2) in 2 g of ethyl alcohol, 0.1 g of acetylacetone, 0.1 g of tetraethyl orthotitanate and 100 g of purified water ) And mixed at room temperature for 2 hours to prepare. Further, 2.5 g of a 5% by mass aqueous solution of the anionic surfactant (1) was mixed to obtain a hydrophilic layer coating solution (3).
[Coating method]
The hydrophilic layer coating solution (3) is bar-coated on the float glass plate (thickness 2 mm) coated with the first layer coating solution (1) used in Example 16, and oven-dried at 150 ° C. for 30 minutes. Then, a hydrophilic layer having a dry coating amount of 3.0 g / m ² was formed to prepare a hydrophilic member.
The evaluation results are shown in Table 1.

[Comparative Example 4]
A hydrophilic member was prepared by forming a hydrophilic layer in the same manner as in Example 21 except that the specific betaine compound was changed to the comparative compound (1).
The evaluation results are shown in Table 1.

[Example 22]
The hydrophilic layer coating solution (3) was bar coated on a polyethylene terephthalate (PET) substrate (thickness 50 μm) coated with the first layer coating solution (2) used in Example 18, and the oven was heated at 150 ° C. for 30 minutes. It dried and formed the hydrophilic layer of dry coating amount 3.0g / m < ² >, and produced the hydrophilic member.
The evaluation results are shown in Table 1.

Example 23
A hydrophilic member was produced by forming a hydrophilic layer in the same manner as in Example 21 except that the substrate was changed to an alkali degreased aluminum substrate (thickness: 100 μm).
The evaluation results are shown in Table 1.

If an example of the field | area which can apply the hydrophilic member of this invention is given, as a use which the board | substrate which can permeate | transmit visible light is applicable, as a vehicle rear-view mirror, bathroom mirror, toilet mirror, dental mirror, road Mirrors such as mirrors; glasses lenses, optical lenses, camera lenses, endoscope lenses, illumination lenses, semiconductor lenses, copier lenses; prisms; window glass for buildings and surveillance towers; Railroad vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, spaceship-like vehicle window glass; automobiles, rail vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, Windshields for motorcycles, ropeway gondola, amusement park gondola, spacecraft vehicles; protective goggles, sports goggles, protective mask shields, sports masks Field, helmet shield, glass frozen food display cases; cover glass measuring instruments, and the like films for attached to the article surface and the like.
Other applicable applications include building materials, building exteriors, building interiors, window frames, window glass, structural members, vehicle exteriors and coatings, machinery and article exteriors, dust covers and coatings, traffic signs, and various display devices. , Advertising towers, noise barriers for roads, noise barriers for railways, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, plastic houses, vehicle lighting cover, Housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking range, kitchen hood, ventilation fan, and film for attaching to the surface of the article, Housing, parts, exterior, and coating of household electrical products, housing, parts, exterior, and coating of OA equipment products, and films to be attached to the surface of the article Gerare, the application range is wide.

Claims (15)

  (A) Zwitterionic low molecular weight compound, (B) hydrophilic polymer, (C) alkoxide compound containing an element selected from Si, Ti, Zr, and Al, and (D) hydrophilic film formation containing a metal complex catalyst Composition.   The metal complex catalyst (D) 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 1, which is composed of an oxo or hydroxy oxygen compound selected from the group consisting of:   The hydrophilic film-forming composition according to claim 1 or 2, wherein the (A) zwitterionic low-molecular compound has a betaine structure.   The composition for forming a hydrophilic film according to claim 1, wherein the hydrophilic polymer (B) is a hydrophilic polymer having a silane coupling group at a polymer terminal or a side chain. The hydrophilic film-forming composition according to claim 4, wherein the hydrophilic polymer having a silane coupling group at the polymer terminal is a compound having at least a structure represented by the following general formula (1).

The hydrophilic polymer having the structure represented by the general formula (1) is a silane represented by the structural unit (iii) at least one terminal of the polymer unit represented by the structural units (i) and (ii). Has a coupling group.
In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and m is 0, 1 Or, 2 is represented, x and y represent a composition ratio when x + y = 100, and x: y represents a range of 100: 0 to 1:99. L ¹ , L ² and L ³ each independently represents a single bond or an organic linking group, and Y ¹ and Y ² each independently represent —N (R ⁷ ) (R ⁸ ), —OH, —NHCOR. ⁷ , —CONH ₂ , —CON (R ⁷ ) (R ⁸ ), —COR ⁷ , —CO ₂ M or —SO ₃ M, wherein R ⁷ and R ⁸ are each independently a hydrogen atom or An alkyl group having 1 to 8 carbon atoms is represented, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or onium. The hydrophilic film-forming composition according to claim 4, wherein the hydrophilic polymer having a silane coupling group in the polymer side chain is a compound having a structure represented by at least the following general formula (2).

In the general formula (2), R ¹ ~R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹¹ represents a single bond or a polyvalent organic linking group. L ¹² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. n represents an integer of 1 to 3. p and q represent a composition ratio when p + q = 100, and p: q represents a range of 99: 1 to 0: 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group 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.   Furthermore, (E) The composition for hydrophilic film formation in any one of Claims 1-6 containing colloidal silica.   The hydrophilic member which coated the composition for hydrophilic film formation in any one of Claims 1-7.   (A) A zwitterionic low-molecular compound, (B) a hydrophilic polymer, and (D) a hydrophilic film-forming composition containing a metal complex catalyst.   The metal complex catalyst (D) 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 9, which is composed of an oxo or hydroxy oxygen compound selected from:   The hydrophilic film-forming composition according to claim 9 or 10, wherein the (A) zwitterionic low-molecular compound has a betaine structure.   The composition for forming a hydrophilic film according to claim 9, wherein the hydrophilic polymer (B) is a hydrophilic polymer having a silane coupling group in a polymer side chain. The composition for forming a hydrophilic film according to claim 12, wherein the hydrophilic polymer having a silane coupling group in the polymer side chain is a compound having a structure represented by at least the following general formula (2).

In the general formula (2), R ¹ ~R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹¹ represents a single bond or a polyvalent organic linking group. L ¹² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. n represents an integer of 1 to 3. p and q represent a composition ratio when p + q = 100, and p: q represents a range of 99: 1 to 0: 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group 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.   Furthermore, the composition for hydrophilic film formation in any one of Claims 9-13 containing (E) colloidal silica.   The hydrophilic member which coated the composition for hydrophilic film formation in any one of Claims 9-14.