JP2010030293A - Hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic member having a hydrophilic layer excellent in scratch resistance (dry scratch resistance), water rub resistance (wet scratch resistance) and antifouling properties. <P>SOLUTION: The hydrophilic member comprises at least the hydrophilic layer on a base material. The hydrophilic layer is formed of a composition including a hydrophilic polymer, which contains ≥30 mol% structural unit containing a hydrophilic group in one molecule thereof and contains a hydrolyzable silyl group, and has 10-100% swelling rate, 50-2,000 kgf/mm<SP>2</SP>elastic modulus and ≤20° water drop contact angle at 20°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydrophilic member.

  2. Description of the Related Art Conventionally, paint finishing has been performed to protect buildings, civil engineering structures, automobiles, and the like, impart design properties, and improve aesthetics. In particular, with the advent of highly durable paints such as fluororesin paints, acrylic silicon resin paints, and polyurethane resin paints in recent years, great progress has been made regarding the protection of housings. However, these highly durable paints generally have a hydrophobic or oleophilic surface due to the inherent properties of the resin. Therefore, when oil or the like adheres to these surfaces as a soiling substance, it cannot be easily removed, and accumulation may significantly reduce the functions and characteristics of products / members having the surface. It was. In addition, in products / members exposed to high humidity conditions or rain, there is a problem that the light transmission is hindered by irregular reflection of light in products / members having a transparent function due to adhesion of water droplets. . Even in products and members having an inorganic surface such as glass and metal, the antifouling property against the adhesion of dirt substances such as oil is not sufficient, and the antifogging property due to adhesion of water droplets is not sufficient. Especially in glass for automobiles and glass for building materials, there are cases where hydrophobic pollutants such as urban dust, combustion products such as carbon black contained in the exhaust gas of automobiles, oils and fats, sealant elution components adhere, In many cases, it is difficult to secure a field of view through the glass (reflected in the case of a mirror) due to adhesion, and there has been a strong demand for imparting antifouling and antifogging functions.

From the viewpoint of antifouling properties, assuming that the soiling substance is an organic substance such as oil, it is necessary to reduce the interaction with the material surface, that is, to make it hydrophilic or to make it oil repellent in order to prevent soiling. In addition, for anti-fogging properties, it is necessary to provide extended wettability (that is, hydrophilicity) that spreads the attached water droplets uniformly on the surface, or to impart water repellency that facilitates removal of the attached water droplets. Therefore, many of the antifouling and antifogging materials currently under investigation depend on hydrophilicity, water repellency and oil repellency.
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.

  As another member having a surface hydrophilic function, the use of titanium oxide as a photocatalyst has been conventionally known. This is based on the oxidative decomposition function and the hydrophilization function of organic matter by light irradiation. For example, in Patent Document 1, when a photocatalyst-containing layer is formed on the surface of a substrate, the surface becomes highly hydrophilic in response to photoexcitation of the photocatalyst. If this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, and water circulation members, these composite materials have excellent antifogging and antifouling functions. It has been reported that it can be granted. Components coated with titanium oxide on the glass surface are used as self-cleaning materials in window glass for building materials and windshields for automobiles. It was inevitable that its properties deteriorated due to accumulation of dirt over a long period of time. Moreover, it cannot be said that the film strength is sufficient, and it is necessary to improve durability. Self-cleaning films with titanium oxide layers on plastic substrates are also used in automotive side mirrors, etc., but there is a need for hydrophilic materials that do not have sufficient film strength and have better wear resistance. It was done.

  Further, as antifouling / antifogging materials based on water / oil repellency, silicone compounds and fluorine compounds are mainly used. For example, Patent Document 2 discloses an antifouling material having a substrate surface coated with terminal silanol organopolysiloxane, Patent Document 3 discloses a material having a silane compound having a polyfluoroalkyl group, and an optical thin film and A combination of a fluoroacrylate and a copolymer of a monomer having an alkoxysilane group is disclosed in Patent Document 4. However, antifouling materials using these silicone compounds and fluorine compounds have insufficient antifouling properties, are difficult to remove dirt such as fingerprints, sebum, sweat, cosmetics, etc., and compounds with low surface energy such as fluorine and silicone As for the surface treatment by, there is a concern about deterioration of the function with time, and development of antifouling / antifogging members having excellent durability has been desired.

  On the other hand, Patent Document 5 proposes an emulsion or water-soluble resin having a silyl group, a compound having an epoxy group, a curable composition containing an organoaluminum compound, and the like. However, the coating films obtained from these curable compositions cannot obtain a sufficiently hydrophilic surface and have low water resistance, antifouling properties, and weather resistance. For this reason, further improvement is desired.

  In order to solve these problems, when a vinyl copolymer having a hydrophilic group and a hydrolyzable silyl group is used for coating to increase the hydrophilicity of the surface, the hydrophilic group is strongly bonded to hydrogen. The film becomes very brittle and scratch resistance is low. In addition, there is a problem that not only the surface but also the inside of the film is hydrophilic, so that it easily swells and water rub resistance is lowered.

  In order to achieve both the hydrophilicity of the surface, the softening of the film quality, and the suppression of swelling, there has been proposed a film in which the film quality is softened by adding latex and the swelling is suppressed (Patent Document 6). However, sufficient hydrophilicity is not obtained because the hydrophilicity of the polymer is low. Moreover, what added the inorganic substance is proposed (patent document 7), However, There existed a problem that it was inferior in the viewpoint of hydrophilic property or brittleness.

International Publication No. 96/29375 Pamphlet JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 JP-A-7-111152 JP-A-9-66658 JP-A-6-145453

  An object of the present invention is to provide a hydrophilic member having a hydrophilic layer excellent in scratch resistance (dry scratch resistance), water rub resistance (wet scratch resistance), and antifouling property.

  The present inventors have intensively studied to improve the dry scratch resistance by softening the film quality in dry, and to improve the wet scratch resistance by suppressing swelling, and solved the above problems by means of the following constitution.

1. A hydrophilic member having at least a hydrophilic layer on a substrate, wherein the hydrophilic layer contains 30 mol% or more of a structural unit containing a hydrophilic group in one molecule and contains a hydrolyzable silyl group It is formed from a composition containing a polymer, the swelling ratio of the hydrophilic layer is 10 to 100%, the elastic modulus is 50 to 2000 kgf / mm ² , and the water droplet contact angle at 20 ° C. is 20 ° or less. A hydrophilic member.
2. 2. The hydrophilic member as described in 1 above, wherein the water droplet contact angle is 15 ° or less.
3. 3. The hydrophilic member as described in 1 or 2 above, wherein the swelling rate is 20 to 60%.
4). 4. The hydrophilic member according to any one of 1 to 3, wherein the elastic modulus is 90 to 1500 kgf / mm ² .
5). The hydrophilic polymer containing 30 mol% or more of the structural unit containing a hydrophilic group in one molecule and containing a hydrolyzable silyl group includes a structure represented by the following general formula (II): The hydrophilic member in any one of 1-4.

{In the general formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and X represents a hydrolyzable silyl group represented by the following general formula (a). L ² and L ³ each independently represent a single bond or a linking group, and Y represents —NHCOR, —CONH ₂ , —N (R) ₂ , —CON (R) ₂ , —COR, —OH, —CO _{2 M, -SO 3 M, -PO} 3 M, -OPO 3 M, - (CH 2 CH 2 O) n H, - (CH 2 CH 2 O) represents the n CH ₃ or n _(R) 3 ^{Z 1} Here, R represents an alkyl group, an aryl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or onium, n represents an integer, and Z ¹ represents a halogen ion. When a plurality of R are present, they may be the same as or different from each other. }
General formula (a): -Si (R < ¹⁰² >) _a- (OR <^101> ) _3-a
{In General Formula (a), R ¹⁰¹ is a hydrogen atom or an alkyl group, R ¹⁰² is a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group, an aryl group and an aralkyl group, and a is an integer of 0 to 2. . When a plurality of R ¹⁰¹ or R ¹⁰² are present, they may be the same as or different from each other. }
6). The hydrophilic member according to any one of 1 to 5 above, wherein the hydrophilic layer further contains a fiber having a width of 3 nm to 1000 nm and a length of 0.1 μm to 100 μm.
7). 7. The hydrophilic member as described in 6 above, wherein the fiber is made of cellulose.
8). The hydrophilic layer is formed through a heat drying step, the heating temperature in the heat drying step is 80 to 160 ° C., and the heating time is 10 minutes to 8 hours. The hydrophilic member according to any one of 7.
9. 9. The hydrophilic member as described in any one of 1 to 8 above, wherein the composition further contains a curing catalyst.
10. 10. The hydrophilic member as described in 9 above, wherein the curing catalyst is a metal complex catalyst.

  ADVANTAGE OF THE INVENTION According to this invention, a hydrophilic member provided with the hydrophilic layer excellent in scratch resistance, water-rubbing resistance, and antifouling property can be provided.

The hydrophilic member of the present invention is a hydrophilic member having at least a hydrophilic layer on a substrate, and the hydrophilic layer contains 30 mol% or more of a structural unit containing a hydrophilic group in one molecule and is hydrolyzed. A composition containing a hydrophilic polymer containing a decomposable silyl group is formed on the substrate by coating and drying. The hydrophilic layer has a swelling ratio of 10 to 100% and an elastic modulus of 50 to 2000 kgf / mm. ^2. A water droplet contact angle at 20 ° C. is 20 ° or less.
Hereinafter, the present invention will be described in more detail.

[Hydrophilic polymer]
The hydrophilic polymer contained in the composition for forming the hydrophilic layer (also referred to as hydrophilic composition) contains 30 mol% or more of a structural unit containing a hydrophilic group in one molecule, and is a hydrolyzable silyl group. including.

  The main chain structure of the hydrophilic polymer is not particularly limited. Preferred main chain structures include acrylic resin, methacrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolac type phenol resin, polyester resin, synthetic rubber, natural rubber, etc. An acrylic resin and a methacrylic resin are particularly preferable. The hydrophilic polymer may be a copolymer, and the copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

The hydrolyzable silyl group means a group that reacts with water to generate silanol (Si—OH), and is preferably represented by the following general formula (a).
General formula (a): -Si (R < ¹⁰² >) _a- (OR <^101> ) _3-a
In general formula (a), R ¹⁰¹ is a hydrogen atom or an alkyl group, R ¹⁰² is a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group, an aryl group and an aralkyl group, and a is an integer of 0 to 2. . When a plurality of R ¹⁰¹ or R ¹⁰² are present, they may be the same as or different from each other.

When R ¹⁰¹ represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹⁰² represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹⁰² represents an aryl group, an aryl group having 6 to 25 carbon atoms is preferable, and when it represents an aralkyl group, an aralkyl group having 7 to 12 carbon atoms is preferable. Groups are preferred.

The hydrolyzable silyl group is preferably a hydrolyzable silyl group bonded to a carbon atom.
One or more hydrolyzable silyl groups may be present at the end of the polymer main chain, or one or more may be present at the side chain. When two or more hydrolyzable silyl groups are included, the two or more hydrolyzable silyl groups may be the same as or different from each other.

  The hydrolyzable silyl group can form a chemical bond by reacting with a hydrolyzed polycondensate of an alkoxide (also referred to as a metal alkoxide) containing an element selected from Si, Ti, Zr, and Al described later. Moreover, hydrolyzable silyl groups may form a chemical bond. The chemical bond in this case includes a covalent bond, an ionic bond, a coordination bond, and a hydrogen bond in the same manner as usual. The chemical bond is preferably a covalent bond. The hydrophilic polymer is preferably water-soluble, and preferably becomes water-insoluble by reacting with a hydrolysis or polycondensate of a metal alkoxide.

  The hydrophilic group possessed by the hydrophilic polymer is preferably a carboxyl group, an alkali metal salt of a carboxyl group, a sulfonic acid group, an alkali metal salt of a sulfonic acid group, a hydroxy group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group. And the like. These groups may be present at any position in the polymer. A polymer structure in which a plurality of polymers are bonded directly from a polymer main chain or via a linking group, or bonded to a polymer side chain or a graft side chain, is preferred.

  The hydrophilic polymer used in the present invention is preferably a polymer having a metal alkoxide, which will be described later, and a group that forms a bond by the action of a catalyst or the like. As the group that forms a bond with the metal alkoxide compound by the action of the catalyst, in addition to the hydrolyzable silyl group represented by the general formula (a), a carboxyl group, an alkali metal salt of a carboxy group, a carboxylic anhydride group, Amino group, hydroxy group, epoxy group, methylol group, mercapto group, isocyanate group, block isocyanate group, alkoxytitanate group, alkoxyaluminate group, alkoxyzirconate group, ethylenically unsaturated group, ester group, tetrazole group, etc. These reactive groups are exemplified.

  The structural unit containing a hydrophilic group is preferably contained in an amount of 40 mol% or more, more preferably 50 mol% or more in one molecule of the hydrophilic polymer. The structural unit containing a hydrolyzable silyl group is preferably contained in an amount of 1 mol% or more, more preferably 2 mol% or more, and further preferably 3 mol% or more in one molecule of the hydrophilic polymer.

  A linking group is preferably interposed between the repeating unit containing a hydrophilic group and the hydrolyzable silyl group, or between the repeating unit containing a hydrophilic group and the main chain. In addition, it is also preferable to have a linking group between the hydrolyzable silyl group and the main chain and / or between the hydrophilic group and the main chain.

  The hydrophilic polymer is preferably a hydrophilic polymer including a structure represented by the following general formula (I), (II) or (III).

In the general formulas (I), (II) and (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen. Represents an atom or a hydrocarbon group, X represents a hydrolyzable silyl group represented by the general formula (a), and A, L ¹ , L ² , L ³ , L ⁴ , and L ⁵ are each independently Represents a single bond or a linking group, and Y represents —NHCOR, —CONH ₂ , —N (R) ₂ , —CON (R) ₂ , —COR, —OH, —CO ₂ M, —SO ₃ M, —PO _3. M, —OPO ₃ M, — (CH ₂ CH ₂ O) _n H, — (CH ₂ CH ₂ O) _n CH ₃ or N (R) ₃ Z ¹ , where R is an alkyl group, an aryl group Or an aralkyl group, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, or onium , N represents an integer, Z ¹ represents a halogen ion, and B represents a group having a structure represented by the following general formula (IV).

In general formula (IV), the definitions of R ¹¹ , R ¹² , L ⁶ and Y are the same as the definitions of R ³ , R ⁴ , L ² and Y in general formula (II).

  Since many hydrolyzable silyl groups per molecule can be introduced and a very good curability can be obtained by drying at room temperature, a hydrophilic polymer having a structure represented by the general formula (II) is obtained. More preferred.

(Hydrophilic polymer having a structure represented by the general formula (I))
The hydrophilic polymer having a structure represented by the general formula (I) is, for example, a chain transfer agent (described in radical polymerization handbook (NTS, Mikiharu Tsunoike, Takeshi Endo)) or Iniferter (Macromolecules 1986, 19, p287). -(Described in (Otsu)) in the presence of a hydrophilic monomer (eg, acrylamide, acrylic acid, potassium salt of 3-sulfopropyl methacrylate) by radical polymerization. Examples of chain transfer agents include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane. Alternatively, a hydrophilic monomer (eg, acrylamide) may be radically polymerized using a radical polymerization initiator having a reactive group without using a chain transfer agent.

The hydrophilic polymer having the structure represented by the general formula (I) is a hydrophilic polymer having a hydrolyzable silyl group at the terminal. In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or 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 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ¹ and R ² 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 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, alkylthio groups, arylthio groups, amino 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-arylsulfamo 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 phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

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

Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) 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.

  Of these, a hydroxymethyl group is preferred from the viewpoint of hydrophilicity.

A and L ¹ each represents a single bond or a linking group. Here, when A and L ¹ represent a linking group, A and L ¹ represent a polyvalent linking group composed of a nonmetallic atom, and any one of a carbon atom, a nitrogen atom, an oxygen atom, a hydrogen atom, and a sulfur atom is represented. Including 0 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 It is preferably composed of sulfur atoms. Specifically, it is preferably selected from —N <, an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof, —O—, —S—, —CO—, —NH—, and It is preferable that it is a bivalent coupling group chosen from these combinations.
More specific examples of the linking group include the following or those constituted by combining them.

A and L ¹ are more preferably —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ —, or -CH ₂ - is.

In general formula (I), Y represents —NHCOR, —CONH ₂ , —N (R) ₂ , —CON (R) ₂ , —COR, —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M. _{, -OPO 3 M, - (CH} 2 CH 2 O) n H, - (CH 2 CH 2 O) represents the n CH ₃ or n _(R) 3 ^{Z 1,} wherein, R represents an alkyl group, an aryl group, Or represents an aralkyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium, n represents an integer, and Z ¹ represents a halogen ion. Moreover, when it has several R like -CON (R) ₂ , R may couple | bond together and it may form the ring and the formed ring is oxygen atoms, a sulfur atom, a nitrogen atom, etc. It may be a heterocycle containing a heteroatom. When a plurality of R are present, they may be the same as or different from each other. R may further have a substituent, and examples of the substituent that can be introduced here include the same substituents that can be introduced when R ¹ and R ² are alkyl groups. it can.

R preferably represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Specific examples of R 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.
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.

The _{Y, -NHCOCH 3, -CONH 2,} -CON (CH 3) 2, -COOH, -SO 3 - NMe 4 +, -SO 3 - K +, - (CH 2 CH 2 O) n H, morpholyl Groups and the like are preferred. More _{preferably, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -SO 3 - K +, - (CH 2 CH 2 O) n H, is.

  n preferably represents an integer of 1 to 100.

  The hydrophilic polymer having the structure represented by the general formula (I) is, for example, a chain capable of radical polymerization represented by the following general formula (i) and radical polymerization represented by the following general formula (ii). It can be synthesized by radical polymerization using a silane coupling agent having mobility. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a hydrolyzable silyl group is introduced at the end of the polymer main chain in radical polymerization.

In the above formulas (i) and (ii), A, R ¹ , R ² , L ¹ , X, and Y are synonymous with those in the general formula (I). These compounds are commercially available and can also be easily synthesized. The radically polymerizable monomer represented by the general formula (i) has a hydrophilic group Y, and this monomer becomes one structural unit in the hydrophilic polymer.

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

  The mass average molecular weight of the hydrophilic polymer containing the structure represented by the general formula (I) 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 of the hydrophilic polymer having a structure represented by the general formula (I) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

(Hydrophilic polymer having a structure represented by the general formula (II))
In the general formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and specific examples and preferred ranges thereof are those represented by R ^{1 in the} general formula (I). , R ² . L ² and L ³ each independently represent a single bond or a linking group, and specific examples and preferred ranges thereof are the same as those of L ^{1 in the} general formula (I). The definitions of Y and X are the same as those in formula (I), and specific examples and preferred ranges are also the same.

In General Formula (II), L ³ has a single bond or one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. More preferably, it is a linking group.

Each compound for synthesizing the hydrophilic polymer having the structure represented by the general formula (II) is commercially available or can be easily synthesized.
Any conventionally known method can be used as the radical polymerization method for synthesizing the hydrophilic polymer having the structure represented by the general formula (II).
Specifically, general radical polymerization methods include, for example, New Polymer Experiments 3 (1996, Kyoritsu Shuppan), Polymer Synthesis and Reaction 1 (Polymer Society of Japan, 1992, Kyoritsu Shuppan), New Experiment Described in Chemistry Course 19 (1978, Maruzen), Polymer Chemistry (I) (Edited by Chemical Society of Japan, 1996, Maruzen), Synthetic Polymer Chemistry (Materials Engineering Course, 1995, Tokyo Denki University Press) These can be applied.

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

  The mass average molecular weight of the hydrophilic polymer having a structure represented by the general formula (II) 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.

The copolymerization ratio of the hydrophilic polymer containing the structure represented by the general formula (II) is such that the molar ratio (m ₂ ) of the structural units containing Y and the molar ratio (n ₂ ) of the structural units containing X are: _{m 2 / n 2 = 30 /} 70~99 / 1 range is _preferred, more preferably _{m 2 / n 2 = 40 /} 60~98 / 2, m 2 / n 2 = 50 / 50~97 / 3 is the most preferable. If m ₂ / n ₂ is 30/70 or more, the hydrophilicity is not insufficient. On the other hand, if m ₂ / n ₂ is 99/1 or less, the hydrolyzable silyl group amount is sufficient and sufficient. Curing is obtained and the film strength is sufficient.
The copolymerization ratio can be measured with a nuclear magnetic resonance apparatus (NMR) or a calibration curve prepared with a standard substance and measured with an infrared spectrophotometer.

  Specific examples of the hydrophilic polymer having the structure represented by the general formula (II) are shown below together with the mass average molecular weight (M.W.), but the present invention is not limited thereto. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or a block copolymer contained in the described molar ratio.

(Hydrophilic polymer having a structure represented by the general formula (III))
Examples of the hydrophilic polymer having a structure represented by the general formula (III) include a hydrophilic graft polymer obtained by introducing a side chain having a hydrophilic group into a trunk polymer having a reactive group.

In the general formula (III), the definitions of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as the definitions of R ¹ and R ^{2 in} the general formula (I), and specific examples and preferred ranges are also the same. is there. The definitions of L ⁴ and L ⁵ are the same as the definition of L ^{1 in} the general formula (I), and specific examples and preferred ranges are also the same. B has a group having the structure represented by the general formula (IV), and the definitions of R ¹¹ , R ¹² , L ⁶ and Y in the general formula (IV) are as follows. The definitions of R ³ , R ⁴ , L ² and Y are the same, and specific examples and preferred ranges are also the same. The definition of X is the same as the definition of X in the general formula (I), and specific examples and preferred ranges are also the same.

  This hydrophilic graft polymer can be prepared using a method generally known as a method for synthesizing a graft polymer. Specifically, a general method for synthesizing a graft polymer is described in “Graft Polymerization and its Applications” by Fumio Ide, published in 1977, “Polymer Publishing”, and “New Polymer Experiments 2, Polymer Synthesis / Reaction "edited by Polymer Society of Japan, Kyoritsu Shuppan Co., Ltd. 1995, and these can be applied.

  As a synthesis method of the graft polymer, basically, 1. 1. Polymerize the branch monomer from the trunk polymer. 2. Link the branch polymer to the trunk polymer. It can be divided into three methods of copolymerizing a branch polymer with a trunk polymer (macromer method). Any of these three methods can be used to produce the hydrophilic graft polymer used in the present invention, but “3. Macromer method” is particularly excellent from the viewpoint of production suitability and control of the membrane structure. ing.

  The synthesis of graft polymer using a macromonomer is described in the aforementioned “New Polymer Experiments 2, Polymer Synthesis / Reaction” edited by Polymer Society of Japan, Kyoritsu Publishing Co., Ltd. 1995. It is also described in detail in Yamashita Yu et al., “Macromonomer Chemistry and Industry”, IPC, 1989. The graft polymer used in the present invention is obtained by first copolymerizing a hydrophilic macromonomer (corresponding to a precursor of a hydrophilic polymer side chain) synthesized by the above method and a monomer having a reactive group. Can be synthesized.

  Among the hydrophilic macromonomers, particularly useful are macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylstyrene sulfonic acid, and salts thereof Sulfonic acid macromonomer derived from the monomer of amide, amide macromonomer such as acrylamide and methacrylamide, amide macromonomer derived from N-vinylcarboxylic amide monomer such as N-vinylacetamide and N-vinylformamide, Macromonomers derived from hydroxyl group-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acetate Rate, a macromonomer derived from alkoxy group or ethylene oxide group-containing monomers such as polyethylene glycol acrylate. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer of the present invention. Among these macromonomers, the useful polymer has a mass average molecular weight in the range of 400 to 100,000, preferably 1000 to 50,000, and particularly preferably 1500 to 20,000. If the molecular weight is 400 or more, effective hydrophilicity is obtained, and if it is 100,000 or less, the polymerizability with the copolymerization monomer forming the main chain tends to be high, both of which are preferable.

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

  As the hydrophilic polymer having a structure represented by the general formula (III), those having a mass average molecular weight of 1,000,000 or less are preferably used, more preferably 1,000 to 1,000,000, and still more preferably 20,000 to 100,000. Is. If the weight average molecular weight is 1,000,000 or less, handling properties such as the ability to form a uniform coating film is reduced without lowering the solubility in a solvent when preparing a coating solution for forming a hydrophilic coating. Is preferable.

  Although the specific example of the hydrophilic polymer which has a structure represented by general formula (III) below is shown below with the mass mean molecular weight (MW) below, this invention is not limited to these. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or a block copolymer contained in the described molar ratio.

The copolymerization ratio of the hydrophilic polymer having the structure represented by the general formula (III) can be arbitrarily set so that the amount of the hydrophilic group Y is within the above range. Preferably, the molar ratio (m ₃ ) of the structural unit containing Y and the molar ratio (n ₃ ) of the structural unit containing X is preferably in the range of m ₃ / n ₃ = 30/70 to 99/1, m ₃ / n ₃ = 40/60 to 98/2 is more preferable, and m ₃ / n ₃ = 50/50 to 97/3 is most preferable. If m ₃ / n ₃ is 30/70 or more, the hydrophilicity is not insufficient. On the other hand, if m ₃ / n ₃ = 99/1 or less, the hydrolyzable silyl group amount is sufficient and sufficient. Curing is obtained and the film strength is sufficient.
The copolymerization ratio can be measured with a nuclear magnetic resonance apparatus (NMR) or a calibration curve prepared with a standard substance and measured with an infrared spectrophotometer.

The hydrophilic composition in this invention may contain the hydrophilic polymer containing the structure represented with general formula (I), (II) or (III) individually or in 2 types or more.
The hydrophilic polymer having a structure represented by the general formula (I), (II) or (III) is preferably used in an amount of 20 to 99.5% by mass based on the total solid content of the hydrophilic composition, 30 More preferably, ˜99.5% by mass is used.

  Preferred mass ratio when the hydrophilic composition contains a hydrophilic polymer containing a structure represented by the general formula (I) and a hydrophilic polymer containing a structure represented by the general formula (II) or (III) Is (hydrophilic polymer containing a structure represented by the general formula (I) / hydrophilic polymer containing a structure represented by the general formula (II) or (III)) is 50/50 to 5/95 .

  The hydrophilic polymer having a structure represented by the general formula (I), (II) or (III) forms a crosslinked film in a state where it is mixed with a hydrolysis or polycondensate of a metal alkoxide. The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the viscosity measured at 20 ° C. of a 5% aqueous solution of the hydrophilic polymer is 0.1 to 100 mPa · s, preferably When it is in the range of 0.5 to 70 mPa · s, more preferably 1 to 50 mPa · s, good film properties are provided. The viscosity can be measured with an E-type viscometer (trade name: RE80L, manufactured by Tokyo Keiki Co., Ltd.).

Solvents used in the synthesis of the hydrophilic polymer in the present invention include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl. Acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, toluene, ethyl acetate, methyl lactate, lactic acid Examples include ethyl, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
As the radical polymerization initiator used for synthesizing the hydrophilic polymer, known compounds such as an azo initiator, a peroxide initiator, and a redox initiator can be used.

[Fiber]
The hydrophilic layer of the hydrophilic member of the present invention preferably further contains a fiber, and more preferably contains a fiber having a width of 3 nm to 1000 nm and a length of 0.1 μm to 100 μm.
The width of the fiber means the length in the minor axis direction and is measured by an electron microscope. The length of the fiber means the length in the long axis direction and is measured by an electron microscope.
Examples of the fiber include an organic fiber and an inorganic fiber.
Preferred examples of the organic fiber include fibers made of cellulose, polyolefin, polyamide, polyurethane, polyester, fluorine polymer, polylactic acid, polyvinyl alcohol, nylon, polycarbonate, polyimide, and derivatives thereof.
Preferred examples of the inorganic fiber include fibers made of carbon nanofibers, glass fibers, and the like.
In the present invention, the fiber is more preferably a fiber made of cellulose from the viewpoints of flexibility and hydrophilicity.
The width of the fiber is more preferably 3 nm to 500 nm, further preferably 3 nm to 100 nm. The length of the fiber is more preferably 0.1 μm to 10 μm.

Such fibers can be synthesized by bulk mechanical emulsification / oxidation treatment, polymer alloy melt spinning, electrospinning, and the like, and are also commercially available. As a commercial item, serisch FD-100G (made by Daicel Chemical Industries Ltd.) etc. are mentioned, for example.
If the fiber content is too large, the film quality becomes brittle, and if it is too small, sufficient film strength cannot be obtained, so that it is preferably 0.01 to 70% by mass relative to the total solid content of the hydrophilic composition, 0.1-20 mass% is further more preferable.

By containing the fiber, the hydrophilic layer can maintain the film strength even when it swells when wet, without impairing the flexible film quality when dry. Accordingly, it is possible to produce a hydrophilic member having excellent dry / wet scratch resistance. Moreover, when transparency is required, it is preferable that the width of the fiber is 50 nm or less because transparency is not impaired.
When a hydrophilic layer that is particularly flexible and has high dry / wet scratch resistance is desired, a hydrophilic polymer having a structure represented by the general formula (I) and a hydrophilic polymer having a structure represented by the general formula (II) It is particularly preferable to mix a functional polymer and further add fibers. This is because the film quality is sufficiently flexible by adding a hydrophilic polymer having a structure represented by the general formula (I) with few crosslinking groups, and the film strength is not impaired by adding fibers to this flexible film quality. This is because it can be reinforced.

[Crosslinking agent]
When the hydrophilic composition in the present invention contains a hydrophilic polymer containing the structure represented by the general formula (I), it is preferable to contain a crosslinking agent in order to obtain good curability. When the hydrophilic composition contains a hydrophilic polymer containing the structure represented by the general formula (II) or the general formula (III), good curability can be obtained even when no crosslinking agent is contained. In order to obtain a coating film having very excellent film strength, a crosslinking agent may be contained.
As the crosslinking agent, an alkoxide compound (also referred to as a metal alkoxide) containing an element selected from Si, Ti, Zr, and Al is particularly preferable. A metal alkoxide is a hydrolyzable polymerizable compound having a functional group capable of being hydrolyzed and polycondensed in its structure and serving as a cross-linking agent, and has a cross-linked structure due to polycondensation of metal alkoxides. It forms a strong cross-linked film and can also be chemically bonded to the hydrophilic polymer.
The metal alkoxide is preferably represented by the following general formula (V-1) or general formula (V-2). In the formula, R ²⁰ represents a hydrogen atom, an alkyl group or an aryl group, R ²¹ represents an alkyl group or an aryl group, Z represents Si, Ti or Zr, and m represents an integer of 0 to 2. The number of carbon atoms when R ²⁰ and R ²¹ 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 2000 or less.

^{_{(R 20) m -Z- (OR}} 21) 4-m (V-1)
_{^{Al- (OR 21) 3 (V}} -2)

Specific examples of the hydrolyzable compound represented by the general formula (V-1) or the general formula (V-2) are shown below, but the present invention is not limited thereto.
When Z is Si, that is, the hydrolyzable compound containing silicon includes, for example, trimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, γ- Examples include chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like. Among these, particularly preferred are trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and the like.

When Z is Ti, i.e., including titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl Examples include trimethoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate.
When Z is Zr, that is, the one containing zirconium can include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.
In the case where the central metal is Al, that is, examples of the hydrolyzable compound containing aluminum include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, triisopropoxy aluminate and the like. be able to.

  Among the above, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and 3-aminopropyltrimethoxysilane are particularly preferable.

  When the metal alkoxide compound selected from Si, Ti, Zr, and Al uses a hydrophilic polymer including the structure represented by the general formula (I), 1 to 80% by mass is preferably used, and more preferably 5 to 70% by mass. When using a hydrophilic polymer containing a structure represented by the general formula (II) or general formula (III), it is preferably used in an amount of 0 to 80% by mass based on the total solid content of the hydrophilic composition. More preferably, 0 to 70% by mass is used.

[Curing catalyst]
In the hydrophilic composition of the present invention, a hydrolyzable silyl group-containing hydrophilic polymer and a cross-linking agent such as a metal alkoxide compound are dissolved in a solvent and stirred well, so that these components are hydrolyzed and polycondensed. An organic-inorganic composite sol solution is formed, and a hydrophilic layer having high hydrophilicity and high film strength is formed by the sol solution. In preparing the organic-inorganic composite sol solution, it is preferable to use a curing catalyst in order to promote hydrolysis and polycondensation reaction.
As the curing catalyst used in the present invention, an acidic catalyst, a basic catalyst or a metal complex is preferably used.

(Acid catalyst, basic catalyst)
As the curing catalyst used in the present invention, a catalyst that promotes a reaction that causes hydrolysis and polycondensation of the crosslinking agent such as the metal alkoxide compound to cause a bond with the hydrolyzable silyl group-containing hydrophilic polymer is selected. Alternatively, the basic compound is used as it is, or the acid or basic compound is dissolved in a solvent such as water or alcohol (hereinafter, these are collectively referred to as an acidic catalyst and a basic catalyst, respectively) Can be used. The concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acidic catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its R ³⁰ COOH. Examples thereof include substituted carboxylic acids in which R ³⁰ in the structural formula is substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, etc., and basic catalysts include ammoniacal bases such as aqueous ammonia, ethylamine and aniline, etc. And amines.

(Metal complex catalyst)
The catalyst that can be used in the hydrophilic composition of the present invention is particularly preferably a metal complex.
The metal complex catalyst that can be used in the hydrophilic composition of the present invention promotes hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al, and causes a bond with a hydrophilic polymer. it can. Particularly preferred metal complex catalysts include 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 enolic active hydrogen compounds. Metal complexes composed of selected oxo or hydroxy oxygen containing compounds.
Among the 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. Among them, 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 , 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-heptanone, ketoalcohols such as 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl- Monoethanolamine, diethanol Amino alcohols such as amine and triethanolamine, methylol melamine, methylol urea, methylol acrylamide, enol active compounds such as malonic acid diethyl ester, methyl group, methylene group or carbonyl carbon of acetylacetone (2,4-pentanedione) The compound which has a substituent is mentioned.

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

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

Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aco complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, but in particular, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( acetylacetonato) titanium complex salt, zirconium tris (ethylacetoacetate), titanium (di -i- propoxide) bis (acetylacetonate), aluminum _{acetylacetonate, (ZrO (C 2 H 3} O 2) 2 is 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 satisfying the improvement of coating solution aging stability and film surface quality, and high hydrophilicity and high durability.

In addition to the above metal complex catalyst, the acidic catalyst and the basic catalyst may be used in combination.
The above metal complex catalyst can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.

  It is preferable that 0.1-20 mass% is used for a curing catalyst with respect to the total solid of a hydrophilic composition, and it is more preferable that 1-10 mass% is used.

[Inorganic fine particles]
The hydrophilic composition in the present invention may contain inorganic fine particles in order to improve hydrophilicity, prevent cracking of the film, and improve film strength. Inorganic fine particles are particularly preferred because of their high hydrophilicity. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned.
The inorganic fine particles preferably have an average particle size of 10 nm to 10 μm, and more preferably 0.5 μm to 3 μm. Within the above range, it is possible to form a coating film that is stably dispersed in the coating film, sufficiently maintains the film strength of the coating film, and has high durability and excellent hydrophilicity.
Among the inorganic fine particles as described above, a colloidal silica dispersion is particularly preferable and can be easily obtained as a commercial product.
The content of the inorganic fine particles is preferably 80% by mass or less, and more preferably 50% by mass or less, based on the total solid content of the hydrophilic composition.

The various additives that can be used in the hydrophilic composition as necessary are described below.
[Surfactant]
In the present invention, a surfactant may be used 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 in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the nonvolatile component. Moreover, surfactant can be used individually or in combination of 2 or more types.

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

[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance and durability of the coating film.
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.
Although the addition amount of a ultraviolet absorber is suitably selected according to the objective, Generally, it is preferable that it is 0.5-15 mass% in conversion of solid content.

[Antioxidant]
In order to improve the stability of the hydrophilic composition in the present invention, an antioxidant can be added. Examples of the antioxidant include European Patent Application Nos. 223739, 309401, 309402, 310551, 310552, 457416, German Patent Application Publication No. 3435443, JP-A Nos. 54-262047, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples include those described in JP-A-3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount of antioxidant is suitably selected according to the objective, it is preferable that it is 0.1-8 mass% in conversion of solid content.

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

[Polymer compound]
In order to adjust the physical properties of the coating film, various polymer compounds can be added to the hydrophilic composition in 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 copolymers obtained by copolymerization of acrylic monomers are preferred. Furthermore, a copolymer containing a carboxyl group-containing monomer, a methacrylic acid alkyl ester, or an acrylic acid alkyl ester as a structural unit is also preferably used.
The addition amount of the polymer compound is appropriately selected according to the purpose, but is preferably 0.001 to 20% by mass, and 0.01 to 15% by mass with respect to the total solid content of the hydrophilic composition. It is more preferable that

[Antimicrobial agent]
In order to impart antibacterial, antifungal and antialgal properties to the hydrophilic member of the present invention, the hydrophilic composition can contain an antibacterial agent. In forming the hydrophilic layer, it is preferable to contain a hydrophilic antibacterial agent or a water-soluble antibacterial agent. By containing a hydrophilic antibacterial agent or a water-soluble antibacterial agent, a surface hydrophilic member excellent in antibacterial property, antifungal property, and algaeproof property can be obtained without impairing the surface hydrophilicity.
As the antibacterial agent, it is preferable to add a compound that does not lower the hydrophilicity of the hydrophilic member. Examples of such an antibacterial agent include inorganic antibacterial agents and water-soluble organic antibacterial agents. As the antibacterial agent, those exhibiting a bactericidal effect against fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, fungi such as fungi and yeast, and the like are used.
The addition amount of the antibacterial agent is appropriately selected according to the purpose, but is generally 0.001 to 10% by mass and 0.005 to 5% by mass with respect to the total solid content of the hydrophilic composition. Preferably, 0.01 to 3 mass% is more preferable, 0.02 to 1.5 mass% is particularly preferable, and 0.05 to 1 mass% is most preferable. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. If the content is 10% by mass or less, the hydrophilicity is not lowered and the film strength is not adversely affected.

In addition to this, as necessary, for example, latex, leveling additives, matting agents, waxes for adjusting film physical properties, in order to improve the adhesion to the substrate, in a range that does not inhibit hydrophilicity A tackifier or the like can be contained.
The latex is not particularly limited, and examples thereof include the same as the water-dispersible latex in the undercoat layer described later. A commercially available latex may be used. Examples of commercially available products include Nipol LX421 (manufactured by Nippon Zeon Co., Ltd.).
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 low molecular weight tackifying resins having a polymerizable unsaturated bond.

〔Base material〕
The hydrophilic member of the present invention can be produced by applying a hydrophilic composition onto a substrate and drying to form a coating film (hydrophilic layer).
The substrate is not particularly limited, but any of glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, a combination thereof, and a laminate thereof can be suitably used. A particularly preferred substrate is a glass substrate or a plastic substrate.
As the glass substrate, any glass such as soda glass, lead glass or borosilicate glass may be used. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do. In addition, the hydrophilic layer can be applied as it is with the base glass, but for the purpose of improving the adhesion of the hydrophilic layer, if necessary, the surface is hydrophilized by oxidation or roughening on one or both sides. Can be applied. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

  The plastic substrate is not particularly limited, but polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, polystyrene, polycarbonate, Examples include films or sheets of polymethylpentene, polysulfone, polyetherketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyethersulfone, and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. In addition, in terms of optical properties, it is often preferable to have excellent transparency, but depending on the application, translucent or printed materials may be used. Various thicknesses of the plastic substrate can be appropriately selected depending on applications. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for a plane or the place where intensity | strength is requested | required. In the case of a plastic substrate, as in the case of a glass substrate, surface hydrophilization treatment is performed on one or both surfaces by an oxidation method or a roughening method, etc., as necessary, in order to improve the adhesion of the hydrophilic layer. Can do.

(Undercoat layer)
One or more undercoat layers can be provided between the substrate and the hydrophilic layer. As the material for the undercoat layer, a hydrophilic resin or water-dispersible latex can be used.

Examples of hydrophilic resins include polyvinyl alcohol (PVA), cellulose 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.
Furthermore, hydrolysis condensates of metal alkoxides typified by polysiloxane and the like are preferable, and the compounds described as the crosslinking agent can be used.
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, gelatins, and hydrolysis condensates of metal alkoxides is preferable. In particular, a hydrolysis condensate of polyvinyl alcohol (PVA) resin, gelatin, and metal alkoxide is preferable.

  Examples of the water-dispersible latex include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.

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

[Layer structure when using hydrophilic members]
The hydrophilic member can be used by appropriately adding another layer according to the purpose, application, form, and place of use. The layer structure added as needed is described below.

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

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

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

[Form of hydrophilic member]
The hydrophilic member may be supplied in the form of a sheet, a roll, or a ribbon, or may be supplied as a material that has been cut in advance so as to be attached to an appropriate substrate.

[Physical properties of hydrophilic layer]
(Water drop contact angle)
The hydrophilicity is generally measured by a water droplet contact angle. The hydrophilic member of the present invention has a surface airborne water droplet contact angle measured at 20 ° C. of 20 ° or less, preferably 15 ° or less.

(Swell rate)
The hydrophilic layer of the hydrophilic member of the present invention has a swelling rate of 10 to 100%.
The swelling rate represents how much the layer thickness increases when the dry state changes to the wet state. The swelling ratio can be calculated by the following equation by calculating the layer thickness of the glass substrate sample on which the hydrophilic layer is formed using an ellipsometry in a dry state and a wet state.
Swelling rate (%) = (wet film thickness-dry film thickness) / (dry film thickness) × 100
The hydrophilic layer is preferably formed to a thickness of 300 nm or less.
In general, in the case of a hydrophilic layer, the swelling rate increases if the hydrophilicity of the surface is improved. The swelling rate is preferably 20 to 60%.

(Elastic modulus)
The elastic modulus can be measured by a method called nanoindentation. This method obtains the elastic modulus by accurately measuring the load and the position (displacement) of the indenter when the indenter is pressed against the surface of the measurement material (thin film) and the load is changed quasi-statically. is there.
Here, in the nanoindentation method, the elastic modulus (E) is defined by the following formula (see JP 2001-349815 A).
E = (π / 2A) ^1/2 dP / dh [where A is the contact area of the indenter at the maximum load, and dP / dh is the slope of the unloading curve at the maximum load. dP represents the displacement of the load, and dh represents the displacement of the indentation depth of the indenter. ]

The measurement depth is preferably not affected by the substrate. Specifically, 1/10 of the film thickness is preferable, and 1/20 of the film thickness is more preferable.
The indenter to be used is not particularly limited, but a Belkovic indenter and a Vickers indenter are preferable.
As a measuring device, for example, a Fischer scope HM500 (manufactured by Fischer Instruments), Nano Indenter G200 (manufactured by MTS), UMIS-2000 (manufactured by CSIRO), DUH-211 (manufactured by Shimadzu Corporation), NI1100 (manufactured by Elionix) , TriboScope (manufactured by HYSITRON) can be used for measurement. In any apparatus, it is desirable that the resolution is μN and the resolution of the indentation depth is nm.

When the value of the elastic modulus is too large, the film quality is brittle and external stress tends to concentrate, so that the scratch resistance is poor. On the other hand, if the value of the elastic modulus is too small, the film is greatly deformed by stress, so that the scratch resistance is lowered. Therefore, the elastic modulus of the hydrophilic layer is 50 to 2000 kgf / mm ² , and preferably 90 to 1500 kgf / mm ² .
In general, in the case of a hydrophilic coating film, the elastic modulus increases due to the interaction of hydrophilic groups in the coating film, resulting in brittleness. Therefore, it is important to design in a direction that lowers the elastic modulus of the hydrophilic layer.
Specific methods for reducing the elastic modulus of the hydrophilic layer include, for example, adjusting and selecting the length of the linking group, the type of the crosslinking group, the type of the hydrophilic group, and the amount of the hydrophilic group. It is done.

When applying (using or pasting) a hydrophilic member provided with a hydrophilic layer to a window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic layer in the present invention is excellent in transparency, and even if the film thickness is large, the transparency is not impaired and compatibility with durability is possible.
The thickness of the hydrophilic layer is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 20 μm. When the film thickness is 0.01 μm or more, it is preferable because sufficient hydrophilicity and durability can be obtained. When the film thickness is 100 μm or less, there is no problem in film-forming properties such as cracks.

  Transparency can be evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably 100% to 70%, more preferably 95% to 75%, and most preferably in the range of 95% to 80%. By being in this range, the hydrophilic member provided with a hydrophilic layer can be applied to various applications without obstructing the field of view.

[Method for producing hydrophilic member]
The hydrophilic member of the present invention can be produced by applying a hydrophilic composition on a suitable substrate, heating and drying to form a hydrophilic layer. The heating temperature and heating time for forming the hydrophilic layer are not particularly limited as long as the solvent in the sol solution is removed and a strong film can be formed, but heating is performed from the viewpoint of hydrophilicity and film strength. The temperature is preferably 80 to 160 ° C, more preferably 100 to 150 ° C. The heating time is preferably 10 minutes to 8 hours, more preferably 30 minutes to 2 hours.

  The hydrophilic member can be produced by a known application method, and is not particularly limited. For example, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a film applicator method, or screen printing. Methods such as coating, bar coating, brush coating, and sponge coating are applicable.

  The coating amount is not particularly limited, but generally a range of about 0.1 μm to 500 μm is sufficient.

Although the use which can apply the hydrophilic composition concerning this invention, a hydrophilic layer, and a hydrophilic member is illustrated, it is not limited to these.
Vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, lighting lenses, semiconductor lenses, and copying machines Lenses such as lenses; prisms; window glass for buildings and monitoring towers; glass for other building materials; various vehicles such as automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, etc. Windshields; Windshields for various vehicles such as automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola; protective goggles, sports goggles, protective Mask shield, sports mask shield, helmet shield, frozen food display case glass; measuring instrument cover glass, building material, outer wall Building exteriors such as roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, bicycles, exteriors and paintings of vehicles such as motorcycles, exteriors of machinery and equipment, dustproof covers and Paint, traffic signs, various display devices, advertising towers, sound barriers for roads, sound barriers for railways, bridges, guardrail exteriors and paints, tunnel interiors and paints, insulators, solar battery covers, solar water heater heat collection covers, greenhouses , Vehicle lighting cover, housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking range, kitchen hood, exhaust fan, signage, transportation Signs, noise barriers, greenhouses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors, solar battery covers, solar water heater covers, etc. Pavement, outdoor lighting, artificial waterfall / artificial fountain stone / tile, bridge, greenhouse, exterior wall material, sealer between walls and glass, guardrail, veranda, vending machine, air conditioner outdoor unit, outdoor bench, various display devices, shutter , Toll booths, toll boxes, roof gutters, vehicle lamp protection covers, dust covers and coatings, painting of machinery and equipment, exterior and coating of advertising towers, structural members, housing equipment, toilets, bathtubs, washstands, lighting fixtures , Kitchen utensils, tableware, tableware dryer, sink, cooking range, kitchen hood, ventilation fan, window rail, window frame, tunnel inner wall, tunnel lighting, window sash, heat exchanger fins, pavement, bathroom toilet mirror, Greenhouse ceilings, vanities, automobile bodies, snow country roofing materials, antennas, power transmission lines and films that can be attached to the surface of the above articles, medical diagnostic device components, medical Includes medical catheters, personal computer and television displays, cosmetic containers, filters, automotive aluminum wheels, camera finders, CCD cover glasses, printing device components, patches, etc.

  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, was prepared, and the surface of the plate glass was hydrophilized by UV / O ₃ treatment for 10 minutes to obtain a coating substrate. The coating liquid having the composition shown in Table 1 was stirred at 25 ° C. for 2 hours, applied to a coating substrate with a coating bar, and then dried at 150 ° C. for 30 minutes to form a hydrophilic layer having a thickness of 3.0 μm. . In this way, a hydrophilic member was obtained.

[Examples 2-27, Comparative Examples 1-5]
A hydrophilic layer was formed in the same manner as in Example 1 except that the coating liquid having the composition shown in Table 1 was used and the coating liquid was dried at the heating temperature and drying time shown in Table 1.
The preparation methods or sources of the components shown in Table 1 are described below.

[Synthesis of hydrophilic polymer (1)]
A 500 ml three-necked flask was charged with 11.9 g of acrylamide, 11.1 g of acrylamide-3- (ethoxysilyl) propyl, and 260 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methyl) under a nitrogen stream at 80 ° C. 1.7 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. Thereafter, the reaction solution was poured into 2 liters of acetone, and the precipitated solid was collected by filtration. The obtained solid was washed with acetone to obtain a hydrophilic polymer (1). The mass after drying was 22.1 g. The mass average molecular weight of the polymer determined by GPC (polyethylene oxide standard) was 25000.
Thereafter, the hydrophilic polymers used in Examples and Comparative Examples were synthesized by the same method as described above and used for evaluation. The hydrophilic polymers, curing catalysts, crosslinking agents, surfactants and other additives used in the examples and comparative examples are shown below.

(Curing catalyst)
Catalyst (1): Titanium (di-i-propoxide) bis (acetylacetonate) (manufactured by Wako Pure Chemical Industries, Ltd.)
Catalyst (2): Aluminum acetylacetonate (manufactured by Wako Pure Chemical Industries, Ltd.)
Catalyst (3): Zircozol ZA-30 (ZrO (C ₂ H ₃ O ₂ ) ₂ aqueous solution, manufactured by Daiichi Rare Elemental Chemical Co., Ltd.)

(Crosslinking agent)
Cross-linking agent (1): Tetramethoxysilane (Wako Pure Chemical Industries, Ltd.)
Crosslinking agent (2): 3-aminopropyltrimethoxysilane (ALDRICH)
(Surfactant):

(Other additives)
Latex (1): Nipol LX421 (manufactured by Nippon Zeon Co., Ltd.)
Cellulose fiber (1): Dispersed bleached hardwood kraft pulp in an aqueous solution in which 2,2,6,6-tetramethyl-1-piperidine-N-oxyl and NaBr are dissolved, and an aqueous NaClO solution and NaOH are added to adjust the pH to 10 To obtain a cellulose dispersion (width: 3 nm to 5 nm, length: 2 μm to 3 μm).
Cellulose fiber (2): A bacterial cellulose dispersion was prepared with reference to Japanese Patent Application Laid-Open No. 2005-60680 (width: 30 nm to 60 nm, length: 1 μm to 100 μm).
Cellulose fiber (3): Serisch FD-100G (manufactured by Daicel Chemical Industries, Ltd., width: 10 nm to 100 nm, length: about 100 μm)

[Evaluation of hydrophilic member]
(Elastic modulus)
The measurement was performed using a Belkovic indenter, and the indentation depth hm at the maximum load Pa was set to 1/10 of the film thickness of the hydrophilic layer. Film hardness meter: Fischer scope HM500 (manufactured by Fischer Instruments Co., Ltd.) was used to measure 10 points each for loading time: 10 s and unloading time: 10 s.

(Swell rate)
The film thickness in a dry state and a wet state was calculated using ellipsometry, and the swelling ratio was calculated by the following formula.
Swelling rate (%) = (wet film thickness-dry film thickness) / (dry film thickness) × 100
The dry film thickness was measured at room temperature of 20 ° C. and humidity of 50 RH%, and the wet film thickness was measured after being immersed in pure water for 10 minutes.
The measurement was performed at three points using a spectroscopic ellipsometry M-2000U (manufactured by JA Woollam Co., Ltd.), and the average value was taken.

(Contact angle)
The aerial water droplet contact angle (θ) at 20 ° C. was measured three times, and the average was taken as the value of the water droplet contact angle (measured with DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.).

(Pencil hardness: dry scratch resistance)
A test (tested with a pencil scratch hardness tester 553-M manufactured by Yasuda Seiki Seisakusho) was performed in accordance with JIS K 5400.

(Water rub resistance: wet scratch resistance)
Abrasion test: After the coating film was reciprocated 1000 times, 3000 times, 5000 times, and 15000 times with a 500 g load with a non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fibers Co., Ltd.) containing water, it was visually checked for scratches as follows. Evaluated.
◎◎: No damage after 15000 round trips ◎: No damage after 5000 round trips, 15000 round trips
◯: Not damaged at 3000 round trips, damaged at 5000 round trips △: Not damaged at 1000 round trips, damaged at 3000 round trips ×: Damaged at 1000 round trips

(Flexibility)
The coating solution was applied to an aluminum plate so that the coating film thickness was 0.3 mm, and dried at 150 ° C. for 30 minutes. This sample was tested according to JIS K5600-5-1 and evaluated visually as follows. A mandrel having a diameter of 2 mm was used.
◎: White turbidity, no cracks ○: White turbidity occurs ×: Cracks occur

(Anti-fouling property)
A slurry is prepared by suspending 5 g of carbon black (FW-200, manufactured by Dexa) in 95 g of water, spray-coated on the surface of the hydrophilic member so that the whole is uniform, and then dried at 60 ° C. for 1 hour. It was. The sample was washed with gauze, washed with gauze, and the carbon black after being dried was measured for lightness difference (ΔL) (using MINOLTA spectrophotometer CM2600d) and evaluated as follows. . The smaller the absolute value of the ΔL value, the less the change in brightness and the better the antifouling property.
A: Absolute value of ΔL is less than 0.5 ○: Absolute value of ΔL is 0.5 or more to less than 1 Δ: Absolute value of ΔL is 1 or more to less than 2 ×: Absolute value of ΔL is 2 or more

  The evaluation results according to the evaluation method are shown in Table 1.

The hydrophilic members of Examples 1 to 27 can be said to be hydrophilic members excellent in dry scratch resistance, wet scratch resistance, flexibility, and antifouling properties.
By comparing Examples 4 and 17 with other examples, it can be seen that dry scratch resistance is improved when the elastic modulus of the hydrophilic layer is low and the flexibility is high.
Moreover, it turns out that it is excellent in antifouling property, so that the water droplet contact angle of a hydrophilic layer is small and hydrophilicity is high from the comparison with Example 4, 17, 23, 27 and another Example.
Furthermore, from the comparison between Examples 10 and 15 and other examples, the hydrophilic polymer containing the structure represented by the general formula (I) in the hydrophilic composition and the structure represented by the general formula (II) It turns out that dry scratch resistance improves by using together with the hydrophilic polymer to contain.
Since Comparative Example 1 is brittle and has low hydrophilicity, it is inferior in dry scratch resistance, flexibility, and antifouling properties. Comparative Examples 2 and 3 are poor in antifouling property and wet scratch resistance because of low hydrophilicity and high swelling rate. Since Comparative Example 4 is too soft and has low hydrophilicity, it is inferior in dry scratch resistance and antifouling properties. Since Comparative Example 5 is brittle and has low hydrophilicity, it is inferior in dry scratch resistance, flexibility, and antifouling properties.
By contrast with Examples 1-11 and Examples 12-15, it turns out that wet flaw resistance improves further by adding a cellulose fiber.

Claims (10)

A hydrophilic member having at least a hydrophilic layer on a substrate, wherein the hydrophilic layer contains 30 mol% or more of a structural unit containing a hydrophilic group in one molecule and contains a hydrolyzable silyl group It is formed from a composition containing a polymer, the swelling ratio of the hydrophilic layer is 10 to 100%, the elastic modulus is 50 to 2000 kgf / mm ² , and the water droplet contact angle at 20 ° C. is 20 ° or less. A hydrophilic member.   The hydrophilic member according to claim 1, wherein the water droplet contact angle is 15 ° or less.   The hydrophilic member according to claim 1 or 2, wherein the swelling ratio is 20 to 60%. The hydrophilic member according to claim 1, wherein the elastic modulus is 90 to 1500 kgf / mm ² . The hydrophilic polymer containing 30 mol% or more of structural units containing a hydrophilic group in one molecule and containing a hydrolyzable silyl group contains a structure represented by the following general formula (II): Item 5. The hydrophilic member according to any one of Items 1 to 4.

{In the general formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and X represents a hydrolyzable silyl group represented by the following general formula (a). L ² and L ³ each independently represent a single bond or a linking group, and Y represents —NHCOR, —CONH ₂ , —N (R) ₂ , —CON (R) ₂ , —COR, —OH, —CO _{2 M, -SO 3 M, -PO} 3 M, -OPO 3 M, - (CH 2 CH 2 O) n H, - (CH 2 CH 2 O) represents the n CH ₃ or n _(R) 3 ^{Z 1} Here, R represents an alkyl group, an aryl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or onium, n represents an integer, and Z ¹ represents a halogen ion. When a plurality of R are present, they may be the same as or different from each other. }
General formula (a): -Si (R < ¹⁰² >) _a- (OR <^101> ) _3-a
{In General Formula (a), R ¹⁰¹ is a hydrogen atom or an alkyl group, R ¹⁰² is a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group, an aryl group and an aralkyl group, and a is an integer of 0 to 2. . When a plurality of R ¹⁰¹ or R ¹⁰² are present, they may be the same as or different from each other. }   The hydrophilic member according to claim 1, wherein the hydrophilic layer further contains fibers having a width of 3 nm to 1000 nm and a length of 0.1 μm to 100 μm.   The hydrophilic member according to claim 6, wherein the fiber is made of cellulose.   The hydrophilic layer is formed through a heat drying step, the heating temperature in the heat drying step is 80 to 160 ° C, and the heating time is 10 minutes to 8 hours. The hydrophilic member in any one of -7.   The hydrophilic member according to claim 1, wherein the composition further contains a curing catalyst.   The hydrophilic member according to claim 9, wherein the curing catalyst is a metal complex catalyst.