WO2010076872A1

WO2010076872A1 - Hydrophilic member and method for producing fin material for heat exchangers

Info

Publication number: WO2010076872A1
Application number: PCT/JP2009/071262
Authority: WO
Inventors: 誠福田; 智史田中
Original assignee: 富士フイルム株式会社
Priority date: 2009-01-05
Filing date: 2009-12-21
Publication date: 2010-07-08
Also published as: JP2010155441A

Abstract

Disclosed is a hydrophilic member having excellent hydrophilicity, antifouling properties, lubricity, adhesion and anti-rust properties. Also disclosed is a method for producing a fin material for heat exchangers having excellent hydrophilicity, antifouling properties, lubricity, adhesion and anti-rust properties. The hydrophilic member is characterized in that a hydrophilic layer, which is formed from a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group, is provided on a base, and a lubricating layer having a friction coefficient of 0.05-0.25 is provided on the hydrophilic layer. The method for producing a fin material for heat exchangers is characterized in that the surface of a fin material for heat exchangers, which has a hydrophilic layer that is formed by coating an aluminum plate surface with a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group, and then drying the coating thereon, is coated with a lubricant composition and then the coating is dried thereon, so that the lubricant composition is adsorbed on or impregnated into the hydrophilic layer, thereby forming a lubricating layer having a friction coefficient of 0.05-0.25.

Description

Method for producing hydrophilic member and fin material for heat exchanger

The present invention is a hydrophilic member excellent in hydrophilicity, antifouling properties, friction resistance, adhesion, and rust prevention, and heat exchange excellent in hydrophilicity, antifouling properties, friction resistance, adhesion, and rust prevention properties. The present invention relates to a method for manufacturing a device fin material.

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

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

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

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

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

Moreover, the heat exchanger of an air conditioner is mentioned as a use of a hydrophilic member. A heat exchanger of an air conditioner includes a pipe that moves a heat medium and fins that absorb heat in the air or dissipate heat in the heat medium. In a room air conditioner, a copper pipe is used by penetrating a thin plate aluminum of about 0.1 mm, which is a fin material. In the fin material, the condensed water generated at the time of cooling becomes water droplets and stays between the fins, so that a bridge of water is generated and the cooling capacity is lowered. In addition, the adhering of dust or the like between the fins similarly reduces the cooling capacity.
In order to solve these problems, it is known to treat the surface of the fin material of the heat exchanger with a hydrophilic composition (see, for example, Patent Documents 9 to 11).
As a heat exchanger treated with a hydrophilic composition, for example, Patent Document 12 is known.

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

Also, when processing the hydrophilic member into a heat exchanger or the like, there is a problem that the die of the press machine is worn if the friction coefficient of the member is high. In order to solve this problem, a structure in which a lubricating layer is provided on a hydrophilic layer of a hydrophilic member has been proposed (see, for example, Patent Documents 7 and 8).

However, in addition to hydrophilicity, further improvements in lubricity, antifouling properties, adhesion, and rust resistance are desired.

Japanese Laid-Open Patent Publication No. 64-86101 Japanese Laid-Open Patent Publication No. 4-338901 Japanese Patent Publication No. 6-29332 Japanese Unexamined Patent Publication No. 7-16940 International Publication No. 96/29375 Japanese Unexamined Patent Publication No. 2007-254265 Japanese Unexamined Patent Publication No. 6-39347 Japanese Laid-Open Patent Publication No. 9-14888 Japanese Unexamined Patent Publication No. 2003-201577 Japanese Unexamined Patent Publication No. 2005-232269 Japanese Unexamined Patent Publication No. 2005-75841 Japanese Unexamined Patent Publication No. 2007-225174

The object of the present invention is to solve the above-mentioned problems of the prior art, hydrophilic members excellent in hydrophilicity, antifouling properties, lubricity, adhesion, and rust prevention, and hydrophilic properties, antifouling properties, lubricity, adhesion It is providing the manufacturing method of the fin material for heat exchangers excellent in property and rust prevention property.

The present invention is as follows.

[1]
A lubricating layer having a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on a substrate, and having a friction coefficient of 0.05 to 0.25 on the hydrophilic layer. A hydrophilic member characterized by comprising:
[2]
The hydrophilic member according to [1], wherein a water droplet contact angle of the hydrophilic member is 20 ° or less.
[3]
The hydrophilic member according to [1] or [2], wherein the lubricating layer is a lubricating layer containing at least one type of lubricant selected from the group consisting of polyethylene glycol and polypropylene glycol .
[4]
The hydrophilic member according to [3], wherein the polyethylene glycol and the polypropylene glycol have a mass average molecular weight of 1000 to 4000.
[5]
The hydrophilic member according to any one of [1] to [4], wherein the lubricating layer has a thickness of 0.01 to 0.3 μm.
[6]
The hydrophilic layer contains 50 mass of the hydrophilic polymer (I) containing the structure represented by the following general formula (I-1) and the structure represented by the following general formula (I-2) with respect to the total solid content. The hydrophilic member according to any one of [1] to [5], which is obtained by applying and drying a hydrophilic composition containing at least%.

In the general formulas (I-1) and (I-2), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ^{101 and} L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

[7]
The hydrophilic composition contains a hydrolyzable silyl group-containing hydrophilic polymer containing the hydrophilic polymer (I) in an amount of 80% by mass or more based on the total solid content, and in the general formula (I-2) A ¹⁰¹ represents —CONH ₂ , —CONH (R ⁵ ), or —CON (R ⁵ ) ₂ (wherein R ⁵ independently represents a linear, branched, or cyclic alkyl group). The hydrophilic member according to [6], which is characterized.
[8]
The hydrophilic member according to any one of [1] to [7], wherein the substrate is an aluminum plate.
[9]
[1] A fin material using the hydrophilic member according to any one of [8].
[10]
The aluminum fin material whose fin material as described in [9] is a product made from aluminum.
[11]
[10] A heat exchanger using the aluminum fin material according to [10].
[12]
An air conditioner using the heat exchanger according to [11].
[13]
A lubricant composition is applied to the surface of a fin material for a heat exchanger having a hydrophilic layer formed by applying a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group to the surface of an aluminum plate and drying. A method for producing a fin material for a heat exchanger, comprising applying and drying to adsorb or impregnate a lubricant composition in a hydrophilic layer to form a lubricating layer having a friction coefficient of 0.05 to 0.25 .
[14]
The method for producing a fin material for a heat exchanger as described in [13], wherein the drying temperature of the hydrophilic composition and the lubricant composition is independently 130 to 230 ° C.

According to the present invention, a hydrophilic member excellent in hydrophilicity, antifouling property, lubricity, adhesion, and rust prevention and a heat exchanger excellent in hydrophilicity, antifouling property, friction resistance, adhesion, and rust prevention property The manufacturing method of a fin material can be provided.

Hereinafter, the present invention will be described in detail.
The hydrophilic member of the present invention has a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on a substrate, and further has a friction coefficient of 0.05. Having a lubricating layer of ~ 0.25.
The water droplet contact angle of the hydrophilic member is preferably 20 ° or less, preferably 15 ° or less, more preferably 10 ° or less. It is preferable that the water droplet contact angle is 20 ° or less because excellent hydrophilicity can be exhibited.

[Hydrophilic composition]
The hydrophilic layer can be formed by applying and drying a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group.

The hydrophilic polymer having a hydrolyzable silyl group is a hydrophilic polymer (I) having a structure represented by the following general formula (I-1) and a structure represented by the following general formula (I-2). Is preferred.

In the general formulas (I-1) and (I-2), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In addition to being able to maintain high hydrophilicity by using a hydrophilic polymer (I) containing an alkoxysilyl group that forms a hydrophilic structure and a crosslinked structure, such as polyacrylamide, as a composition that imparts hydrophilicity, hydrophilicity can be maintained. This is presumably because the water adhering to the hydrophilic surface does not dissolve out the hydrophilic layer and has excellent long-term water resistance.

[Hydrophilic polymer (I) including structure represented by general formula (I-1) and structure represented by general formula (I-2)]

In the general formulas (I-1) and (I-2), R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each represents a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In the general formulas (I-1) and (I-2), R ¹⁰¹ to R ¹⁰⁸ each independently represents 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 ¹⁰¹ to R ¹⁰⁸ 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, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, アルキル -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-reelcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N ′ Alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureate group, N', N'-dialkyl- N-arylureido group, N′-aryl-Ν-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl- N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group,

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfa Yl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphono group _(-PO 3 _(alkyl) 2), diaryl phosphono group _(-PO 3 _(aryl) 2), alkyl aryl phosphono group (- PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (Aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) And its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphine group Phonooxy group (—OPO (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphono Examples thereof include an oxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), a morpholino group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

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

Of these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-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, the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Preferably, it is a straight chain having 1 to 12 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms, more preferably a branched structure having 3 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms, and More preferable examples include cyclic alkylene groups having 5 to 10 carbon atoms, and further preferably 5 to 8 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group are chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, hydroxymethyl group, methoxymethyl group, methoxyethoxy group. Ethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonyl group Group, allyloxycarbonyl butyl group,

Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoyl Methyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Thrill Suphonatohexyl 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.

Among the above, a hydroxymethyl group is preferable from the viewpoint of hydrophilicity.

L ¹⁰¹ to L ¹⁰² each represents a single bond or an organic linking group. Here, the single bond means that the main chain of the polymer and A ¹⁰¹ or Si atom are directly bonded without a connecting chain.
When L ¹⁰¹ to L ¹⁰² represent an organic linking group, L ¹⁰¹ to L ¹⁰² represent a polyvalent linking group composed of a nonmetallic atom, including 0 to 60 carbon atoms and 0 to 10 nitrogen atoms. It consists of atoms, 0 to 50 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Specifically, it is preferably selected from —N <, an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof, —O—, —S—, —CO—, —NH—, or A combination containing —O— or —S— or —CO— or —NH— is preferably a divalent linking group.
More specific examples of the linking group include the following structural units or those formed by combining them.

In the general formula (I-1), L ¹⁰¹ is a single bond or one structure selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. A linking group having the above is preferable.

In general formula (I-2), A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ). , —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , -NHSO ₂ R _d , -SO ₂ N (R _a ) (R _b ), -N (R _a ) (R _b ) (R _c ), -N (R _a ) (R _b ) (R _c ) ( _{_{_{_{R g), - PO 3 (}}}} R e) (R f), - OPO 3 (R e) (R f), or _-PO 3 represents an _{_{(R d) (R e)}} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R _d is a linear, branched or cyclic group. R _e and R _f are each independently a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 8), an alkali metal, It represents an alkaline earth metal or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. In addition, —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) R _a to R _g may be bonded to each other to form a ring for (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ) The formed ring may be a heterocycle containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. R _a to R _g may further have a substituent, and the substituents that can be introduced here are the same as the substituents that can be introduced when R ¹ to R ⁸ are alkyl groups. Can be listed.
A ¹⁰¹ is preferably —CONH ₂ , —CONH (R ⁵ ), or —CON (R ⁵ ) ₂ . In the formula, R ⁵ represents a linear, branched or cyclic alkyl group.

In R _a to R _f and R ⁵ , the linear, branched or cyclic alkyl group specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. And 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, and cyclopentyl group. .
In addition, in R _a to R _g , preferable examples of the alkali metal include lithium, sodium, and potassium, the alkaline earth metal includes barium, and the onium includes ammonium, iodonium, sulfonium, and the like.
Examples of the halogen ion include fluorine ion, chlorine ion, bromine ion, inorganic anion includes nitrate anion, sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion, etc., organic anion includes methanesulfonate anion, Preferable examples include trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, p-toluenesulfonate anion and the like.

The A ^101, _{_{specifically, -NHCOCH 3, -CONH 2, -CON}} (CH 3) 2, -COOH, -SO 3 - NMe 4 +, -SO 3 - K +, - (CH 2 CH 2 O) _n H, morpholyl group and the like are preferable. More preferred are —NHCOCH ₃ , —CONH ₂ , —CON (CH ₃ ) ₂ , —SO ₃ ⁻ K ⁺ , — (CH ₂ CH ₂ O) _n H. In the above, n preferably represents an integer of 1 to 100.

P represents an integer of 1 to 3, preferably 2 to 3, more preferably 3.

In the hydrophilic polymer (I) having the structure represented by the general formulas (I-1) and (I-2), x and y are represented by the general formula (I-1) in the hydrophilic polymer (I). Represents the composition ratio of the structural unit represented by formula (I-2). x is 0 <x <100, and y is 0 <y <100. x is preferably in the range of 1 <x <90, and more preferably in the range of 1 <x <50. y is preferably in the range of 10 <y <99, and more preferably in the range of 50 <y <99.

The copolymerization ratio of the hydrophilic polymer (I) having a structure represented by the general formulas (I-1) and (I-2) is such that the amount of the general formula (I-2) having a hydrophilic group is within the above range. Can be set arbitrarily. Preferably, the molar ratio (y) of the structural units of the general formula (I-2) and the molar ratio (x) of the structural units of the general formula (I-1) having a hydrolyzable silyl group amount are y / x = The range of 30/70 to 99/1 is preferable, y / x = 40/60 to 98/2 is more preferable, and y / x = 50/50 to 97/3 is most preferable. If y / x is 30/70 or more, the hydrophilicity is not insufficient. On the other hand, if y / x = 99/1 or less, the hydrolyzable silyl group amount is sufficient and sufficient curing is obtained. The film strength is also sufficient.

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

Specific examples of the hydrophilic polymer (I) containing the structures represented by the general formulas (I-1) and (I-2) are shown below together with their mass average molecular weights (MW). The invention is not limited to these examples. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or block copolymer contained in the described molar ratio.

Each compound for synthesizing the hydrophilic polymer (I) having a structure represented by the general formulas (I-1) and (I-2) is commercially available or can be easily synthesized.
As the radical polymerization method for synthesizing the hydrophilic polymer (I) having the structure represented by the general formulas (I-1) and (I-2), any of conventionally known methods can be used. .
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 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.

In the hydrophilic composition, a hydrophilic polymer (II) having a structure represented by the following general formulas (II-1) and (II-2) may be used in combination with the hydrophilic polymer (I).

[Hydrophilic polymer (II) including structures represented by general formulas (II-1) and (II-2)]

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

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

In the general formulas (II-1) and (II-2), R ²⁰¹ to R ²⁰⁵ each independently represents a hydrogen atom or a hydrocarbon group, and hydrocarbons in the case where R ²⁰¹ to R ²⁰⁵ represent a hydrocarbon group. Examples of the group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, the same compounds as those described for R ¹⁰¹ to R ¹⁰⁸ in the general formulas (I-1) and (I-2) can be given.
L ²⁰¹ and L ²⁰² each independently represents a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer is directly bonded to the A ²⁰¹ and Si atoms without a connecting chain. When L ²⁰¹ and L ²⁰² each represent a polyvalent organic linking group, specific examples and preferred examples thereof may be the same as those described for L ¹⁰¹ in the general formula (I-1).
A ²⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Specific examples and preferred examples of A ²⁰¹ include the same examples as those described for A ¹⁰¹ in formula (I-2).
q represents an integer of 1 to 3. Preferably it is 2 to 3, more preferably 3.

L ²⁰¹ and L ²⁰² are more preferably —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ —, —CH ₂ —.

The hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2) is, for example, a chain transfer agent (radical polymerization handbook (NTS, Mikiji Tsunoike, Takeshi Endo) In the presence of Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)) by radical polymerization of a hydrophilic monomer (eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate). Can be synthesized. 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 (II) having a structure represented by the general formulas (II-1) and (II-2) includes a radical polymerizable monomer represented by the following general formula (i) and a general formula (ii) ) Can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.

In the general formulas (i) and (ii), R ²⁰¹ to R ²⁰⁵ , L ²⁰¹ , L ²⁰² , A ²⁰¹ , and q have the same meanings as those in the general formula (II-1). These compounds are commercially available and can also be easily synthesized. The radically polymerizable monomer represented by the general formula (i) has a hydrophilic group ^A201 , and this monomer becomes one structural unit in the hydrophilic polymer.

In the hydrophilic polymer (II) containing the structures represented by the general formulas (II-1) and (II-2), the number of moles of the structural unit of the general formula (II-1) having a hydrolyzable silyl group amount On the other hand, the number of moles of the structural unit of the general formula (II-2) is preferably in the range of 1000 to 10 times, more preferably in the range of 500 to 20 times, and most preferably in the range of 200 to 30 times. If it is 30 times or more, the hydrophilicity is not insufficient. On the other hand, if it is 200 times or less, the amount of hydrolyzable silyl groups is sufficient, sufficient curing is obtained, and the film strength is also sufficient.

The mass average molecular weight of the hydrophilic polymer (II) having a structure represented by the general formulas (II-1) and (II-2) is preferably 1,000 to 1,000,000, and 1,000 to 500,000. 000 is more preferable, and 1,000 to 200,000 is most preferable.

Specific examples of the hydrophilic polymer (II) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. In specific examples, * represents a bonding position to the polymer.

In the hydrophilic composition, when the hydrophilic polymer (I) and the hydrophilic polymer (II) are used in combination, the ratio (mass ratio) of the hydrophilic polymer (I) / hydrophilic polymer (II) is preferably 5/95. Is in the range of ˜95 / 5, more preferably in the range of 40/60 to 95/5, and most preferably in the range of 60/40 to 90/10.

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

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

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

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

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

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

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

The measurement of the copolymerization ratio of the hydrophilic polymer (I) can be carried out by preparing a calibration curve with a nuclear magnetic resonance apparatus (NMR) or a standard substance and measuring with an infrared spectrophotometer.

The hydrophilic composition in this invention can use hydrophilic polymer (I) individually or in mixture of 2 or more types.
From the viewpoint of curability and hydrophilicity, the hydrophilic polymer (I) is preferably used in an amount of 20 to 99.5% by mass, preferably 30 to 99.5% by mass, based on the total solid content of the hydrophilic composition. More preferably.

The hydrophilic composition comprises 50% by mass or more of the hydrophilic polymer (I) containing the structure represented by the general formula (I-1) and the structure represented by the general formula (I-2) based on the total solid content. It is preferable to contain.

The hydrophilic composition contains a hydrolyzable silyl group-containing hydrophilic polymer containing the hydrophilic polymer (1) in an amount of 80% by mass or more based on the total solid content, and A in the general formula (I-2) ¹⁰¹ preferably represents —CONH ₂ , —CONH (R ⁵ ), or —CON (R ⁵ ) ₂ (wherein R ⁵ independently represents a linear, branched or cyclic alkyl group). .

The above-mentioned hydrophilic polymer (I) forms a crosslinked film in a state of being mixed with a hydrolyzed and polycondensed product of metal alkoxide. The hydrophilic polymer (I), which is an organic component, is involved in film strength and film flexibility. In particular, the viscosity of the hydrophilic polymer (I) is 0.1 to 100 mPa · s (5% aqueous solution, 20% When the temperature is in the range of 0.5 to 70 mPa · s, more preferably 1 to 50 mPa · s, good film properties can be obtained.

[Crosslinking agent]
When the hydrophilic composition contains the hydrophilic polymer (II), it is preferable to contain a crosslinking agent in order to obtain good curability. In addition, in the case where the hydrophilic composition (I) is contained in the hydrophilic composition, good curability can be obtained even when the crosslinking agent is not contained, but in order to obtain a coating film having extremely excellent film strength. May contain a crosslinking agent.

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. A strong cross-linked film can be formed and further chemically bonded to the hydrophilic polymer. The metal alkoxide can be represented by general formula (V-1) or general formula (V-2), in which R ²⁰ represents a hydrogen atom, an alkyl group or an aryl group, and R ²¹ and R ²² represent an alkyl group or Represents an aryl group, Z represents Si, Ti or Zr, and m represents an integer of 0-2. When R ²⁰ and R ²¹ represent an alkyl group, the carbon number is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group. This compound is a low molecular compound and preferably has a molecular weight of 2000 or less.

(R ²⁰ ) _m -Z- (OR ²¹ ) _4-m (V-1)
Al- (OR ²² ) ₃ (V-2)

Specific examples of the metal alkoxide 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.
Further, when the central metal is Al, that is, examples of those containing aluminum in the hydrolyzable compound include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, triisopropoxy aluminate, and the like. be able to.

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

The metal alkoxide compound selected from Si, Ti, Zr, and Al is preferably used in an amount of 0 to 80% by mass based on the total solid content of the hydrophilic composition when the hydrophilic polymer (I) is used. More preferably, 0 to 70% by mass is used. When the hydrophilic polymer (II) is used, it is preferably used in an amount of 0 to 80% by weight, more preferably 0 to 70% by weight, based on the total solid content of the hydrophilic composition.

〔catalyst〕
In the hydrophilic composition of the present invention, preferably, the hydrophilic polymer (I), more preferably the hydrophilic polymer (II), a crosslinking agent such as a crosslinking agent, is dissolved in a solvent and stirred well, These components are hydrolyzed and polycondensed to form an organic-inorganic composite sol solution, and this sol solution forms a hydrophilic film having high hydrophilicity and high film strength. In the preparation of the organic-inorganic composite sol solution, it is preferable to use a catalyst in order to promote hydrolysis and polycondensation reaction. By using a catalyst, the drying temperature for forming the hydrophilic layer can be set low, and thermal deformation on the substrate can be suppressed.

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

The type of acidic catalyst or basic catalyst is not particularly limited. However, when it is necessary to use a highly concentrated catalyst, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RCOOH. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline, and the like. Etc.

In addition to the above catalyst, a Lewis acid catalyst comprising a metal complex can also be preferably used. Particularly preferred catalysts are metal complex catalysts, metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, enolic active hydrogen compounds It is a metal complex comprised from the oxo or hydroxy oxygen containing compound chosen from these.
Among constituent metal elements, 2A group elements such as Mg, Ca, Sr and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a β-diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetate Ketoesters such as ethyl and butylacetoacetate, 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, diethanolamine Amino alcohols such as ethanol, triethanolamine, enol active compounds such as methylol melamine, methylol urea, methylol acrylamide, diethyl malonate, 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 straight-chain or branched alkyl groups having 1 to 3 carbon atoms, acyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxy groups, alkoxyalkyl groups, and acetylacetone The substituents that substitute for the methylene group are carboxyl groups, both straight-chain or branched carboxyalkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms, and the substituents that substitute for the carbonyl carbon of acetylacetone are carbon atoms. Is an alkyl group of 1 to 3, in which case a hydrogen atom is added to the carbonyl oxygen to form a hydroxyl group.

Specific examples of preferred acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid Acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol.
Of these, acetylacetone and diacetylacetone are particularly preferred. The complex of the above acetylacetone derivative and the above metal element is a mononuclear complex in which 1 to 4 molecules of the acetylacetone derivative are coordinated per metal element, and the coordinateable bond of the acetylacetone derivative is the coordinateable bond of the metal element. 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. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, and among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

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

The catalyst is preferably used in the range of 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the total solid content in the hydrophilic composition of the present invention. Moreover, a catalyst may be used independently or may be used together 2 or more types.

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

(Surfactant)
In the present invention, a surfactant is preferably used in order to improve the surface state of the hydrophilic composition and the undercoat layer composition. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a fluorine surfactant.

The nonionic surfactant used in the present invention is not particularly limited, and conventionally known nonionic surfactants 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 Oxyethylenepropyl sulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

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

More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. In addition, fluorine-based surfactants described in JP-A Nos. 62-170950, 62-226143, and 60-168144 are also preferred.
The surfactant is used in the hydrophilic composition of the present invention in an amount of preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content. Moreover, surfactant can be used individually or in combination of 2 or more types.

Specific examples of preferable surfactants are shown below, but the present invention is not limited thereto.

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

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

(Antioxidant)
In order to improve the stability of the hydrophilic member of the present invention, an antioxidant can be added to the hydrophilic composition. Examples of the antioxidant include European Published Patent No. 223739, No. 309401, No. 309402, No. 310551, No. 310552, No. 4594416, German Published Patent No. 3435443. JP, 54-85535, 62-262447, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
The addition amount is appropriately selected according to the purpose, but is preferably 0.1 to 8% by mass in terms of solid content.

(Polymer compound)
In order to adjust the film properties of the hydrophilic layer, various polymer compounds can be added to the hydrophilic composition of the present invention as long as the hydrophilicity is not inhibited. High molecular compounds include acrylic polymer, polyvinyl alcohol resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin, rubber resin 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 “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.

[Hydrophilic member]
The hydrophilic member in this invention has a hydrophilic layer formed with the said hydrophilic composition on the base material chosen from acrylic, polycarbonate, polyester, stainless steel, aluminum, etc., for example.
The hydrophilic member of the present invention has a hydrophilic layer formed by coating a hydrophilic composition on a substrate, and the hydrophilic composition is the hydrophilic composition described above. It is possible to provide a hydrophilic member that has excellent hydrophilicity, friction resistance, antifouling property, and adhesion and can maintain excellent lubricity for a long period of time.
The hydrophilic member of the present invention may further have an undercoat layer between the base material and the hydrophilic layer in order to improve the adhesion between the base material and the hydrophilic layer.
Here, the undercoat layer is preferably formed by applying the above-described composition containing the catalyst, thereby further improving the adhesion between the substrate and the hydrophilic layer. Can do. Here, the catalyst is preferably a non-volatile catalyst as described above.
The catalyst is used in the composition for an undercoat layer in an amount of preferably 0 to 50% by mass, more preferably 1 to 25% by mass, based on the total solid content. Moreover, a catalyst may be used independently or may be used together 2 or more types.

In addition, the undercoat layer is preferably formed by applying a composition containing the above-described crosslinking agent, and thereby, more reliably, adhesion between the substrate and the hydrophilic layer. Can be improved.
The crosslinking agent is preferably used in the range of 5 to 99% by mass, more preferably 10 to 95% by mass, based on the total solid content in the composition for the undercoat layer. Moreover, a crosslinking agent may be used independently or may be used together 2 or more types.

The hydrophilic composition and the composition for the undercoat layer may contain zirconia chloride, nitrate, alkoxide, and organic complex from the viewpoints of wear resistance, acid resistance, and alkali resistance. Examples of the zirconia chloride include zirconium chloride, zirconium oxychloride (octahydrate), chlorine-containing zirconium alkoxide Zr (OC _m H _{2m + 1} ) _x Cl _y (m, x, y: integer, x + y = 4). Examples of the zirconium nitrate include zirconium oxynitrate (dihydrate). Examples of the zirconium alkoxide include zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, zirconium butoxide, zirconium t-butoxide and the like. Examples of the organic complex include acetylacetone derivatives. Specifically, tetrakis (acetylacetonato) zirconium, bis (acetylacetonato) zirconium dibutoxide, bis (acetylacetonato) zirconium dichloride, Trakis (3,5-heptanedionate) zirconium, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate) zirconium, bis (2,2,6,6-tetramethyl-3, 5-heptanedionate) zirconium diisopropoxide and the like.
The zirconium compound is preferably used in the range of 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the total solid content in the hydrophilic composition and the composition for the undercoat layer of the present invention. .
A hydrophilic layer can be formed by applying such a hydrophilic composition onto a suitable substrate and drying. That is, the hydrophilic member of the present invention has a hydrophilic layer formed by applying a hydrophilic composition on a substrate, heating and drying. The hydrophilic member of the present invention comprises a hydrophilic polymer (I) having a structure in which the hydrophilic layer is represented by the general formula (I-1) and the structure represented by the general formula (I-2). It is preferably obtained by applying and drying a hydrophilic substance containing 50% by mass or more with respect to the minute.
In the formation of the hydrophilic layer, as the heating and drying conditions after applying the hydrophilic composition, the drying temperature is preferably 100 to 230 ° C. from the viewpoint of efficiently forming a high-density crosslinked structure, More preferably, the temperature is 130 to 200 ° C. When the drying temperature is low, sufficient crosslinking reaction does not proceed and the strength of the coating film is lowered. When the temperature is too high, the coating film is liable to crack, and the antifogging property is partially insufficient. The drying time is preferably 5 seconds to 1 hour. More preferably, it is 10 seconds to 30 minutes. If the drying time is short, the coating strength may be lowered due to insufficient drying. If the drying time is excessively longer than necessary, the substrate may deteriorate.

The hydrophilic member of the present invention can be prepared by a known coating 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. Methods such as screen printing, bar coater, brush coating, and sponge coating can be applied.

The center line average roughness Ra of the surface of the hydrophilic layer is preferably 10 nm to 100 nm.
The Tg of the hydrophilic layer is preferably 40 ° C. to 150 ° C. from the viewpoint of coating film strength. The elastic modulus of the hydrophilic layer is preferably 1 GPa to 7 GPa.
The surface property of the hydrophilic layer adjusts the particle size and content of the inorganic fine particles used, the surface roughness of the substrate itself, the viscosity of the hydrophilic composition, the heating temperature of the hydrophilic layer, the speed, and the like. However, the present invention is not limited to this.

An intermediate layer may be provided between the base material and the hydrophilic layer as necessary for improving adhesion.
For example, when the substrate is an aluminum plate, an intermediate layer may be provided between the aluminum plate and the hydrophilic layer for the purpose of improving the anticorrosion property and adhesion to the substrate. The intermediate layer is not particularly limited. Hydrophilic layers having different compositions may be provided, or a known anticorrosion layer represented by a chromate system may be provided.

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

Preparation of hydrophilic composition The hydrophilic composition was prepared by dissolving a hydrophilic polymer having a hydrolyzable silyl group, a crosslinking agent, a catalyst, a surfactant and a specific alkoxide in a solvent such as ethanol and then stirring. Can be implemented. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time during which stirring is continued is preferably in the range of 1 to 72 hours. A composite sol solution can be obtained.

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

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

(Lubricating layer)
The lubricating layer in the present invention has a friction coefficient of 0.05 to 0 provided on a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on a substrate. .25 is a lubricating layer. The friction coefficient of the lubricating layer is preferably 0.06 to 0.24, and more preferably 0.08 to 0.22.
The coefficient of friction is not particularly limited, but can be measured by a known method using a Bowden-Leven type friction tester.
The lubricant layer can be formed of a lubricant composition. The lubricant contained in the lubricant composition includes nonionic hydrophilic properties such as polyethylene glycol (PEG) and polypropylene glycol (PPG), or copolymers thereof. A polymer or a surfactant can be mentioned, and preferably polyethylene glycol (PEG) or polypropylene glycol, or a copolymer polymer thereof, more preferably polyethylene glycol or polypropylene glycol. These may be used alone or in combination.
By using polyethylene glycol or polypropylene glycol as the lubricant, it is possible to impart lubricity without impairing the hydrophilicity of the hydrophilic layer.
The molecular weight of the lubricant is preferably 200 to 10,000, more preferably 400 to 6000, and still more preferably 1000 to 4000. If it exists in this range, it is preferable from the reason that the lubricity robustness and the hydrophilic property of a hydrophilic layer are not impaired.
A commercially available lubricant may be used, and it may be synthesized by a known method. When polyethylene glycol or polypropylene glycol is used as the lubricant, it can be obtained from a commercial product.
The content of the lubricant in the lubricant composition is preferably 0.01 to 50% by mass, more preferably 0.1 to 20% by mass, and 0.5 to 10% by mass. Further preferred.

The lubricant composition preferably further contains a surfactant.
Preferred examples of the surfactant used in the lubricant composition include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorine surfactants. Is a nonionic surfactant, an anionic surfactant, or a cationic surfactant, more preferably a nonionic surfactant or an anionic surfactant. Specifically, the above-described surfactant can be used.
The content of the surfactant in the lubricant composition is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and more preferably 0.5 to 5% with respect to the hydrophilic polymer. More preferably, it is mass%.

The lubricant composition preferably further contains a solvent.
As the solvent used in the lubricant composition, water and alcohols such as methanol, ethanol and propanol can be preferably used, and water is more preferable.
The content of the solvent in the lubricant composition is preferably 50 to 99.99% by mass, more preferably 80 to 99.9% by mass, and further preferably 90 to 99.5% by mass. preferable.

Preparation of Lubricant Composition The lubricant composition can also be prepared by the same method as the above hydrophilic composition.

The hydrophilic member of the present invention can be obtained by applying the lubricant composition of the present invention on the hydrophilic layer and drying it. That is, the hydrophilic member of the present invention is formed by applying a hydrophilic composition on a substrate, heating and drying to form a hydrophilic layer, applying a lubricant composition thereon, heating and drying. Thus, it is obtained by forming a lubricating layer.
The heating and drying conditions of the lubricant composition are preferably about 5 seconds to 1 hour in the temperature range of 100 to 230 ° C., and 10 to 10 in the temperature range of 130 to 200 ° C. from the viewpoint of decomposition and evaporation. It is more preferable to dry for 2 to 30 minutes.
Moreover, as a heating means of the lubricant composition and the hydrophilic composition, it is preferable to use a known means, for example, a dryer having a temperature adjusting function.

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

The hydrophilic member of the present invention may have an undercoat layer by applying a composition for an undercoat layer on a substrate as necessary, and heating and drying.
The heating and drying conditions for the undercoat layer composition are preferably about 2 minutes to 1 hour in the temperature range of 50 to 200 ° C. from the viewpoint of efficiently forming a high-density crosslinked structure, It is more preferable to dry in the temperature range of 160 ° C. for 5 to 30 minutes.
Moreover, as a heating means of the undercoat composition, it is preferable to use a known means, for example, a dryer having a temperature adjusting function.

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

〔Base material〕
The substrate used in the present invention is not particularly limited, but glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, tile, rubber, latex, combinations thereof, those Any laminate can be suitably used. Particularly preferred substrates are flexible flexible substrates such as plastics and metals. By using a flexible base material, it is possible to freely deform the article, and not only the degree of freedom of the attaching operation and the attaching place is increased, but also the durability can be increased.
The plastic substrate used in the present invention is not particularly limited, but the substrate used as an optical member is selected in consideration of optical characteristics such as transparency, refractive index, dispersibility, and the like, It is selected in consideration of various physical properties such as physical properties such as strength such as impact resistance and flexibility, heat resistance, weather resistance, and durability. Plastic base materials include polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, poly Examples thereof include films or sheets of sulfone, polyether ketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyether sulfone and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use. The thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having a thickness of about 6 to 50 μm is used. Further, 50 to 400 μm is used for a flat surface or where strength is required.

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

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

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

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

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

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

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

The base material used in the present invention may be a base material that has been surface-treated as described above and has an anodized film as it is. However, in order to further improve the adhesion with the upper layer, if necessary, The micropore enlargement treatment or sealing treatment of the anodized film and the surface hydrophilization treatment soaked in an aqueous solution containing a hydrophilic compound described in Japanese Patent No. 253181 and Japanese Patent Application Laid-Open No. 2001-322365 are appropriately selected. It can be carried out. Of course, the enlargement process and the sealing process are not limited to those described above, and any conventionally known method can be performed.
For example, as the sealing treatment, in addition to the vapor sealing, a single treatment with fluorinated zirconic acid, a treatment with sodium fluoride, or a vapor sealing with addition of lithium chloride is possible.

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

Sealing treatment with an aqueous solution containing an inorganic fluorine compound Preferred examples of the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound include metal fluorides.
Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluorinated titanate, fluorinated zirconic acid, fluorinated titanic acid, hexafluorosilicic acid, nickel fluoride, iron fluoride, fluorinated phosphoric acid, and ammonium fluorinated phosphate. Of these, sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.

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

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

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

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

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

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

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

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

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

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

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

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

Layer structure when using hydrophilic member When the hydrophilic member of the present invention is used in anticipation of the appearance of antifouling properties and / or antifogging effects, another layer is appropriately formed according to the purpose, form and place of use. Can be used. The layer structure added as needed is described below.

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

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

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

Form of structure The hydrophilic member having the hydrophilic layer of the present invention may be supplied in the form of a sheet, a roll or a ribbon, and may be cut in advance to be attached to an appropriate substrate. It can also be supplied.

When the hydrophilic member coated with the hydrophilic layer of the present invention is applied (used or attached) to a window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic layer of the present invention is excellent in transparency, and even when the film thickness is large, the transparency is not impaired and compatibility with durability is possible. The thickness of the hydrophilic layer of the present invention is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 20 μm. When the film thickness is 0.01 μm or more, it is preferable to obtain sufficient hydrophilicity and durability, and when the film thickness is 100 μm or less, there is no problem in film forming properties such as cracks, which is preferable.
The dry coating amount of the hydrophilic layer is preferably 0.01 g / m ² to 100 g / m ² , more preferably 0.02 g / m ² to 80 g / m ² , particularly preferably 0.05 g / m ² to 50 g / m. ^By setting it to ² , the above-mentioned film thickness can be obtained.
The thickness of the lubricating layer is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm, and most preferably 0.1 μm to 0.3 μm. When the film thickness is 0.001 μm or more, sufficient hydrophilicity and durability can be obtained, and when the film thickness is 1 μm or less, there is no problem in film forming properties such as cracking, which is preferable.
Preferably the dry coating amount of the lubricating layer is ^{0.001g / m 2 ~ 1g / m} 2, more preferably ^{0.005g / m 2 ~ 0.5g / m} 2, and most preferably 0.01g / m ² ~ 0. By setting it to 3 g / m ² , the above film thickness can be obtained.
The thickness of the undercoat layer is preferably 0.01 μm to 100 μm, more preferably 0.02 μm to 80 μm, and particularly preferably 0.05 μm to 50 μm.
The dry coating amount of the undercoat layer composition is preferably 0.01 g / m ² to 100 g / m ² , more preferably 0.02 g / m ² to 80 g / m ² , particularly preferably 0.05 g / m ² to 50 g / m ^2. with m ^2, it is possible to obtain a film thickness of the.
Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably from 100% to 70%, more preferably from 95% to 75%, and most preferably from 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.

The hydrophilic member of the present invention, as described above, applies the hydrophilic composition and, if necessary, the composition for the undercoat layer onto an appropriate substrate, and is heated and dried to form a hydrophilic layer. Next, the lubricant composition is applied thereon, heated and dried to form a lubricating layer having a friction coefficient of 0.05 to 0.25.
As a method for applying the undercoat layer composition, the hydrophilic composition, and the lubricant composition, a known coating method can be employed. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film Applicator methods, screen printing methods, bar coater methods, brush coating, sponge coating, and the like can be applied.

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

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

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

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

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

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

Moreover, it is preferable to use the fin material which concerns on this invention for a heat exchanger. Since the heat exchanger using the fin material according to the present invention has excellent hydrophilicity, antifouling property and durability thereof, it is possible to prevent water droplets and dust from adhering between the fins. it can. Examples of the heat exchanger include heat exchangers used for indoor coolers, air conditioners, construction machine oil coolers, automobile radiators, capacitors, and the like.
Moreover, it is preferable to use the heat exchanger using the fin material according to the present invention for an air conditioner. Since the fin material according to the present invention has excellent hydrophilicity, antifouling property and sustainability thereof, it is possible to provide an air conditioner in which problems such as a decrease in cooling capacity as described above are improved. . The air conditioner may be any one of a room air conditioner, a packaged air conditioner, a car air conditioner, and the like.
In addition, publicly known techniques (for example, JP 2002-106882 A, JP 2002-156135 A, etc.) can be used for the heat exchanger and the air conditioner of the present invention, and are not particularly limited.

The heat exchanger fin material has a hydrophilic layer formed by applying and drying a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on the surface of an aluminum plate. And applying a lubricant composition containing at least one substance selected from the group consisting of polyethylene glycol and polypropylene glycol, and drying to adsorb or impregnate the lubricant composition in the hydrophilic layer. Can be produced by forming a lubricating layer having a thickness of 0.05 to 0.25.
The drying temperature of the hydrophilic composition and the lubricant composition is preferably 130 to 230 ° C.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

<Aluminum base degreasing treatment>
An aluminum plate (A1200, thickness 0.1 mm) was immersed in an alkaline cleaning liquid (Yokohama Yushi Co., Ltd., Semi-clean A 5 mass% aqueous solution) for 10 minutes, and washing with water was repeated three times.

<Synthesis of Polymer A-1>
A 500 ml three-necked flask is charged with 13.2 g of acrylamide, 11.6 g of acrylamide-3- (ethoxysilyl) propyl and 280 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methyl) under a nitrogen stream at 80 ° C. 1.8 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 hydrophilic polymer A-1. The mass after drying was 23.6 g. The mass average molecular weight of the polymer determined by GPC (polyethylene oxide standard) was 22,000.
Thereafter, Polymers A-2 to A-5 used in Examples and Polymers A-9 to A-10 used in Comparative Examples were synthesized by the same method as described above. The structures of polymers A-1 to A-5 and polymers A-9 to A-10 are shown below.

<Synthesis of polymer B>
30 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 52 g of dimethylformamide were placed in a three-necked flask and heated to 65 ° C. in a nitrogen stream, and 2,2′-azobis (2,4-dimethylvaleronitrile) 0. 38 g was added to start the reaction. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of ethyl acetate, and a solid precipitated. Then, it filtered, wash | cleaned sufficiently with ethyl acetate, and dried. In this way, Polymer B-1 was obtained. The mass average molecular weight of the polymer B determined by GPC (polyethylene oxide standard) was 11,000.
Thereafter, the polymers B-2 to B-3 used in the examples were synthesized by the same method as described above. The structures of the polymers B-1 to B-3 are shown below.

Examples 1 to 42 and Comparative Examples 1 to 11
<Hydrophilic composition>
As shown in Tables 1 to 3 below, a hydrophilic polymer was dissolved in pure water, a catalyst solution was added and stirred for 2 hours, and an aqueous surfactant solution was added and stirred. In Tables 1 to 3, the amounts of the surfactant and the catalyst are the amounts excluding the solvent.
<Lubricant composition>
As shown in Tables 1 to 3 below, polyethylene glycol (PEG) (manufactured by Wako Pure Chemical Industries, Ltd.), polypropylene glycol (PPG) (manufactured by Wako Pure Chemical Industries, Ltd.), and polyacrylamide (Wako Pure Chemical Industries, Ltd.) are added to pure water. (Manufactured by Yakuhin Co., Ltd.) or polyvinylpyrrolidone (PVP) (manufactured by Wako Pure Chemical Industries, Ltd.) and an aqueous surfactant solution were prepared.
<Application>
A hydrophilic composition was applied to a degreased aluminum plate with a # 8 bar, and heated and dried at the temperatures shown in Tables 1 to 3 for 15 seconds to form a hydrophilic layer. Further, the lubricant composition was applied thereon with a # 3 bar and heated and dried at the temperatures shown in Tables 1 to 3 for 15 seconds to form a lubricating layer, which was used as a test piece.
The drying temperatures in Tables 1 to 3 are the drying temperatures of both the hydrophilic layer and the lubricating layer, and when there is no lubricating layer, the drying temperature of only the hydrophilic layer.
The film thicknesses in Tables 1 to 3 were calculated by cutting the test piece and observing the cross section with SEM.
[Evaluation]
The obtained test piece was evaluated as follows. The evaluation results are shown in Tables 4 to 6 below.
<Surface shape>
Since there was no problem in any of the hydrophilic layers, the coated surface shape of only the lubricating layer was confirmed by visual observation.
○: No problem △: Unevenness ×: Repelling-: No lubrication layer <Hydrophilicity>
The contact angle of distilled water was measured with Kyowa Interface Science DROP MASTER 500.
○: 14 ° or less Δ: 15 to 20 ° ×: 21 ° or more <Adhesion>
The cellophane tape was adhered on the hydrophilic layer and then peeled off, and it was visually confirmed whether the lubricating layer and the hydrophilic layer were peeled off.
○: No peeling △: Partial peeling ×: Full peeling <Anti-fouling>
Take 0.2g of palmitic acid in a 50ml glass container, cover with a test piece so that the lubricating layer is exposed to palmitic acid, aerate at 105 ° C / 1 hour, wash with running water for 30 minutes, and dry at 80 ° C / 30 minutes. One cycle was measured, and the contact angle after 5 cycles was measured.
◎: 30 ° or less ○: 31-40 ° △: 41-70 ° ×: 71 ° or more <Friction coefficient>
Measured using a Bowden-Leben type friction tester (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of steel ball diameter: 3/16 inch, load: 0.2 kgf, sliding speed: 3.87 mm / sec, temperature: 24 ° C. did.
○: 0.15 or less Δ: 0.16 to 0.25 ×: 0.25 or more <rust prevention>
A test was conducted in accordance with JIS Z2371, and the rating number (RN) was examined from the corrosion area rate.
○: RN ≧ 9.5 ×: RN <9.5

Hereinafter, the hydrophilic polymers A-6 to A-8 used in Comparative Examples and the catalyst solutions and surfactant aqueous solutions used in Examples and Comparative Examples are shown in Tables 1 to 3.

<Polymers A-6 to 8>
Polymer A-6: Polyacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
Polymer A-7: Polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
Polymer A-8: Polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

<Catalyst solution>
Catalyst 1: 1.8 g of ethanol, 0.1 g of acetylacetone, 0.1 g of tetraethoxytitanium and 0.015 g of distilled water were mixed and prepared by stirring for 1 hour.
Catalyst 2: Zircozole ZA-30 (ZrO (C ₂ H ₃ O ₂ ) ₂ aqueous solution, manufactured by Daiichi Rare Elemental Chemical Co., Ltd.) Catalyst 3: Orgatechs TC-310 ((OH) ₂ Ti [OCH (CH ₃ ) COOH] ₂ aqueous solution, manufactured by Matsumoto Kosho Co., Ltd.)

<Surfactant aqueous solution>
A 5% by mass aqueous solution of an anionic surfactant having the following structural formula was used.

From Tables 4 to 6, it is clear that the hydrophilic member of the present invention is excellent in hydrophilicity, antifouling properties, friction resistance, adhesion, and rust prevention properties.

According to the present invention, a hydrophilic member excellent in hydrophilicity, antifouling property, lubricity, adhesion, and rust prevention property and heat excellent in hydrophilicity, antifouling property, friction resistance, adhesion property, and rust prevention property The manufacturing method of the fin material for exchangers can be provided.
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Jan. 5, 2009 (Japanese Patent Application No. 2009-000382), the contents of which are incorporated herein by reference.

Claims

A lubricating layer having a hydrophilic layer formed from a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group on a substrate, and having a friction coefficient of 0.05 to 0.25 on the hydrophilic layer. A hydrophilic member characterized by comprising:
The hydrophilic member according to claim 1, wherein a water droplet contact angle of the hydrophilic member is 20 ° or less.
The hydrophilic member according to claim 1 or 2, wherein the lubricating layer is a lubricating layer containing at least one lubricant selected from the group consisting of polyethylene glycol and polypropylene glycol.
The hydrophilic member according to claim 3, wherein the polyethylene glycol and polypropylene glycol have a mass average molecular weight of 1000 to 4000.
The hydrophilic member according to any one of claims 1 to 4, wherein the lubricating layer has a thickness of 0.01 to 0.3 µm.
The hydrophilic layer contains 50 mass of the hydrophilic polymer (I) containing the structure represented by the following general formula (I-1) and the structure represented by the following general formula (I-2) with respect to the total solid content. The hydrophilic member according to any one of claims 1 to 5, which is obtained by applying and drying a hydrophilic composition containing at least%.

In the general formulas (I-1) and (I-2), R 101 to R 108 each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L 101 and L 102 each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A 101 represents —OH, —OR a , —COR a , —CO 2 R e , —CON (R a ) (R b ), —N (R a ) (R b ), —NHCOR d , —NHCO 2 R a , —OCON (R a ) (R b ), —NHCON (R a ) (R b ), —SO 3 R e , —OSO 3 R e , —SO 2 R d , —NHSO 2 R d , —SO 2 N (R a ) (R b ), —N (R a ) (R b ) (R c ), —N (R a ) (R b ) (R c ) (R g ), —PO 3 (R e ) (R f ), —OPO 3 (R e ) (R f ), or —PO 3 (R d ) (R e ). Here, R a , R b and R c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R d represents a linear, branched or cyclic alkyl group, R e and R f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R g represents a halogen ion, an inorganic anion, or an organic anion.
The hydrophilic composition contains a hydrolyzable silyl group-containing hydrophilic polymer containing the hydrophilic polymer (I) in an amount of 80% by mass or more based on the total solid content, and in the general formula (I-2) A 101 represents —CONH 2 , —CONH (R 5 ), or —CON (R 5 ) 2 (wherein R 5 independently represents a linear, branched, or cyclic alkyl group). The hydrophilic member according to claim 6, wherein
The hydrophilic member according to any one of claims 1 to 7, wherein the substrate is an aluminum plate.
A fin material using the hydrophilic member according to any one of claims 1 to 8.
An aluminum fin material, wherein the fin material according to claim 9 is made of aluminum.
A heat exchanger using the aluminum fin material according to claim 10.
An air conditioner using the heat exchanger according to claim 11.
A lubricant composition is applied to the surface of a fin material for a heat exchanger having a hydrophilic layer formed by applying a hydrophilic composition containing a hydrophilic polymer having a hydrolyzable silyl group to the surface of an aluminum plate and drying. A method for producing a fin material for a heat exchanger, comprising applying and drying to adsorb or impregnate a lubricant composition in a hydrophilic layer to form a lubricating layer having a friction coefficient of 0.05 to 0.25 .
The method for producing a fin material for a heat exchanger according to claim 13, wherein the drying temperature of the hydrophilic composition and the lubricant composition is independently 130 to 230 ° C.