JP2010070735A - Hydrophilic composition, hydrophilic member, fin material, heat exchanger, and air conditioner - Google Patents

Abstract

[PROBLEMS] To provide a hydrophilic composition capable of providing a hydrophilic member having sufficient hydrophilicity, abrasion resistance, antifouling property and adhesion, and capable of maintaining excellent lubricity for a long period of time, and use thereof Provided hydrophilic member, fin material, heat exchanger, and air conditioner.
A hydrophilic polymer (I) having a specific structure having a hydrophilic group and a silane coupling group in the side chain, and a hydrophilic structure having a specific structure having a hydrophilic group in the side chain and a silane coupling group at the end of the polymer chain. A hydrophilic composition containing at least one of the polymers (II) and (C) a polyalkylene oxide, wherein a dynamic friction coefficient of a film formed by the hydrophilic composition is 0.3 or less; A hydrophilic composition.
[Selection figure] None

Description

  The present invention provides a hydrophilic composition capable of providing a hydrophilic member having sufficient hydrophilicity, abrasion resistance, antifouling property and adhesion, and capable of maintaining excellent lubricity for a long period of time. The present invention relates to the used hydrophilic member, fin material, heat exchanger, and air conditioner.

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 there is a problem that it is difficult to remove dirt.

Various techniques have been proposed for forming on the surface a dirt prevention function that makes it difficult to get dirt on the surface of a solid member or that makes it easy to remove the attached dirt. In particular, as a combination of an antireflection member and an antifouling member, for example, an antireflection film composed mainly of silicon dioxide and an antifouling and wear resistant material treated with a compound containing an organosilicon substituent (for example, Patent Document 1), and antifouling and wear-resistant CRT filters (for example, see Patent Document 2) in which the substrate surface is coated with terminal silanol organopolysiloxane have 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 salt (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 about a decrease in antifouling performance over time, and therefore, development of an antifouling member having excellent antifouling properties is desired.

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

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

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

JP-A 64-86101 JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 International Publication No. 96/29375 Pamphlet Newspaper "Chemical Industry Daily" article dated January 30, 1995

  An object of the present invention is to provide a hydrophilic composition capable of providing a hydrophilic member having sufficient hydrophilicity, abrasion resistance, antifouling property and adhesion, and capable of maintaining excellent lubricity for a long time, and It is providing the hydrophilic member used for this, a fin material, a heat exchanger, and an air conditioner.

By adding a hydrophilic polymer having a silane coupling group and a polyalkylene oxide to the hydrophilic composition, the present inventors can impart excellent antifouling properties to the hydrophilic composition, and It has been found that excellent lubricity can be maintained for a long time by combining a silanol group hydrolyzed by a ring group and a hydroxyl group contained in polyalkylene oxide.
That is, the present invention is as follows.

[1]
(A) hydrophilic polymer (I) having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2), and (B) the following general formula At least one hydrophilic polymer (II) having a structural unit represented by (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain;
(C) a hydrophilic composition containing polyalkylene oxide,
A hydrophilic composition, wherein the coating formed of the hydrophilic composition has a coefficient of dynamic friction of 0.3 or less.

(In 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 represent Each independently represents a single bond or a polyvalent organic linking group, x and y represent a composition ratio, x represents a number such that 0 <x <100, y represents 0 <y <100, and 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) where, R a, R b} and R _c each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group; R _d represents a linear, branched or cyclic alkyl group _; and R _e and R _f each independently Represents a hydrogen atom or a linear, branched or cyclic alkyl group, 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 formula (II-1) and ^(II-2), .q representing each is R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group represents an integer of 1 to ^{3, L 201} and ^{L 202} are Each independently 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 ), wherein R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, and R _d represents Represents a linear, branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.)
[2]
[5] The hydrophilic composition as described in [1], wherein the polyalkylene oxide (C) is contained in an amount of 5% by mass or more based on a nonvolatile component of the hydrophilic composition.
[3]
The hydrophilic composition as described in [1] or [2], wherein the (C) polyalkylene oxide has a mass average molecular weight of 200 or more.
[4]
The hydrophilic composition comprises (A) the hydrophilic polymer (I) and (B) the hydrophilic polymer (II), and the (A) hydrophilic polymer (I) and the (B) hydrophilic polymer. Any one of [1] to [3], wherein the mass ratio to (II) ((A) hydrophilic polymer / (B) hydrophilic polymer) is in the range of 95/5 to 50/50 The hydrophilic composition as described.
[5]
The hydrophilic composition according to any one of [1] to [4], wherein the hydrophilic composition further contains (D) a catalyst.
[6]
The hydrophilic composition as described in [5], wherein the catalyst (D) is a non-volatile catalyst.
[7]
The hydrophilic composition according to any one of [1] to [6], wherein the hydrophilic composition further contains (E) an alkoxide compound of an element selected from Si, Ti, Zr, and Al. .
[8]
A hydrophilic member comprising a hydrophilic layer formed of the hydrophilic composition according to any one of [1] to [7] on a substrate.
[9]
The hydrophilic member according to [8], wherein an undercoat layer is provided between the substrate and the hydrophilic layer.
[10]
The hydrophilic member according to [9], wherein the undercoat layer is formed of a composition for undercoat layer containing (D) a catalyst.
[11]
The hydrophilic member according to [10], wherein the catalyst (D) contained in the undercoat layer is a non-volatile catalyst.
[12]
The undercoat layer is formed by further applying (E) a composition containing an alkoxide compound of an element selected from Si, Ti, Zr, and Al [9] to [11] The hydrophilic member according to any one of [11].
[13]
An undercoat layer composition is applied on a substrate, heated and dried to form an undercoat layer. The hydrophilic composition is applied onto the undercoat layer, and heated and dried to form an overcoat layer. The hydrophilic member according to any one of [9] to [12], wherein
[14]
The fin body;
And a hydrophilic layer provided on at least a part of the surface of the fin body, wherein the hydrophilic layer is coated with the hydrophilic composition according to any one of [1] to [7]. The fin material characterized by being made.
[15]
The fin material according to [14], wherein the fin body is made of aluminum.
[16]
[15] A heat exchanger using the fin material according to [15].
[17]
[16] An air conditioner using the heat exchanger according to [16].

  According to the present invention, a hydrophilic composition capable of providing a hydrophilic member having sufficient hydrophilicity, abrasion resistance, antifouling property and adhesion, and capable of maintaining excellent lubricity for a long time, and A hydrophilic member, a fin material, a heat exchanger, and an air conditioner using the same can be provided.

Hereinafter, the present invention will be described in detail.
The hydrophilic composition of the present invention is
(A) hydrophilic polymer (I) having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2), and (B) the following general formula At least one hydrophilic polymer (II) having a structural unit represented by (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain;
(C) a hydrophilic composition containing polyalkylene oxide,
The dynamic friction coefficient of the film formed of the hydrophilic composition is 0.3 or less.

(In 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 represent Each independently represents a single bond or a polyvalent organic linking group, x and y represent a composition ratio, x represents a number such that 0 <x <100, y represents 0 <y <100, and 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) where, R a, R b} and R _c each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group; R _d represents a linear, branched or cyclic alkyl group _; and R _e and R _f each independently Represents a hydrogen atom or a linear, branched or cyclic alkyl group, 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 formula (II-1) and ^(II-2), .q representing each is R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group represents an integer of 1 to ^{3, L 201} and ^{L 202} are Each independently 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 ), wherein R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, and R _d represents Represents a linear, branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.)

  Hydrophilic polymer (I) having a hydrophilic group and a silane coupling group in the side chain in the presence of polyalkylene oxide, and a hydrophilic polymer having a hydrophilic group in the side chain and a silane coupling group at the end of the polymer chain The surface of the hydrophilic layer having a crosslinked structure formed by at least one hydrolysis and condensation polymerization of the conductive polymer (II) has sufficient hydrophilicity, abrasion resistance, antifouling property and adhesion, and is excellent The lubricity can be maintained for a long time. Specifically, at least one of the hydrophilic polymer (I) and the hydrophilic polymer (II) and the polyalkylene oxide are dissolved in a suitable solvent and stirred, whereby hydrolysis and polycondensation proceed in the system. A sol-like hydrophilic composition is obtained, which is coated on a substrate and dried to have a hydrophilic functional group on the substrate surface. The hydrophilic polymer (I) and the hydrophilic polymer (II) An organic film having a crosslinked structure formed by reaction of silane coupling groups contained in at least one of the above is formed. Here, since polyalkylene oxide has a low Тg, it is considered that due to this, the surface of the coating becomes very slippery and a coating excellent in lubricity can be obtained. Furthermore, when the hydroxyl group contained in the polyalkylene oxide reacts with a silanol group in which the silane coupling group is hydrolyzed, the polyalkylene oxide that is usually easily eluted with water or the like may be immobilized on the hydrophilic polymer. Probably, the lubricity of the coating is maintained for a long time.

  Below, each component contained in the hydrophilic composition of this invention is demonstrated.

[(A) Hydrophilic polymer (I) having a structural unit represented by general formula (I-1) and a structural unit represented by general formula (I-2) (hereinafter referred to as “(A) specific hydrophilicity Also called “polymer”))]

In 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 formula (I-1) and ^{(I-2), R 101} ~R 108 each independently represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ^{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-alkylsulfur group Sulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H) (Aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group _(-OPO 3 _(alkyl) 2), diaryl phosphonooxy group _(-OPO 3 _(aryl) 2), An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as an alkylphosphonatooxy group), mono Arylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group It is done.

In these substituents, specific examples of the alkyl group include those alkyl groups similarly mentioned in R ¹ to R ^8, 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, A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoy Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group Group, phosphonooxy group, phosphonatooxy group, aryl group, and alkenyl group.

  On the other hand, 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 include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a hydroxymethyl group, a methoxymethyl group, and a 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, Torilho Phonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

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

L ^{101 to} L ¹⁰² represent a single bond or an organic linking group. Here, the single bond means that the polymer main chain and X are directly bonded without a linking 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, 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 General Formula (I-1), L ¹⁰¹ represents 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.
L ¹⁰² is selected from the group consisting of —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ — and —CH ₂ —. A linking group having one or more selected structures is preferred.

In the 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 each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 8), an alkali metal, R 1 represents an alkaline earth metal or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. _{Further, -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 _f 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 _f may further have a substituent, and the substituents that can be introduced here are the same as those exemplified as the substituents that can be introduced when R ^{101 to} R ¹⁰⁸ are alkyl groups. Can be listed.

Specific examples of the linear, branched or cyclic alkyl group in R _{a to} R _f include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an 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.
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.
In addition, fluorine ions, chlorine ions, bromine ions are used as halogen ions, nitrate anions, sulfate anions, tetrafluoroborate anions, hexafluorophosphate anions are used as inorganic anions, and methanesulfonate anions and trifluoro ions are used as organic anions. Preferred examples include lomethane sulfonate anion, nonafluorobutane sulfonate anion, p-toluene sulfonate 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 _{preferably, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -SO 3 - K +, - (CH 2 CH 2 O) n H, is. In the above, n preferably represents an integer of 1 to 100.

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

  In the hydrophilic polymer including the structures represented by the general formulas (I-1) and (I-2), x and y are the structures represented by the general formula (Ia) in the (A) specific hydrophilic polymer. The composition ratio of the unit and the structural unit represented by the general formula (Ib) is represented. 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) including the structures 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 unit of the general formula (I-2) and the molar ratio (x) of the structural unit 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 polymer containing the structures represented by the general formulas (I-1) and (I-2) is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, 1,000 to 200,000 is most preferred.

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

Each compound for synthesizing the hydrophilic polymer including the structures represented by the general formulas (I-1) and (I-2) is commercially available, and can be easily synthesized.
Any conventionally known method can be used as the radical polymerization method for synthesizing the hydrophilic polymer containing the structures represented by the general formulas (I-1) and (I-2).
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 Lecture 19 (1978, Maruzen), Polymer Chemistry (I) (Edited by The Chemical Society of Japan, 1996, Maruzen), Synthetic Polymer Chemistry (Materials Engineering Lecture, 1995, Tokyo Denki University Press) These can be applied.

[Hydrophilic polymer (II) having a structural unit represented by the following general formula (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain (hereinafter, “(B) Specific hydrophilic polymer”))]

In general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to ^{3, L 201} and ^{L 202} each represents a single bond or a polyvalent organic linking group. A ²⁰¹ is _{-OH, -OR a, -COR a,} -CO 2 R e, -CON (R a) (R b), - N (R a) (R b), - NHCOR d, -NHCO 2 R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, 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 following general formula (II-2) and has a polymer chain. It preferably has a partial structure represented by the following general formula (II-1) at the end of

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, there may be mentioned the same ones as mentioned in R ¹⁰¹ to R ¹⁰⁸ in the general formula (I-1) and (I-2).
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 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 2-3, More preferably, it is 3.

L ²⁰¹ and L ²⁰² are —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ — and —CH ₂ —. A linking group having at least one structure selected from the group consisting of

  The hydrophilic polymer containing the structure represented by the general formulas (II-1) and (II-2) is, for example, a chain transfer agent (described in the radical polymerization handbook (NTS, Mikiji Tsunoike, Go Endo)). And Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)) can be synthesized by radical polymerization of a hydrophilic monomer (eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate). 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 including the structures represented by the general formulas (II-1) and (II-2) is represented by the following general formula (i) and a radically polymerizable monomer represented by the following general formula (i). In the radical polymerization, it 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 above formula (i) and ^{(ii), R 201 ~R 205} , L 201, L 202, A 201, q is the same as defined 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) including 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 500 to 20 times, and most preferably 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 weight average molecular weight of the hydrophilic polymer (II) including the structures 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.

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

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

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

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

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

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

  The proportion of these other monomers used in the synthesis of the copolymer needs to be an amount sufficient to improve various physical properties, but the function as a hydrophilic film is sufficient. (A) Specific hydrophilicity In order to sufficiently obtain the advantage of adding at least one of the polymers (I) and (B) the specific hydrophilic polymer (II), the ratio is preferably not too large. Therefore, the preferred total proportion of other monomers in at least one of (A) the specific hydrophilic polymer (I) and (B) the specific hydrophilic polymer (II) is preferably 80% by mass or less, and more preferably It is 50 mass% or less.

  The copolymerization ratio of the specific hydrophilic polymer (I) or (II) can be measured with a nuclear magnetic resonance apparatus (NMR) or a calibration curve prepared with a standard substance and measured with an infrared spectrophotometer.

The hydrophilic composition in the present invention may be the specific hydrophilic polymer (I) or (II) alone or in admixture of two or more, but the hydrophilic composition comprises the specific hydrophilic polymer (I) and the specific hydrophilic polymer. In the case of containing (II), the mass ratio of the specific hydrophilic polymer (I) and the specific hydrophilic polymer (II) is preferably in the range of 95/5 to 50/50, and is in this range. Thus, a hydrophilic member excellent in hydrophilicity and antifouling property is obtained.
At least one of the specific hydrophilic polymer (I) and the specific hydrophilic polymer (II) is used in an amount of 20 to 99.5% by mass based on the total solid content of the hydrophilic composition from the viewpoint of curability and hydrophilicity. It is preferable that 30 to 99.5% by mass is used.

  The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the hydrophilic polymer has a viscosity of 0.1 to 100 mPa · s (5% aqueous solution, measured at 20 ° C.), preferably When it is in the range of 0.5 to 70 mPa · s, more preferably 1 to 50 mPa · s, good film properties are provided.

[(C) polyalkylene oxide]
The (C) polyalkylene oxide according to the present invention refers to those in which alkylene chains are connected by an ether bond and have repeating units. (C) When a film is formed using a hydrophilic composition containing polyalkylene oxide, it is unevenly distributed on the surface in the drying process. This is because (C) polyalkylene oxide is more hydrophobic than (A) hydrophilic polymer and / or (B) hydrophilic polymer and is therefore more likely to be unevenly distributed at the hydrophobic air interface which is more stable. . Thereby, excellent lubricity is expressed. Moreover, although the specific example of (C) polyalkylene oxide is given to the following, this invention is not limited to this. Examples thereof include polyethylene oxide (PEO), polypropylene oxide (PPO), polybutylene oxide (PBO), and the like, and a block copolymer (PEO-PPO-) in which a PEO unit, a PPO unit, and a PEO unit are combined in this order. PEO) can also be mentioned.
Further, the terminal hydroxyl group of the polyalkylene oxide may be modified with a substituent to such an extent that the lubricity is not deteriorated, but it is desirable that at least one hydroxyl group has at least one from the viewpoint of improving the antifouling property. Examples of the terminal substituent include 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. , Hydrocarbon groups such as neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and allyl group. These hydrocarbon groups may have a substituent, and specifically, (A) can be mentioned in the same manner as those mentioned for R ^{1 to} R ⁸ of the specific hydrophilic polymer.
Furthermore, the (C) polyalkylene oxide may be a random copolymer, block copolymer, or graft copolymer with other monomer components to the extent that flexibility is not deteriorated. Although the synthesis method is described below, it is not limited to this. The random copolymer is a copolymer with a monomer having two or more functional groups that react with a terminal hydroxyl group. For example, dicarboxylic acid (halide), diisocyanate, tetracarboxylic anhydride, diglycidyl compound and the like can be mentioned. The block copolymer is a copolymer with a polymer having two or more functional groups that react with a terminal hydroxyl group. Specifically, the polymer of the said compound is mentioned. Examples of the graft copolymer include those obtained by polymerizing a monomer having a polyalkylene oxide in the side chain. Examples thereof include polymers of methacryloyl polyethylene oxide and methacryloyl polyethylene oxide methyl ether.
The mass average molecular weight of the (C) polyalkylene oxide according to the present invention (hereinafter also simply referred to as molecular weight) is preferably 200 or more, and preferably 100,000 or less from the viewpoint of being less likely to volatilize during drying during film formation. 200 to 80,000 is more preferable, and 200 to 50,000 is most preferable. By being 200 or more, there is no possibility that (C) polyalkylene oxide volatilizes even in the drying process. By being 50,000 or less, it tends to be unevenly distributed on the surface of the film in the drying process. The glass transition temperature (Tg) of the (C) polyalkylene oxide according to the present invention is preferably 20 ° C. or lower, and more preferably 10 ° C. or lower.
(C) The polyalkylene oxide is preferably 5% by mass or more, more preferably 5 to 45% by mass, in order to ensure lubricity with respect to the hydrophilic composition of the present invention and the non-volatile component. More preferably, it is used in the range of 10 to 40% by mass.
(C) The polyalkylene oxide can be easily obtained as a commercial product, and can also be obtained by a known synthesis method such as anionic polymerization.

As described above, the hydrophilic composition of the present invention is configured such that the coefficient of dynamic friction of the coating formed from the hydrophilic composition is at least 0.3 or less, whereby excellent lubricity of the coating is achieved. Can be granted. Here, the lower limit value of the dynamic friction coefficient of the coating is not particularly limited, but the lower the better. In the hydrophilic composition of the present invention, the coefficient of dynamic friction of the film formed from the hydrophilic composition is preferably 0.30 or less, more preferably 0.25 or less.
The method of setting the dynamic friction coefficient of the film formed of the hydrophilic composition to 0.3 or less is not particularly limited, but in the hydrophilic composition, the type and content of the hydrophilic polymer and polyalkylene oxide are appropriately selected. Thus, it is possible to obtain a hydrophilic composition in which the dynamic friction coefficient of the film formed of the hydrophilic composition is 0.3 or less.
The dynamic friction coefficient can be measured, for example, with a surface measuring machine manufactured by “HEIDON-18 type” Shinto Kagaku Co., Ltd. under conditions of a load of 50 g with a 5 mmφ steel ball and a pulling speed of 30 cm / min. It is.

[(D) Catalyst]
In the hydrophilic composition and the composition for undercoat layer of this invention, it is preferable to contain (D) a catalyst. (D) By containing a catalyst, the reaction of (A) the specific hydrophilic polymer and / or (B) the specific hydrophilic polymer can be promoted, or (C) the reaction of the polyalkylene oxide can be promoted. (D) As the catalyst, an acid or a basic compound is used as it is, or an acid or a basic compound dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst inclusive) , Also referred to as a basic catalyst). The concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

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

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

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

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

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

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

  Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aco complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, and among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

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

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

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

  The catalyst (D) according to the present invention is used in the hydrophilic composition of the present invention in an amount of preferably 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the nonvolatile component. Moreover, (D) a catalyst may be used independently or may be used together 2 or more types.

[(E) Alkoxide Compound of Element Selected from Si, Ti, Zi, Al]
In the present invention, the hydrophilic composition preferably contains (E) an alkoxide compound of an element selected from Si, Ti, Zr, and Al (hereinafter also referred to as (E) a specific alkoxide).
(E) In the hydrolysis / polycondensation in the system by including the specific alkoxide, (A) the specific hydrophilic polymer and / or (B) the silane coupling group contained in the specific hydrophilic polymer and (E) the specific alkoxide Since the reactive functional sites that form crosslinks increase due to the hydrolyzed polymerizable functional group, an organic-inorganic composite film having a higher density and a strong crosslink structure is formed. Further, it is considered that the strength becomes high, excellent wear resistance is exhibited, and high surface hydrophilicity can be maintained for a long period of time. Further, when water adheres to the surface having a very high hydrophilicity, the surface area with the air interface increases because the water spreads, the drying speed of water becomes very fast, and a coating film having excellent quick drying properties is obtained.
(E) The alkoxide compound of an element selected from Si, Ti, Zr, and Al, which is a specific alkoxide used in the present invention, has a polymerizable functional group in its structure and serves as a crosslinking agent. It is a decomposition polymerizable compound, and forms a strong film having a crosslinked structure by condensation polymerization with (A) the specific hydrophilic polymer and / or (B) the specific hydrophilic polymer.
(E) The specific alkoxide is preferably a compound represented by the following general formula (V). In forming a crosslinked structure in order to cure the hydrophilic film, the (A) specific hydrophilic polymer and / B (B) The specific hydrophilic polymer and (E) the specific alkoxide represented by the general formula (V) are mixed, coated on the substrate surface, heated and dried.

In the general formula (V), R ¹⁷ represents a hydrogen atom, an alkyl group or an aryl group, R ¹⁸ represents an alkyl group or an aryl group, Y represents Si, Ti or Zr, and k represents an integer of 0 to 2. To express. When R ¹⁷ and R ¹⁸ 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 1000 or less.

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

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

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

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 of the present invention described above. Thus, a hydrophilic member having sufficient hydrophilicity, abrasion resistance, antifouling property and adhesion and capable of maintaining excellent lubricity for a long period of time can be obtained.
The hydrophilic member of the present invention may further have an undercoat layer between the substrate and the hydrophilic layer in order to improve the adhesion between the substrate and the hydrophilic layer.
Here, the undercoat layer is preferably formed by applying the above-described composition containing the catalyst (D), thereby further improving the adhesion between the substrate and the hydrophilic layer. Can be made. Here, the catalyst (D) is preferably a non-volatile catalyst as described above.
(D) The catalyst is preferably used in the composition for the undercoat layer in the range of 0 to 50% by mass, more preferably 1 to 25% by mass with respect to the nonvolatile component. Moreover, (D) 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 an alkoxide compound of an element selected from (E) Si, Ti, Zr, and Al. In addition, the adhesion between the substrate and the hydrophilic layer can be improved.
(E) The specific alkoxide is used in the composition for an undercoat layer in an amount of preferably 5 to 99% by mass, more preferably 10 to 95% by mass with respect to the nonvolatile component. Moreover, (E) specific alkoxide may be used independently or may be used together 2 or more types.

[Other ingredients]
Various compounds can be used in combination with the hydrophilic composition and the composition for the undercoat layer according to the purpose as long as the effects of the present invention are not impaired. Hereinafter, components that can be used in combination will be described.

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

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

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

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

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

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

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

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

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

Natural antibacterial agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crabs and shrimp shells.
In the present invention, Nikko's “trade name Holon Killer Bees Sera” made of aminometal in which a metal is compounded on both sides of an amino acid is preferable.
These are not transpirationable, easily interact with the polymer and crosslinker component of the hydrophilic layer, can be stably molecularly dispersed or solid dispersed, the antibacterial agent is easily exposed to the surface of the topcoat layer, and Even if it is splashed with water, it does not elute, and the effect can be maintained for a long time without affecting the human body. Moreover, it can disperse | distribute stably with respect to a topcoat layer or a coating liquid, and deterioration of a topcoat layer or a coating liquid does not occur.
Among the antibacterial agents, silver-based inorganic antibacterial agents and water-soluble organic antibacterial agents are most preferable because of their great antibacterial effects. In particular, silver zeolite in which silver is supported on zeolite, which is a silicate carrier, antibacterial agent in which silver is supported on silica gel, 2-bromo-2-nitro-1,3-propanediol, TPN, TBZ, BCM, OBPA ZPT is preferred. Particularly preferred commercially available silver zeolite antibacterial agents include “Zeomic” from Shinagawa Fuel, “Sylwell” from Fuji Silysia Chemical, and “Bactenone” from JEOL. In addition, Toa Gosei's “Novalon” in which silver is supported on an inorganic ion exchanger ceramic, “Atomy Ball” from Catalytic Chemical Industry, and “Suneyeback P” as a triazine antibacterial agent are also preferred.

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

[Inorganic fine particles]
The hydrophilic composition and the undercoat layer composition of the present invention may contain inorganic fine particles in order to improve the cured film strength and hydrophilicity of the film to be formed. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned.
The inorganic fine particles preferably have an average particle size 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 layer, sufficiently retains the film strength, 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 and the undercoat layer composition of the present invention in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, based on the nonvolatile components. The The inorganic fine particles can be used alone or in combination of two or more.

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

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

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

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

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

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

[Preparation of hydrophilic composition]
The hydrophilic composition is prepared by (A) a specific hydrophilic polymer and / or (B) a specific hydrophilic polymer, (C) a polyalkylene oxide, (E) a catalyst and (F) a specific alkoxide, if necessary, ethanol, etc. It can carry out by stirring after melt | dissolving in this solvent. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and organic inorganic A composite sol solution can be obtained.

  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 and the like is preferable.

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

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

The hydrophilic member of the present invention can be obtained by coating such a solution containing the composition for an undercoat layer of the present invention and a solution containing a hydrophilic composition on an appropriate substrate and drying. That is, in the hydrophilic member of the present invention, an undercoat layer composition is applied on a substrate, heated and dried to form an undercoat layer, and the hydrophilic composition is applied thereon, heated and dried. Thus, it is obtained by forming an overcoat layer.
As heating and drying conditions, from the viewpoint of efficiently forming a high-density cross-linked structure, it is preferably performed in a temperature range of 50 to 200 ° C. for about 2 minutes to 1 hour, and in a temperature range of 80 to 160 ° C. It is more preferable to dry for 5 to 30 minutes. Moreover, as a heating means, it is preferable to use a well-known means, for example, the dryer etc. which have a temperature control function.

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

〔substrate〕
The substrate used in the present invention is not particularly limited, but glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, tile, rubber, latex, combinations thereof, and lamination thereof Any body can be suitably used. A particularly preferable substrate is a flexible substrate having flexibility such as plastic or metal. By using a flexible substrate, the deformation of the article can be freely performed, and not only the degree of freedom of attachment work and the place of attachment is increased, but also the durability can be increased. Usually, when the (D) trifunctional or bifunctional alkoxysilane used in the present invention is used for the undercoat layer, the surface of the undercoat layer becomes hydrophobic. There is a concern of insufficient adhesion. For this reason, it has been considered that there is a problem in using (D) trifunctional or bifunctional alkoxysilane for the undercoat layer of the hydrophilic member. However, in the present invention, a special effect can be exhibited due to the combination with the hydrophilic polymer having a silane coupling group.
The plastic substrate used in the present invention is not particularly limited, but a substrate used as an optical member is selected in consideration of optical characteristics such as transparency, refractive index, and dispersibility, and various types can be used depending on the purpose of use. It is selected in consideration of physical properties such as physical properties such as strength such as impact resistance and flexibility, heat resistance, weather resistance, and durability. Plastic substrates include polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, polysulfone. And films or sheets of polyether ketone, acrylic, nylon, fluororesin, polyimide, polyether imide, polyether sulfone and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use. The thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for the place where it is used for a plane or intensity | strength is requested | required.

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

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

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

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

As the metal thin plate, 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 substrate 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. The surface treatment facilitates improving the hydrophilicity of the substrate and ensuring the adhesion between the undercoat layer and the substrate. Prior to the roughening treatment of 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 substrate can be performed by a well-known method.

As the substrate used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is. However, in order to further improve the adhesion with the upper layer, JP-A-2001-253181 is necessary. Appropriately selected from the micropore enlargement treatment and sealing treatment of the anodized film and surface hydrophilization treatment immersed in an aqueous solution containing a hydrophilic compound, as described in Japanese Patent Laid-Open No. 2001-322365. Can do. 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 sealing with hot water are particularly preferable. Hole treatment is preferred. Each will be described below.

<Sealing treatment with an aqueous solution containing an inorganic fluorine compound>
As the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.
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 fluoride titanate, potassium fluoride titanate, zirconate fluoride, titanate fluoride, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphor fluoride, ammonium fluoride phosphate It is done. 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.
Further, 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.
Further, 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.
A 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, more preferably 100 seconds or shorter, and 20 seconds or shorter. More preferred.

<Sealing treatment with water vapor>
Examples of the sealing treatment with water vapor include 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 water vapor pressure 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.

<Hydrophilic treatment>
The hydrophilization treatment is described in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734, and 3,902,734. There are such alkali metal silicate methods. In this method, the support 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 A metal oxide such as (Indium Tin Oxide); a metal halide 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, security glass, highly heat-insulated 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 polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.

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

[Layer structure when using hydrophilic members]
When the hydrophilic member of the present invention is used in anticipation of the appearance of antifouling and / or antifogging effects, it may be used by appropriately adding another layer depending on the purpose, form and place of use. it can. The layer structure added as needed is described below.

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

2) Release layer When the hydrophilic member of the present invention has the adhesive layer, a release layer can be further added. The release layer preferably contains a release agent in order to give release properties. As the release agent, generally, a silicone release agent composed of polyorganosiloxane, a fluorine compound, a long-chain alkyl modified product of polyvinyl alcohol, a long-chain alkyl modified product of polyethyleneimine, and the like can be used. In addition, various release agents such as a hot melt type release agent, a monomer type release agent that cures a release monomer by radical polymerization, cationic polymerization, polycondensation reaction, etc., and other, acrylic-silicone copolymer Resin, acrylic-fluorine-based copolymer resin, and copolymer-based resin such as urethane-silicone-fluorine-based copolymer resin, and resin blends of silicone-based resin and acrylic-based resin, 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 topcoat layer (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 a suitable substrate.

[Form of structure]
The structure having the hydrophilic layer of the present invention may be supplied in the form of a sheet, a roll, or a ribbon, or may be supplied as a pre-cut material for attaching to a suitable substrate.

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 of the present invention is preferably 0.01 g / m ^{2 to} 100 g / m ² , more preferably 0.02 g / m ^{2 to} 80 g / m ² , and particularly preferably 0.05 g / m ² to. By setting it to 50 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.
Preferably the dry coating amount of the undercoat layer composition ^{0.01g / m 2 ~100g / m 2} , more preferably ^{0.02g / m 2 ~80g / m 2} , particularly preferably 0.05g / m ² ~50g / By setting m ² , the above film thickness can be obtained.
Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably 100% to 70%, more preferably 95% to 75%, and most preferably in the range of 95% to 80%. By being in this range, the hydrophilic member provided with a hydrophilic layer can be applied to various applications without obstructing the field of view.

As described above, the hydrophilic member of the present invention can be obtained by applying the composition for the undercoat layer and the hydrophilic composition on a suitable substrate, heating and drying to form a surface hydrophilic layer. it can.
As a method for applying the composition for the undercoat layer and the hydrophilic composition, a known coating method can be adopted, for example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method, screen printing. Methods such as coating, bar coating, brush coating, and sponge coating can be applied.

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

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

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 composition for forming a hydrophilic film 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 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 a degreased surface and an aluminum plate subjected to chemical conversion treatment as necessary. It is preferable that the surface of the fin body material made of aluminum is subjected to a chemical conversion treatment from the viewpoint 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 the aluminum thin plate used for the fin body of the heat exchanger fin material, according to JIS standard, pure aluminum plate such as 1100, 1050, 1200, 1N30, Al-Cu 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, a well-known technique (for example, Unexamined-Japanese-Patent No. 2002-106882, Unexamined-Japanese-Patent No. 2002-156135 etc.) can be used for the heat exchanger and air conditioner of this invention, and it does not restrict | limit in particular.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
(Synthesis of specific hydrophilic polymer (1))
A 300 ml three-necked flask was charged with 28.3 g of acrylamide, 27.5 g of acrylamide-3- (triethoxysilyl) propyl, and 85 g of 1-methoxy-2-propanol, and 2,2′-azobis (2- 0.7 g of dimethyl methylpropionate) was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The solution was put into 2 liters of n-hexane, and the precipitated solid was collected by filtration. After the obtained solid was washed with n-hexane, the specific hydrophilic polymer (I-1) was obtained. The mass after drying was 53.2 g. It was a polymer having a mass average molecular weight of 22,000 according to GPC (polyethylene oxide standard).
Thereafter, the specific polymer used in the examples was synthesized by the same method as described above and used for evaluation.

Example 1
[Hydrophilic sol-gel solution]
100 g of purified water, 11.3 g of (A) specific hydrophilic polymer (I-1), and 2.0 g of (C) polyethylene oxide (molecular weight: 400) were mixed and prepared by stirring at room temperature for 2 hours.
[Hydrophilic composition]
The hydrophilic sol-gel solution was mixed with 116 g of purified water and 2.3 g of a 5% by weight aqueous solution of the following surfactant to obtain a hydrophilic composition.

[Coating method]
An alkali degreased aluminum substrate (thickness: about 100 μm) is prepared, and the hydrophilic composition is bar-coated on the aluminum substrate and oven-dried at 150 ° C. for 30 minutes to obtain a dry coating amount of 0.4 g / m ² . A hydrophilic layer was formed.

(Example 2)
In Example 1, a hydrophilic member was prepared in the same manner as in Example 1 except that 0.05 g of 1N hydrochloric acid aqueous solution was added as a catalyst (D) to the hydrophilic sol-gel solution.

(Example 3)
In Example 1, a hydrophilic member was prepared in the same manner as in Example 1 except that 0.1 g of acetylacetone and 0.1 g of tetraethyl orthotitanate were added as a (D) catalyst to the hydrophilic sol-gel solution.

(Examples 4 to 10)
(C) A hydrophilic member was prepared in the same manner as in Example 3 except that polyethylene oxide (molecular weight: 400) was changed to the following.
Example 4: (C) polyethylene oxide (molecular weight: 600)
Example 5: (C) polyethylene oxide (molecular weight: 1,000)
Example 6: (C) Polyethylene oxide (molecular weight: 20,000)
Example 7: (C) polyethylene oxide (molecular weight: 100,000)
Example 8: (C) polypropylene oxide (molecular weight: 600)
Example 9: (C) polypropylene oxide (molecular weight: 30,000)
Example 10: (C) Polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer (molecular weight: 2,000)

(Examples 11 to 13)
(C) A hydrophilic member was prepared in the same manner as in Example 3 except that the addition amount of polyethylene oxide (molecular weight: 400) was changed to the following amount.
Example 11: 0.6 g
Example 12: 5.0 g
Example 13: 11.6 g

(Examples 14 to 17)
(A) A hydrophilic member was prepared in the same manner as in Example 3 except that the specific hydrophilic polymer (I-1) was changed to the following.
Example 14: (A) Specific hydrophilic polymer (I-2)
Example 15: (A) Specific hydrophilic polymer (I-11)
Example 16: (B) Specific hydrophilic polymer (II-71)
Example 17: (B) Specific hydrophilic polymer (II-82)

(Examples 18 and 19)
A hydrophilic member was prepared in the same manner as in Example 3 except that the catalyst (D) added to the hydrophilic sol-gel solution was changed to the following.
Example 18: Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) 0.2 g
Example 19: 0.2 g of zirconium chelate compound
In a reactor equipped with a stirrer, 50 g of tetrabutoxyzirconium and 20 g of ethyl acetoacetate were added and stirred at room temperature for 1 hour to obtain a zirconium chelate compound.

(Examples 20 and 21)
In Example 3, a hydrophilic member was prepared in the same manner as in Example 3 except that the following compound was added to the hydrophilic sol-gel solution.
Example 20: (E) tetramethoxysilane 0.5 g
Example 21: (E) tetraethoxy titanate 0.5 g

(Examples 22 to 24)
A hydrophilic member was prepared in the same manner as in Example 3 except that the substrate was changed to the following.
Example 22: Glass substrate hydrophilized by UV / ozone treatment (thickness 1.1 mm)
Example 23: Polyethylene terephthalate substrate (50 μm in thickness) whose surface has been hydrophilized by glow treatment
Example 24: TAC substrate (30 μm thick) whose surface has been hydrophilized by saponification treatment

(Examples 25 and 26)
A hydrophilic member was prepared in the same manner as in Example 3 except that 0.5 g of the following compound was added to the hydrophilic composition of Example 3.
Example 25: TBZ (manufactured by China Kogyo Co., Ltd.) (antibacterial agent 1)
Example 26: Zeomic (manufactured by Sinanen Co., Ltd.) (antibacterial agent 2)

(Comparative Example 1)
A surface hydrophilic member of Comparative Example 1 was obtained in the same manner as in Example 3 except that (C) polyethylene oxide (molecular weight: 400) was omitted.

(Comparative Example 2)
A surface hydrophilic member of Comparative Example 2 was obtained in the same manner as in Example 3, except that the amount of (C) polyethylene oxide (molecular weight: 400) added was 0.2 g.

(Comparative Example 3)
In Example 6, in place of (A) the specific hydrophilic polymer (1) of the present invention, a comparative hydrophilic polymer (i) (mass average molecular weight 15000) outside the scope of the present invention having the following structure was used. Obtained the surface hydrophilic member of Comparative Example 3 in the same manner.

(Example 27)
[Sol-gel solution for undercoat layer]
8.0 g of (E) tetramethoxysilane was mixed in 14.2 g of ethyl alcohol and 50 g of purified water, and the mixture was stirred at room temperature for 2 hours to prepare.
[Composition for undercoat layer]
2.8 g of a 5% by weight aqueous solution of the surfactant used in Example 1 and 240 g of purified water were mixed with the sol-gel solution for the undercoat layer to obtain a coating solution.
[Coating method]
An alkali degreased aluminum substrate (thickness of about 100 μm) is prepared, and the undercoat layer composition is bar-coated on the aluminum substrate and oven-dried at 150 ° C. for 30 minutes to obtain a dry coating amount of 0.1 g / m ^2. An undercoat layer was formed. After sufficiently cooling to room temperature, the hydrophilic composition of Example 3 was bar coated and oven dried at 150 ° C. for 30 minutes to form a top coat layer having a dry coating amount of 0.4 g / m ^2. Got.

(Example 28)
In Example 27, a hydrophilic member was prepared in the same manner as in Example 27 except that 0.05 g of a 1N hydrochloric acid aqueous solution was added to the sol-gel solution for the undercoat layer (D) and (E) tetramethoxysilane was changed to the following. did.
Example 28: 4.0 g of (E) tetramethoxysilane, 4.0 g of (E) methyltrimethoxysilane

(Examples 29 to 31)
In Example 28, a hydrophilic member was prepared in the same manner as in Example 28 except that the (D) catalyst of the sol-gel solution for undercoat layer was changed to the following.
Example 29: 0.1 g of acetylacetone, 0.1 g of tetraethyl orthotitanate
Example 30: Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) 0.2 g
Example 31: 0.2 g of zirconium chelate compound
In a reactor equipped with a stirrer, 50 g of tetrabutoxyzirconium and 20 g of ethyl acetoacetate were added and stirred at room temperature for 1 hour to obtain a zirconium chelate compound.

(Examples 32 and 33)
A hydrophilic member was prepared in the same manner as in Example 29 except that the addition amount of (E) tetramethoxysilane and (E) methyltrimethoxysilane in the sol-gel solution for undercoat layer was changed to the following.
Example 32: (E) Tetramethoxysilane 4.8 g, (E) Methyltrimethoxysilane 3.2 g
Example 33: (E) Tetramethoxysilane 5.6 g, (E) Methyltrimethoxysilane 2.4 g

(Examples 34 and 35)
A hydrophilic member was prepared in the same manner as in Example 29 except that the combination of (E) tetramethoxysilane and (E) methyltrimethoxysilane in the sol-gel solution for undercoat layer was changed to the following.
Example 34: (E) Tetraethoxysilane, (E) Methyltrimethoxysilane Example 35: (E) Tetramethoxysilane, (E) Ethyltrimethoxysilane

(Examples 36 to 44)
A hydrophilic member was obtained in the same manner as in Example 29 except that the hydrophilic layer in Example 29 was changed to the hydrophilic layer in the following Examples.
Example 36: hydrophilic layer of Example 4 Example 37: hydrophilic layer of Example 5 Example 38: hydrophilic layer of Example 8 Example 39: hydrophilic layer of Example 10 Example 40: Example Example 14: Hydrophilic layer of Example 15 Example 42: Hydrophilic layer of Example 16 Example 43: Hydrophilic layer of Example 17 Example 44: Hydrophilic layer of Example 20

(Examples 45 to 47)
A hydrophilic member was prepared in the same manner as in Example 29 except that the substrate was changed to the following.
Example 45: Glass substrate hydrophilized by UV / ozone treatment (thickness 1.1 mm)
Example 46: Polyethylene terephthalate substrate having a surface hydrophilized by glow treatment (thickness 50 μm)
Example 47: TAC substrate (30 μm thick) whose surface has been hydrophilized by saponification treatment

(Examples 48 and 49)
A hydrophilic member was obtained in the same manner as in Example 29 except that the hydrophilic layer in Example 29 was changed to the hydrophilic layer in the following Examples.
Example 48: hydrophilic layer of Example 25 Example 49: hydrophilic layer of Example 26

(Comparative Example 4)
A surface hydrophilic member of Comparative Example 4 was obtained in the same manner as in Example 29 except that (C) polyethylene oxide (molecular weight: 400) was removed.

(Comparative Example 5)
In Example 29, a surface hydrophilic member of Comparative Example 5 was obtained in the same manner as in Example 29 except that the amount of (C) polyethylene oxide (molecular weight: 400) added was 0.1 g.

(Example 50)
[Hydrophilic sol-gel solution]
100 g of purified water, (A) 8.5 g of specific hydrophilic polymer (I-1), (B) 2.8 g of specific hydrophilic polymer (II-71), (C) 2.0 g of polyethylene oxide (molecular weight: 400) Prepared by mixing and stirring at room temperature for 2 hours.
[Hydrophilic composition]
116 g of purified water and 2.3 g of a 5% by weight aqueous solution of the surfactant used in Example 1 were mixed with the hydrophilic sol-gel solution to obtain a hydrophilic composition.
[Coating method]
An alkali degreased aluminum substrate (thickness: about 100 μm) was prepared, and the undercoat layer composition of Example 29 was bar coated onto the aluminum substrate, followed by oven drying at 150 ° C. for 30 minutes, and a dry coating amount of 0.1 g. An undercoat layer of / m ² was formed. After sufficiently cooling to room temperature, the above hydrophilic composition is bar coated and oven dried at 150 ° C. for 30 minutes to form a top coat layer having a dry coating amount of 0.4 g / m ² to obtain a hydrophilic member. It was.

(Example 51)
A hydrophilic member was obtained in the same manner as in Example 50 except that (B) the specific hydrophilic polymer (II-71) was changed to (B) the specific hydrophilic polymer (II-82) in Example 50.

(Examples 52 and 53)
In Example 50, a hydrophilic member was obtained in the same manner as in Example 50 except that (A) the specific hydrophilic polymer (I-1) was changed to the following.
Example 52: (A) Specific hydrophilic polymer (I-2)
Example 53: (A) Specific hydrophilic polymer (I-11)

(Examples 54 and 55)
In Example 50, a hydrophilic member was obtained in the same manner as in Example 50 except that the undercoat layer was changed to that used in the following Examples.
Example 54: Undercoat layer of Example 32 Example 55: Undercoat layer of Example 33

(Examples 56 to 58)
In Example 50, a hydrophilic member was obtained in the same manner as in Example 50 except that (C) polyethylene oxide (molecular weight: 400) was changed to the following.
Example 56: (C) polyethylene oxide (molecular weight: 600)
Example 57: (C) polyethylene oxide (molecular weight: 1,000)
Example 58: (C) Polypropylene oxide (molecular weight: 600)

(Example 59)
In Example 50, a hydrophilic member was prepared in the same manner as in Example 50 except that the following compound was added to the hydrophilic sol-gel solution.
Example 59: (E) tetramethoxysilane 0.5 g

(Examples 60 to 62)
A hydrophilic member was prepared in the same manner as in Example 50 except that the substrate was changed to the following.
Example 60: Glass substrate hydrophilized by UV / ozone treatment (thickness 1.1 mm)
Example 61: Polyethylene terephthalate substrate having a surface hydrophilized by glow treatment (thickness 50 μm)
Example 62: TAC substrate whose surface is hydrophilized by saponification treatment (thickness: 30 μm)

(Examples 63 and 64)
A hydrophilic member was prepared in the same manner as in Example 50 except that 0.5 g of the following compound was added to the hydrophilic composition of Example 50.
Example 63: TBZ (manufactured by China Kogyo Co., Ltd.) (antibacterial agent 1)
Example 64: Zeomic (manufactured by Sinanen Co., Ltd.) (antibacterial agent 2)

(Comparative Example 6)
A surface hydrophilic member of Comparative Example 6 was obtained in the same manner as in Example 50 except that (C) polyethylene oxide (molecular weight: 400) was omitted.

(Comparative Example 7)
A surface hydrophilic member of Comparative Example 5 was obtained in the same manner as in Example 50 except that the amount of (C) polyethylene oxide (molecular weight: 400) added was changed to 0.4 g.

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

[Evaluation of antifouling properties]
Put 0.2 g of palmitic acid in a sample bottle with a capacity of 50 ml, cover the mouth part of the sample bottle with the surface on which the hydrophilic member surface obtained above is formed facing down, at 105 ° C. Heated in an oven for 30 minutes. Further, it was washed with running water (2 L / h) for 30 minutes and dried at 80 ° C. for 30 minutes. This cycle was repeated 5 times and the contact angle was measured.
○: Contact angle is less than 30 ° △: Contact angle is 30 ° or more and less than 50 ° ×: Contact angle is 50 ° or more

[Evaluation of adhesion]
The hydrophilic member obtained above was immersed in purified water for 200 hours, dried, and then visually observed for film peeling.
○: No peeling △: Partial peeling ×: Whole peeling

(Dynamic friction coefficient)
About the hydrophilic member obtained above, the dynamic friction coefficient was measured with a surface measuring machine manufactured by “HEIDON-18 type” Shinto Kagaku Co., Ltd. under the conditions of a load of 50 g with a 5 mmφ steel ball and a pulling speed of 30 cm / min. It can be said that the lower the dynamic friction coefficient, the better the lubricity.

[Evaluation of water resistance]
A 120 cm ² size hydrophilic member was rubbed 10 times with a sponge and loaded in water under a load of 1 kg, and the remaining film ratio was measured from the weight change before and after that. The water resistance was judged by the remaining film ratio. If the water resistance is high, it can be said that the wear resistance is high.
○: Remaining film ratio is 80% or more Δ: Remaining film ratio is 60% or more and less than 80% ×: Remaining film ratio is less than 60%

[Evaluation of durability]
The hydrophilic member obtained above was cut into a size of 3 cm × 6 cm and immersed in 100 ml of purified water for 30 minutes. After drying, the dynamic friction coefficient was measured by the above method, and the durability was judged by the difference between the dynamic friction coefficient before and after immersion. It can be said that the smaller this difference is, the longer the lubricity can be maintained. Evaluation of the comparative example evaluated the member using (C) polyalkylene oxide.
○: Difference in dynamic friction coefficient is less than 0.1 Δ: Difference in dynamic friction coefficient is 0.2 or more and less than 0.1 ×: Difference in dynamic friction coefficient is less than 0.2

  Each evaluation result is shown in Tables 1 to 3 below.

  As shown in Table 1, the hydrophilic member using the hydrophilic composition of the present invention is excellent in lubricity in addition to exhibiting sufficient hydrophilicity, antifouling property, adhesion and wear resistance. On the other hand, in Comparative Example 1, since (C) polyethylene oxide was not used in the hydrophilic layer, the film was particularly inferior in lubricity. Further, in Comparative Example 2, although (C) polyethylene oxide was used, it was not possible to satisfy the numerical range of the dynamic friction coefficient specified in the present invention because the addition amount was small, and a film with insufficient lubricity became. Furthermore, in Comparative Example 3, the antifouling property was inferior because the hydrophilic polymer specified in the present invention was not used. Moreover, the comparative example 3 was also inferior to adhesiveness and water resistance.

  As shown in Table 2, it was confirmed that the hydrophilic member has improved adhesion by further having an undercoat layer between the substrate and the hydrophilic layer.

  As shown in Table 3, even when (A) the specific hydrophilic polymer and (B) the specific hydrophilic polymer are mixed and used, the hydrophilic member using the hydrophilic composition of the present invention has sufficient hydrophilicity. In addition to exhibiting properties, antifouling properties, adhesion and wear resistance, it has excellent lubricity.

  In Tables 4-6, each material used by the Example and the comparative example was described collectively.

(Note) PEO: Polyethylene oxide PPO: Polypropylene oxide PEO-PPO-PEO: Block copolymer in which PEO unit, PPO unit and PEO unit are bonded in this order TMOS: Tetramethoxysilane TEOS: Tetraethoxysilane TEOT: Tetraethoxy titanate TEOA: Triethoxyaluminate MTMS: Methyltrimethoxysilane ETMS: Ethyltrimethoxysilane DMDMS: Dimethyldimethoxysilane Ti: Catalyst consisting of acetylacetone and tetraethyl orthotitanate Al: Ethylacetoacetate aluminum diisopropylate Zr: Zirconium chelate Compound

Claims (17)

(A) hydrophilic polymer (I) having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2), and (B) the following general formula At least one hydrophilic polymer (II) having a structural unit represented by (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain;
(C) a hydrophilic composition containing polyalkylene oxide,
A hydrophilic composition, wherein the coating formed of the hydrophilic composition has a coefficient of dynamic friction of 0.3 or less.

(In 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 represent Each independently represents a single bond or a polyvalent organic linking group, x and y represent a composition ratio, x represents a number such that 0 <x <100, y represents 0 <y <100, and 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) where, R a, R b} and R _c each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group; R _d represents a linear, branched or cyclic alkyl group _; and R _e and R _f each independently Represents a hydrogen atom or a linear, branched or cyclic alkyl group, 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 formula (II-1) and ^(II-2), .q representing each is R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group represents an integer of 1 to ^{3, L 201} and ^{L 202} are Each independently 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 ), wherein R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, and R _d represents Represents a linear, branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.)   2. The hydrophilic composition according to claim 1, wherein the polyalkylene oxide (C) is contained in an amount of 5% by mass or more based on a non-volatile component of the hydrophilic composition.   The hydrophilic composition according to claim 1 or 2, wherein the (C) polyalkylene oxide has a mass average molecular weight of 200 or more.   The hydrophilic composition comprises (A) the hydrophilic polymer (I) and (B) the hydrophilic polymer (II), and the (A) hydrophilic polymer (I) and the (B) hydrophilic polymer. The mass ratio ((A) hydrophilic polymer / (B) hydrophilic polymer) to (II) is in the range of 95/5 to 50/50, according to any one of claims 1 to 3. Hydrophilic composition.   The hydrophilic composition according to claim 1, wherein the hydrophilic composition further contains (D) a catalyst.   The hydrophilic composition according to claim 5, wherein the catalyst (D) is a non-volatile catalyst.   The hydrophilic composition according to claim 1, wherein the hydrophilic composition further contains (E) an alkoxide compound of an element selected from Si, Ti, Zr, and Al.   A hydrophilic member comprising a hydrophilic layer formed of the hydrophilic composition according to claim 1 on a substrate.   The hydrophilic member according to claim 8, further comprising an undercoat layer between the substrate and the hydrophilic layer.   The hydrophilic member according to claim 9, wherein the undercoat layer is formed of a composition for an undercoat layer containing (D) a catalyst.   The hydrophilic member according to claim 10, wherein the catalyst (D) contained in the undercoat layer composition is a non-volatile catalyst.   The hydrophilic member according to claim 9, wherein the undercoat layer further contains (E) an alkoxide compound of an element selected from Si, Ti, Zr, and Al.   An undercoat layer composition is applied onto a substrate, heated and dried to form an undercoat layer. The hydrophilic composition is applied onto the undercoat layer, and heated and dried to form an overcoat layer. It is made, The hydrophilic member in any one of Claims 9-12 characterized by the above-mentioned. The fin body;
A fin material comprising a hydrophilic layer provided on at least a part of a surface of the fin body, wherein the hydrophilic layer is coated with the hydrophilic composition according to any one of claims 1 to 7. The fin material characterized by becoming.   The fin material according to claim 14, wherein the fin body is made of aluminum.   A heat exchanger using the fin material according to claim 15.   An air conditioner using the heat exchanger according to claim 16.