JP2009235129A - Hydrophilic composition and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic composition for forming a hydrophilic layer having high hydrophilicity and film strength, and to provide a hydrophilic member provided with the hydrophilic layer. <P>SOLUTION: The hydrophilic composition comprises (A) a hydrophilic polymer having a silicon atom having a hydroxy group and/or a hydrolyzable functional group, and (B) a crosslinking agent having two or more silicon atoms having a hydroxy group and/or a hydrolyzable functional group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydrophilic member having various anti-fouling properties, anti-fogging properties, quick drying properties such as water on various substrate surfaces, and excellent friction resistance and scratch resistance.

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 surface of a transparent substrate in which a high refractive index layer and a low refractive index layer made of a metal oxide or the like are laminated, and a surface of a transparent substrate such as an inorganic or organic fluoride compound is used. Known are those in which a low refractive index layer is formed as a single layer, or those in which a coating layer containing transparent fine particles is formed on the surface of a transparent plastic film substrate and external light is irregularly reflected by the uneven surface. These anti-reflective optical member surfaces, like the optical members described above, can easily be contaminated with fingerprints, sebum, and other dirt when used by humans. In addition to the problem, the surface of the antireflection film usually has fine irregularities, and there is a problem that it is difficult to remove dirt.

Various techniques have been proposed for forming on the surface an anti-smudge function that makes it difficult to get dirt on the surface of a solid member or that makes it easier to remove the attached dirt. In particular, as a combination of an antireflection member and an antifouling member, for example, an 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 hydrogen atom (for example, see Patent Document 4) has been proposed.
However, the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and the surface energy such as fluorine and silicon is low. The surface treatment with a material is concerned with a decrease in antifouling performance over time, and therefore, development of an antifouling member having excellent antifouling properties and durability is desired.

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

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

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

In order to achieve the above-mentioned problems, the anti-fogging and anti-fogging properties of the hydrophilic surface with a cross-linked structure by hydrolyzing and condensation-polymerizing the hydrophilic polymer and the alkoxide are focused on the characteristics of the sol-gel organic-inorganic hybrid film. It has been found that it exhibits fouling and has good wear resistance (see Patent Document 6). A hydrophilic surface layer having such a crosslinked structure can be easily obtained by combining a specific hydrophilic polymer having a reactive group at its terminal and a crosslinking agent.
However, the conventional hydrophilic material has a drawback that it lacks flexibility when a film is formed on a film-like substrate.
JP-A 64-86101 JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 International Publication No. 96/29375 Pamphlet JP 2002-361800 A Newspaper "Chemical Industry Daily" article dated January 30, 1995

  An object of the present invention is to provide a hydrophilic composition which is excellent in hydrophilicity and film strength and can form a flexible hydrophilic layer, and a hydrophilic member provided with the hydrophilic layer.

(1) (A) a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group, and (B) two silicon atoms having at least one of a hydroxyl group and a hydrolyzable functional group The hydrophilic composition containing the crosslinking agent which has the above.
(2) (A) The hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group has a structural unit represented by the following general formula (a-2), and is a polymer The hydrophilic polymer (A1) having a partial structure represented by the following general formula (a-1) at the chain end and / or the structural unit represented by the following general formula (a-3), and the following general formula It is a hydrophilic polymer (A2) which has a structural unit represented by (a-4), The hydrophilic composition as described in said (1) characterized by the above-mentioned.

In general formulas (a-1), (a-2), (a-3) and (a-4), R ^{1 to} R ¹³ each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ^{1 to} L ⁴ each independently represents a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and represents a number satisfying x + y = 100. n and m represent an integer of 1 to 3. Y ¹ and Y ² are —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 A structural unit having at least one structure selected from the group consisting of ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ) To express. Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.
(3) The hydrophilic composition contains (C) a catalyst that promotes a reaction of a hydrophilic polymer having a silicon atom having at least one of the hydroxyl group and the hydrolyzable functional group (A). The hydrophilic composition according to (1) or (2).
(4) The hydrophilic composition as described in any one of (1) to (3) above, wherein the catalyst (C) is a nonvolatile catalyst.
(5) The hydrophilic composition contains (D) an alkoxide compound of an element selected from Si, Ti, Zr, and Al, according to any one of (1) to (4), Hydrophilic composition.
(6) The hydrophilic composition includes the hydrophilic polymer (A1) and the hydrophilic polymer (A2), and the mass ratio of the hydrophilic polymer (A1) to the hydrophilic polymer (A2) (hydrophilic polymer ( The hydrophilic composition according to any one of (2) to (5), wherein A1) / hydrophilic polymer (A2)) is in the range of 5/95 to 50/50.
(7) A hydrophilic member comprising a hydrophilic layer formed from the hydrophilic composition according to any one of (1) to (6) on a substrate.
(8) The hydrophilic member according to (7), wherein an undercoat layer is provided between the substrate and the hydrophilic layer.
(9) The hydrophilic member according to (8), wherein the undercoat layer is formed from a composition containing (c) a catalyst.
(10) The hydrophilic member according to (9), wherein the catalyst (c) contained in the undercoat layer is a non-volatile catalyst.
(11) The (8) to (8) above, wherein the undercoat layer is formed from a composition containing (d) an alkoxide compound of an element selected from Si, Ti, Zr, and Al. (10) The hydrophilic member according to any one of (10).
(12) A fin material coated with the hydrophilic composition according to any one of (1) to (6).
(13) The fin material as described in (12) above, wherein the water contact angle is 40 ° or less after 5 cycles of aeration with palmitic acid for 1 hour, washing with water for 30 minutes, and drying for 30 minutes.
(14) An aluminum fin material, wherein the fin material according to (13) is made of aluminum.
(15) A heat exchanger using the aluminum fin material according to (14).
(16) An air conditioner using the heat exchanger according to (15).

  Since the hydrophilic composition according to the present invention contains (A) a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group (hereinafter referred to as (A) a hydrophilic polymer). , “A silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group” (that is, a silane coupling group) reacts to form a hydrophilic layer composed of an organic-inorganic composite film having a crosslinked structure. A high-strength film can be obtained. Therefore, a hydrophilic layer having excellent wear resistance and scratch resistance can be formed.

  Further, the hydrophilic composition according to the present invention contains (B) a cross-linking agent having two or more silicon atoms having at least one of a hydroxyl group and a hydrolyzable functional group (hereinafter referred to as (B) cross-linking agent). As a result, (B) a reaction between the silane coupling group of the crosslinking agent and (A) the silane coupling group of the hydrophilic polymer results in the formation of more crosslinked structures, resulting in a more dense and strong crosslinked structure. An organic-inorganic composite film can be formed. Therefore, according to the hydrophilic composition of the present invention, a highly hydrophilic hydrophilic layer can be formed while maintaining high hydrophilicity.

  Furthermore, unexpectedly, according to the hydrophilic composition containing the crosslinking agent (B), the flexibility of the film could be improved. This is considered to be because (A) the connection between the hydrophilic polymers became flexible by the organic linking group for linking the silane coupling group of the crosslinking agent or the inorganic linking group having an organic functional group. .

As an example of a specific embodiment of the present invention, (A) a hydrophilic polymer and (B) a crosslinking agent are dissolved in a suitable solvent and stirred, whereby hydrolysis / polycondensation proceeds, and a sol-like hydrophilic property is obtained. An organic-inorganic composite film (hydrophilic layer) having a hydrophilic functional group on the substrate surface is obtained by applying the hydrophilic composition to the substrate surface to form a film, and drying. Can be formed.
In a preferred embodiment, the hydrophilic composition contains (D) an alkoxide compound of an element selected from Si, Ti, Zr, and Al (hereinafter referred to as (D) an alkoxide compound). (D) By including an alkoxide compound, the reaction site which forms bridge | crosslinking increases in hydrolysis and polycondensation, and the organic-inorganic composite membrane | film | coat which has a higher density and firm bridge | crosslinking structure can be formed. It is considered that the hydrophilic layer made of this organic-inorganic composite film has higher strength, exhibits excellent wear resistance, and can maintain high hydrophilicity for a long period of time.

  ADVANTAGE OF THE INVENTION According to this invention, the hydrophilic composition which can form the hydrophilic layer which has high hydrophilic property, film | membrane strength, and a softness | flexibility on the surface of various board | substrates can be provided. Therefore, it is possible to provide a hydrophilic member that has antifouling properties, antifogging properties, quick drying properties such as water, and can exhibit excellent friction resistance and scratch resistance. Moreover, since cracks (cracks) and peeling of the film are eliminated, it can be used for flexible substrates (PET, TAC).

Hereinafter, preferred embodiments of the hydrophilic composition and the hydrophilic member according to the present invention will be described. [Hydrophilic composition]
[(A) hydrophilic polymer]
The hydrophilic layer is formed from a hydrophilic composition containing at least (A) a hydrophilic polymer (that is, (A) a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group). .
More specifically, (A) a hydrophilic polymer is dissolved in a solvent and stirred well, so that these components are hydrolyzed and polycondensed to form a hydrophilic neat organism that is an organic-inorganic composite sol solution. be able to. And, with this sol solution, a hydrophilic film having high hydrophilicity and high film strength can be formed.

  (A) It is preferable that the hydrophilic polymer has a silanol group or a hydrolyzable silyl group at a terminal portion and / or a side chain of the polymer. The hydrolyzable silyl group is a group that reacts with water to produce silanol (Si—OH). For example, one or more methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- This refers to an alkoxy group such as a butoxy group, or a combination of chlorine and the like.

(A) The hydrophilic polymer is preferably the following hydrophilic polymer (A1) and / or the following hydrophilic polymer (A2).
-Hydrophilic polymer (A1) which has a structural unit represented by the following general formula (a-2), and has the partial structure represented by the following general formula (a-1) at the terminal of a polymer chain.
-Hydrophilic polymer (A2) which has a structural unit represented by the following general formula (a-3), and a structural unit represented by the following general formula (a-4).

In general formulas (a-1), (a-2), (a-3) and (a-4), R ^{1 to} R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. .
Examples of the hydrocarbon group when R ^{1 to} R ¹³ represent a hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
R ¹ , R ² , R ¹² and R ¹³ are preferably a methyl group, an ethyl group, a propyl group or an isopropyl group from the viewpoints of effects and availability.
R ^{3 to} R ⁵ and R ^{6 to} R ¹¹ are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability.

These hydrocarbon groups may further have a substituent.
When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and the alkylene group.
Here, as the substituent, a monovalent nonmetallic atomic group excluding hydrogen is used. 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'- Rukyureido 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, Ryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino Group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group,

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfur group Sulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H) (Aryl)) and conjugated base groups thereof (hereinafter referred to as aryl phosphonate groups), phosphonooxy groups (-OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonatooxy group”), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugate base group thereof (hereinafter referred to as an alkylphosphonatooxy group), mono Arylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group It is done.

Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, Group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, and a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

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

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Rubonirubuchiru group,

  Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group , Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phos Phonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphos Onatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1 -Propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like can be mentioned.

L ^{1 to} L ⁴ each independently represents a single bond or a polyvalent organic linking group.
Here, the single bond means that the main chain of the polymer and X ¹ and Y ¹ are directly bonded without a linking chain.
An organic linking group refers to a linking group consisting of non-metallic atoms, specifically 0 to 200 carbon atoms, 0 to 150 nitrogen atoms, 0 to 200 oxygen atoms. , Consisting of 0 to 400 hydrogen atoms and 0 to 100 sulfur atoms (however, all of carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms and sulfur atoms are 0) Never). More specific examples of the linking group include the following structural units or combinations thereof.

L ¹ and L ² may be formed from a polymer or oligomer, and specifically, preferably include polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene, and the like made of an unsaturated double bond monomer. Other preferred examples include poly (oxyalkylene), polyurethane, polyurea, polyester, polyamide, polyimide, polycarbonate, polyamino acid, polysiloxane, etc., preferably polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene More preferred are polyacrylates and polymethacrylates.
The structural unit used for these polymers and oligomers may be one type or two or more types. In addition, when L ¹ is a polymer or oligomer, the number of constituent elements is not particularly limited, and the molecular weight is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and 1,000 to 200,000 is most preferred.

x and y represent a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and represents a number satisfying x + y = 100. x is preferably in the range of 10 <x <99, and more preferably in the range of 50 <x <99. y is preferably in the range of 1 <y <90, and more preferably in the range of 1 <y <50.
n and m represent an integer of 1 to 3.

Y ¹ and Y ² are —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 A structural unit having at least one structure selected from the group consisting of ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ) To express. Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.
_{Further, -CON (R a) (R} b), - OCON (R a) (R b), - NHCON (R a) (R b), - SO 2 N (R a) (R b) -PO 3 (R _e ) (R _f ), -OPO ₃ (R _e ) (R _f ), -PO ₂ (R _d ) (R _e ), -N (R _a ) (R _b ) (R _c ) or -N (R _a ) (R _b ) (R _c ) (R _g ) R _{a to} R _g may be bonded to each other to form a ring, and the formed ring is an oxygen atom, sulfur atom, nitrogen It may be a heterocycle containing a heteroatom such as an atom. R _{a to} R _g may further have a substituent, and examples of the substituent that can be introduced here include those mentioned above as the substituent that can be introduced.

Specific examples of R _a , R _b or R _c include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, and s-butyl. Preferred examples include a group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.

Specific examples of R _d include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, t-butyl, and isopentyl. Preferred examples include a group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
R _e, specifically as R _f, in addition to the alkyl groups mentioned R _d, a hydrogen atom; lithium, sodium, alkali metals such as potassium, calcium, alkaline earth such as barium metal, or ammonium, Examples include onium such as iodonium and sulfonium.
R _{d to} R _f may be bonded to each other to form a ring, and the formed ring may be a hetero ring containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. R _{d to} R _f may further have a substituent, and examples of the substituent that can be introduced here include those described above as the substituent that can be introduced. R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, and may further have a substituent. Examples of the substituent that can be introduced here include the above-described substituents that can be introduced. Those mentioned as groups can be mentioned as well.

Specific examples of R _g include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a nitrate anion, a sulfate anion, or a tetrafluoroborate anion, in addition to the alkyl groups listed as R _{a to} R _c Inorganic anions such as hexafluorophosphate anion, and organic anions such as methanesulfonate anion, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, and p-toluenesulfonate anion.
Y ¹ and ^{Y _{2, -CO 2 - Na +, -CONH}} 2, -SO 3 - Na +, -SO 2 NH 2, -PO 3 H 2 and the like are preferable.

  (A) The molecular weight of the specific hydrophilic polymer is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 1,000 to 200,000.

The aforementioned hydrophilic polymer (A) may be used alone or in combination of two or more. When the hydrophilic polymer (A1) and the hydrophilic polymer (A2) are mixed and used, the mass ratio of the hydrophilic polymer (A1) and the hydrophilic polymer (A2) contained in the hydrophilic composition (hydrophilic polymer (A1 ) / Hydrophilic polymer (A2)) is in the range of 5/95 to 50/50. The ratio is preferably 8/92 to 45/55, and more preferably 10/90 to 40/60.
By setting the mass ratio of the hydrophilic polymer (A1) and the hydrophilic polymer (A2) within the above range, the adhesiveness and the stain resistance are excellent while maintaining good hydrophilicity.

  Specific examples of the hydrophilic polymer (A1) [Exemplary compounds (I-1) to (I-50)] and specific examples of the hydrophilic polymer (A2) [Exemplary compounds (II-1) to (II-) 50)] together with its mass average molecular weight (M.W.) is shown below, but the present invention is not limited thereto. In addition, the polymer of the specific example shown below means that it is a random copolymer in which each structural unit described is contained by the described molar ratio.

As a polymerization method of the hydrophilic polymer (A1), radical polymerization is performed using a radical-polymerizable monomer represented by the structural unit and a compound having a chain transfer ability in radical polymerization, or a radical initiator. Can be synthesized. That is, in the latter, since the compound having a reactive group has chain transfer ability or radical initiation ability, it is possible to synthesize a polymer having a reactive group introduced at the end of the polymer main chain in radical polymerization.
As the polymerization method of the hydrophilic polymer (A2), any of the conventionally known methods can be used as the radical polymerization method.
This reaction mode is not particularly limited, but bulk reaction, solution reaction, suspension reaction, etc. may be performed in the presence of a radical polymerization initiator or irradiation with a high-pressure mercury lamp. Specifically, general radical polymerization methods include, for example, New Polymer Experimental Science 3, Polymer Synthesis and Reaction 1 (Edited by the Society of Polymer Science, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I) (Edited by Chemical Society of Japan, Maruzen), Materials Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

Further, (A) the hydrophilic polymer may be a copolymer with another monomer as described later. Examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. These known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.
The total proportion of these other monomers used for the synthesis of the copolymer other than the structural unit represented by the general formula is preferably 80% by mass or less, and more preferably 50% by mass or less.

  (A) The hydrophilic polymer is preferably 5 to 95% by mass, more preferably 15 to 90% by mass, and most preferably 20% from the viewpoint of curability and hydrophilicity with respect to the nonvolatile component of the hydrophilic composition. It is contained in a range of ˜85% by mass. Here, the “nonvolatile component” refers to a component excluding a volatile solvent.

[(B) Crosslinking agent]
The crosslinking agent (B) that can be used in the present invention is a compound having two or more silicon atoms having at least one of a hydroxyl group and a hydrolyzable functional group. The number of silicon atoms having at least one of a hydroxyl group and a hydrolyzable functional group is preferably 2 to 50, more preferably 2 to 40, and still more preferably 3 to 20. When it exists in this range, film strength can be made favorable, and when a hydrophilic composition is prepared, it does not gel or rapidly increase in viscosity. Further, such a crosslinking agent having two or more silicon atoms having at least one of a hydroxyl group and a hydrolyzable functional group is not usually used because there is a concern that the hydrophilicity of the film is greatly reduced. In (A), since the hydrophilic polymer used was highly hydrophilic, an effect more than expected could be exhibited. Furthermore, since (B) the crosslinking agent has appropriate organic and inorganic properties, (A) it is possible to impart flexibility and strong bonding to the crosslinked structure of the hydrophilic polymer.
Here, the silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group is preferably a partial structure represented by the following general formula (b).

In general formula (b), R <^14> , R < ¹⁵ > represents a hydrogen atom or a hydrocarbon group (preferably C1-C8) each independently. a represents an integer of 1 to 3.

Examples of the hydrocarbon group when R ¹⁴ and R ¹⁵ represent a hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ¹⁴ and R ¹⁵ 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, and examples of the substituent that can be introduced here include those that can be introduced when R ^{1 to} R ¹³ are hydrocarbon groups. The same can be cited as well.

(B) A preferred form of the crosslinking agent is a compound in which two or more (preferably 2 to 50) groups represented by the general formula (b) are linked by a linking group.
Such a linking group may be a divalent or higher valent linking group, and may be an organic linking group or an inorganic linking group, but an organic linking group is preferred from the viewpoint of improving flexibility. Here, the organic linking group means a linking group composed of non-metallic atoms, specifically, 1 to 200 carbon atoms, 0 to 150 nitrogen atoms, 0 to 200 atoms. Of oxygen atoms, 0 to 400 hydrogen atoms, and 0 to 100 sulfur atoms. More specific examples of the linking group can be the same as those exemplified for L ^{1 to} L ⁴ .

The inorganic linking group means a linking group composed of a metal atom. Examples of the metal include a silicon atom, a titanium atom, a zirconium atom, and an aluminum atom. Among these, a silicon atom and a titanium atom are preferable, and a silicon atom is more preferable.
In the case of an inorganic linking group, it is preferable to have an organic substituent, and specific examples of the organic substituent include the hydrocarbon groups exemplified as R ^{1 to} R ¹⁴ .

The (B) cross-linking agent according to the present invention may be used alone or in combination of two or more.
(B) The crosslinking agent is preferably used in the hydrophilic composition of the present invention in the range of 1 to 50% by mass, more preferably 2 to 40% by mass with respect to the nonvolatile component.
(B) A commercially available product can be easily obtained as the crosslinking agent, and can also be obtained by a known synthesis method, for example, a hydrosilylation reaction between a trialkoxysilane and a diallyl group-containing compound.
Specific examples of (B) the crosslinking agent are shown below, but the present invention is not limited to these. Among specific examples, (1), (2), (5), (6), (16), (17), (19), (20), (39), and (41) are particularly preferable.

[(C) Catalyst]
The hydrophilic composition preferably contains (A) a catalyst (C) that promotes the reaction of the hydrophilic polymer (hereinafter referred to as (C) catalyst). (C) By containing a catalyst, in preparation of the above-mentioned organic-inorganic composite sol liquid, a hydrolysis and a polycondensation reaction are accelerated | stimulated and practically preferable reaction efficiency can be obtained.

(C) The catalyst is preferably a non-volatile catalyst. Here, a non-volatile catalyst means a catalyst having a boiling point other than 125 ° C., in other words, a boiling point of 125 ° C. or higher, or a catalyst having no boiling point (such as thermal decomposition, Including things that do not wake up).
Preferably, the catalyst (C) is an acidic catalyst or a basic catalyst that promotes a reaction that causes hydrolysis and polycondensation of the (D) alkoxide compound described later to cause a bond with the hydrophilic polymer (A).

The acidic catalyst or basic catalyst is an acid compound or basic compound used as it is, or in a state where the acidic compound or basic compound is dissolved in a solvent such as water or alcohol (hereinafter, these are all included, respectively) An acidic catalyst or a basic catalyst may also be used.
The concentration at which the acidic compound or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acidic compound or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acidic compound 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 kind of the acidic catalyst and 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, and sulfonic acids such as benzenesulfonic acid. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline.

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

  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, ethyl acetoacetate, butyl acetoacetate Such as ketoesters, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and the like, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy- Keto alcohols such as 2-pentanone, 4-hydroxy-4-methyl-2-heptanone and 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl-monoethanolamine, diethanolamine , Triethanol Amino alcohols such as min, methylol melamine, methylol urea, methylol acrylamide, enol active compounds such as malonic acid diethyl ester, etc., acetylacetone (2,4-pentanedione) methyl group, methylene group or carbonyl carbon has a substituent Compounds.

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

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

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

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

(C) The catalyst is preferably used in the range of 0 to 50 mass%, more preferably 5 to 25 mass% with respect to the nonvolatile components in the hydrophilic composition. Further, (C) the catalyst may be used alone or in combination of two or more.

[(D) Alkoxide Compound of Element Selected from Si, Ti, Zi, Al]
The hydrophilic composition preferably contains (D) an alkoxide compound of an element selected from Si, Ti, Zr, and Al (hereinafter referred to as (D) alkoxide compound).
The (D) alkoxide compound is preferably a hydrolyzable polymerizable compound having a polymerizable functional group in its structure and functioning as a crosslinking agent. When such a (D) alkoxide compound is contained in the hydrophilic composition together with the (A) hydrophilic polymer, when the hydrophilic composition is applied to the substrate surface and heated and dried, (A) hydrophilic The polymerizable polymer and the (D) alkoxide compound can be polycondensed to form a strong film having a crosslinked structure.
More specifically, the (D) alkoxide compound is preferably an alkoxide compound represented by the following general formula (D-1).

In General Formula (D-1), R ^d1 represents a hydrogen atom, an alkyl group, or an aryl group, R ^d2 represents an alkyl group or an aryl group, Y represents Si, Al, Ti, or Zr, and k is 0 to 0 Represents an integer of 2. When R ^d1 and R ^d2 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 alkoxide compound represented by the general formula (D-1) are shown below, but the present invention is not limited thereto.
When Y is Si, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltrimethoxysilane, Ethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-amino Propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane It can be mentioned. Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

When Y is Al, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like can be mentioned.
When Y is Ti, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl trimethoxy titanate, methyl triethoxy titanate, Examples thereof include ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate.
When Y is Zr, for example, a zirconate corresponding to the compound exemplified as containing titanium may be mentioned.
Among these, an alkoxide compound in which Y is Si is preferable from the viewpoint of film properties.

(D) The alkoxide compound 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. (D) An alkoxide compound may be used individually by 1 type, or may be used together 2 or more types.
(D) The alkoxide compound can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.

[Other ingredients]
In addition to the essential components, various compounds can be used in the hydrophilic composition in accordance with the purpose as long as the effects of the present invention are not impaired. Hereinafter, components that can be used in combination will be described.
(Surfactant)
In order to improve the coating surface of the hydrophilic composition, it is preferable to use a surfactant. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.

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

  It does not specifically limit as an anionic surfactant, A conventionally well-known thing 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.

It does not specifically limit as a cationic surfactant, A conventionally well-known thing can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.
Among the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. Can be used.

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

(Antimicrobial agent)
In order to impart antibacterial, antifungal and antialgal properties, the hydrophilic composition may contain an antibacterial agent. In forming the hydrophilic layer, it is preferable to contain a hydrophilic / water-soluble antibacterial agent. By including a hydrophilic / water-soluble antibacterial agent, a hydrophilic member excellent in antibacterial, antifungal and antialgal properties can be obtained without impairing surface hydrophilicity.
As the antibacterial agent, it is preferable to use 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 on fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, fungi such as fungi and yeast, and the like are used.

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

The content of the antibacterial agent is generally 0.001 to 10% by mass, preferably 0.005 to 5% by mass, based on the nonvolatile components in the hydrophilic composition, 0.01 -3 mass% is more preferable, 0.02-1.5 mass% is especially preferable, and 0.05-1 mass% is the most preferable. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. Also,
When 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 may contain inorganic fine particles for the purpose of improving the cured film strength and hydrophilicity of the hydrophilic film to be formed. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified.
The inorganic fine particles preferably have an average particle diameter of 5 nm to 10 μm, more preferably 0.5 to 3 μm. Within the above range, it is possible to form a film that is stably dispersed in the hydrophilic layer, sufficiently retains the film strength of the hydrophilic layer, and is excellent in hydrophilicity. The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.

  The inorganic fine particles are used in the hydrophilic composition in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, based on the nonvolatile components. The inorganic fine particles can be used alone or in combination of two or more.

(UV absorber)
From the viewpoint of improving the weather resistance and durability of the hydrophilic member, an ultraviolet absorber can be added to the hydrophilic composition.
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)
An antioxidant can be added to the hydrophilic composition to improve stability. 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 order to ensure the formation of a uniform coating film during the formation of the hydrophilic layer, it is also effective to appropriately add an organic solvent to the hydrophilic composition.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
In this case, it is effective to add VOC (volatile organic solvent) in a range that does not cause a problem, and the amount thereof is preferably 0 to 50% by mass, more preferably based on the entire coating liquid when forming the hydrophilic member. Is in the range of 0-30% by weight.

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

The hydrophilic composition can contain zirconia chloride, nitrate, alkoxides and organic complexes from the viewpoint 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 hydrophilic composition as a nonvolatile component in the range of 0 to 50% by mass, more preferably 5 to 25% by mass.

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

  The solvent used in preparing the hydrophilic composition is not particularly limited as long as each component can be uniformly dissolved and dispersed. For example, an aqueous solvent such as methanol, ethanol, and water is preferable.

  As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming the hydrophilic layer can utilize a sol-gel method. Regarding the sol-gel method, Sakuo Sakuo, “Science of Sol-Gel Method”, Agne Jofusha Co., Ltd. (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by Latest Sol-Gel Method” It is described in detail in a book such as the Technical Center (published) (1992), and the methods described therein can be applied.

[Hydrophilic member]
[Hydrophilic layer]
A hydrophilic layer can be formed by coating a hydrophilic composition on various substrate surfaces and heating or drying.
The coating method can be a known method, and is not particularly limited. For example, spray coating, dip coating, flow coating, spin coating, roll coating, film applicator, screen printing, bar printing Methods such as a coater method, brush coating, and sponge coating can be applied.
In the formation of the hydrophilic layer, as the heating and drying conditions after coating with the hydrophilic composition, from the viewpoint of efficiently forming a high-density crosslinked structure, in the temperature range of 50 to 200 ° C. for 2 minutes to It is preferable to carry out for about 1 hour, and it is more preferable to dry in the temperature range of 80 to 160 ° C. for 5 to 30 minutes. Moreover, as a heating means, it is preferable to use a well-known means, for example, the dryer etc. which have a temperature control function.

Moreover, when coating a board | substrate with a hydrophilic composition, a catalyst can be mixed just before a coating. Specifically, it is preferable to apply within 1 hour immediately after catalyst mixing. If the catalyst is mixed and then coated after standing for a long time, the viscosity of the hydrophilic composition increases, 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.

The thickness of the hydrophilic layer is preferably 0.01 μm to 100 μm, more preferably 0.02 μm to 80 μm, and most preferably 0.05 μm to 50 μm. When the film thickness is 0.01 μm or more, it is preferable because sufficient hydrophilicity and durability can be obtained. When the film thickness is 100 μm or less, there is no problem in film forming properties such as cracking, which is preferable.
The dry coating amount of the hydrophilic layer, preferably ^{0.01g / m 2 ~100g / m 2} , more preferably ^{0.02g / m 2 ~80g / m 2} , particularly preferably from 0.05g / m ² ~50g / with m ^2, it is possible to obtain a film thickness of the.

[Undercoat layer]
An undercoat layer is preferably provided between the substrate and the hydrophilic layer.
The adhesion between the substrate and the hydrophilic layer is realized by the reaction between the substrate surface and the reactive groups of the hydrophilic layer. Actually, when there are not so many reactive groups on the substrate, the hydrophilic layer can be adhered through an undercoat layer rich in reactive groups.
The undercoat layer preferably contains (c) a catalyst, and (c) the catalyst is preferably a non-volatile catalyst. By using a non-volatile catalyst for the undercoat layer, it can be present in the film while maintaining its activity without volatilization even in the drying process when forming the undercoat layer or the hydrophilic layer. As a result, the cross-linking reaction can be further advanced over time, and the coating film has a very high strength. Further, since the non-volatile catalyst exists at the interface with the substrate without losing the activity, the reaction between the substrate and the hydrophilic layer proceeds with time, and high adhesion can be realized.

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

  Although it does not specifically limit as a silane coupling agent, What has the functional group which shows acidity or alkalinity is mentioned, More specifically, peroxo acid, carboxylic acid, carbohydrazone acid, carboxymidic acid, sulfonic acid, sulfinic acid Silane coupling agents having a functional group showing acidity such as sulfenic acid, selenonic acid, selenic acid, selenic acid, telluronic acid, and the above alkali metal salts, or a basic functional group such as amino group It is done.

  (C) A catalyst is used in the composition for undercoat layer formation, Preferably it is 0-50 mass% with respect to a non-volatile component, More preferably, it is used in 5-25 mass%. Further, (c) the catalyst may be used alone or in combination of two or more.

The undercoat layer is obtained by hydrolyzing and polycondensing a composition having at least (d) an alkoxide compound of an element selected from Si, Ti, Zr, and Al and a nonvolatile (c) catalyst. It is preferable. (D) Examples of the alkoxide compound of an element selected from Si, Ti, Zr, and Al include the same alkoxide compounds as those described above.
(D) The alkoxide compound of an element selected from Si, Ti, Zr, and Al is preferably 5 to 95% by mass, more preferably 10 to 90% by mass with respect to the nonvolatile component in the undercoat layer forming composition. Used in the range of%. Further, (d) the alkoxide compound of an element selected from Si, Ti, Zr, and Al may be used alone or in combination of two or more. It was.

  In the undercoat layer, a non-volatile catalyst is contained without losing activity, and in particular when it is also present on the surface thereof, when a hydrophilic layer is further provided on the undercoat layer, The adhesion at the interface between the undercoat layer and the hydrophilic layer is extremely high.

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

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

Examples of the water-dispersible latex include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.
The above hydrophilic resin and water-dispersible latex may be used alone or in combination of two or more, or a hydrophilic resin and a water-dispersible latex may be used in combination.
Moreover, you may use the crosslinking agent which bridge | crosslinks the said hydrophilic resin and water-dispersible latex.
As a crosslinking agent, the crosslinking agent which forms bridge | crosslinking with a well-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 include compounds, silane coupling agents such as tetraalkoxysilane, metal cross-linking agents such as acetylacetonate of aluminum, copper, and iron (III), and polymethylol compounds such as trimethylolmelamine and pentaerythritol. Among these thermal crosslinking agents, a water-soluble crosslinking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic layer.
Wherein the hydrophilic resin and / or water-dispersible latex total amount of the undercoat layer is preferably from 0.01 to 20 g / m ^2, 0.1 to 10 g / m ² is more preferable.

The undercoat layer forming composition can also be adjusted by the same method as the above hydrophilic film forming composition. A plurality of undercoat layers may be provided.
The thickness of the undercoat layer is preferably 0.01 μm to 100 μm, more preferably 0.02 μm to 80 μm, and most preferably 0.05 μm to 50 μm.
The dry coating amount of the undercoat layer forming composition is preferably 0.01 g / m ^{2 to} 100 g / m ² , more preferably 0.02 g / m ^{2 to} 80 g / m ² , and particularly preferably 0.05 g / m ^2. ~ 50g /
With m ^2, it is possible to obtain a film thickness of the.

[Other layers]
The hydrophilic member of the present invention can be used by appropriately adding another layer depending on the purpose, form and place of use. The layer structure added as needed is described below.
1) Adhesive layer When the hydrophilic member of the present invention is used by being attached to another substrate, a pressure-sensitive adhesive that is a pressure-sensitive adhesive is preferably used as an adhesive layer on the back surface of the substrate. As an adhesive, what is generally used for an adhesive sheet, such as a rubber adhesive, an acrylic adhesive, a silicone adhesive, a vinyl ether adhesive, and a styrene adhesive, can be used.
When an optically transparent material is required, an adhesive for optical use is selected. When a pattern such as coloring, semi-transparency, or matte 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 resin, a terpene resin, a petroleum resin, a styrene resin, and a hydrogenation resin such as these can be used alone or in combination.
The adhesive strength of the adhesive is generally called strong adhesion, and is 200 g / 25 mm or more, preferably 300 g / 25 mm or more, and more preferably 400 g / 25 mm or more. In addition, the adhesive force here is based on JIS Z 0237 and is a value measured by a 180 degree peel test.

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

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

〔substrate〕
The substrate is not particularly limited, but glass, plastic, metal, tile, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, a combination thereof, and a laminate thereof can be suitably used. . Particularly preferred substrates are glass substrates, plastic substrates, and aluminum substrates.
Glass plates 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 (Indium Tin
A glass plate provided with an inorganic compound layer formed of a metal oxide such as Oxide; a metal halide such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride; 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 hydrophilic layer can be applied as it is with the base glass, but if necessary, surface hydrophilic treatment is performed on one side or both sides by an oxidation method, a roughening method or the like for the purpose of improving the adhesion of the hydrophilic layer. be able to. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

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

  The plastic substrate 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 physical properties such as resistance It is selected in consideration of physical properties such as strength such as impact 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, ethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, polysulfone. And films or sheets of polyether ketone, acrylic, nylon, fluororesin, polyimide, polyether imide, polyether sulfone and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use. The thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for a plane or the place where intensity | strength is requested | required.

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

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

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

[Manufacture of hydrophilic members]
In the hydrophilic member of the present invention, a hydrophilic composition containing the (A) hydrophilic polymer and (B) a crosslinking agent is applied on a substrate, and preferably heated and dried to form a hydrophilic layer. Can be manufactured. The heating temperature and heating time for forming the hydrophilic layer are not particularly limited as long as the solvent and the time in which the solvent in the sol solution can be removed and a strong film can be formed. It is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour.
A known method can be used as the coating method, and there is no particular limitation. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method, screen printing method, bar printing Methods such as a coater method, brush coating, and sponge coating can be applied.

[Form / Use]
The form of the hydrophilic member of the present invention is not particularly limited, and can be a sheet form, a roll form, a ribbon form, or the like. An adhesive layer or the like may be provided on the back surface of the substrate so that it can be attached to another member.

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

  When applying (using, pasting) to a window glass or the like, transparency is important from the viewpoint of ensuring visibility. 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%.

In addition, when the antifouling effect is expected for the hydrophilic member of the present invention, the substrate is made of, for example, metal, tile, ceramics, wood, stone, cement, concrete, fiber, fabric, in addition to glass and plastic, Any of paper, combinations thereof, and laminates thereof can be suitably used. Particularly preferred substrates are glass substrates, plastic substrates, and aluminum substrates.
Applications with antifouling components include building materials, building exteriors such as exterior walls and roofs, building interiors, window rails, window sashes, window frames, window glass, shutters, screen doors, structural members, automobiles, railways Exterior and painting of vehicles such as vehicles, aircraft, ships, bicycles and motorcycles, exteriors of machinery and equipment, dustproof covers and coatings, signboards, traffic signs, various display devices, advertising towers, noise barriers for roads, and soundproofing for railways Walls, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, soundproof walls, solar battery covers, solar water heater and other heat collector covers, plastic houses, vehicle lighting cover, tent materials, reflectors, Streetlight, pavement, outdoor lighting, artificial waterfall / artificial fountain stone / tile, bridge, greenhouse, exterior wall material, sealer between walls and glass, guardrail, veranda, vending machine, air conditioner indoor unit, air conditioner room Machine, heat exchanger fins, outdoor benches, shutters, toll booths, toll boxes, roof tiles, housing equipment, toilet bowls, bathtubs, wash basins, mirrors, lighting fixtures, lighting covers, kitchenware, dishes, dishwashers, dish drying A bowl, a sink, a cooking range, a kitchen hood, a ventilation fan, and a film to be attached to the surface of the article.
It can also be applied to snow country roofing materials, antennas, power transmission lines, etc., and in that case, characteristics excellent in snow accretion prevention can be obtained.

In addition, when the hydrophilic member of the present invention is expected to have quick drying properties such as water, the base material is, for example, metal, tile, ceramics, wood, stone, cement, concrete, fiber, in addition to glass and plastic. Any of fabrics, papers, combinations thereof, and laminates thereof can be suitably used. Particularly preferred substrates are glass substrates, plastic substrates, and aluminum substrates.
The above-mentioned use is mentioned as a use which can apply a member which has quick-drying effects, such as water. In addition, when each product has a drying step, the drying time can be shortened and the productivity can be improved.

Among the above uses, the hydrophilic member according to the present invention is preferably applied to a fin material, and is preferably applied to an aluminum fin material. That is, it is preferable to apply the hydrophilic composition according to the present invention to a fin material (preferably an aluminum fin material) to form a hydrophilic layer on the surface of the fin material.
Aluminum fin materials used for heat exchangers such as indoor air conditioners and automobile air conditioners have water droplets formed by condensed water generated during cooling and staying between the fins. In addition, the adhering of dust or the like between the fins similarly reduces the cooling capacity. With respect to these problems, by applying the hydrophilic member of the present invention to the fin material, a fin material excellent in hydrophilicity, antifouling property, and sustainability thereof can be obtained. 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 material include a degreased surface and an aluminum plate subjected to chemical conversion treatment as necessary. It is preferable that the fin material made of aluminum has a surface subjected to 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 a thin plate such as aluminum used for the fin material for heat exchanger, according to JIS standard, pure aluminum plate such as 1100, 1050, 1200, 1N30, Al-Cu alloy plate such as 2017, 2014, 3003, 3004, etc. Any of Al-Mn alloy plates, Al-Mg alloy plates such as 5052 and 5083, and Al-Mg-Si alloy plates such as 6061 may be used, and the shape thereof may be either a sheet or a coil. But it ’s okay.

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. . As the air conditioner, any of room air conditioner, packaged air conditioner, car air conditioner, etc. may be used.
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 to these examples.
(Synthesis of hydrophilic polymer (I-1))
In a 200 ml three-necked flask, 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethylformamide were added, and 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) under a nitrogen stream at 65 ° C. The reaction was started by adding. After stirring for 6 hours, the solution was returned to room temperature and poured into 1.5 L of methanol, and a solid precipitated. The obtained solid was washed with acetone, and then the hydrophilic polymer (I-1) as the exemplified compound (I-1) was obtained. The mass after drying was 21.7 g. It was a polymer having a mass average molecular weight of 9,000 according to GPC (polyethylene oxide standard).

(Synthesis of hydrophilic polymer (II-1))
A 500 ml three-necked flask is charged with 56.9 g of acrylamide, 11.6 g of acrylamide-3- (ethoxysilyl) propyl, and 280 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methyl) under a nitrogen stream at 80 ° C. 2.3 g of dimethyl propionate) was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The mixture was put into 2 liters of acetone, and the precipitated solid was collected by filtration. The obtained solid was washed with acetone, and then hydrophilic polymer (II-1) which is the exemplified compound (II-1) was obtained. The mass after drying was 65.6 g. It was a polymer having a mass average molecular weight of 22,000 according to GPC (polyethylene oxide standard).
Thereafter, the hydrophilic polymer used in the examples was synthesized by the same method as described above and used for evaluation.

Example 1
[Hydrophilic sol-gel solution]
In 100 g of purified water, (A) 10 g of the hydrophilic polymer (I-1) as a hydrophilic polymer, (B) 1.5 g of the cross-linking agent (5) as a cross-linking agent are mixed and stirred at room temperature for 2 hours. Prepared.
[Hydrophilic composition]
The hydrophilic sol-gel solution was mixed with 2.5 g of a 5% by mass aqueous solution of the following anionic surfactant to obtain a hydrophilic composition.
[Coating method]
An alkali degreased aluminum substrate (thickness of 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 0.7 g / m ² . A hydrophilic layer was formed to obtain a hydrophilic member of Example 1. The thickness of the hydrophilic layer was 0.7 μm.

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

(Example 3)
A hydrophilic member of Example 3 was prepared in the same manner as in Example 2 except that the catalyst (C) in Example 2 was changed to the following.
Example 3: 0.2 g of titanium acetylacetonate
0.1 g of acetylacetone and 0.1 g of tetraethyl orthotitanate were added to the hydrophilic sol-gel solution.

(Examples 4 and 5)
A hydrophilic member was prepared in the same manner as in Example 3 except that the hydrophilic polymer (A) in Example 3 was changed to the following.
Example 4: Hydrophilic polymer (I-2) (Exemplary compound (I-2))
Example 5: Hydrophilic polymer (I-11) (Exemplary compound (I-11))

(Examples 6 and 7)
A hydrophilic member was prepared in the same manner as in Example 3 except that the crosslinking agent (B) in the hydrophilic composition in Example 3 was changed to the following.
Example 6: Crosslinking agent (39) (Exemplary Compound (39))
Example 7: Crosslinking agent (41) (Exemplary Compound (41))

(Examples 8 and 9)
A hydrophilic member was prepared in the same manner as in Example 3 except that the catalyst (C) in Example 3 was changed to the following.
Example 8: Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) 0.2 g
Example 9: 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.

(Example 10)
In Example 3, a hydrophilic member was prepared in the same manner as in Example 3 except that the following compound was added as the (D) alkoxide compound to the hydrophilic sol-gel solution.
Example 10: (D) 0.5 g of tetramethoxysilane

Example 11
[Sol-gel solution for undercoat]
200 g of ethyl alcohol, 10 g of acetylacetone as the catalyst (c), 10 g of tetraethyl orthotitanate, and 100 g of purified water were mixed with 8 g of tetramethoxysilane as the (d) alkoxide compound and stirred at room temperature for 2 hours to prepare.
[Composition for undercoat layer]
30 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 450 g of purified water were mixed with 500 g of the sol-gel solution for undercoat layer to obtain a coating solution.
[Coating method]
An alkali-degreased aluminum substrate (thickness: about 100 μm) is prepared, and the undercoat layer composition is bar-coated on the aluminum substrate and oven-dried at 100 ° C. for 30 minutes, and the dry coating amount is 0.2 g / m. ^Two subbing layers were formed. The thickness of the undercoat layer was 0.2 μm. After sufficiently cooling at room temperature, the hydrophilic layer of Example 3 was formed on the undercoat layer to obtain the hydrophilic member of Example 11.

Example 12
The hydrophilic layer of Example 10 was formed on the undercoat layer of Example 11 to obtain the hydrophilic member of Example 12.

(Examples 13 and 14)
A hydrophilic member was prepared in the same manner as in Example 11 except that (A) the specific hydrophilic polymer in Example 11 was changed to the following.
Example 15: Hydrophilic polymer (I-2)
Example 16: Hydrophilic polymer (I-11)

(Examples 15 and 16)
A hydrophilic member was prepared in the same manner as in Example 11 except that the crosslinking agent (B) in the hydrophilic composition in Example 11 was changed to the following.
Example 15: Crosslinker (39)
Example 16: Crosslinking agent (41)

(Example 17)
A hydrophilic member of Example 17 was prepared in the same manner as in Example 11 except that the substrate was changed to a polyethylene terephthalate substrate (thickness: 50 μm) whose surface was hydrophilized by glow treatment.

(Examples 18 and 19)
A hydrophilic member was prepared in the same manner as in Example 17 except that (A) the specific hydrophilic polymer in Example 17 was changed to the following.
Example 18: Hydrophilic polymer (I-2)
Example 19: Hydrophilic polymer (I-11)

(Examples 20 and 21)
A hydrophilic member was prepared in the same manner as in Example 17 except that the crosslinking agent (B) in the hydrophilic composition in Example 17 was changed to the following.
Example 20: Crosslinker (39)
Example 21: Crosslinker (41)

(Example 22)
A hydrophilic member of Example 22 was prepared in the same manner as in Example 11 except that the substrate was changed to a TAC substrate (30 μm thick) whose surface was hydrophilized by saponification.

(Examples 23 and 24)
A hydrophilic member was prepared in the same manner as in Example 22 except that the hydrophilic polymer (A) in Example 22 was changed to the following.
Example 23: Hydrophilic polymer (I-2)
Example 24: hydrophilic polymer (I-11)

(Examples 25 and 26)
A hydrophilic member was prepared in the same manner as in Example 22 except that the crosslinking agent (B) in the hydrophilic composition in Example 22 was changed to the following.
Example 25: Crosslinking agent (39)
Example 26: Crosslinking agent (41)

(Examples 27 and 28)
A hydrophilic member was prepared in the same manner as in Example 11 except that the following compound was added to the hydrophilic composition of Example 11.
Example 27: Additive 1 (zirconium oxychloride 2.0 g)
Example 28: Antibacterial agent 1 (TBZ (manufactured by China Kogyo Co., Ltd.) 0.5 g)

(Comparative Example 1)
A hydrophilic member of Comparative Example 1 was obtained in the same manner as in Example 10 except that (B) the crosslinking agent (5) was omitted.

(Comparative Example 2)
A hydrophilic member of Comparative Example 2 was obtained in the same manner as in Example 12 except that (B) the crosslinking agent (5) was omitted.

(Example 29)
[Hydrophilic sol-gel solution]
In 100 g of purified water, (A) 10 g of the hydrophilic polymer (II-1) as the hydrophilic polymer and (B) 1.5 g of the crosslinking agent (5) as the crosslinking agent are mixed and stirred at room temperature for 2 hours to prepare. did.
[Hydrophilic composition]
The hydrophilic sol-gel solution was mixed with 2.5 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 to obtain a hydrophilic composition.
[Coating method]
An alkali degreased aluminum substrate (thickness of 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 0.7 g / m ² . A hydrophilic layer was formed to obtain a hydrophilic member of Example 29. The thickness of the hydrophilic layer was 0.7 μm.

(Example 30)
A hydrophilic member of Example 30 was prepared in the same manner as in Example 29 except that 0.05 g of a 1N hydrochloric acid aqueous solution was added as a catalyst (C) to the hydrophilic sol-gel solution of Example 29.

(Example 31)
A hydrophilic member of Example 31 was prepared in the same manner as in Example 30 except that (C) the catalyst was changed to the following in Example 30.
Example 31: 0.2 g of titanium acetylacetonate
0.1 g of acetylacetone and 0.1 g of tetraethyl orthotitanate were added to the hydrophilic sol-gel solution.

(Examples 32 and 33)
A hydrophilic member was prepared in the same manner as in Example 31 except that (A) the specific hydrophilic polymer was changed to the following in Example 31.
Example 32: Hydrophilic polymer (II-3) (Exemplary compound (II-3))
Example 33: Hydrophilic polymer (II-11) (Exemplary compound (II-11))

(Examples 34 and 35)
A hydrophilic member was prepared in the same manner as in Example 31 except that the crosslinking agent (B) in the hydrophilic composition in Example 31 was changed to the following.
Example 34: Crosslinking agent (39)
Example 35: Crosslinking agent (41)

(Examples 36 and 37)
A hydrophilic member was prepared in the same manner as in Example 31 except that the catalyst (C) in Example 31 was changed to the following.
Example 36: Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) 0.2 g
Example 37: 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.

(Example 38)
In Example 31, a hydrophilic member was prepared in the same manner as in Example 31 except that the following compound was added as the (D) alkoxide compound to the hydrophilic sol-gel solution.
Example 38: (D) 0.5 g of tetramethoxysilane

(Example 39)
[Sol-gel solution for undercoat]
200 g of ethyl alcohol, 10 g of acetylacetone as the catalyst (c), 10 g of tetraethyl orthotitanate, and 100 g of purified water were mixed with 8 g of tetramethoxysilane as the (d) alkoxide compound and stirred at room temperature for 2 hours to prepare.
[Composition for undercoat layer]
30 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 450 g of purified water were mixed with 500 g of the sol-gel solution for undercoat layer to obtain a coating solution.
[Coating method]
An alkali degreased aluminum substrate (thickness: about 100 μm) is prepared, and the undercoat layer composition is bar-coated on the aluminum substrate and oven-dried at 100 ° C. for 10 minutes to obtain a dry coating amount of 0.2 g / m ^2. An undercoat layer was formed. The thickness of the undercoat layer was 0.2 μm.
After sufficiently cooling at room temperature, the hydrophilic layer of Example 31 was formed on the undercoat layer to obtain the hydrophilic member of Example 39.

(Example 40)
The hydrophilic layer of Example 38 was formed on the undercoat layer of Example 39 to obtain the hydrophilic member of Example 40.

(Examples 41 and 42)
A hydrophilic member was prepared in the same manner as in Example 39 except that the hydrophilic polymer (A) in Example 39 was changed to the following.
Example 41: hydrophilic polymer (II-3)
Example 42: hydrophilic polymer (II-11)

(Examples 43 and 44)
A hydrophilic member was prepared in the same manner as in Example 39 except that the crosslinking agent (B) in the hydrophilic composition in Example 39 was changed to the following.
Example 43: Crosslinking agent (39)
Example 44: Crosslinking agent (41)

(Example 45)
A hydrophilic member of Example 45 was prepared in the same manner as Example 39 except that the substrate was changed to a polyethylene terephthalate substrate (thickness 50 μm) whose surface was hydrophilized by glow treatment.

(Examples 46 and 47)
A hydrophilic member was prepared in the same manner as in Example 45 except that the hydrophilic polymer (A) in Example 45 was changed to the following.
Example 46: hydrophilic polymer (II-3)
Example 47: hydrophilic polymer (II-11)

(Examples 48 and 49)
A hydrophilic member was prepared in the same manner as in Example 45 except that the crosslinking agent (B) in the hydrophilic composition in Example 45 was changed to the following.
Example 48: Crosslinking agent (39)
Example 49: Cross-linking agent (41)

(Example 50)
A hydrophilic member of Example 50 was prepared in the same manner as Example 39 except that the substrate was changed to a TAC substrate (30 μm thick) whose surface was hydrophilized by saponification.

(Examples 51 and 52)
A hydrophilic member was prepared in the same manner as in Example 50 except that the hydrophilic polymer (A) in Example 50 was changed to the following.
Example 51: hydrophilic polymer (II-3)
Example 52: Hydrophilic polymer (II-11)

(Examples 53 and 54)
A hydrophilic member was prepared in the same manner as in Example 50 except that the hydrophilic agent (B) in the hydrophilic composition in Example 50 was changed to the following.
Example 53: Crosslinking agent (39)
Example 54: Crosslinking agent (41)

(Examples 55 and 56)
A hydrophilic member was prepared in the same manner as in Example 39 except that the following compound was added to the hydrophilic composition of Example 39.
Example 55: Additive 1 (zirconium oxychloride 2.0 g)
Example 56: Antibacterial agent 1 (TBZ (manufactured by China Industrial Co., Ltd.) 0.5 g)

(Comparative Example 3)
A hydrophilic member of Comparative Example 3 was obtained in the same manner as in Example 31, except that (B) the crosslinking agent (5) was omitted.

(Comparative Example 4)
A hydrophilic member of Comparative Example 4 was obtained in the same manner as in Example 39 except that (B) the crosslinking agent (5) was omitted.

(Comparative Example 5)
In Example 31, in place of the hydrophilic polymer (II-1), a comparative hydrophilic polymer (1) having the following structure and outside the scope of the present invention [in Table 1, “Comparative polymer (1)” is described. The hydrophilic member of Comparative Example 5 was obtained in the same manner except that was used.

(Comparative Example 6)
In Example 39, the hydrophilic property of Comparative Example 6 was similarly used except that, instead of the hydrophilic polymer (II-1), a comparative hydrophilic polymer (1) outside the scope of the present invention having the following structure was used. A member was obtained.

(Comparative Example 7)
In place of the hydrophilic film according to the present invention, a photocatalytic film (manufactured by Toyo Porcelain Co., Ltd., Hydrotect) is pasted on the glass substrate surface used in the above examples to form a hydrophilic surface. A sex member was obtained.

(Example 57)
[Hydrophilic sol-gel solution]
In 100 g of purified water, (A) 2.5 g of the hydrophilic polymer (I-1) as the hydrophilic polymer, 7.5 g of the hydrophilic polymer (II-1), (B) the crosslinking agent (5) 1 as the crosslinking agent 0.5 g, (C) 0.1 g of acetylacetone as a catalyst and 0.1 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 2 hours to prepare.
[Hydrophilic composition]
The hydrophilic sol-gel solution was mixed with 2.5 g of a 5% by mass aqueous solution of the following anionic surfactant to obtain a hydrophilic composition.
[Sol-gel solution for undercoat]
200 g of ethyl alcohol, 10 g of acetylacetone as the catalyst (c), 10 g of tetraethyl orthotitanate, and 100 g of purified water were mixed with 8 g of tetramethoxysilane as the (d) alkoxide compound and stirred at room temperature for 2 hours to prepare.
[Composition for undercoat layer]
30 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1 and 450 g of purified water were mixed with 500 g of the sol-gel solution for undercoat layer to obtain a coating solution.
[Coating method]
An alkali-degreased aluminum substrate (thickness: about 100 μm) is prepared, and the undercoat layer composition is bar-coated on the aluminum substrate and oven-dried at 100 ° C. for 30 minutes, and the dry coating amount is 0.2 g / m. ^Two subbing layers were formed. The thickness of the undercoat layer was 0.2 μm. After sufficiently cooling at room temperature, the hydrophilic composition was bar-coated on the undercoat layer and oven dried at 150 ° C. for 30 minutes to form a hydrophilic layer having a dry coating amount of 0.7 g / m 2. 57 hydrophilic members were obtained.

(Examples 58 and 59)
A hydrophilic member was prepared in the same manner as in Example 57 except that (A) the hydrophilic polymer (I-1) in Example 57 was changed to the following.
Example 58: hydrophilic polymer (I-2)
Example 59: hydrophilic polymer (I-11)

(Examples 60 and 61)
A hydrophilic member was prepared in the same manner as in Example 57 except that (A) the hydrophilic polymer (II-1) in Example 57 was changed to the following.
Example 60: hydrophilic polymer (II-3)
Example 61: hydrophilic polymer (II-11)

(Examples 62 and 63)
A hydrophilic member was prepared in the same manner as in Example 57 except that the addition amount of the hydrophilic polymer (I-1) and hydrophilic polymer (II-1) in the hydrophilic sol-gel solution was changed to the following.
Example 62: 0.5 g of hydrophilic polymer (I-1), 9.5 g of hydrophilic polymer (II-1)
Example 63: 5.0 g of hydrophilic polymer (I-1), 5.0 g of hydrophilic polymer (II-1)

(Examples 64 and 65)
A hydrophilic member was prepared in the same manner as in Example 57 except that the crosslinking agent (B) in the hydrophilic composition in Example 57 was changed to the following.
Example 64: Crosslinking agent (39)
Example 65: Crosslinking agent (41)

Example 66
In Example 57, a hydrophilic member was prepared in the same manner as in Example 57 except that the following compound was added as the (D) alkoxide compound to the hydrophilic sol-gel solution.
Example 66: (D) 0.5 g of tetramethoxysilane

(Example 67)
A hydrophilic member of Example 67 was prepared in the same manner as Example 57 except that the substrate was changed to a polyethylene terephthalate substrate (thickness 50 μm) whose surface was hydrophilized by glow treatment.

Example 68
A hydrophilic member was prepared in the same manner as in Example 67 except that the crosslinking agent (B) in the hydrophilic composition in Example 67 was changed to the following.
Example 68: Crosslinking agent (39)

(Example 69)
A hydrophilic member was prepared in the same manner as in Example 67 except that (A) the hydrophilic polymer (I-1) in Example 67 was changed to the following.
Example 69: Hydrophilic polymer (I-2)

(Example 70)
A hydrophilic member was prepared in the same manner as in Example 67 except that (A) the hydrophilic polymer (II-1) in Example 67 was changed to the following.
Example 70: Hydrophilic polymer (II-3)

(Example 71)
A hydrophilic member of Example 71 was prepared in the same manner as in Example 57 except that the substrate was changed to a TAC substrate (thickness 30 μm) whose surface was hydrophilized by saponification.

(Example 72)
A hydrophilic member was prepared in the same manner as in Example 71 except that the crosslinking agent (B) in the hydrophilic composition in Example 71 was changed to the following.
Example 72: Crosslinker (39)

(Example 73)
A hydrophilic member was prepared in the same manner as in Example 71 except that (A) the hydrophilic polymer (I-1) in Example 71 was changed to the following.
Example 73: Hydrophilic polymer (I-2)

(Example 74)
A hydrophilic member was prepared in the same manner as in Example 67 except that (A) the hydrophilic polymer (II-1) in Example 71 was changed to the following.
Example 74: hydrophilic polymer (II-3)
The above configurations are summarized in Tables 1 to 3.

[Evaluation of hydrophilic member]
[Surface free energy]
The hydrophilicity of the hydrophilic layer surface is generally measured with a water droplet contact angle (Kyowa Interface Science Co., Ltd., DropMaster 500). However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and further 5 ° or less, and there is a limit to the mutual comparison of hydrophilicity. . On the other hand, as a method for evaluating the degree of hydrophilicity of the solid surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, as an example, the surface free energy was measured using the Zisman plot method. Specifically, an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration. After measuring the contact angle in air and 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. Cos θ = 1, that is, the surface tension when 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 the higher the surface free energy value, the higher the hydrophilicity.

[Evaluation of wear resistance]
The surface of the obtained hydrophilic member is rubbed 250 reciprocally under a load of 1000 g with a 30 mm × 30 mm non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.), and the appearance change before and after that is visually observed.
◎: There are no scratches on the surface before and after rubbing. ○: There are about 15 scratches. △: There are about 5 scratches.

[Scratch strength]
Starting from 5 g on a 0.1 mm diameter sapphire needle, the surface of the hydrophilic layer was scanned by applying a weight in increments of 5 g, and the weight at which scratching occurred was evaluated (measured with a scratch strength tester Type 18S manufactured by Shinto Kagaku Co., Ltd.). Durability is better when there is no damage even if the load is large.

[Evaluation of antifouling properties]
0.2 g of palmitic acid was placed in a 50 ml glass container, the mouth of the glass container was covered with the hydrophilic member of 50 mm square obtained above, and aerated at 100 ° C. for 1 hour in an oven. Then, it was immersed in running water for 30 minutes and dried at 80 ° C. for 30 minutes. This was defined as one cycle, and after 5 cycles, the water droplet contact angle (Kyowa Interface Science Co., Ltd., DropMaster 500) was measured.
◎: Less than 10 ° ○: 10 ° or more, less than 20 ° △: 20 ° or more, less than 40 ° ×: 40 ° or more

[Flexibility evaluation]
The hydrophilic member obtained above was perforated with an office paper punch from the top, and the edge portion was observed with a scanning electron microscope.
◎: No crack, no break ○: No crack, but some breaks △: No crack, but many breaks ×: There are cracks Each evaluation result is shown in Tables 4-6 below .

  As mentioned above, it turns out that the hydrophilic member of an Example is excellent in any item compared with the thing of a comparative example.

Claims (16)

  (A) a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group, and (B) a bridge having two or more silicon atoms having at least one of a hydroxyl group and a hydrolyzable functional group A hydrophilic composition containing an agent. (A) The hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group has a structural unit represented by the following general formula (a-2), and the end of the polymer chain A hydrophilic polymer (A1) having a partial structure represented by the following general formula (a-1) and / or a structural unit represented by the following general formula (a-3) and the following general formula (a- It is a hydrophilic polymer (A2) which has a structural unit represented by 4), The hydrophilic composition of Claim 1 characterized by the above-mentioned.

In general formulas (a-1), (a-2), (a-3) and (a-4), R ^{1 to} R ¹³ each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ^{1 to} L ⁴ each independently represents a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and represents a number satisfying x + y = 100. n and m represent an integer of 1 to 3. Y ¹ and Y ² are —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 A structural unit having at least one structure selected from the group consisting of ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ) To express. Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.   The said hydrophilic composition contains the catalyst (C) which accelerates | stimulates the reaction of the hydrophilic polymer which has a silicon atom which has at least any one of the said (A) hydroxyl group and a hydrolyzable functional group, It is characterized by the above-mentioned. 3. The hydrophilic composition according to 1 or 2.   The hydrophilic composition according to claim 1, wherein the catalyst (C) is a non-volatile catalyst.   The hydrophilic composition according to claim 1, wherein the hydrophilic composition contains (D) an alkoxide compound of an element selected from Si, Ti, Zr, and Al.   The hydrophilic composition includes the hydrophilic polymer (A1) and the hydrophilic polymer (A2), and the mass ratio of the hydrophilic polymer (A1) to the hydrophilic polymer (A2) (hydrophilic polymer (A1) / The hydrophilic composition according to any one of claims 2 to 5, wherein the hydrophilic polymer (A2) is in the range of 5/95 to 50/50.   A hydrophilic member comprising a hydrophilic layer formed from the hydrophilic composition according to claim 1 on a substrate.   The hydrophilic member according to claim 7, further comprising an undercoat layer between the substrate and the hydrophilic layer.   The hydrophilic member according to claim 8, wherein the undercoat layer is formed from a composition containing (c) a catalyst.   The hydrophilic member according to claim 9, wherein the catalyst (c) contained in the undercoat layer is a non-volatile catalyst.   11. The undercoat layer is formed of (d) a composition containing an alkoxide compound of an element selected from Si, Ti, Zr, and Al. The hydrophilic member described in 1.   The fin material which apply | coated the hydrophilic composition in any one of Claims 1-6.   The fin material according to claim 12, wherein the water contact angle is 40 ° or less after 5 cycles of aeration with palmitic acid for 1 hour, washing with water for 30 minutes, and drying for 30 minutes.   An aluminum fin material, wherein the fin material according to claim 13 is made of aluminum.   A heat exchanger using the aluminum fin material according to claim 14.   An air conditioner using the heat exchanger according to claim 15.