JP2009191169A - Composition for forming hydrophilic membrane, and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming a hydrophilic membrane giving excellent defogging property, contamination-proofing property, wearing-resistance, in particular, water dirt deposition resistance onto a surface of a support, and a hydrophilic member. <P>SOLUTION: The composition for forming the hydrophilic membrane contains (A) a hydrophilic polymer having at least one functional group represented by general formula (1) in a molecule and having a mass average molecular weight in a range of 5,000-120,000, and (B) a metal complex catalyst. The hydrophilic member is characterized in that the support is coated with the composition for forming the hydrophilic membrane. In general formula (1), R<SP>1</SP>represents a hydrocarbon group, R<SP>2</SP>represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 or 2. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrophilic film-forming composition and a hydrophilic member that impart excellent antifogging properties, antifouling properties, and abrasion resistance, particularly stain resistance, to a support surface.

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 a stain prevention function having performances such as making it difficult to get dirt on the surface of a solid member and facilitating removal of adhered dirt. In particular, as a combination of an antireflection member and an antifouling member, for example, an antireflection film made mainly of silicon dioxide and an antifouling and friction resistant material treated with a compound containing an organosilicon substituent (for example, Patent Document 1), and antifouling and friction-resistant CRT filters (see, for example, 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 (see, for example, Patent Document 4) has been proposed.

  However, the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and 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 that can be used in any part.

  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 friction 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 the terminal and a crosslinking agent.

However, when the tap water is attached to the hydrophilic surface layer in a film form and dried, a white deposit (hereinafter referred to as scale) is attached. This member is supposed to be used around water, and it can be said that the adhesion of water stain is an essential performance. However, removal of scale is very difficult, and generally a strong alkaline cleaning agent is used, but it is not suitable for this member. Further, scrubbing with a scrubbing brush or the like results in numerous scratches on the film surface.
Prior art for scale adhesion includes scale cleaner (see, for example, Patent Document 7), member formed with a water slidable (hydrophobic) coating (for example, see Patent Document 8), and water for diffusing on the surface of the member. Although the technique which provides a fine groove | channel (for example, refer patent document 9) etc. is mentioned, all are not applicable to a hydrophilic film | membrane, The technique which gave scale resistance to the hydrophilic film | membrane until now has not been reported.
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 Japanese Patent Application No. 2006-256215 JP 2004-107464 A International Publication No. 01/44592 Pamphlet JP 2003-276101 A Newspaper "Chemical Industry Daily" article dated January 30, 1995

  An object of the present invention is to provide a hydrophilic film-forming composition and a hydrophilic member that impart excellent antifogging properties, antifouling properties, and abrasion resistance, and particularly water stain adhesion, to the surface of a support.

（一般式（１）中、Ｒ¹は炭化水素基を表し、Ｒ²は水素原子又は炭化水素基を表し、ｍは１又は２の整数を表す。）
〔２〕
（Ａ−１）前記親水性ポリマーが下記一般式（Ｉ）で表される構造を有することを特徴とする〔１〕に記載の親水性膜形成用組成物。 As a main cause of the above-mentioned scale adhesion, the present inventors have a large amount of silanol groups remaining on the surface of the member. When tap water adheres to a film, the silicate contained in the water binds to the silanol groups as it dries. And it was estimated that it would accumulate. Accordingly, as a result of research on the sol-gel organic-inorganic hybrid hydrophilic film, the present inventors succeeded in imparting scale adhesion resistance by reducing the number of silanol groups present on the surface of the member.
Also, in order to increase the film strength, an attempt is usually made to promote condensation polymerization by strengthening the drying conditions, but a lot of electric power is required to enhance the drying conditions, resulting in a decrease in productivity. The present inventors aimed at promoting apparent polycondensation and focused on the molecular weight of the hydrophilic polymer, and found that when a polymer having a molecular weight of 5000 or more was used, high film strength was exhibited.
That is, the present invention is as follows.
[1]
(A) A hydrophilic polymer having at least one functional group represented by the following general formula (1) in the molecule and having a mass average molecular weight in the range of 5000 to 120,000 and (B) a metal complex catalyst. A composition for forming a hydrophilic film.

(In general formula (1), R ¹ represents a hydrocarbon group, R ² represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 or 2.)
[2]
(A-1) The hydrophilic film-forming composition as described in [1], wherein the hydrophilic polymer has a structure represented by the following general formula (I).

(In general formula (I), R ¹ represents a hydrocarbon group, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represents a hydrogen atom or a hydrocarbon group. X1 and y1 are composition ratios. X1 is 0 <x1 <100, y1 is 0 <y1 <100, and x1 + y1 = 100, m is an integer of 1 or 2. L ¹ and L ² are each independently a single number. Y represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), — NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , — NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), -P _{3 (R e) (R f} ), -. OPO 3 (R e) (R f), or an _{-PO 3 (R d) (R} e) where, R _a, R _b and R _c are Each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an alkali metal, alkaline earth metal or an onium,, R _g represents a linear, branched or cyclic alkyl group, a halogen atom, an inorganic anion or an .R _a to R represents an organic anion, _g may combine with each other to form a ring.)
[3]
The hydrophilic film-forming composition as described in [1] or [2], wherein the hydrophilic polymer has a mass average molecular weight in the range of 20,000 to 120,000.
[4]
(A-2) The hydrophilic film forming material according to [1], wherein the hydrophilic polymer is a copolymer of a structural unit having an acidic functional group and a structural unit having a basic functional group. Composition.
[5]
(A-2) The hydrophilic film-forming composition as described in [1] or [4], wherein the hydrophilic polymer has a structure represented by the general formula (II).

(In the general formula (II), R ¹ represents a hydrocarbon group, and R ² , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² each independently represents a hydrogen atom or a hydrocarbon group. X2 and y2 represent a composition ratio, x2 is 0 <x2 <50, y2 is 0 <y2 <100, and represents a number such that (x2 × 2) + y2 = 100, m is an integer of 1 or 2 L ² , L ³ and L ⁴ each independently represents a single bond or an organic linking group, A represents an acidic functional group, and B represents a basic functional group.
[6]
The metal complex catalyst (B) is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table, β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, and enolic active hydrogen compound. The composition for forming a hydrophilic film according to any one of [1] to [5], which is composed of an oxo or hydroxy oxygen compound selected from:
[7]
[1] A hydrophilic member, wherein the hydrophilic film forming composition according to any one of [1] to [6] is coated on a support.

  According to the present invention, there are provided a hydrophilic film-forming composition that imparts excellent antifogging properties, antifouling properties, abrasion resistance, in particular, water stain adhesion property to a support surface, and a hydrophilic member using the same. The

Hereinafter, the present invention will be described in more detail.
The component (A) of the present invention is a hydrophilic polymer having at least one functional group represented by the following general formula (1) in the molecule, and the hydrophilic monomer component is preferably copolymerized. Although not limited, the hydrophilic polymer particularly suitable for the present invention will be described below.

In general formula (1), R ¹ represents a hydrocarbon group, R ² represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 or 2.

(A-1) A hydrophilic polymer represented by the following general formula (I) (hereinafter also referred to as “(A-1) specific hydrophilic polymer”).

(In general formula (I), R ¹ represents a hydrocarbon group, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represents a hydrogen atom or a hydrocarbon group. X1 and y1 are composition ratios. X1 is 0 <x1 <100, y1 is 0 <y1 <100, and x1 + y1 = 100, m is an integer of 1 or 2. L ¹ and L ² are each independently a single number. Y represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), — NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , — NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), -P _{3 (R e) (R f} ), -. OPO 3 (R e) (R f), or an _{-PO 3 (R d) (R} e) where, R _a, R _b and R _c are Each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an alkali metal, alkaline earth metal or an onium,, R _g represents a linear, branched or cyclic alkyl group, a halogen atom, an inorganic anion or an .R _a to R represents an organic anion, _g may combine with each other to form a ring.)

In the general formula (1), R ¹ represents a hydrocarbon group (preferably having 1 to 8 carbon atoms), and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon. Represents a group (preferably having 1 to 8 carbon atoms). Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group (preferably having a carbon number of 8 or less) 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 is preferably a methyl group or an ethyl group from the viewpoints of effects and availability, and R ^{2 to} R ⁶ are preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoints of effects and availability. is there.

These hydrocarbon groups may further have a substituent.
When the alkyl group has a substituent, the substituted alkyl group is constituted by a bond between a substituent and an alkylene group, and here, a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent. Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N ′ -Alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group,

  N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureate group, N ′, N′-dialkyl -N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl -N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group Mino 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-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group phosphono group ( —PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl Phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-O O ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), diaryl phosphonooxy group (-OPO ₃ (aryl) ₂₎ , An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as an alkylphosphonatooxy group), A monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group Can be mentioned.

Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group Cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, phosphonophenyl phenyl group and the like. 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, phenoxymethyl, methylthiomethyl, tolylthiomethyl, ethylaminoethyl, diethylaminopropyl, morpholinopropyl, acetyloxymethyl, benzoyloxymethyl, N-cyclohexylcarbamoyloxyethyl, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Carbonyl butyl group,

  Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoyl Methyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Torilho Phonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

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

Y represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _{a , -OCON (R a) (R} b), - NHCON (R a) (R b), - SO 3 R e, -OSO 3 R e, -SO 2 R d, -NHSO 2 R d, -SO 2 N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R _d is a linear, branched or cyclic group. R _e and R _f each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group (preferably 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 (preferably having 1 to 8 carbon atoms), a halogen atom, an inorganic anion, or an organic anion. R _{a to} R _g may be bonded to each other to form a ring.
The preferred _{Y, -OH, -COR a, -NHCO} 2 R a, -CON (R a) (R b), - N (R a) (R b), - CO 2 R e, -SO 3 R _e , more preferably —CONH ₂ , —CO ₂ R _e , —SO ₃ R _e where R _e and R _f are each independently a hydrogen atom or a linear, branched or cyclic alkyl group (preferably carbon 1 to 8) are expressed. Moreover, about -CON (R ^e ) (R _f ), R _e and R _f may be bonded to each other to form a ring, and the formed ring is a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. It may be a heterocycle containing an atom. R _e and R _f may further have a substituent, and the substituents that can be introduced here are the same as those exemplified as the substituents that can be introduced when R _{a to} R _d are alkyl groups. Can be listed.

Specific examples of the linear, branched or cyclic alkyl group in R _e and R _f include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, and 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 are preferable.

_Examples of the alkali metal, alkaline earth metal, or onium in R _e and R _f include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as calcium and barium; and oniums such as ammonium, iodonium, and sulfonium. Can be mentioned.
Further, as specifically it is _{Y, -NHCOCH 3, -CONH 2,} -COOH, -SO 3 - NMe 4 +, a morpholino group, etc. are preferable.

  x1 and y1 represent a composition ratio, x1 is 0 <x1 <100, y1 is 0 <y1 <100, and represents a number that satisfies x1 + y1 = 100. x1 is preferably in the range of 50 <x1 <100, and more preferably in the range of 70 <x1 <100. y1 is preferably in the range of 0 <y1 <50, more preferably in the range of 0 <y1 <30.

(A-1) The mass average molecular weight of the specific hydrophilic polymer is preferably 5,000 to 120,000, more preferably 10,000 to 100,000, and most preferably 20,000 to 100,000.
When the mass average molecular weight is less than 5,000, the strength of the obtained hydrophilic membrane is lowered. On the other hand, when the mass average molecular weight exceeds 120,000, the hydrophilic layer-forming coating solution has poor storage stability, the viscosity of the coating solution increases with time, and in some cases gels, making it difficult to handle. From the viewpoint of good film strength and easy handling of the coating liquid for forming the hydrophilic layer, the above range is preferable.

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

(A-2) Hydrophilic polymer represented by general formula (II) (hereinafter also referred to as “(A-2) specific hydrophilic polymer”)

(In the general formula (II), R ¹ represents a hydrocarbon group, and R ² , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² each independently represents a hydrogen atom or a hydrocarbon group. X2 and y2 represent a composition ratio, x2 is 0 <x2 <50, y2 is 0 <y2 <100, and represents a number such that (x2 × 2) + y2 = 100, m is an integer of 1 or 2 L ² , L ³ and L ⁴ each independently represents a single bond or an organic linking group, A represents an acidic functional group, and B represents a basic functional group.

In the above general formula (II), R ¹ , R ² , R ⁵ , R ⁶ , L ² and m have the same meaning as in general formula (I). R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or a hydrocarbon group, and examples of the hydrocarbon group include the specific examples of R ³ , R ⁴ , R ⁵ , and R ⁶ in formula (I) From the viewpoints of the effect and availability, a hydrogen atom, a methyl group or an ethyl group is preferred.
L ³ and L ⁴ each independently represent a single bond or an organic linking group, and the organic linking group has the same meaning as L ¹ and L ² in formula (I).
A is a partial structure having an acidic functional group, specifically, a carboxylic acid group (—COOH), a sulfonic acid group (—SO ₃ H), a sulfinic acid group (—SO ₂ H), or a sulfenic acid (—SOH). ), Phosphoric acid groups (—OPO ₃ H ₂ ), phosphonic acid groups (—PO ₃ H ₂ ), boronic acid groups (—B (OH) ₂ ), and partial structures having a phenol group (—PhOH) are preferred. More preferably, it is a partial structure having a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a sulfonic acid group, or a sulfinic acid group.
B is a partial structure having a basic functional group, specifically an amino group (primary amine group (—NH ₂ ), secondary amino group (—NRH), tertiary amino group (—NR ₂ )). A cyclic amino group (pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, thiadiazole ring, triazine ring, tetrazine ring) Partial structure.

  x2 and y2 represent composition ratios, x2 is 0 <x2 <50, y2 is 0 <y2 <100, and represents a number such that (x2 × 2) + y2 = 100. x2 is preferably in the range of 25 <x2 <50, more preferably in the range of 35 <x2 <50. y2 is preferably in the range of 0 <y2 <50, more preferably in the range of 0 <y2 <30.

(A-2) The mass average molecular weight of the specific hydrophilic polymer is preferably 5,000 to 120,000, more preferably 10,000 to 100,000, and most preferably 20,000 to 100,000.
When the mass average molecular weight is less than 5,000, the strength of the obtained hydrophilic membrane is lowered. On the other hand, when the mass average molecular weight exceeds 120,000, the hydrophilic layer-forming coating solution has poor storage stability, the viscosity of the coating solution increases with time, and in some cases gels, making it difficult to handle. From the viewpoint of good film strength and easy handling of the coating liquid for forming the hydrophilic layer, the above range is preferable.

  Specific examples of the specific hydrophilic polymer (A-2) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

Each of the compounds for synthesizing the (A-1) specific hydrophilic polymer or (A-2) the specific hydrophilic polymer of the present invention is commercially available, and can also be easily synthesized.
As the radical polymerization method for synthesizing (A-1) the specific hydrophilic polymer or (A-2) the specific hydrophilic polymer, any conventionally known method can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experimental Science 3, Polymer Synthesis and Reaction 1 (Edited by the Society of Polymer Science, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I) (Edited by Chemical Society of Japan, Maruzen), Materials Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

  The specific 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.

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

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

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

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

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

  The proportion of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but the function as a hydrophilic film is sufficient. (A-1) In order to sufficiently obtain the advantage of adding the hydrophilic polymer or the specific hydrophilic polymer (A-2), it is preferable that the ratio is not too large. Accordingly, the preferred total proportion of (A-1) specific hydrophilic polymer or (A-2) other monomer in the specific hydrophilic polymer is preferably 80% by mass or less, more preferably 50% by mass or less. .

  The (A-1) specific hydrophilic polymer or the (A-2) specific hydrophilic polymer according to the present invention is a viewpoint of curability and hydrophilicity with respect to the nonvolatile component of the hydrophilic film forming composition of the present invention. Therefore, it is preferably contained in the range of 5 to 95% by mass, more preferably 15 to 90% by mass, and most preferably 20 to 85% by mass. These may be used alone or in combination of two or more. Here, the non-volatile component refers to a component excluding a volatile solvent.

(B) Metal complex catalyst The metal complex catalyst used in the composition for forming a hydrophilic film of the present invention promotes hydrolysis and polycondensation of silane coupling groups in the hydrophilic polymer, and bonds the hydrophilic polymers to each other. It plays a role to cause. Particularly preferred metal complex catalysts include metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, and enolic active hydrogen compounds. It is a metal complex composed of a selected oxo or hydroxy oxygen-containing compound.
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.

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

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

  Specific examples of preferred acetylacetone derivatives include acetylacetone, ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, Examples include acetoacetic acid, acetopropionic acid, diacetoacetic acid, 3,3-diacetopropionic acid, 4,4-diacetobutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, and 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. The behavior of the metal complex in the silica sol-gel reaction is described in detail in J. Sol-Gel. Sci. And Tec. 16.209 (1999). The following scheme is estimated as the reaction mechanism. That is, in the coating solution, the metal complex has a coordinated structure and is stable, and in the dehydration condensation reaction that starts in the heat drying process after coating, it is considered that crosslinking is promoted by a mechanism similar to an acid catalyst. In any case, the use of this metal complex has led to the improvement of coating solution aging stability and film surface quality, as well as high hydrophilicity and high durability.

In addition to the above-mentioned metal complex catalyst, a catalyst that promotes hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al and can cause a bond with a hydrophilic polymer is used in combination. May be. Examples of such a catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and the structural formula represented by RCOOH. Compounds having an acidity such as substituted carboxylic acids in which R is substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, etc., or basic compounds such as ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline Is mentioned.
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.
The metal complex catalyst is used in the hydrophilic film-forming composition of the present invention as a nonvolatile component, preferably in the range of 0.1 to 50% by mass, more preferably 0.5 to 20% by mass. Moreover, (B) a metal complex catalyst may be used independently or may be used together 2 or more types.

<Surfactant>
In the present invention, it is preferable to use a surfactant in order to improve the coated surface state of the hydrophilic film-forming composition. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

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

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

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.

  Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

  More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the composition.

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

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

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

Natural antibacterial agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crabs and shrimp shells.
In the present invention, Nikko's “trade name Holon Killer Bees Sera” made of aminometal in which a metal is compounded on both sides of an amino acid is preferable.
These are not transpirationable, easily interact with the polymer and crosslinker component of the hydrophilic layer, can be stably 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, “Novalon” manufactured by Toa Gosei, in which silver is supported on an inorganic ion exchanger ceramic, “Atomy Ball” manufactured by Catalytic Chemical Industry, and “Sun Eye Back P” used as a triazine-based antibacterial agent are also preferable.

  The content of the antibacterial agent is generally 0.001 to 10% by mass, preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, and 0.02 to 1.5%. Mass% is particularly preferable, and 0.05 to 1 mass% is most preferable. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. Further, if the content is 10% by mass or less, the hydrophilicity is not lowered, the aging is not deteriorated, and the antifouling property and the antifogging property are not adversely affected.

<Inorganic fine particles>
The composition for forming a hydrophilic film of the present invention may contain inorganic fine particles in order to improve the cured film strength of the hydrophilic film and to improve hydrophilicity and water retention.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 μm to 3 μm. The above range is preferable because it can be stably dispersed in the hydrophilic film and can sufficiently maintain the film strength and hydrophilicity.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the hydrophilic film forming composition.

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

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

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

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

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

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

  The plastic substrate used in the present invention is not particularly limited, but polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol And films or sheets of polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetherketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyethersulfone, and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. In addition, in terms of optical properties, it is often preferable to have excellent transparency, but depending on the application, translucent or printed materials may be used. 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.

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

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

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

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

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

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

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

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

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

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

2) Release layer When the hydrophilic member of the present invention has the adhesive layer, a release layer can be further added. In order to give mold release properties to the mold release layer, it is preferable to contain a mold release agent. As the release agent, generally, a silicone release agent composed of polyorganosiloxane, a fluorine compound, a long-chain alkyl modified product of polyvinyl alcohol, a long-chain alkyl modified product of polyethyleneimine, and the like can be used. In addition, various release agents such as a hot melt type release agent, a monomer type release agent that cures a release monomer by radical polymerization, cationic polymerization, polycondensation reaction, etc., and other acrylic-silicone copolymer 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 release layer or the hydrophilic polymer layer used for the undercoat layer can be used. The protective layer is peeled off after the hydrophilic member is attached to an appropriate substrate.

[Form of structure]
The structure having a hydrophilic layer of the present invention may be provided in the form of a sheet, a roll, or a ribbon, and may be supplied as a pre-cut for pasting on an appropriate substrate. .

[Surface free energy]
The hydrophilicity of the hydrophilic layer surface is generally measured by the water droplet contact angle. 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, the surface free energy was measured using the Zisman plot method as an example. Specifically, using the property that an aqueous solution of an inorganic electrolyte such as magnesium chloride increases in surface tension with the concentration, after measuring the contact angle in the air at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship, and the surface tension when cos θ = 1, that is, contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and it can be said that the higher the surface free energy value, the higher the hydrophilicity.
A hydrophilic layer whose surface free energy measured by such a method is in the range of 70 mN / m to 95 mN / m, preferably 72 mN / m to 93 mN / m, more preferably 75 mN / m to 90 mN / m is hydrophilic. Excellent performance and good performance.

When the hydrophilic member of the present invention is applied (used or pasted) to a window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic member of the present invention is excellent in transparency, and even when the film thickness is large, the transparency is not impaired, and compatibility with durability is possible. The thickness of the hydrophilic film of the present invention is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 20 μm. When the film thickness is 0.01 μm or more, sufficient hydrophilicity and durability can be obtained, and when the film thickness is 100 μm or less, there is no problem in film forming properties such as cracking, which is preferable.
Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably 100% to 70%, more preferably 95% to 75%, and most preferably in the range of 95% to 80%. By being in this range, the hydrophilic member provided with a hydrophilic film can be applied to various applications without obstructing the field of view.

  The hydrophilic member of the present invention may be formed by dispersing or dissolving each of the necessary components described above in a solvent to prepare a coating solution, and curing the coating formed on an appropriate substrate by heat. it can.

  For example, by dissolving the specific hydrophilic polymer (A-1) or (A-2) and the (B) metal complex catalyst in a solvent and stirring well, the silane coupling group portion of the specific hydrophilic polymer component It hydrolyzes and further partially undergoes condensation polymerization to form a hydrophilic layer forming coating solution, whereby a hydrophilic film having high hydrophilicity and high film strength is formed.

  The preparation of the coating solution for forming the hydrophilic layer when the composition for forming the hydrophilic film is coated on the support comprises (A-1) or (A-2) the specific hydrophilic polymer, and (B) the metal. It can be carried out by dissolving the complex catalyst in a solvent and stirring. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation are advanced to form a hydrophilic layer. A coating solution can be obtained.

The hydrophilic member of the present invention can be obtained by applying a hydrophilic layer forming coating solution on an appropriate substrate, heating and drying to form a surface hydrophilic layer. 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.
The hydrophilic member of the present invention can be prepared by a known coating method, and is not particularly limited. For example, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a film applicator method. Methods such as screen printing, bar coater, brush coating, and sponge coating can be applied.

The hydrophilic member of the present invention can be applied to, for example, a transparent glass substrate or a transparent plastic substrate, a lens, a prism, a mirror or the like when an antifogging effect is expected.
As the glass, any glass such as soda glass, lead glass and borosilicate glass may be used. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do.
Applications that can be applied with anti-fogging effects include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, internal vision Lenses such as mirror lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; window glass for buildings and surveillance towers; 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.

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

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

[Synthesis of Exemplified Compound 1]
A 500 ml three-necked flask is charged with 50 g of acrylamide, 74 g of acrylamide- (diethoxymethylsilyl) propyl, and 290 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methylpropionic acid) dimethyl under a nitrogen stream at 80 ° C. 1.5 g was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The mixture was put into 2 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with acetone, the specific hydrophilic polymer as the exemplified compound (1) was obtained. The mass after drying was 120 g. It was a polymer having a weight average molecular weight of 30,000 according to GPC (polyethylene oxide standard).

[Synthesis of Exemplified Compound 17]
A 500 ml three-necked flask was charged with 15 g of acrylic acid, 33 g of dimethylaminopropyl acrylamide, 25 g of acrylamide- (diethoxymethylsilyl) propyl, and 170 g of 1-methoxy-2-propanol, and 2,2′-azobis ( 0.7 g of dimethyl 2-methylpropionic acid) was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The mixture was put into 2 liters of acetone, and the precipitated solid was collected by filtration. After the obtained solid was washed with acetone, the specific hydrophilic polymer as the exemplified compound (2) was obtained. The mass after drying was 70 g. It was a polymer having a weight average molecular weight of 30,000 according to GPC (polyethylene oxide standard).
Thereafter, the specific hydrophilic polymer used in the examples was synthesized by the same method as described above and used for evaluation.

[Example 1]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the first layer coating solution (1) having the following composition is spun The coating was applied and oven-dried at 100 ° C. for 10 minutes to form a first layer having a dry coating amount of 1.0 g / m ² . After sufficiently cooling at room temperature, the hydrophilic layer coating solution (1) is bar-coated on the first layer coating surface as a second layer, oven dried at 150 ° C. for 30 minutes, and a dry coating amount of 3.0 g / m ² . A second layer was formed to obtain a hydrophilic member.

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

<Sol-gel preparation liquid (1)>
Into 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate and 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at room temperature for 2 hours to prepare.

Anionic surfactant

<Hydrophilic layer coating solution (1)>
・ 500g of the following sol-gel preparation (2)
-5.0 g of 5% by weight aqueous solution of the above anionic surfactant

<Sol-gel preparation liquid (2)>
30 g of a specific hydrophilic polymer (Exemplary Compound 2, mass average molecular weight 30,000) is mixed in 200 g of ethyl alcohol, 0.25 g of acetylacetone, 0.3 g of tetraethyl orthotitanate, and 300 g of purified water, and stirred at room temperature for 2 hours. Prepared.

(Evaluation) The following evaluation was performed on the hydrophilic member. The evaluation results are shown in Table 6.
Antifouling property (oil-based ink): A line was drawn with an oil-based ink (Mitsubishi Pencil Co., Ltd. oil-based marker), and water was poured on to determine whether it would flow down in three stages.
◎: Ink can be taken within 30 seconds. ○: Ink can be taken within 1 minute. △: Ink can be taken after 1 minute. ×: Ink cannot be removed even after 2 minutes and over 10 minutes. One drop of tap water was dropped on the membrane surface, dried at room temperature, and then washed with distilled water five times, and then visually judged according to the following criteria.
○: No adhesion of scale is observed.
Δ: Slight adhesion is observed when exposed to light.
X: Adhering clearly.
Scratch test: Starting from 5 g on a 0.1 mm diameter sapphire needle, applying 5 g increments to scan the surface of the member and evaluating the weight at which scratching occurred (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.
Water resistance: A 120 cm ² size hydrophilic member was rubbed 10 times with a sponge and loaded in water under a load of 1 kg, and the residual film ratio was measured from the weight change before and after that.

[Comparative Examples 1-3]
The hydrophilic members of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the specific hydrophilic polymer was changed to the following comparative polymer and the mass average molecular weight was changed as shown in Table 1 below.
The comparative polymer having a weight average molecular weight of Comparative Example 3 caused gelation during the preparation of the sol-gel preparation liquid, and a hydrophilic member could not be prepared.

[Examples 2 to 5]
A hydrophilic member was prepared and evaluated in the same manner as in Example 1 except that the mass average molecular weight of the specific hydrophilic polymer (Exemplary Compound 2) was changed as shown in Table 2.

[Examples 6 to 10]
A hydrophilic member was prepared and evaluated in the same manner as in Example 1 except that the specific hydrophilic polymer was changed as shown in Table 3.

[Examples 11 to 15]
The first layer coating solution (2) having the following composition is spin-coated (1000 rpm, 30 seconds) on a SUS substrate (thickness 1.1 mm) whose surface has been hydrophilized by UV / O ₃ treatment for 10 minutes, and then heated at 100 ° C. for 2 minutes. Dried to form a layer with a dry coating weight of 0.5 g / m ² . The water droplet contact angle of the first layer was 80 °. Further, a first layer coating solution (3) having the following composition was spin-coated (1000 rpm, 30 seconds) on the first layer and dried in an oven at 100 ° C. for 10 minutes to obtain a dry coating amount of 0.5 g / m ² . A first layer having a two-layer structure was formed. The water droplet contact angle of the layer formed from the first layer coating solution (3) was 10 °. Subsequently, a hydrophilic member was prepared in the same manner as in Example 1 except that the specific hydrophilic polymer was applied as shown in Table 4 on the first layer having the two-layer structure. The evaluation results are shown in Table 6.

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

<First layer coating solution (3)>
-PVA105 aqueous solution (Kuraray, solid content 6%) 130g
・ Glyoxal aqueous solution (Tokyo Kasei, solid content 40%) 50g
・ Ethylene glycol diglycidyl ether (Tokyo Kasei) 10g
・ Methanol silica (Nissan Chemical, solid content 30%) 30g
-Anionic surfactant described in Example 1 5 mass% aqueous solution 20 g
・ Water 7600g

[Examples 16 to 20]
A polyethylene terephthalate (PET) substrate (thickness 50 μm) whose surface is hydrophilized by glow treatment is prepared, and the first layer coating solution (2) having the above composition is spin-coated (1000 rpm for 30 seconds) and oven-dried at 100 ° C. for 2 minutes. A first layer having a dry coating amount of 0.5 g / m ² was formed. The water droplet contact angle of the first layer was 80 °. Then, the hydrophilic member was created by the method similar to Example 1 except having apply | coated specific hydrophilic polymer like Table 5 on the 1st layer. The evaluation results are shown in Table 6.

Claims (7)

(A) A hydrophilic polymer having at least one functional group represented by the following general formula (1) in the molecule and having a mass average molecular weight in the range of 5000 to 120,000 and (B) a metal complex catalyst. A composition for forming a hydrophilic film.

(In general formula (1), R ¹ represents a hydrocarbon group, R ² represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 or 2.) (A-1) The hydrophilic film-forming composition according to claim 1, wherein the hydrophilic polymer has a structure represented by the following general formula (I).

(In general formula (I), R ¹ represents a hydrocarbon group, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represents a hydrogen atom or a hydrocarbon group. X1 and y1 are composition ratios. X1 is 0 <x1 <100, y1 is 0 <y1 <100, and x1 + y1 = 100, m is an integer of 1 or 2. L ¹ and L ² are each independently a single number. Y represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), — NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , — NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), -P _{3 (R e) (R f} ), -. OPO 3 (R e) (R f), or an _{-PO 3 (R d) (R} e) where, R _a, R _b and R _c are Each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an alkali metal, alkaline earth metal or an onium,, R _g represents a linear, branched or cyclic alkyl group, a halogen atom, an inorganic anion or an .R _a to R represents an organic anion, _g may combine with each other to form a ring.)   The composition for forming a hydrophilic film according to claim 1 or 2, wherein the hydrophilic polymer has a mass average molecular weight in the range of 20,000 to 120,000.   (A-2) The hydrophilic film-forming film according to claim 1, wherein the hydrophilic polymer is a copolymer of a structural unit having an acidic functional group and a structural unit having a basic functional group. Composition. (A-2) The hydrophilic film-forming composition according to claim 1 or 4, wherein the hydrophilic polymer has a structure represented by the general formula (II).

(In the general formula (II), R ¹ represents a hydrocarbon group, R ² , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ^1.
2 , each independently represents a hydrogen atom or a hydrocarbon group. x2 and y2 represent composition ratios, x2 is 0 <x2 <50, y2 is 0 <y2 <100, and represents a number such that (x2 × 2) + y2 = 100. m represents an integer of 1 or 2. L ² , L ³ and L ⁴ each independently represents a single bond or an organic linking group, A represents an acidic functional group, and B represents a basic functional group. )   The metal complex catalyst (B) is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and a β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, enolic active hydrogen compound. The composition for forming a hydrophilic film according to any one of claims 1 to 5, which is composed of an oxo or hydroxy oxygen compound selected from the group consisting of:   A hydrophilic member, wherein the hydrophilic film-forming composition according to any one of claims 1 to 6 is coated on a support.