JP2008073963A - Hydrophilic member and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface hydrophilic member with advantages such as excellent hydrophilic nature, successful wear resistance, water resistance, durability and weatherability, especially outstanding adhesion between a base and a hydrophilic layer, formed on the surface of various kinds of the base, and a manufacturing method of the hydrophilic member. <P>SOLUTION: This hydrophilic member comprises a base overlaid with an intermediate layer and a hydrophilic film, overlaying the former, which is obtained by applying the film containing (a) a hydrophilic polymer, (b) a metallic alkoxide compound selected from the group consisting of Si, Ti, Zr and Al and (c) a metallic complex catalyst. Further, the intermediate layer is obtained by applying the intermediate layer containing at least one kind of coupling agent or its hydrolyzate, and is a layer bonded with the hydrophilic film through a condensation reaction. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a surface hydrophilic member and a method for producing the same, and more particularly, a hydrophilic surface layer excellent in hydrophilicity, water resistance, durability and weather resistance, and particularly excellent in adhesion between a substrate and a hydrophilic layer. It is related with a surface hydrophilic member provided with, and its manufacturing method.

  Products and members having a resin film surface are used in a wide range of fields, and are used after being processed and imparted with functions according to the purpose. However, those surfaces generally exhibit hydrophobicity and lipophilicity due to the inherent properties of the resin. Therefore, if oil or the like adheres to these surfaces as a soiling substance, they cannot be easily removed, and accumulation may significantly reduce the functions and characteristics of products / members having the surface. It was. In addition, in products / members exposed to high humidity conditions or rain, there is a problem that the light transmission is hindered by irregular reflection of light in products / members having a transparent function due to adhesion of water droplets. . Even in products / members having an inorganic surface such as glass or metal, it cannot be said that the antifouling property against adhesion of dirt substances such as oil is sufficient, and the antifogging property due to adhesion of water droplets is not sufficient. Especially in glass for automobiles and glass for building materials, there are cases where hydrophobic pollutants such as urban dust, combustion products such as carbon black contained in exhaust gas of automobiles, oils and fats, sealant elution components adhere, In many cases, it is difficult to secure a field of view through adhesion (reflection in the case of a mirror) due to adhesion, and it has been strongly demanded to impart antifouling and antifogging functions.

From the viewpoint of antifouling properties, assuming that the soiling substance is an organic substance such as oil, it is necessary to reduce the interaction with the material surface, that is, to make it hydrophilic or to make it oil repellent in order to prevent soiling. In addition, for anti-fogging properties, it is necessary to provide extended wettability (that is, hydrophilicity) that spreads the attached water droplets uniformly on the surface, or to impart water repellency that facilitates removal of the attached water droplets. Therefore, many of the antifouling and antifogging materials currently under investigation depend on hydrophilicity, water repellency and oil repellency.
Conventionally proposed surface treatment methods for hydrophilization, such as etching treatment and plasma treatment, are highly hydrophilized, but their effects are temporary and maintain the hydrophilized state for a long time. I can't. A surface hydrophilic coating film using a hydrophilic graft polymer as one of hydrophilic resins has also been proposed (Non-patent Document 1). According to this report, although this coating film has a certain degree of hydrophilicity, it cannot be said that the compatibility with the substrate is sufficient, and higher durability is required.

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

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

International Publication No. 96/29375 Pamphlet JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 Chemical Daily, January 30, 1995

  The object of the present invention is excellent in water resistance, durability and weather resistance, having excellent hydrophilicity on various substrate surfaces and having better wear resistance, and in particular, adhesion between the substrate and the hydrophilic layer. An object of the present invention is to provide a surface hydrophilic member excellent in the above and a method for producing the same.

In order to achieve the above-mentioned problem, as a result of conducting research while focusing on the characteristics of the hydrophilic graft polymer, the present inventors have obtained a crosslinked structure formed by hydrolyzing and polycondensing a hydrophilic polymer and a metal alkoxide. The above-mentioned object can be achieved by a surface layer provided with a hydrophilic polymer in which the surface layer having such a crosslinked structure has a reactive group at its terminal, or a hydrophilic polymer having a graft chain is combined with a crosslinking agent. In addition, the intermediate layer containing a coupling agent (hereinafter also referred to as an adhesive layer) is coated between the hydrophilic layer and the base material, thereby allowing the base material and the hydrophilic layer to adhere to each other. As a result, the present invention was completed.
That is, the present invention is as follows.

(1) An intermediate layer, and a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, and Al, and c) a metal complex catalyst are coated on the substrate. The intermediate layer is coated with at least one coupling agent or a hydrolyzate thereof, and is bonded to the hydrophilic layer by a condensation reaction. The hydrophilic member characterized by the above-mentioned.
(2) The hydrophilic member according to (1), wherein the substrate is made of at least one selected from an inorganic material, an organic material, and a metal material.
(3) The hydrophilic member of (1), wherein the coupling agent is a compound represented by the following general formula [1].
General formula [1] M- (R) _n
(In the general formula [1], M represents a metal having a valence of 2 to 5, n represents an integer corresponding to the valence of the metal, R represents an organic group, and n R's are And may be the same or different, and at least two of the n Rs are groups reactive with metal alkoxides and / or hydrophilic polymers.)
(4) The c) metal complex catalyst is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table, and β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, enolic active hydrogen compound The hydrophilic member as defined in (1) above, which is composed of an oxo- or hydroxy-oxygen-containing compound selected from the group consisting of
(5) The hydrophilic member of (1), wherein the hydrophilic polymer of a) is represented by at least one selected from the following general formulas (I) and (II).

In formulas (I) and (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X is reactive. Group (carboxyl group, salt thereof, carboxylic anhydride group, amino, hydroxyl, epoxy group, methylol, mercapto, isocyanate, block isocyanate group, alkoxysilyl group, alkoxytitanate group, alkoxyaluminate group, alkoxyzirconate group, Represents an ethylenically unsaturated double bond, an ester bond, a tetrazole group), A and L ¹ , L ² , and L ³ each independently represent a single bond or a linking group, and Y represents —NHCOR ⁷ , —CONH ₂ , Represents —CON (R ⁷ ) ₂ , —COR ⁷ , —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M, —OPO ₃ M or —N (R ⁷ ) ₃ Z ¹ , R ⁷ An alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, M represents a hydrogen atom, an alkali metal, alkaline earth metal or an onium, Z ¹ represents a halogen ion, B represents the formula (III) .

In formula (III), R ¹ , R ² , L ¹ and Y are the same as those in formulas (I) and (II).

(6) A coating solution containing at least one coupling agent or a hydrolyzate thereof is applied onto the substrate, and then selected from a) a hydrophilic polymer, b) Si, Ti, Zr, and Al. A method for producing a hydrophilic member, in which an aqueous solution containing a metal alkoxide compound and c) a metal complex catalyst is applied, heated and dried to coat a hydrophilic film.

In addition, the following embodiments are preferable.
(7) The hydrophilic member according to (2), wherein the inorganic material is at least one selected from ceramic, cement, concrete, stone, and asphalt.
(8) The hydrophilic member according to (1) or (4), wherein the c) metal complex catalyst is Ti (acac) ₂ .
(9) The hydrophilic member according to (1), wherein the hydrophilic coating further contains d) colloidal silica.
(10) The hydrophilic member according to (1), wherein the hydrophilic coating has a surface free energy of 70 mN / m to 95 mN / m.
(11) The hydrophilic member according to (1), wherein a) the hydrophilic group density of the hydrophilic polymer is 1 to 30 meq / g.
(12) The hydrophilic member of (1), wherein the viscosity of the a) hydrophilic polymer is 0.1 to 100 cPs (5% aqueous solution).
(13) The hydrophilic member according to (1), wherein the hydrophilic film has a light transmittance of 100% to 70%.

In the present invention, the hydrophilic polymer has a crosslinked structure formed by hydrolyzing and polycondensing a metal alkoxide, and the hydrophilic polymer is chemically bonded at the terminal or is a crosslinked structure. Since the polymer has a graft polymer structure in which a hydrophilic polymer is bonded to a chemically bonded main chain, the surface of the hydrophilic polymer chain is very high in mobility and excellent in hydrophilicity.
The crosslinked structure obtained by hydrolyzing and polycondensing metal alkoxide is a cured film having a high crosslinking density, and forms a highly durable and durable film. Therefore, the hydrophilic layer provided on the base material such as glass substrate or plastic substrate always provides a normal hydrophilic layer surface without causing a failure such as cracking when bending during handling such as manufacturing. it can.

In addition, the hydrophilic member of the present invention can provide a cured film having a high crosslinking density by hydrolysis and polycondensation of the metal alkoxide even though the surface hydrophilicity is very high. It is difficult to contain, and therefore, stickiness due to environmental humidity (especially under high humidity conditions) is suppressed, and it is effective for preventing adhesion of the back surface when the structure is stored repeatedly. That is, it is possible to suppress failures such as peeling due to back surface adhesion of the structure overlying the hydrophilic layer surface during storage of the structure.
Moreover, by having an intermediate layer in which a coupling agent or a hydrolyzate-containing material is applied between the base material and the intermediate layer, the intermediate layer is bonded to the hydrophilic film by a condensation reaction, In order to improve the adhesion between the hydrophilic layer and the hydrophilic layer, it is possible to maintain high hydrophilicity over a long period of time even for outdoor use and water use, etc., and a hydrophilic member with excellent antifouling property and durability Can be provided.

  The present invention is described in detail below. The surface hydrophilic member of the present invention has an intermediate layer in which a coupling agent or a product containing a hydrolyzate thereof is coated on a suitable base material such as glass or plastic, a hydrophilic polymer chain, and Hydrophilic film (hydrophilic layer or hydrophilic layer) having a crosslinked structure formed by hydrolysis and polycondensation of a metal alkoxide selected from Si, Ti, Zr, and Al, and bonded to the intermediate layer by a condensation reaction However, the hydrophilic layer having such a crosslinked structure is appropriately composed of a metal alkoxide compound described in detail later, a compound having a hydrophilic functional group capable of forming a hydrophilic graft chain, and It can form suitably using a suitable catalyst. Among metal alkoxides, Si alkoxides are preferable from the viewpoint of reactivity and availability, and specifically, compounds used for silane coupling agents can be suitably used.

  In the present invention, the above-described crosslinked structure formed by hydrolysis and polycondensation of the metal alkoxide is hereinafter appropriately referred to as a sol-gel crosslinked structure. Such a hydrophilic layer in which one end of the polymer chain is not fixed and the mobility of the polymer chain is large is represented by, for example, general formula (I) having (A) a reactive group such as a silane coupling group at the end. A polymer compound represented by the general formula (II) having the reactive group as a side chain of the trunk polymer, (B) a hydrolyzable metal alkoxide compound, and the hydrolysis and polymerization It can be easily formed by preparing a hydrophilic coating liquid composition containing a metal complex catalyst that causes condensation, and applying and drying it to form a surface hydrophilic layer. Below, each component contained in the hydrophilic coating liquid composition for forming the hydrophilic layer which is this preferable aspect is demonstrated.

[Hydrophilic polymer]
The hydrophilic polymer used in the present invention is a polymer having a hydrophilic group and a group that forms a bond with a metal alkoxide compound selected from Si, Ti, Zr, and Al by the action of a catalyst or the like. The hydrophilic group is preferably a carboxy group, an alkali metal salt of a carboxy group, a sulfonic acid group, an alkali metal salt of a sulfonic acid group, a hydroxyl group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group or the like. Can be mentioned. These groups may be present at any position in the polymer. A polymer structure in which a plurality of polymers are bonded directly from a polymer main chain or via a linking group, or bonded to a polymer side chain or a graft side chain, is preferred. Examples of the group that forms a bond with the metal alkoxide compound by the action of a catalyst include a carboxyl group, an alkali metal salt of a carboxy group, a carboxylic anhydride group, an amino group, a hydroxy group, an epoxy group, a methylol group, a mercapto group, an isocyanate group, Examples thereof include reactive groups such as a block isocyanate group, an alkoxysilyl group, an alkoxytitanate group, an alkoxyaluminate group, an alkoxyzirconate group, an ethylenically unsaturated group, an ester group, and a tetrazole group. The polymer structure having a hydrophilic group and a group that forms a bond with a metal alkoxide compound by the action of a catalyst or the like includes an ethylenically unsaturated group (for example, an acrylate group, a methacrylate group, an itaconic acid group, a crotonic acid group, a cinnamic acid group). Styrene group, vinyl group, allyl group, vinyl ether group, vinyl ester group, etc.), polymer obtained by vinyl polymerization, polycondensation polymer such as polyester, polyamide, polyamic acid, etc., addition polymer such as polyurethane, etc. Preferred examples include natural cyclic polymer structures such as cellulose, amylose and chitosan. Specific examples include structures represented by general formulas (I) and (II).

In formulas (I) and (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X is reactive. Group (carboxyl group, salt thereof, carboxylic anhydride group, amino, hydroxyl, epoxy group, methylol, mercapto, isocyanate, block isocyanate group, alkoxysilyl group, alkoxytitanate group, alkoxyaluminate group, alkoxyzirconate group, Represents an ethylenically unsaturated double bond, an ester bond, a tetrazole group), A and L ¹ , L ² , and L ³ each independently represent a single bond or a linking group, and Y represents —NHCOR ⁷ , —CONH ₂ , Represents —CON (R ⁷ ) ₂ , —COR ⁷ , —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M, —OPO ₃ M or —N (R ⁷ ) ₃ Z ¹ , R ⁷ An alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, M represents a hydrogen atom, an alkali metal, alkaline earth metal or an onium, Z ¹ represents a halogen ion, B represents the formula (III) .

In formula (III), R ¹ , R ² , L ¹ and Y are the same as those in formulas (I) and (II).

The hydrophilic polymer used in the present invention has a reactive group and a hydrophilic group. There may be a case where the reactive group is present only at one end of the main chain, or a case where a plurality of reactive groups are present in the main chain.
The “reactive group” means a functional group capable of forming a chemical bond by reacting with a hydrolysis or polycondensate of a metal alkoxide. Moreover, reactive groups may form a chemical bond. The hydrophilic polymer is preferably water-soluble, and preferably becomes water-insoluble by reacting with a hydrolysis or polycondensate of a metal alkoxide.
The chemical bond includes a covalent bond, an ionic bond, a coordination bond, and a hydrogen bond in the usual meaning. The chemical bond is preferably a covalent bond.
The reactive group is generally the same as the reactive group contained in the crosslinking agent of the polymer, and is a compound that can form a crosslink by heat or light. The crosslinking agent is described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981).

Examples of reactive groups are carboxyl (HOOC-), salts thereof (MOOC-, where M is a cation), carboxylic anhydride groups (eg monovalent groups derived from succinic anhydride, phthalic anhydride or maleic anhydride). ), Amino (H ₂ N—), hydroxyl (HO—), epoxy group (eg, glycidyl group), methylol (HO—CH ₂ —), mercapto (HS—), isocyanate (OCN—), block isocyanate Group, alkoxysilyl group, alkoxy titanate group, alkoxy zirconate group, ethylenically unsaturated double bond, ester bond, tetrazole group. As the reactive group, an alkoxysilyl group is most preferable. One end may have two or more reactive groups. Two or more reactive groups may be different from each other.

It is preferable that a linking group is interposed between the repeating unit of the hydrophilic polymer and the reactive group, or between the repeating unit of the hydrophilic polymer and the main chain. The linking groups A and L ¹ , L ² and L ³ are each independently a single bond, or —O—, —S—, —CO—, —NH—, —N <, an aliphatic group, an aromatic group, a complex It is preferably selected from cyclic groups and combinations thereof. The linking group is preferably —O—, —S—, —CO—, —NH—, or a combination containing —O—, —S—, —CO— or —NH—.

(Hydrophilic polymer having a reactive group at the terminal (I))
Hydrophilic polymers having a reactive group at one end are, for example, chain transfer agents (described in radical polymerization handbook (NTS, Mikiji Tsunoike, Takeshi Endo)) and Iniferter (Macromolecules 1986, 19, p287- (Otsu)). In the presence of a hydrophilic monomer (eg, acrylamide, acrylic acid, potassium salt of 3-sulfopropyl methacrylate) by radical polymerization. Examples of chain transfer agents include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane. Alternatively, a hydrophilic monomer (eg, acrylamide) may be radically polymerized using a radical polymerization initiator having a reactive group (eg, carboxyl) without using a chain transfer agent.
The mass average molecular weight of the hydrophilic polymer having a reactive group at one end is preferably 1,000,000 or less, more preferably 1,000 to 1,000,000, and most preferably 2,000 to 100,000.

The polymer compound represented by the general formula (I) is a hydrophilic polymer having a reactive group at the terminal. In the general formula ^{(I), R 1, R} 2 each independently represents a hydrocarbon group having 8 or less hydrogen atom or a carbon. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ¹ and R ² are preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoints of effects and availability.

  These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and the alkylene group, and a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkylamino groups, acyloxy groups, 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-dialkyl Carbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfuryl group Famoyl group, N-alkyl-N- Lillesulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group, phosphonooxy group, phosphonate An oxy group, an aryl group, and an alkenyl group are mentioned.

  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, Allyloxymethyl group, phenoxymethyl group, methylthiomethyl, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N -Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonyl Bonirubuchiru 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.

A and L ¹ represent a single bond or an organic linking group. Here, when A and L ¹ represent an organic linking group, A and L ¹ represent a polyvalent linking group composed of a nonmetallic atom, specifically, 1 to 60 carbon atoms, 0 To 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 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 —NHCOR ⁷ , —CONH ₂ , —CON (R ⁷ ) ₂ , —COR ⁷ , —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M, —OPO ₃ M, or —N ( R ⁷ ) ₃ Z ¹ , wherein R ⁷ represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group, and M represents a hydrogen atom, an alkali metal, or an alkaline earth. It represents a similar metal or onium, and Z ¹ represents a halogen ion. Also, if having a plurality of R ⁷ as -CON (R ⁷⁾ _2, may form a ring by bonding R ⁷ together, and the formed ring is an oxygen atom, a sulfur atom, a nitrogen It may be a heterocycle containing a heteroatom such as an atom. R ⁷ may further have a substituent, and examples of the substituent that can be introduced here include those listed as the substituents that can be introduced when R ¹ and R ² are alkyl groups. Can do.

Specific examples of R ⁷ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, Preferable examples include isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group. Examples of M include a hydrogen atom; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as calcium and barium; or an onium such as ammonium, iodonium and sulfonium. The Y, _{specifically, -NHCOCH 3, -CONH 2, -COOH} , -SO 3 - NMe 4 +, morpholyl group and the like.

  Specific examples (Exemplary Compound 1 to Exemplified Compound 38) of a) hydrophilic polymers that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

  The hydrophilic polymer exemplified above uses a radical polymerizable monomer represented by the following general formula (i) and a silane coupling agent having chain transfer ability in the radical polymerization represented by the following general formula (ii). Can be synthesized by radical polymerization. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.

In the above formula (i) and ^{(ii), A, R 1} ~R 2, L 1, Y is as defined in the above formula (I). These compounds are commercially available and can be easily synthesized.

(Hydrophilic polymer having multiple reactive groups (II))
As the hydrophilic polymer having a plurality of reactive groups represented by the above formula (II), a hydrophilic graft polymer obtained by introducing a hydrophilic polymer side chain into a trunk polymer having a functional group capable of reacting with a metal alkoxide is used. be able to.
In the above formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent the same substituent as R ¹ and R ² in the above formula (I). L ² and L ³ have the same meaning as L ^{1 in the} above formula (I). B is represented by the above formula (III), and R ¹ , R ² , L ¹ and Y in the formula (III) are the same as those in the formulas (I) and (II). X is synonymous with the above formula (I).
This hydrophilic graft polymer can be prepared using a method generally known as a method for synthesizing a graft polymer. Specifically, a general method for synthesizing a graft polymer is described in “Graft Polymerization and its Applications” by Fumio Ide, published in 1977, “Polymer Publishing”, and “New Polymer Experiments 2, Polymer Synthesis / Reaction "edited by Polymer Society of Japan, Kyoritsu Shuppan Co., Ltd. 1995, and these can be applied.

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

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

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

  Examples of the reactive functional group of the monomer having a functional group that can be copolymerized with the hydrophilic macromonomer and that can react with the crosslinking agent (hereinafter, appropriately referred to as a reactive functional group) include a carboxyl group or a salt thereof, an amino group, Examples include hydroxyl groups, phenolic hydroxyl groups, epoxy groups such as glycidyl, methyl groups, (block) isocyanate groups, and silane coupling agents. Common monomers include “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha [1981], “Ultraviolet curing system” by Kiyomi Kato, published by Technical Center [1989], “UV / EB curing handbook” (Raw material edition) "written by Kiyotaka Kato, Polymer publication society [1985]," Practical technology of new photosensitive resin "written by Kiyoshi Akamatsu, CMMC publication (pages 102-145) [1987], etc. Monomer. Specifically, (meth) acrylic acid or its alkali, amine salt, itaconic acid or its alkali, amine salt, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, represented by the following formula (1) A phenolic hydroxyl group-containing monomer such as glycidyl methacrylate, allyl glycidyl ether, N-methylol methacrylamide, 2-methacryloyloxyethyl isocyanate, and a blocked isocyanate monomer such as a blocked isocyanate monomer exemplified by the following formula (2); Examples include vinyl alkoxysilane and γ-methacryloxypropyltrialkoxysilane.

  As these graft polymers, those having a mass average molecular weight of 1,000,000 or less are preferably used, and those having a molecular weight of 1,000 to 1,000,000, more preferably 20,000 to 100,000. When the molecular weight is 1,000,000 or less, there is a problem in handling properties, such as the ability to form a uniform coating film without lowering the solubility in a solvent when preparing a coating solution for forming a hydrophilic coating film, without lowering the solubility in the solvent. This is preferable.

The hydrophilic polymer has a hydrophilic functional group that expresses the hydrophilicity represented by Y in the formula, and the higher the density of this functional group, the higher the surface hydrophilicity, which is preferable. The hydrophilic functional group density can be expressed in terms of moles of functional groups per gram of hydrophilic polymer, preferably 1 to 30 meq / g, more preferably 2 to 20 meq / g, and most preferably 3 to 15 meq / g.
The copolymerization ratio of the hydrophilic polymer (II) can be arbitrarily set so that the amount of the hydrophilic functional group Y falls within the above range. Preferably, the molar ratio (m) of the monomer containing B and the molar ratio (n) of the monomer containing X are preferably in the range of m / n = 30/70 to 99/1, and m / n = 40 / 60 to 98/2 is more preferable, and m / n = 50/50 to 97/3 is most preferable. If m is a ratio of m / n = 30/70 or more, hydrophilicity is not insufficient. On the other hand, if n is a ratio of m / n = 99/1 or more, the reactive group amount is sufficient, Sufficient curing is obtained and the film strength is sufficient.

  The above-mentioned hydrophilic polymer forms a crosslinked film in a state where it is mixed with a hydrolysis and polycondensate of metal alkoxide. The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the hydrophilic polymer has a viscosity of 0.1 to 100 cPs (5% aqueous solution, measured at 25 ° C.), preferably 0.8. When it is in the range of 5 to 70 cPs, more preferably 1 to 50 cPs, good film physical properties are provided.

[Metal alkoxide compound selected from Si, Ti, Zr, and Al]
The metal alkoxide used in the present invention is a hydrolyzable polymerizable compound having a functional group capable of being hydrolyzed and polycondensed in its structure and serving as a crosslinking agent, and the metal alkoxides are polycondensed with each other. Thus, a strong cross-linked film having a cross-linked structure is formed and further chemically bonded to the hydrophilic polymer. The metal alkoxide can be represented by general formula (IV-1) and general formula (IV-2), wherein R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁹ represents an alkyl group or an aryl group. Z represents Si, Ti or Zr, and m represents an integer of 0-2. The number of carbon atoms when R ⁸ and R ⁹ represent an alkyl group is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group. This compound is a low molecular compound and preferably has a molecular weight of 2000 or less.

_{^{(R 8) m -Z- (OR}} 9) 4-m (IV-1)
Al- (OR ⁹ ) ₃ (IV-2)

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

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

〔catalyst〕
The metal complex catalyst that can be used in the formation of the hydrophilic layer of the present invention promotes hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al, and causes a bond with a hydrophilic polymer. Can do. 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, for example, acetylacetone, acetylacetone (2,4-pentanedione), β-diketones such as 2,4-heptanedione, methyl acetoacetate, Ketoesters such as ethyl acetoacetate and butylacetoacetate, hydroxycarboxylic acids and esters thereof such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate, 4-hydroxy-4-methyl-2 -Keto alcohols such as pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N- Methyl-monoethanolamine Amino alcohols such as diethanolamine and triethanolamine, methylol melamine, methylol urea, methylol acrylamide, enol active compounds such as malonic acid diethyl ester, methyl group, methylene group or carbonyl carbon of acetylacetone (2,4-pentanedione) The compound which has a substituent is mentioned.

  A preferred ligand is 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, and among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

  Although the description of the counter salt of the metal complex described above is omitted in this specification, the type of the counter salt is arbitrary as long as it is a water-soluble salt that maintains the neutrality of the charge as the complex compound, such as nitrate, Salt forms such as halogenates, sulfates, phosphates, etc., that ensure stoichiometric neutrality are used. 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.

[Inorganic fine particles]
The hydrophilic layer of the present invention may contain inorganic fine particles in order to improve hydrophilicity, prevent cracking of the film, and improve film strength. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to form a hydrophilic member that is stably dispersed in the hydrophilic layer, sufficiently retains the film strength of the hydrophilic layer, and has high durability and excellent hydrophilicity.
Among the inorganic fine particles as described above, a colloidal silica dispersion is particularly preferable and can be easily obtained as a commercial product.
The content of the inorganic fine particles is preferably 80% by mass or less, and more preferably 50% by mass or less, based on the total solid content of the hydrophilic layer.

[Other ingredients]
Hereinafter, various additives that can be used in the coating solution for forming the hydrophilic layer of the hydrophilic member of the present invention as necessary are described.
1) Surfactant You may add surfactant to the coating liquid for hydrophilic layer formation of the hydrophilic member of this invention.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.

2) Ultraviolet Absorber In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance and durability of the hydrophilic member.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Bezotriazole compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-A-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, Special Tables 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.

3) Antioxidant In order to improve the stability of the hydrophilic member of the present invention, an antioxidant can be added to the hydrophilic layer forming coating solution. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. No. 5, JP-A-54-262447, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, Examples thereof include those described in 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.

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

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

In addition to this, as necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, tackifiers to the extent that hydrophilicity is not impaired 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.

In the hydrophilic member of the present invention, the hydrophilic layer forming coating solution composition is applied onto the coating surface on which the intermediate layer forming coating solution described below is applied, and heated and dried to form a surface hydrophilic layer. Can be obtained at The application can be applied by a known 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 method, bar coater method, Brush coating, sponge coating, etc. can be applied.
The heating temperature and heating time for forming the hydrophilic layer may be any temperature and time at which the solvent in the sol solution can be removed, a strong film can be formed, and a chemical bond can be formed by a condensation reaction with the intermediate layer described later. Although there is no particular limitation, the heating temperature is preferably 150 ° C. or less from the viewpoint of production suitability and the heating time is preferably within 1 hour.

[Intermediate layer (adhesion layer)]
Next, an intermediate layer for imparting adhesion between the hydrophilic layer of the hydrophilic member of the present invention and the substrate will be described.
The intermediate layer in the hydrophilic member of the present invention is formed by coating at least one coupling agent or one containing a hydrolyzate thereof, and is chemically bonded to the hydrophilic layer by a condensation reaction. .

(Coupling agent)
The coupling agent used in the intermediate layer of the hydrophilic member of the present invention alone or as a hydrolyzate thereof has two or more reactive groups in the molecule, and at least one of them binds to the substrate, At least one of the remaining portions is bonded to the hydrophilic polymer and / or metal alkoxide of the hydrophilic layer, thereby crosslinking the substrate and the hydrophilic layer. The coupling agent may be added to the hydrophilic layer, but it is preferable to provide it as a separate layer between the substrate and the hydrophilic layer from the viewpoint of compatibility with hydrophilicity.
In addition, a coupling agent having an acidic or basic functional group is preferable from the viewpoint of promoting the sol-gel reaction of the hydrophilic layer and forming a strong bond. A crosslinking catalyst is added to the hydrophilic layer in order to allow the sol-gel condensation reaction to proceed efficiently. By using a coupling agent having an acidic or basic functional group for the adhesion layer, the adhesion layer and the hydrophilic layer are separated. The condensation reaction of the hydrophilic layer is promoted at the interface, and the adhesion between both layers is strengthened. In addition, a coupling agent having an acidic or basic functional group having adsorptivity such as —SH, —CN, —NH ₂ , —SO ₂ OH, —SOOH, —OPO (OH) ₂ , or —COOH at the terminal is used. As a result, the enhancement of adhesion becomes particularly remarkable.

  A preferred coupling agent of the present invention is represented by the following general formula [1].

General formula [1] M- (R) _n

  In the general formula [1], M represents a metal having a divalent to pentavalent valence, and n represents an integer corresponding to the valence of the metal. R represents a halogen atom or an organic group, and the n Rs may be the same or different, and at least two of the n Rs are groups reactive with metal alkoxides and / or hydrophilic polymers. is there.

  M represents a metal having a valence of 2 to 5. The metal is selected from Group IIB, Group IIIA, Group IIIB, Group IVA, Group IVB, Group VA and Group VB. Preferred metals are Zn, Si, Ge, Sn, Pb, Ti, V, Al, Ga, In, Sb, and Bi, and particularly preferred are Si, Ti, and Al.

Among the organic groups represented by R, examples of the group having reactivity with a metal alkoxide and / or a hydrophilic polymer include (1) vinyl group, allyloxy group, acryloxy group, methacryloxy group, isocyanato group, formyl group, epoxy group, a styryl group, a ureido group, a reactive group such as a halogen, or an alkyl group having them end, (2) _{-SH terminated, -CN, -NH 2, -SO 2} OH, -SOOH, -OPO (OH) ₂ , alkyl group having adsorptive and acidic and basic groups such as —COOH, (3) methoxy group, ethoxy group, isopropoxy group, n-propoxy group, t-butoxy group, n-butoxy group And alkoxy groups, and (4) phenoxy groups. As these alkyl group, alkoxy group and phenoxy group, those having 8 or less carbon atoms are desirable. Further, these alkyl group, alkoxy group and phenoxy group may further have a substituent.
The remaining organic group represented by R may be any group, but preferably has 8 or less carbon atoms at the terminal.

Although the specific example of the coupling agent used for this invention is enumerated, it is not limited to these compounds.
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, aminophenyltrimethoxysilane, 3-amino Propyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (p-chloromethyl) phenyltrimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, (3-glycid Xylpropyl) -3-mercaptopropyldimethoxysilane, vinyltrichlorosilane, tetramethoxysilane, tetraethoxysilane, titanium isopropoxide, titanium diethoxide diethoxide, 3-mercaptopropyltitanium trime Xoxide, 3-mercaptopropyltriethoxygermane, 3-methacryloxypropyltriethoxygermane, aminophenylaluminum dimethoxide, aluminum isopropoxide, 3-aminopropylgermanium triethoxide, aminopropylindium dimethoxyethoxide, 3-glycid Xylpropyltriethoxytin, 3-methacryloxypropyltri-t-butoxytin, N- (2-aminoethyl) -3-aminopropylmethyldimethoxytin, vinyl-tris (2-ethoxymethoxy) lead (IV), 3-methacryl Oxypropyltetramethoxyantimony (V), 3-mercaptopropyl bismuth (III) di-t-pentoxide, 3-aminopropyl vanadium dibutoxide oxide, trihydroxysilylpropyls Examples include sulfonic acid, sodium trihydroxysilylethylcarboxylate, methyl trihydroxysilylpropyl phosphate, and the like.

  In particular, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane having an acidic or basic functional group , Aminophenyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, aminophenylaluminum dimethoxide, 3-aminopropylgermanium triethoxide, aminopropylindium dimethoxyethoxide, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxytin, 3-aminopropylvanadium dibutoxide oxide, trihydroxysilylpropylsulfonic acid, sodium trihydroxysilylethylcarboxylate, B silyl propyl methyl phosphoric acid is preferred.

The intermediate layer can be formed by applying a coating solution containing the above coupling agent on a substrate, and then applying, heating, and drying a hydrophilic layer forming coating solution.
As a coating method, the same method as the hydrophilic layer coating described above can be applied. In addition, the heating temperature is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour, as in the hydrophilic layer.
In addition to the coupling agent, the intermediate layer forming coating solution contains an appropriate solvent and other necessary components.
As a specific example of the solvent, the same solvent as that used for forming the hydrophilic layer can be used. More preferably, water, acetone, methyl ethyl ketone, methanol, ethanol, 1-propanol, chloroform, toluene, ethyl acetate, dioxane, ethylene glycol monomethyl ether, etc. are mentioned. The amount of the solvent used is preferably 50 to 99% by mass, more preferably 70 to 95% by mass with respect to the entire intermediate layer coating solution.
Specific examples of other necessary components include the same inorganic particles and surfactants as those used for forming the hydrophilic layer.

〔Base material〕
The base material used for the hydrophilic member of the present invention is not particularly limited. For example, the base material can be selected from inorganic materials, metal materials, and the like. Ceramic, cement, concrete, stone, asphalt, steel, stainless steel, for automobiles A steel plate or the like can be used. In particular, since inorganic materials and metal materials are excellent in heat resistance, they can be heated at a high temperature, and are excellent in the curing reaction of the hydrophilic layer and the bonding property with the adhesion layer.
More specifically, as applications where dirt is removed by rainfall or water washing, building exteriors such as outer walls and roofs, window frames, flooring, signboards, traffic signs, noise barriers, roads, pavements, centerlines and speeds, etc. Road markings, artificial waterfalls / artificial fountain stones / tiles, bridges, greenhouses, exterior wall materials, guardrails, verandas, outdoor benches, toll booths, toll boxes, roof gutters, exterior and coating of advertising towers, structural members, interiors of buildings Materials, housing equipment, toilets, bathtubs, sinks, vanities, kitchenware, tableware, sinks, cooking ranges, tunnel walls, exterior walls and roofs, building exteriors; window frames; automobiles, rail cars, aircraft, ships, Exterior and painting of vehicles such as bicycles and motorcycles; signboards, traffic signs, noise barriers, vehicle covers, road mirrors, reflectors, shutters, screen doors, solar cell covers, solar water heater covers, street lamps, etc. Outdoor lighting Vending machines, air conditioner outdoor units, various display devices, shutters, dust covers and coatings, painting of machinery and articles, lighting fixtures, tableware dryers, kitchen hoods, ventilation fans, window rails, tunnel lighting, window sashes, heat exchange These are radiating fins for bathrooms, mirrors for bathroom toilets, greenhouse ceilings, bathroom vanities, automobile bodies, films that can be attached to these articles, patches, etc.

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

[Layer structure when using hydrophilic members]
When the hydrophilic member of the present invention is used in anticipation of the appearance of antifouling and / or antifogging effects, it may be used by appropriately adding another layer depending on the purpose, form and place of use. it can. The layer structure added as needed is described below.
1) Adhesive layer When the hydrophilic member of the present invention is used by being affixed 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. The release layer preferably contains a release agent in order to give release properties. As the release agent, generally, a silicone release agent composed of polyorganosiloxane, a fluorine compound, a long-chain alkyl modified product of polyvinyl alcohol, a long-chain alkyl modified product of polyethyleneimine, and the like can be used. In addition, various release agents such as a hot melt type release agent, a monomer type release agent that cures a release monomer by radical polymerization, cationic polymerization, polycondensation reaction, etc., and other acrylic-silicone copolymer Resins, acrylic-fluorine-based copolymer resins, urethane-silicone-fluorine-based copolymer resins, and the like, 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 deterioration of hydrophilicity due to adhesion of dirt substances. As the protective layer, the release layer or the hydrophilic polymer layer used for the undercoat layer can be used. The protective layer is peeled off after the hydrophilic member is attached to an appropriate substrate.

[Form of structure]
The structure having a hydrophilic layer of the present invention may be supplied in the form of a sheet, a roll, or a ribbon, or may be supplied as a material that has been cut in advance in order to be attached to 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 even 5 ° or less, and there is a limit to the mutual comparison of the hydrophilicity. . On the other hand, as a method for evaluating the 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 the higher the surface free energy value, the higher the hydrophilicity.
A hydrophilic layer having a surface free energy measured by such a method in the range of 70 mN / m to 95 mN / m, preferably 72 mN / m to 93 mN / m, more preferably 75 mN / m to 90 mN / m is hydrophilic. Excellent performance.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
A glaze-treated tile (AB02E01, manufactured by Totoki Equipment Co., Ltd.) was prepared, and an adhesion layer coating solution having the following composition was applied by spin coating so that the dry coating amount was 0.1 g / m ² , and 100 ° C. 20 After drying for 2 seconds, the following hydrophilic layer coating solution is applied to the bar and oven dried at 100 ° C. for 10 minutes to form a hydrophilic layer with a dry coating amount of 1.0 g / m ² to produce a hydrophilic member. did. The surface free energy of this hydrophilic member was 87 mN / m, and the surface was very hydrophilic.

<Adhesion layer coating solution>
・ (3-Glycidoxypropyl) trimethoxysilane 10g
・ Ethanol 100g
・ 0.1N nitric acid 0.1g

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

<Sol-gel preparation solution>
In 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.) and 5 g of a hydrophilic polymer having a silane coupling group at the following terminal are mixed. Stir at room temperature for 2 hours to prepare.

<Synthesis of hydrophilic polymer having a silane coupling group at the terminal>
A three-necked flask was charged with 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethylformamide and heated to 65 ° C. under a nitrogen stream to produce 2,2′-azobis (2,4-dimethylvaleronitrile). 0.25 g was added to start the reaction. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of ethyl acetate, and a solid precipitated. Thereafter, filtration was performed, and the product was sufficiently washed with ethyl acetate and dried (yield 21 g). It was confirmed by GPC (polystyrene standard) that the polymer had a mass average molecular weight of 4000. The viscosity of the 5% aqueous solution was 2.5 cPs, and the functional group density of the hydrophilic group was 13.4 meq / g.

(Evaluation) The following evaluation was performed on the hydrophilic member.
Hydrophilicity: Measurement of contact angle of water droplets (measured with DropMaster500 manufactured by Kyowa Interface Science Co., Ltd.).
Water resistance: The hydrophilic member was subjected to a sponge reciprocation 10 times under a load of 1 kg in water, and the remaining film ratio was measured from the mass change before and after that.
Durability Abrasion test: A non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.) was rubbed 100 times with a weight of 500 g, and the contact angles before and after that were measured. Durability is good when the water droplet contact angle shows a low value even after rubbing.
Scratch test: Starting from 10 g on a 1 mm diameter sapphire needle, the surface of the hydrophilic layer was scanned in increments of 10 g, and the weight at which scratching occurred was evaluated (measured with a scratch strength tester Type 18S manufactured by Shinto Kagaku Co., Ltd.). The durability is better when there is no damage even if the load is large.
Antifouling property: A slurry in which 5 g of carbon black (FW-200, manufactured by Dexa) was suspended in 95 g of water was prepared. After spray coating on the surface of the hydrophilic member so as to be uniform, 60 ° C. Dry for 1 hour. The sample was washed with running water, washed with gauze, and the state of carbon black adhesion after drying was measured by visible light reflectance (using Hitachi spectrophotometer U3000). The reflectance was calculated according to the method of JIS standard R3106.
Weather resistance: A hydrophilic member was exposed to a sunshine carbon arc lamp type accelerated weathering tester for 500 hours, and hydrophilicity, water resistance, durability, scratch test, and antifouling property were evaluated according to the above-mentioned methods.

  The results are shown in Table 1. The water droplet contact angle was 5 ° or less, and the hydrophilicity was very high, and the water resistance was very good with a remaining film rate of 100%. There was no decrease in hydrophilicity due to the abrasion test, and in the scratch test, there was no damage up to 50 g, and the durability was excellent. As for the antifouling property, adhesion of carbon black was not observed at all, and the visible light transmittance was 89%, which was equivalent to that of an untreated hydrophilic member, and was good. The weather resistance did not change before and after the weathering treatment in any evaluation, and gave good results.

Examples 2-5
In the adhesion layer coating solution described in Example 1, a hydrophilic member was prepared in the same manner as in Example 1 except that the following coupling agent was used instead of (3-glycidoxypropyl) trimethoxysilane. As a result of evaluation similar to Example 1, as shown in Table 1, it was a favorable result in any evaluation item.

Example 2 N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane Example 3 Trihydroxysilylpropylsulfonic acid Example 4 Sodium trihydroxysilylethylcarboxylate Example 5 Methyl trihydroxysilylpropyl phosphate

Comparative Example 1
A hydrophilic member was prepared in the same manner as in Example 1 except that the adhesion layer described in Example 1 was not applied. As a result of the same evaluation as in Example 1, the hydrophilicity was the same, but the hydrophilic layer was completely or partially removed by the water resistance test and the abrasion test, and the scratch test was scratched at 20 g. It was inferior in durability.

Examples 6-11
In place of the glaze-treated tile described in Example 1, unglazed base tile, artificial marble substrate, concrete substrate, cement substrate, asphalt substrate, automotive steel plate (chemical conversion treatment, electrodeposition coating, intermediate coating on steel plate) A hydrophilic member was prepared in the same manner as in Example 1 except that the coating and top coating were used. As a result of the same evaluation as in Example 1, it was a good result in any evaluation item.

Claims (6)

  Hydrophilic material in which an intermediate layer and a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, and Al, and c) a metal complex catalyst are coated on the substrate. The intermediate layer is coated with at least one coupling agent or a hydrolyzate thereof, and is bonded to the hydrophilic film by a condensation reaction. A hydrophilic member.   The hydrophilic member according to claim 1, wherein the base material comprises at least one selected from an inorganic material, an organic material, and a metal material. The hydrophilic member according to claim 1, wherein the coupling agent is a compound represented by the following general formula [1].
General formula [1] M- (R) _n
(In the general formula [1], M represents a metal having a valence of 2 to 5, n represents an integer corresponding to the valence of the metal, R represents an organic group, and n R's are And may be the same or different, and at least two of the n Rs are groups reactive with metal alkoxides and / or hydrophilic polymers.)   The c) metal complex catalyst is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, enolic active hydrogen compound. The hydrophilic member according to claim 1, comprising a selected oxo- or hydroxy-oxygen-containing compound. The hydrophilic member according to any one of claims 1 to 4, wherein the hydrophilic polymer (a) is represented by at least one selected from the following general formulas (I) and (II).

In the formulas (I) and (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a hydrocarbon group, X represents a reactive group, A and L ¹ , L ² , and L ³ each independently represent a single bond or a linking group, and Y represents —NHCOR ⁷ , —CONH ₂ , —CON (R ⁷ ) ₂ , —COR ⁷ , —OH, —CO ₂ M _{, -SO 3 M, -PO 3 M} , -OPO 3 M or ^-N _{(R 7)} represents a 3 ^{Z 1,} wherein, ^{R 7} represents an alkyl group, an aryl group, an aralkyl group, M represents a hydrogen atom, Alkali metal, alkaline earth metal or onium is represented, Z ¹ represents a halogen ion, and B represents formula (III).

In formula (III), R ¹ , R ² , L ¹ and Y are the same as those in formulas (I) and (II).   A metal alkoxide compound selected from a) a hydrophilic polymer, b) Si, Ti, Zr, and Al by applying a coating solution containing at least one coupling agent or a hydrolyzate thereof on a substrate. C) A method for producing a hydrophilic member, in which an aqueous solution containing a metal complex catalyst is applied, heated and dried to coat a hydrophilic film.