JP2008201812A - Hydrophilic film transfer sheet, hydrophilic structure produced by using the same and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a hydrophilic film on a smooth surface and a curved surface, and a method for producing a hydrophilic film having durability and water resistance. <P>SOLUTION: A hydrophilic member having excellent durability and water-resistance on various members including smooth surface members and curved surface members is produced by forming, on a temporal supporting member, a hydrophilic coating film containing (a) a hydrophilic polymer, (b) a metal alkoxide compound containing a metal selected from Si, Ti, Zr and Al and (c) a catalyst effective for the hydrolysis and polycondensation of the metal alkoxide compound (b) and forming a bond with the hydrophilic polymer (a), wherein the hydrophilic film is formed in a state directing the surface against the temporal supporting member. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrophilic film transfer sheet, a hydrophilic structure, and a method for producing the same, and more specifically, a hydrophilic film transfer sheet excellent in hydrophilicity, durability, water resistance, and storage stability, a hydrophilic structure, and It relates to the 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 As for the surface treatment by, there is a concern about deterioration of the function with time, and development of antifouling / antifogging members 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

An object of the present invention is to provide a hydrophilic film transfer sheet, a hydrophilic structure, and a hydrophilic structure having a hydrophilic film excellent in hydrophilicity on various substrate surfaces and having excellent durability and water resistance and storage stability. It is in providing the manufacturing method.
The present invention also provides a hydrophilic film transfer sheet, a hydrophilic structure, and a method for producing the same, which can easily form a hydrophilic film having a uniform thickness even on a curved substrate having a particularly large area.

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. In addition, the surface layer having a cross-linking structure can achieve the above-mentioned object, and the surface layer having such a cross-linked structure can have a hydrophilic polymer having a reactive group at its terminal or a hydrophilic polymer having a graft chain as a cross-linking agent. It is found that a film having good curability can be obtained by combining, and a hydrophilic film transfer sheet provided with a temporary support on the hydrophilic surface side of this hydrophilic film, and this is applied to a substrate to which hydrophilicity is to be imparted. After providing the side opposite to the hydrophilic surface, that is, the side opposite to the temporary support, the temporary support is peeled off to provide a hydrophilic structure with excellent hydrophilicity, visibility and aesthetics. It found that it is possible to obtain a body. By using the hydrophilic film transfer sheet, a hydrophilic film having a uniform film thickness can be easily formed even on a curved substrate. The present invention is particularly useful in that a hydrophilic film having a large area can be easily formed.
That is, the present invention is as follows.

(1) On the temporary support,
a) hydrophilic polymer,
b) a metal alkoxide compound selected from Si, Ti, Zr, Al,
c) a catalyst that hydrolyzes and polycondenses the metal alkoxide compound of b) to form a bond with the hydrophilic polymer of a),
A hydrophilic film-transfer sheet having a hydrophilic film containing a material with the surface facing the temporary support.
(2) The hydrophilic film transfer sheet according to (1), wherein the hydrophilic film further contains d) colloidal silica.

  (3) The hydrophilic film transfer sheet according to (1) or (2), wherein the hydrophilic polymer of a) is represented by at least one of the following general formulas (I) to (III).

In the general formulas (I) to (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or carbon number 1 And X represents a reactive group (carboxyl group, salt thereof, carboxylic anhydride group, amino, hydroxyl, epoxy group, methylol, mercapto, isocyanate, block isocyanate group, alkoxysilyl group, alkoxy group) Represents a titanate group, an alkoxyaluminate group, an alkoxyzirconate group, an ethylenically unsaturated double bond, an ester bond, or a tetrazole group), and A and L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently represents a single bond or a linking group, Y is _{^{-NHCOR 11, -CONH 2, -CON (}} R 11) 2, -COR 11, -OH, -CO 2 M, -SO 3 M, -PO 3 M, - PO ₃ M or -N (R ¹¹⁾ represents ₃ Z ^1, wherein, R ¹¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth It represents a metal or onium, Z ¹ represents a halogen ion, and B represents the following general formula (IV).

In the general formula (IV), R ¹ , R ² , L ¹ and Y represent the same as those in the general formula (I).

(4) The hydrophilic film transfer sheet according to any one of (1) to (3), wherein a) the hydrophilic group density of the hydrophilic polymer is 1 to 30 meq / g.
(5) The hydrophilic film transfer sheet according to any one of (1) to (4), wherein the viscosity of the a) hydrophilic polymer is 0.1 to 100 cPs (5% aqueous solution).

(6) The hydrophilic film transfer sheet according to any one of (1) to (5), further comprising an adhesive layer on the surface of the hydrophilic film opposite to the temporary support.
(7) The hydrophilic film transfer sheet according to (6), wherein the adhesive layer is made of a transparent adhesive containing any of rubber, acrylic and silicone.

(8) After providing the hydrophilic film in the hydrophilic film transfer sheet according to (1) to (7) on another substrate, the hydrophilic film is formed on the substrate by peeling the support. The manufacturing method of the hydrophilic structure which has.
(9) By providing the hydrophilic film in the hydrophilic film transfer sheet according to (6) or (7) on another substrate via the adhesive layer, and then peeling the temporary support. The manufacturing method of the hydrophilic structure which has a hydrophilic membrane | film | coat on a base material.
(10) The hydrophilic film produced by peeling off the temporary support after providing the hydrophilic film in the hydrophilic film transfer sheet according to any one of (1) to (7) on another substrate. The hydrophilic structure which has on a base material.
(11) By providing the hydrophilic film in the hydrophilic film transfer sheet according to (6) or (7) on another substrate via the adhesive layer, and then peeling the temporary support. A manufactured hydrophilic structure having a hydrophilic film on a substrate.
(12)
On the temporary support,
a) hydrophilic polymer,
b) a metal alkoxide compound selected from Si, Ti, Zr, Al,
And c) hydrolyzing and polycondensing the metal alkoxide compound of b) above, and using the hydrophilic film composition containing a catalyst that causes condensation with the hydrophilic polymer of a) to form a crosslinked structure hydrophilic film. A method for producing a hydrophilic film transfer sheet comprising forming the hydrophilic film transfer sheet.

The hydrophilic film transfer sheet of the present invention was provided in such a manner that the surface of the hydrophilic film (also referred to as a hydrophilic layer) opposite to the temporary support was in contact with another substrate such as glass through an adhesive layer or the like. Thereafter, by peeling off the temporary support, a hydrophilic film can be easily applied. Further, a uniform hydrophilic layer can be formed on a curved substrate and a large area substrate. Can be easily obtained.
Further, due to the action of a specific catalyst, the hydrophilic polymer has a crosslinked structure formed by hydrolysis and condensation polymerization of a metal alkoxide, and the hydrophilic polymer is chemically bonded at the end, Or, because it has a graft polymer structure in which a hydrophilic polymer is bonded to the main chain chemically bonded to the crosslinked structure, the hydrophilic layer polymer chain has a very high mobility and a hydrophilic film with excellent hydrophilicity. Can provide.
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 can always provide a normal hydrophilic film without causing a failure such as a crack with respect to bending during handling such as manufacturing.
Moreover, although the hydrophilic film has a very high surface hydrophilicity, a cured film having a high crosslinking density can be obtained by hydrolysis and polycondensation of the metal alkoxide, so that the hydrophilic layer hardly contains water. 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.

The present invention is described in detail below.
[Transfer sheet]
The hydrophilic film transfer sheet 10 of the present invention has at least a temporary support 5 on the side in contact with the hydrophilic film 1 and the hydrophilic surface 2 as shown in the schematic conceptual diagram enlarged in FIG. The adhesive layer 3 is provided on the opposite side of the hydrophilic coating 1 from the temporary support 5. Furthermore, you may have the undercoat layer 4 between the hydrophilic membrane | film | coat 1 and the temporary support body 5 as needed.
The hydrophilic film 1 is easily provided on the base material 20 by adhering the hydrophilic film transfer sheet 10 to the other base material 20 to be imparted with hydrophilicity through the adhesive layer 3 as necessary. be able to. Thereafter, the temporary support 5 is peeled off to obtain a hydrophilic structure 30 having the hydrophilic film 1 having a hydrophilic surface on the substrate 20, as shown in FIG.

  The base material 20 having the hydrophilic film 1 formed on the surface can control the interaction between the base material surface and the attached water droplets, and high hydrophilic performance is achieved. Moreover, since the hydrophilic film 1 can be pasted by lamination as a transfer sheet, it can be satisfactorily adhered regardless of the shape of the substrate, and a surface-treated substrate excellent in visibility and aesthetics can be obtained. it can.

[Temporary support]
In the present invention, the hydrophilic film as described above is provided on the temporary support.
Examples of the temporary support include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyethylene sulfide, polycarbonate film, and polyimide film.
The thickness of the temporary support is not particularly limited, and is preferably 10 μm to 200 μm.

  The method for providing the hydrophilic film on the temporary support is not particularly limited, and examples thereof include coating, vapor deposition, bonding, and pressure bonding. Preferably, an aqueous solution containing a hydrophilic polymer is prepared, applied to a temporary support, and dried.

  As a coating method, known coating means such as dipping, spraying, spin coating and curtain coating can be used. The coating solution can be used by diluting with an organic solvent, water or the like, if necessary, such as a coating method.

[Undercoat layer]
In the present invention, an undercoat layer can be provided between the temporary support and the hydrophilic film as necessary.
This undercoat layer improves the applicability when applying the coating liquid for forming a hydrophilic film on the temporary support, the coating stability of the formed film, the ease of peeling when peeling the temporary support, and the like. Is.
The undercoat layer is not left on the hydrophilic film immediately after the temporary support is peeled off.
Examples of the material for the undercoat layer include hydrophilic resins such as polyester, polyvinyl alcohol, polyvinyl pyrrolidone, and carboxymethylated cellulose.

[Adhesive layer]
In the present invention, an adhesive layer may be further provided on the hydrophilic film on the side opposite to the temporary support, if necessary. Thereby, it becomes easy to set the hydrophilic membrane | film | coat on another base material.
As the material for the adhesive 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 polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.

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

  In the present invention, the hydrophilic film transfer sheet is provided on a base material to which hydrophilicity is to be imparted via an adhesive layer provided on the base material or an adhesive layer provided on the hydrophilic film transfer sheet as necessary. By adhering, a hydrophilic structure can be easily obtained.

  In the present invention, an underlayer may be provided between the substrate and the hydrophilic film. A base layer that is less susceptible to the influence of the substrate surface or that can be expected to increase functional groups on the substrate surface is more preferable from the viewpoint of improving the durability of the hydrophilic film.

  The method for providing the hydrophilic film on the substrate is not particularly limited, and a known laminating method can be used. For example, when the base material 20 is a flat plate, a roll laminator of the type shown in FIG. 3 can be used. Further, when the substrate 20 has a curved surface such as an automobile windshield, as shown in FIG. 4, the transfer sheet 10 of the present invention can be easily laminated by pulling it with a robot arm 90. A hydrophilic film can be provided on the substrate without unevenness.

[Hydrophilic film]
A cross-linked structure formed by hydrolysis and polycondensation of a metal alkoxide as described above by the action of a catalyst is hereinafter also referred to as a sol-gel cross-linked structure as appropriate in the present invention. 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 a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, Al, c) Prepare a hydrophilic coating solution composition containing a catalyst that hydrolyzes and polycondenses the metal alkoxide compound of b) and causes a bond with the hydrophilic polymer of a), and coats and dries it to the surface. It can be easily formed by forming a 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. 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. In addition, as a polymer structure having a hydrophilic group and a group that forms a bond with the metal alkoxide compound by the action of a catalyst, 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, addition polymer such as polyurethane, Preferred examples include natural product cyclic polymer structures such as cellulose, amylose and chitosan. The hydrophilic polymer of the present invention is preferably a compound represented by any of the following general formulas (I), (II), or (III). These may be used alone or in combination of two or more.

In the general formulas (I) to (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a carbon number. 1 to 8 hydrocarbon groups, X is a reactive group (carboxyl group, salt thereof, carboxylic anhydride group, amino, hydroxyl, epoxy group, methylol, mercapto, isocyanate, block isocyanate group, alkoxysilyl group, Represents an alkoxy titanate group, an alkoxy aluminate group, an alkoxy zirconate group, an ethylenically unsaturated double bond, an ester bond, a tetrazole group), and A and L ¹ , L ² , L ³ , L ⁴ and L ⁵ are independently represents a single bond or a linking group, Y _{^{-NHCOR 11, -CONH 2, -CON (}} R 11) 2, -COR 11, -OH, -CO 2 M, -SO 3 M, -PO 3 , -OPO ₃ M or -N (R ¹¹⁾ represents ₃ Z ^1, wherein, R ¹¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, M represents a hydrogen atom, an alkali metal, alkaline It represents an earth metal or onium, Z ¹ represents a halogen ion, and B represents the following general formula (IV).

In the general formula (IV), R ^1, R ^{2, L 1} and Y have the same meanings as R ^1, R ^{2, L 1} and Y in the general formula (I).

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, alkoxytitanate group, alkoxyaluminate group, alkoxyzirconate 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, 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 be a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy 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.

A and L ^{1 each} represents 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, 0 to 60 carbon atoms, 0 To 10 nitrogen atoms, 0 to 50 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 —NHCOR ¹¹ , —CONH ₂ , —CON (R ¹¹ ) ₂ , —COR ¹¹ , —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M, —OPO ₃ M, or —N ( R ¹¹ ) ₃ Z ¹ , wherein R ¹¹ 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 ¹¹ as -CON (R ¹¹⁾ _2, they may form a ring by bonding R ¹¹ to each other, 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 ¹¹ may further have a substituent, and examples of the substituent that can be introduced here include those listed as substituents that can be introduced when R ¹ and R ² are alkyl groups. Can do.

Specific examples of R ¹¹ 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 have the same meanings as those in formula (I). These compounds are commercially available and can be easily synthesized.

(Hydrophilic polymer having multiple reactive groups (II))
The hydrophilic polymer having a plurality of reactive groups represented by the general formula (II) is 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. Can be used.
In the above general formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ are independently the same as R ¹ and R ² in the above general formula (I). L ² and L ³ have the same meaning as L ^{1 in the} general formula (I). B is represented by the above general formula (IV), and R ¹ , R ² , L ¹ and Y in the general formula (IV) are the same as those in the general formula (I). X has the same meaning as in general formula (I) above.
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 group-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 weight 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. . When the molecular weight is 400 or less, it is difficult to obtain effective hydrophilicity, and when it is 100,000 or more, the polymerizability with the copolymerization monomer forming the main chain tends to be low.

  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, methylol 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 General Technology Center [1989], “UV / EB curing” "Handbook (raw material)" written by Kiyomi Kato, Polymer Publishing Society [1985], "Actual Technology of New Photosensitive Resins" written by Kiyoshi Akamatsu, CMC Publishing (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 weight 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. The molecular weight is preferably 1,000,000 or less from the viewpoints of solubility in a solvent when preparing a coating liquid for forming a hydrophilic film, viscosity of the coating liquid, and handling property that a uniform film can be easily formed.

  The hydrophilic polymer has a hydrophilic functional group that expresses hydrophilicity represented by Y in the formula, and the higher the density of the 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 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 the following general formula (V), wherein R ¹² represents a hydrogen atom, an alkyl group or an aryl group, R ¹³ represents an alkyl group or an aryl group, Z represents Si, Al, Ti Or represents Zr, m represents the integer of 0-2. When R ¹² and R ¹³ represent an alkyl group, the number of carbon atoms 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 12) m -Z- (OR}} 13) 4-m (V)

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

  In addition, when Z is Al, that is, examples of those containing aluminum in the hydrolyzable compound include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like. it can. 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 tri Examples thereof include methoxy 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, zirconate corresponding to the compound exemplified as containing titanium.

〔catalyst〕
In the formation of the hydrophilic layer of the present invention, a catalyst that promotes hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al and causes a bond with a hydrophilic polymer is used. As the catalyst, an acidic compound is used, but a Lewis acid catalyst composed of a metal complex can be preferably used. Particularly preferred catalysts are metal complex catalysts, metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or their esters, amino alcohols, enolic active hydrogen compounds It is a metal complex comprised from the oxo or hydroxy oxygen containing compound chosen from these.
Among constituent metal elements, 2A group elements such as Mg, Ca, St and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

  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 the hydrophilic coating film, a preferable content ratio of a) hydrophilic polymer: b) metal alkoxide compound: c) catalyst is 20% by mass: 70% by mass: 10% by mass.

[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. 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.

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. 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.

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 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.

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

When the hydrophilic member coated with the hydrophilic film of the present invention is used for window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic film 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.
Transparency is evaluated by measuring the light transmittance in the visible light region (380 nm to 780 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 can be obtained by applying the coating solution composition for forming a hydrophilic layer 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 is removed and a strong film can be formed, but the heating temperature is 100 to 300 ° C. The heating time is preferably 10 minutes to 10 hours. More preferably, the heating temperature is preferably 150 ° C. to 200 ° C., and the heating time is preferably 1 to 10 hours. In this case, a member having superior durability and water resistance can be provided by selecting a condition as high as possible at the above temperature and a time as long as possible at the above heating time.

  When the hydrophilic member of the present invention is expected to have an anti-fogging effect, the applicable substrate is a transparent substrate. Applications that can be applied with anti-fogging effects include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, internal vision Lenses such as mirror lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; window glass for buildings and surveillance towers; other building glass; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, Ropeway gondola, amusement park gondola, various vehicle windows; automobiles, rail cars, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, various vehicle windshields Glass; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case Las; including but cover glass measuring instruments, most preferred application is glass for automobiles and building materials.

Moreover, when expecting the antifouling effect to the surface hydrophilic member of the present invention, the applicable substrate may be transparent or opaque.
Applications that have antifouling effects include building materials, building exteriors, building interiors, window frames, window glass, structural members, exteriors of various vehicles, exteriors of machinery and equipment, dustproof covers, traffic signs, Various display devices, advertising towers, sound barriers for roads, sound barriers for railways, bridges, guardrail exteriors and coatings, tunnel interiors and coatings, insulators, solar battery covers, solar water heater heat collection covers, greenhouses, vehicle lighting Covers, housing equipment, toilets, bathtubs, washstands, lighting fixtures, lighting covers, kitchenware, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, exhaust fans, etc. Glass for automobiles and building materials.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
[Example 1]
On the polyethylene terephthalate film (10 cm × 10 cm) having a thickness of 100 μm as a temporary support, the undercoat coating liquid (1) was applied by bar coating and an undercoat layer (thickness 0.2 μm) was previously provided. The hydrophilic coating liquid (1) having the composition was applied by bar coating and then dried at 70 ° C. for 10 minutes to prepare a hydrophilic film transfer sheet provided with a hydrophilic film having a thickness of 0.1 μm.
Further, on the hydrophilic film of the above hydrophilic film transfer sheet, an epoxy transparent adhesive (GM9002 manufactured by Brennie Giken Co., Ltd.) was applied by bar coating to form an adhesive layer having a thickness of 20 μm.
The hydrophilic film transfer sheet is attached to the surface of 10 mm thick white glass (10 cm × 10 cm) exposed to UV ozone cleaner (NL-UB253, manufactured by Nippon Laser Electronics Co., Ltd.) for 10 minutes via the adhesive layer. Then, the temporary support was peeled off to obtain a hydrophilic structure (1).
When the contact angle of the water droplets in the prepared hydrophilic structure (1) was measured, it had a high hydrophilicity of 2.3 °.
Moreover, the hydrophilic structure (1) was excellent in visibility without any particular problem in that the object was seen through it.

<Undercoat coating solution (1)>
・ Methyl ethyl ketone 40g
・ Propylene glycol monomethyl ether 80g
・ Epoxy compound (Epicoat 1009) 10g
・ Isocyanate (Takenate D110N) 10g

<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>
200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate, 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 g of hydrophilic polymer (1) having a silane coupling group at the following terminal Were mixed and stirred at room temperature for 2 hours to prepare.

<Synthesis of hydrophilic polymer (1)>
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.

[Example 2]
A hydrophilic structure was prepared in the same manner as in Example 1 except that the support was changed to polyimide and the drying conditions were changed to 10 minutes at 100 ° C.
When the contact angle of the water droplets in the prepared hydrophilic structure (2) was measured, it had a high hydrophilicity of 2.3 °.
Moreover, the hydrophilic structure (2) had no particular problem in terms of seeing an object through it, and was excellent in visibility.

[Example 3]
A hydrophilic structure (3) was prepared in the same manner as in Example 1 except that the undercoat layer was not provided and the temporary support was plasma-treated for 30 seconds.
When the contact angle of the water droplets in the created hydrophilic structure (3) was measured, it had a high hydrophilicity of 2.2 °.
Moreover, the hydrophilic structure (3) had no particular problem in that it could be seen through it, and was excellent in visibility.

[Example 4]
A hydrophilic structure (4) was prepared in the same manner as in Example 1 except that the hydrophilic polymer (1) was changed to the hydrophilic polymer (2).

<Synthesis of hydrophilic polymer (2)>
A 500 ml three-necked flask is charged with 56.9 g of acrylamide, 11.6 g of acrylamide-3- (ethoxysilyl) propyl, and 280 g of 1-methoxy-2-propanol. 2.3 g of dimethyl propionate) was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The mixture was put into 2 liters of acetone, and the precipitated solid was collected by filtration. The obtained solid was washed with acetone to obtain a hydrophilic polymer (2). The mass after drying was 65.6 g. It was a polymer having a mass average molecular weight of 8,500 by GPC (polyethylene oxide standard).

[Comparative Example 1]
In place of the hydrophilic film according to the present invention, a photocatalytic film (manufactured by Toyo Porcelain Co., Ltd., Hydrotect) was attached to the glass surface to form a hydrophilic surface, whereby a surface hydrophilic member of Comparative Example 1 was obtained.

[Evaluation of friction resistance]
The surface of the obtained hydrophilic member is rubbed with a nonwoven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.) under a load of 200 g for 250 reciprocations, and the appearance change before and after that is visually observed.
○: No scratches on the surface before and after rubbing △: About one scratch ×: Many scratches exist

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

[Evaluation of anti-fogging property]
The hydrophilic member obtained above was exposed to water vapor for 1 minute under an indoor fluorescent lamp in the daytime, separated from the water vapor, and then placed in an environment of 25 ° C. and RH 10%. The degree of fogging and its change under a fluorescent lamp were sensory evaluated in three stages according to the following criteria.
○: No cloudiness is observed Δ: Cloudy, but recovers within 10 seconds, no cloudiness is seen ×: Cloudy, no cloudiness recovers even after 10 seconds

[Evaluation of moisture resistance]
The hydrophilic member obtained above was placed in a high-temperature and high-humidity layer at 60 ° C. and RH 90%, taken out after 1000 hours, and evaluated by measuring the water droplet contact angle.
The results are shown in the table below.

It is an expansion schematic conceptual diagram of a section showing an example of a hydrophilic membrane transfer sheet of the present invention. It is an expansion schematic conceptual diagram of a section showing an example of the hydrophilic structure of the present invention. It is the schematic which shows one method of providing the hydrophilic film | membrane transfer sheet of this invention on a flat base material. It is the schematic which shows one method which provides the hydrophilic film | membrane transfer sheet of this invention on a phase-like base material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrophilic film 2 Hydrophilic surface 3 Adhesive layer 4 Undercoat layer 5 Temporary support 10 Hydrophilic film transfer sheet 20 Base material 30 Hydrophilic structure 90 Robot arm

Claims (9)

On the temporary support,
a) hydrophilic polymer,
b) a metal alkoxide compound selected from Si, Ti, Zr, Al,
c) a catalyst that hydrolyzes and polycondenses the metal alkoxide compound of b) to form a bond with the hydrophilic polymer of a),
Hydrophilic film transfer sheet having a hydrophilic film containing The hydrophilic film transfer sheet according to claim 1, wherein the hydrophilic polymer of a) is represented by at least one of the following general formulas (I) to (III).

In the general formulas (I) to (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or carbon number 1 And X represents a reactive group (carboxyl group, salt thereof, carboxylic anhydride group, amino, hydroxyl, epoxy group, methylol, mercapto, isocyanate, block isocyanate group, alkoxysilyl group, alkoxy group) Represents a titanate group, an alkoxyaluminate group, an alkoxyzirconate group, an ethylenically unsaturated double bond, an ester bond, or a tetrazole group), and A, L ¹ , L ² , L ³ , L ⁴ and L ⁵ are independent of each other. Represents a single bond or a linking group, and Y represents —NHCOR ¹¹ , —CONH ₂ , —CON (R ¹¹ ) ₂ , —COR ¹¹ , —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M, — OPO ₃ M Represents _{^{-N (R 11) 3 Z 1}} . Here, R ¹¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or onium, and Z ¹ represents a halogen ion. B represents the following general formula (IV).

In the general formula (IV), R ¹ , R ² , L ¹ and Y represent the same as those in the general formula (I).   The hydrophilic film transfer sheet according to claim 1, further comprising an adhesive layer on a surface of the hydrophilic film opposite to the temporary support.   The hydrophilic film transfer sheet according to claim 3, wherein the adhesive layer is made of a transparent adhesive containing any of rubber, epoxy, acrylic, and silicone.   After providing the said hydrophilic film in the hydrophilic film transfer sheet in any one of Claims 1-4 on another base material, it has a hydrophilic film on a base material by peeling the said temporary support body. A method for producing a hydrophilic structure.   The hydrophilic film by peeling off the temporary support after providing the hydrophilic film in the hydrophilic film transfer sheet according to claim 3 or 4 on the other substrate through the adhesive layer. The manufacturing method of the hydrophilic structure which has this on a base material.   The hydrophilic film produced by peeling the temporary support after providing the hydrophilic film in the hydrophilic film transfer sheet according to claim 1 on another substrate. The hydrophilic structure which has.   The hydrophilic film produced by peeling the temporary support after providing the hydrophilic film in the hydrophilic film transfer sheet according to claim 6 or 7 on another substrate through the adhesive layer. A hydrophilic structure having a conductive film on a substrate. On the temporary support,
a) hydrophilic polymer,
b) a metal alkoxide compound selected from Si, Ti, Zr, Al,
And c) hydrolyzing and polycondensing the metal alkoxide compound of b) above, and using the hydrophilic film composition containing a catalyst that causes condensation with the hydrophilic polymer of a) to form a crosslinked structure hydrophilic film. A method for producing a hydrophilic film transfer sheet comprising forming the hydrophilic film transfer sheet.

Images