JP2007136781A - Glass structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass structure having a surface-hydrophilic layer which has high hydrophilicity and good abrasion resistance and is excellent in transparency and preservation stability. <P>SOLUTION: In the glass structure having a hydrophilic surface based on a hydrophilic coat, a hydrophilic member produced by applying a hydrophilic polymer (a), a metal alkoxide selected from Si, Ti, Zr and Al (b), and the hydrophilic coat obtained by the hydrolysis/polycondensation of the metal alkoxide (b) on a plastic substrate, is stuck on a glass surface through an adhesive layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a surface hydrophilic member, and in particular, to a surface hydrophilic glass structure including a hydrophilic surface layer excellent in hydrophilicity, durability, transparency, and storage stability.

  Resin films are used for various purposes, but their surfaces are generally hydrophobic. Also, few inorganic materials such as glass and metal have high hydrophilicity. When the surface of a substrate using resin film or inorganic material is made hydrophilic, the adhered water droplets spread uniformly on the substrate surface to form a uniform water film. It is useful for preventing devitrification due to moisture and ensuring visibility in rainy weather. In addition, combustion products such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oil and fat and sealant elution components are difficult to adhere. Therefore, it is useful for various applications.

  Conventionally proposed surface treatment methods for hydrophilization, such as etching treatment and plasma treatment, are highly hydrophilized, but their effects are temporary and maintain the hydrophilized state for a long time. I can't. 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.

  In addition, as another film having excellent surface hydrophilicity, a film using titanium oxide has been conventionally known. For example, in Patent Document 1, when a photocatalyst-containing layer is formed on the substrate surface, the photocatalyst is photoexcited. It is disclosed that the surface is highly hydrophilized, and if this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, water-circulating members, etc., these composite materials have excellent anti-fogging properties. It has been reported that functions such as antifouling can be imparted. However, a hydrophilic film using titanium oxide does not have sufficient film strength, and a hydrophilic material having better wear resistance has been demanded.

International Publication No. 96/29375 Pamphlet Chemical Daily, January 30, 1995

  An object of the present invention is to provide a surface hydrophilic glass structure having a surface hydrophilic layer having excellent hydrophilicity on the surface and better abrasion resistance, and having a surface hydrophilic layer having excellent transparency and storage stability. There is.

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. The present invention was completed by finding that it can be easily obtained by combining the above.
That is, the present invention is as follows.

(1) On a plastic substrate, a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, and Al, and a hydrophilic film obtained by hydrolyzing and polycondensing b) metal alkoxide were coated. The glass structure which has a hydrophilic surface based on this hydrophilic film which affixed the hydrophilic member on the glass surface through the contact bonding layer.
(2) The glass structure according to (1), wherein the hydrophilic coating contains a catalyst that causes a bond with the hydrophilic polymer of a).
(3) The glass structure according to (1), wherein the hydrophilic coating further includes d) colloidal silica.
(4) The glass structure according to (1), wherein the application surface of the plastic substrate is a substrate subjected to a hydrophilic treatment in advance.

(5) The glass structure 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, or 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 , _{^{-CON (R 7) 2, -COR}} 7, represents _{-OH, -CO 2 M, -SO 3} M, -PO 3 M, and -OPO ₃ M or -N (R ⁷⁾ ₃ Z ¹ Wherein, R ⁷ 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 earth metal or an onium, Z ¹ represents a halogen ion, B is Formula (III) is represented.

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

(6) The glass structure according to (1), wherein the hydrophilic film has a surface free energy of 70 mN / m to 95 mN / m.
(7) The glass structure according to (1), wherein a) the hydrophilic group density of the hydrophilic polymer is 1 to 30 meq / g.
(8) The glass structure according to (1), wherein a) the hydrophilic polymer has a viscosity of 0.1 to 100 cPs (5% aqueous solution).
(9) The glass structure 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 mobility of the hydrophilic layer polymer chain is very high, and a surface excellent in hydrophilicity can be provided.
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. For this reason, it is possible to use a thin plastic substrate that is weak and has little cushioning effect, and it is difficult to crack due to bending or pushing, and not only flat glass but also non-planar glass structures such as curved mirrors. Excellent application.
In addition, the hydrophilic film of the glass structure of the present invention has a hydrophilic layer because a cured film having a high crosslinking density can be obtained by hydrolysis and polycondensation of the metal alkoxide even though the surface hydrophilicity is very high. Has the property of hardly containing water, and therefore, stickiness due to environmental humidity (especially under high humidity conditions) is suppressed, and it is effective in preventing the back surface adhesion 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. The glass structure of the present invention has a crosslinked structure formed by hydrolysis and polycondensation of a metal alkoxide having a hydrophilic polymer chain on a suitable plastic substrate and selected from Si, Ti, Zr, and Al. However, the hydrophilic layer having such a crosslinked structure forms a hydrophilic graft chain with the metal alkoxide compound described in detail later. It can form suitably using the compound which has a hydrophilic functional group which can be obtained. 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. Or a hydrophilic compound containing the polymer compound represented by the general formula (II) having the reactive group as a side chain of the trunk polymer and (B) a hydrolyzable metal alkoxide compound. It can be easily formed by preparing a liquid composition, coating 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. As the hydrophilic group, 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 hydroxy group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a phosphoric acid group, Functional groups such as alkali metal salts of phosphoric acid groups, oxyphosphoric acid groups, and alkali metal salts of oxyphosphoric acid groups may 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. 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, or 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 , _{^{-CON (R 7) 2, -COR}} 7, represents _{-OH, -CO 2 M, -SO 3} M, -PO 3 M, and -OPO ₃ M or _{^{-N (R 7) 3 Z 1}} , Here, R ⁷ 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, Z ¹ represents a halogen ion, and B represents Formula (III) is represented.

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. Further, the 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 include, for example, chain transfer agents (described in the 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 500,000.

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, 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, 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 the same 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 - K +, morpholyl group, -OPO ₃ H ₂ and the like are preferable.

  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 viewpoints of production suitability and film structure control. 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 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 edition) "written by Kiyosuke Kato, Polymer Publishing Society [1985]," Actual Technology of New Photosensitive Resins "written by Kiyoshi Akamatsu, published by CMC (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 5,000 to 500,000. When the molecular weight exceeds 1,000,000, there is a problem in handling properties such as poor solubility in a solvent when preparing a coating solution for forming a hydrophilic coating, or a high viscosity of the coating solution, making it difficult to form a uniform coating. There is a concern that it will come out, which is not 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 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)
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. 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 general formula (IV), wherein R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, R ⁹ represents an alkyl group or an aryl group, and Z represents Si, Al, Ti or Zr is represented, 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)

  Specific examples of the hydrolyzable compound represented by the general formula (IV) 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, tetraethoxysilane, 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.

  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., those containing titanium include, 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〕
The hydrophilic layer of the present invention can use an inorganic acid such as nitric acid or hydrochloric acid or a base such as ammonia, a Lewis acid catalyst made of a metal complex, or the like for promoting gelation. 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. Among them, complexes obtained from Zr, Al and Ti are excellent and preferable.

  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 such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate, 4-hydroxy-4-methyl-2- Ketone 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.

[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 can be preferably mentioned.
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]
Below, the various additives which can be used for the coating liquid for hydrophilic layer formation of the glass structure of this invention as needed are described.
1) Surfactant You may add surfactant to the coating liquid for hydrophilic layer formation of the glass structure 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 layer form of the glass structure.
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 An antioxidant can be added to improve the stability of the hydrophilic layer of the glass structure of the present invention. 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 glass structure of the present invention, it is also effective to add an appropriate 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 solution for forming the hydrophilic layer of the glass structure of the present invention within the range not inhibiting the hydrophilicity in order to adjust the film properties of the hydrophilic layer. . Examples of polymer 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.

[Plastic substrate]
The plastic substrate used in the present invention is not particularly limited, but polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, Examples thereof include films or sheets of polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetherketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyethersulfone, and the like. Among them, a plastic substrate such as polyester such as polyethylene terephthalate and polyethylene naphthalate, cellulose resin such as polycarbonate, triacetyl cellulose, and diacetyl cellulose is particularly preferable. In addition, in terms of optical properties, it is often preferable to have excellent transparency, but depending on the application, translucent or printed materials may be used. The thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for a plane or the place where intensity | strength is requested | required.

For the purpose of improving the adhesion between the plastic substrate and the hydrophilic layer, one or both surfaces of the plastic substrate 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.
Furthermore, one or more undercoat layers can be provided. As the material for the undercoat layer, a hydrophilic resin or water-dispersible latex can be used.

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

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

[Adhesive layer]
For the adhesive layer of the present invention, a pressure sensitive adhesive which is a pressure sensitive adhesive is preferably used. 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.

[Form of structure]
The glass structure of the present invention is obtained by attaching a hydrophilic member in which the above-described hydrophilic film is coated on a plastic substrate to a glass surface through an adhesive layer.
The glass used in the present invention is not particularly limited, but glass such as soda glass, lead glass, and borosilicate glass may be used. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do.

[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, the surface free energy was measured using the Zisman plot method as an example. Specifically, an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration. After measuring the contact angle in air and at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship. Cos θ = 1, that is, the surface tension when the contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and the higher the surface free energy value, the higher the hydrophilicity.
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 glass structure provided with the hydrophilic coating of the present invention is applied to a 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 (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably 100% to 70%, more preferably 95% to 75%, and most preferably in the range of 95% to 80%. By being in this range, the glass structure provided with a hydrophilic film can be applied to various fields without obstructing the field of view.

  Formation of the hydrophilic film of the glass structure of the present invention can be obtained by applying the hydrophilic coating solution composition onto an appropriate plastic substrate, heating and drying. The heating temperature and heating time for forming the hydrophilic layer are not particularly limited as long as the solvent and the time in which the solvent in the sol solution can be removed and a strong film can be formed. It is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour.

  As a field to which the glass structure of the present invention can be applied, for example, a transparent glass is used as a base material when antifogging effect is expected. Applications for which a glass structure having an antifogging effect can be applied include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, Lenses such as endoscope lenses, illumination lenses, semiconductor lenses, copier lenses; prisms; window glass of buildings and surveillance towers; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola , Amusement park gondola, vehicle window glass such as spacecraft; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, spacecraft Vehicle windshields; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case Glass; a cover glass measuring instruments.

  In addition, when the surface cleaning effect is expected for the glass structure of the present invention, applicable applications include building materials, building exteriors, building interiors, window frames, window glass, structural members, vehicle exteriors and coatings, Exterior of machinery and articles, dust cover and paint, traffic signs, various display devices, advertising tower, road sound barrier, railway sound barrier, bridge, guard rail exterior and paint, tunnel interior and paint, insulator, solar battery cover , Solar water heater heat collection cover, greenhouse, vehicle lighting cover, housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking range Including kitchen hood and ventilation fan.

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 support having an adhesive layer and a release layer having the following composition provided on the back surface of a polyethylene terephthalate substrate (thickness 50 μm) in this order was prepared, and the surface of the support was hydrophilized by glow treatment. The layer coating solution was bar coated and oven dried at 100 ° C. for 10 minutes to form a hydrophilic layer having a dry coating amount of 1.0 g / m ² to produce a structure for a hydrophilic member. The surface free energy of this hydrophilic member was 87 mN / m, and the surface was very hydrophilic. The visible light transmittance of the hydrophilic layer was 95% (measured with a Hitachi spectrophotometer U3000).

<Adhesive layer>
A commercially available acrylic emulsion-type pressure-sensitive adhesive (Emerpol R-140, manufactured by Yushi Kogyo Co., Ltd.) was applied to the back surface of the substrate so as to have a dry thickness of about 20 μm, and dried to provide an adhesive layer. .
<Release layer>
Initiating radical photopolymerization with 150 parts by weight of trimethylolpropane triacrylate (Aronix M-309, manufactured by Toagosei Co., Ltd.) in 100 parts by weight of a 50% by weight concentration solution of polyglycidyl methacrylate (polystyrene equivalent molecular weight: 12,000) 30 parts by mass of 6 parts by mass of an agent (Irgacure 184, manufactured by Ciba Geigy), 6 parts by mass of a cationic photopolymerization initiator (Lordsil 2074, manufactured by Rhodia), and 10 parts by mass of MegaFuck 531A (manufactured by Dainippon Ink & Chemicals, Inc.) A part of the solution dissolved in methyl isobutyl ketone was mixed with stirring to prepare a release layer coating solution.
Next, the release layer coating solution was applied onto the adhesive layer by an extrusion method so as to have a thickness of 30 μm, dried, and irradiated with ultraviolet rays (1 J / cm ² ) to form a release layer.

<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.

The release layer of the structure for a hydrophilic member produced as described above was peeled off, and the adhesive layer surface was attached to glass to produce a glass structure.
In addition, the glass used at this time used the float plate glass which is the most common transparent plate glass.

(Evaluation) The following evaluation was performed on the glass structure.
Hydrophilicity: Measurement of airdrop contact angle (measured with DropMaster500 manufactured by Kyowa Interface Science Co., Ltd.)
Water resistance: A 120 cm ² size hydrophilic member was rubbed with a sponge 10 times in water, and the remaining film ratio was measured from the weight change before and after that.
Durability Abrasion test: Rub 100 times with a non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.), and measure the contact angle before and after that. Durability is good when the water contact angle is low after rubbing.
Scratch test: Starting from 5 g on a 0.1 mm diameter sapphire needle, the surface of the hydrophilic layer was scanned in 5 g increments to evaluate the weight at which scratches occurred (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.
Storage stability (back side adhesion): Adhesion on the back side after stacking 50 pieces of 5cm square glass structures, pressing them with a vise with a torque of 300kg, and aging in a 45 ° C 75% humidity environment for one day.

  As a result, the water droplet contact angle was 5 ° or less, and the hydrophilicity was very high, and the water resistance was 100%, and there was no problem. 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. In the storage stability evaluation, the hydrophilic layer did not adhere to the back surface and was excellent in storage stability.

Examples 2-3
A hydrophilic layer was prepared in the same manner as in Example 1 except that the catalyst was changed to the following. The obtained structure for a hydrophilic member had hydrophilicity, water resistance, durability, scratch resistance and storage stability equivalent to those of Example 1.
Example 2: Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH)
Example 3: Zirconium chelate compound To a reactor equipped with a stirrer, 50 parts of tetrabutoxyzirconium and 20 parts of ethyl acetoacetate were added and stirred at room temperature for 1 hour to obtain a zirconium chelate compound.

Examples 4-9
A hydrophilic layer was prepared in the same manner as in Example 1 except that the hydrophilic polymer was changed to the following. The obtained structure for a hydrophilic member had hydrophilicity, water resistance, durability, scratch resistance and storage stability equivalent to those of Example 1.

Example 4: Hydrophilic polymer 9 described in the specification
Example 5: hydrophilic polymer 13 described in the specification
Example 6: hydrophilic polymer 15 described in the specification
Example 7: hydrophilic polymer 24 as described in the specification
Example 8: hydrophilic polymer 36 as described in the specification

Example 9: hydrophilic polymer having a plurality of reactive groups synthesized as follows [synthesis of hydrophilic polymer having a plurality of reactive groups]
(Synthesis of amide macromonomer)
After dissolving 100 g of acrylamide and 10 g of 3-mercaptopropionic acid in 200 g of ethanol, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 1 g of 2,2-azobisisobutylnitrile (AIBN) thermal polymerization initiator was added and reacted for 8 hours. After the reaction, the white precipitate was filtered and sufficiently washed with methanol to obtain 90 g of a terminal carboxylic acid prepolymer (acid value 0.80 meq / g, molecular weight 1500). 50 g of the obtained prepolymer was dissolved in 150 g of dimethyl sulfoxide, 20 g of glycidyl methacrylate, 1.2 g of N, N-dimethyldodecylamine (catalyst) and 0.2 g of hydroquinone (polymerization inhibitor) were added, and the mixture was 140 ° C. in a nitrogen atmosphere. Reacted for 10 hours. The reaction solution was added to acetone to precipitate the polymer and washed well to obtain 50 g of terminal methacrylate acrylamide macromonomer (weight average molecular weight: 1800). From the H ¹ -NMR (D ₂ O) 6.12, 5.70 ppm methacryloyl group olefin peak and the decrease in acid value, it was confirmed that a polymerizable group could be introduced at the terminal.

(Synthesis of hydrophilic graft polymer (1) using amide macromonomer)
In a flask containing 120 g of dimethyl sulfoxide, 8 g of the above macromonomer, 2 g of γ-methacryloxypropyltrimethoxysilane, 2,2-azobis [2- (2-imidazolin-2-yl) propane] (VA061: trade name, sum) A solution obtained by dissolving 0.2 g of Kogyo Pharmaceutical Co., Ltd. in 35 g of dimethyl sulfoxide was added dropwise at 60 ° C. for 4 hours in a nitrogen atmosphere. Heating was continued for 6 hours after the dropping. The reaction solution was added to acetone and the polymer was precipitated and washed well to obtain 14 g of a hydrophilic polymer having a plurality of reactive groups (molecular weight 120,000, yield 94%).

Example 10
A hydrophilic layer was prepared in the same manner as in Example 1 except that the drying condition after applying the hydrophilic layer coating solution was changed to 80 ° C. for 10 minutes. The obtained structure for a hydrophilic member had hydrophilicity, water resistance, durability, scratch resistance and storage stability equivalent to those of Example 1.

Comparative Example 1
Example 1 except that the release layer of the photocatalytic hydrophilic film (commercially available Hydrotecto Film 1 year type (clear), manufactured by Totoki Equipment Co., Ltd.) is peeled off and the adhesive layer surface is attached to the float glass plate described in Example 1. A glass structure was prepared in the same manner as described above. The hydrophilicity after irradiation with 20 J / cm ² of ultraviolet rays was the same as that of Example 1, but the hydrophilicity decreased in the abrasion test, and in the scratch test, it was damaged at a weight of 5 g. Durability was inferior.

Claims (9)

  A hydrophilic member in which a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, and Al, a hydrophilic film obtained by hydrolyzing and polycondensing b) a metal alkoxide on a plastic substrate. The glass structure which has a hydrophilic surface based on this hydrophilic film which affixed this on the glass surface through the contact bonding layer.   2. The glass structure according to claim 1, wherein the hydrophilic coating contains a catalyst that causes bonding with the hydrophilic polymer of a).   2. The glass structure according to claim 1, wherein the hydrophilic coating further comprises d) colloidal silica.   2. The glass structure according to claim 1, wherein the application surface of the plastic substrate is a substrate that has been subjected to a hydrophilic treatment in advance. 2. The glass structure according to claim 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, or 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 ; Here, R ⁷ 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, Z ¹ represents a halogen ion, and B represents Formula (III) is represented.

In formula (III), R ¹ , R ² , L ¹ and Y are the same as those in formulas (I) and (II).   The glass structure according to claim 1, wherein the hydrophilic film has a surface free energy of 70 mN / m to 95 mN / m.   The glass structure according to claim 1, wherein the density of the hydrophilic group of the a) hydrophilic polymer is 1 to 30 meq / g.   The glass structure according to claim 1, wherein the viscosity of the a) hydrophilic polymer is 0.1 to 100 cPs (5% aqueous solution).   2. The glass structure according to claim 1, wherein the hydrophilic film has a light transmittance of 100% to 70%.