JP2011001423A - Aqueous coating agent for glass plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent for a glass plate satisfying at the same time light transmittance, surface protection, pollution resistance, weatherability, and the like.SOLUTION: The aqueous coating agent for a glass plate includes an aqueous substance of a composite resin (ABC) produced by dissolving or dispersing in an aqueous medium a composite resin (ABC) having the polysiloxane segment (B) of a composite resin (AB) having a polymer segment (A) having neutralized acidic group and a polysiloxane segment (B) bonded chemically with each other, and a polysiloxane segment (C) derived from a condensed product of an alkyltrialkoxy silane (c) having 1-3C alkyl group, in which the segment (B) and segment (C) are bonded via a silicon-oxygen bond, and a hardener (D) for the composite resin (ABC).

Description

  The present invention relates to an aqueous composition that can be used for glass surface treatment. More specifically, the present invention relates to an aqueous coating agent for glass plate suitable for a glass surface treatment coating material having high light transmittance while imparting excellent scratch resistance and the like to the glass surface.

  Conventionally, in order to prevent visible light from being reflected on the surface of a glass plate or other glass article to reduce transparency and light transmittance or to become dazzling, an antireflection treatment has been applied to the surface of the glass article. Has been done. For example, a low-refractive-index antireflection film is known in which a silica sol having a particle size of 5 to 30 nm and a coating liquid containing a hydrolyzate of alkoxysilane in a solvent are applied and cured on a base material (for example, Patent Documents). 1). In this case, the visibility may be reduced by reflected light from inside and outside the automobile. In order to solve such difficulties, a film having a thickness of 110 to 250 nm composed of 5 to 30% by weight of silica particles and a weight of the chain silica particles is 50% or less visible. An automobile window glass plate is proposed in which at least one of glass substrate surfaces having light transmittance (Ya) is coated and irregularities are formed on the film surface (see, for example, Patent Document 2).

  However, although the visibility is improved by the above-described technique, the transmittance is limited to a range of 50 to 10%, and the light transmittance of the glass whose surface is coated is difficult to be reduced. In addition, it is necessary to paint a solvent-based coating agent consisting of chain silica and silica so as to form irregularities in the thin film, surface polishing of the glass plate, masking of the back surface of the substrate, dipping coating that pulls up the substrate at a constant speed, There is a problem in practical use from this point of view, which requires a complicated coating method that requires a long heat treatment such as 100 ° C. for 30 minutes, 250 ° C. for 30 minutes, and 500 ° C. for 1 hour.

  Solar power generation has been attracting attention in recent years due to the growing needs for environmentally friendly products and resource conservation. However, since the surface of the solar cell panel has many glass substrates, it is a member that improves the light transmittance of the surface glass. There is a demand for materials that prevent soiling. As a matter of course, these members are required to have high weather resistance. In this case, a technique of laminating a transparent sheet has been proposed (see, for example, Patent Document 3). However, a coating agent that simultaneously satisfies light transmittance, surface protection, antifouling property, weather resistance, etc. has been found. Absent.

JP-A-8-122501 JP 2000-256040 A JP 2002-134767 A

  The problem to be solved by the present invention is to provide a coating agent for glass that simultaneously satisfies light transmittance, surface protection, antifouling property, weather resistance and the like.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a composite resin (A) in which a polymer segment (A) having a neutralized acid group and a polysiloxane segment (B) are chemically bonded ( The polysiloxane segment (B) of AB) and the polysiloxane segment (C) derived from the condensate (c) of alkyltrialkoxysilane having an alkyl group having 1 to 3 carbon atoms are bonded via a silicon-oxygen bond. Aqueous composition for surface treatment containing an aqueous product of composite resin (ABC) obtained by dissolving or dispersing composite resin (ABC) in an aqueous medium and a curing agent (D) that reacts with this composite resin (ABC) It was found that the product can impart excellent light transmission, scratch resistance, etc. to the glass surface, and the present invention has been completed.

  That is, the present invention relates to a polysiloxane segment (B) of a composite resin (AB) formed by chemically bonding a polymer segment (A) having a neutralized acid group and a polysiloxane segment (B), and an alkyl group. A composite resin (ABC) in which a polysiloxane segment (C) derived from a condensate (c) of an alkyltrialkoxysilane having 1 to 3 carbon atoms is bonded via a silicon-oxygen bond is present in an aqueous medium. Disclosed is an aqueous coating agent for a glass plate, comprising an aqueous solution of a composite resin (ABC) formed by dissolution or dispersion, and a curing agent (D) for the composite resin (ABC).

  The water-based coating agent for glass plate of the present invention can be easily subjected to glass surface treatment with excellent antifouling property and scratch resistance. In particular, it is used for a transparent substrate such as glass as a protective material for automobile applications and solar cell modules. Suitable as a surface protective layer.

  Below, the aqueous coating agent for glass plates which concerns on this invention, and its manufacturing method are demonstrated concretely. The composite resin (ABC), which is a component of the aqueous composition of the present invention, is derived from a polymer segment (A), a polysiloxane segment (B), and a condensate of alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group. Polysiloxane segments (C), each segment having a structure with bonds of “(A)-(B)-(C)”. The aqueous composition is a composition containing the composite resin curing agent (D) in which the composite resin is dissolved or dispersed in an aqueous medium.

  The composite resin (ABC) used in the present invention is a polysiloxane segment of a composite resin (AB) in which a polymer segment (A) having a neutralized acid group and a polysiloxane segment (B) are chemically bonded. A composite resin in which (B) and a polysiloxane segment (C) derived from a condensate (c) of an alkyltrialkoxysilane having 1 to 3 carbon atoms of an alkyl group are bonded via a silicon-oxygen bond For example, a composite resin having a graft structure chemically bonded to a side chain of the polymer segment (A) having a neutralized acid group of the polysiloxane segment (B), or the polymer segment (A) The polysiloxane segment (B) of the composite resin having a block structure in which the polysiloxane segment (B) is chemically bonded to the terminal of the alkyl group, and the alkyl group having 1 to 3 carbon atoms Alkyl condensate of trialkoxysilane and (c) derived from a polysiloxane segment (C) silicon - composite resins having a chemically bonded structure through an oxygen bond.

  The chemical bond between the polymer segment (A) and the polysiloxane segment (B) included in the composite resin (ABC) is not particularly limited. For example, the following structural formula (S-1) or Examples include the bonding mode of the following structural formula (S-2). Among them, the use of a composite resin having the bonding mode of the structural formula (S-1) can form a coating film excellent in weather resistance. preferable. [However, the carbon atom in the structural formula (S-1) constitutes a part of the polymer segment (A), and the silicon atom and the oxygen atom constitute a part of the polysiloxane segment (B). ]

[However, the carbon atom in the structural formula (S-2) constitutes a part of the polymer segment (A), and the silicon atom constitutes a part of the polysiloxane segment (B). ]

  The polymer segment (A) constituting the composite resin (ABC) may be a polymer segment having a neutralized acid group in order to disperse or dissolve the composite resin (ABC) in an aqueous medium. Essentially, among them, the above structural formula (S-1) is easily hydrolyzed and condensed with a hydroxyl group bonded to a silicon atom or a hydrolyzable group bonded to a silicon atom of the polysiloxane segment (B) or its synthesis raw material. As a result of chemical bonding in the bonding mode, a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom together with a neutralized acid group (hereinafter referred to as “hydroxyl group and / or hydrolysis of a silicon atom bond”). It is preferably a polymer segment derived from the polymer (a) having an abbreviated “functional group”. Examples of the polymer (a) include vinyl polymers such as acrylic polymers, fluoroolefin polymers, vinyl ester polymers, aromatic vinyl polymers, and polyolefin polymers, polyurethane polymers, and polyester polymers. , Polyether polymers, and the like. Among them, vinyl polymers and polyurethane polymers are preferable, and acrylic polymers are more preferable.

  Examples of the acid group in the polymer (a) include a carboxyl group, a phosphoric acid group, an acidic phosphoric acid ester group, a phosphorous acid group, a sulfonic acid group, and a sulfinic acid group. Among these, a composite resin (ABC) A carboxyl group is preferred because it is easily introduced into the skeleton.

  Examples of the basic compound used for neutralizing the acid group include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, and 2-dimethylaminoethanol. ; Inorganic basic compounds such as ammonia, sodium hydroxide and potassium hydroxide; quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide and trimethylbenzylammonium hydroxide can be used. Of these, organic amines and ammonia (ammonia water may be used) are preferably used.

  From the viewpoint of maintaining good storage stability of an aqueous dispersion or aqueous solution in which the composite resin (ABC) is dispersed or dissolved in an aqueous medium, the neutralized acid group in the polymer (a). It is preferably present at a rate of 0.1 to 20% by weight, more preferably at a rate of 0.2 to 10% by weight, based on 100% by weight of the composite resin (ABC). preferable.

  Moreover, as a hydrolysable group couple | bonded with the silicon atom in the said polymer (a), if it is a functional group which can produce | generate the hydroxyl group (silanol group) couple | bonded with the silicon atom by being hydrolyzed, Well, for example, halogen atom bonded to silicon atom, alkoxy group bonded to silicon atom, acyloxy group bonded to silicon atom, phenoxy group bonded to silicon atom, mercapto group bonded to silicon atom, amino bonded to silicon atom Group, an amide group bonded to a silicon atom, an aminooxy group bonded to a silicon atom, an iminooxy group bonded to a silicon atom, an alkenyloxy group bonded to a silicon atom, and the hydrolysis reaction can proceed easily. In addition, since a by-product after the reaction can be easily removed, an alkoxy group bonded to a silicon atom is preferable.

  The polymer segment (A) may have other functional groups other than neutralized acid groups, silicon atom-bonded hydroxyl groups, and / or hydrolyzable groups, as long as the effects of the present invention are not impaired. Good. Examples of such other functional groups include unneutralized carboxyl groups, blocked carboxyl groups, carboxylic anhydride groups, hydroxyl groups, blocked hydroxyl groups, cyclocarbonate groups, epoxy groups, carbonyl groups, and primary amide groups. Secondary amide group, carbamate group, polyethylene glycol group, polypropylene glycol group, group shown by following structural formula (S-3), etc. are mentioned.

  Examples of the polysiloxane segment (B) constituting the composite resin (ABC) include a segment derived from a polysiloxane having a silicon atom-bonded hydroxyl group and / or a hydrolyzable group. Examples of the hydrolyzable group bonded to the silicon atom include those similar to the hydrolyzable group bonded to the silicon atom described in the polymer segment (A), and preferred ones are also the same.

  As said polysiloxane segment (B), what has a structure shown by the following general formula (S-4) or (S-5) especially is preferable. Since the polysiloxane segment having the structure represented by the following general formula (S-4) or (S-5) has a three-dimensional network-like polysiloxane structure, the resulting coating film has solvent resistance and weather resistance. It has excellent properties.

[In the general formulas (S-4) and (S-5), R ¹ is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a silicon atom. A bonded methyl group or an ethyl group bonded to a silicon atom. R ¹ is preferably a hydrocarbon group having 4 to 12 carbon atoms bonded to a silicon atom, and more preferably a phenyl group or an alkyl group having 4 carbon atoms. R ² and R ³ are each preferably a methyl group bonded to a silicon atom or an ethyl group bonded to a silicon atom, and more preferably a methyl group bonded to a silicon atom. ]

  The polysiloxane segment having the structure represented by the general formula (S-4) or (S-5) is an organoalkoxysilane, preferably an organic group having 4 to 12 carbon atoms bonded to a silicon atom (hereinafter, “ A monoorganotrialkoxysilane having a silicon atom-bonded organic group having 4 to 12 carbon atoms ”) and / or a methyl group bonded to a silicon atom and / or an ethyl group bonded to a silicon atom (hereinafter referred to as an“ organic group ”). And a segment derived from polysiloxane obtained by hydrolytic condensation of a diorganodialkoxysilane having two of “a silicon atom-bonded methyl group and / or ethyl group”. These polysiloxane segments consist of two organic atom-bonded organic groups having 4 to 12 carbon atoms, silicon atom-bonded hydroxyl groups and / or hydrolyzable groups, and / or silicon atom-bonded methyl groups and / or ethyl groups. And a silicon atom-bonded hydroxyl group and / or hydrolyzable group, and may have any structure of linear, branched, and cyclic.

  Examples of the organic group having 4 to 12 carbon atoms bonded to the silicon atom include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group each having 4 to 12 carbon atoms bonded to the silicon atom. In addition, these organic groups may have a substituent.

  Such an organic group having 4 to 12 carbon atoms bonded to a silicon atom is preferably a hydrocarbon group bonded to a silicon atom, for example, an n-butyl group, an iso-butyl group, or an n-hexyl bonded to a silicon atom. Group, n-octyl group, n-dodecyl group, alkyl group such as cyclohexylmethyl group; cycloalkyl group such as cyclohexyl group, 4-methylcyclohexyl group; aryl group such as phenyl group, 4-methylphenyl group; benzyl group, etc. Among them, a phenyl group bonded to a silicon atom or an alkyl group having 4 carbon atoms bonded to a silicon atom is more preferable.

  The polysiloxane segment (C) constituting the composite resin (ABC) is a segment derived from a condensate (c) of an alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group, and the alkyl group used here The alkyltrialkoxysilane condensate (c) having 1 to 3 carbon atoms has a hydroxyl group bonded to a silicon atom and / or an alkoxy group bonded to a silicon atom.

The alkyltrialkoxysilane condensate (c) preferably has a structure represented by the following general formula (S-6). Since the polysiloxane segment derived from the alkyltrialkoxysilane condensate having the structure represented by the following general formula (S-6) has a three-dimensional network polysiloxane structure, the resulting coating film is solvent resistant. It has excellent properties and weather resistance. [However, R ⁴ in the general formula (S-6) is an alkyl group having 1 to 3 carbon atoms. ]

  As the composite resin (ABC), a coating film excellent in adhesion, rust prevention, and crack resistance can be obtained. Therefore, the polysiloxane segment (B) and the alkyltrialkoxysilane in the composite resin (ABC) are obtained. The polysiloxane segment (C) derived from the condensate (c) and the total amount (B + C) are preferably 15 to 85 parts by weight, more preferably 20 to 50 parts by weight.

  In addition, as the composite resin (ABC), since a coating film having excellent durability and crack resistance is obtained, the polyalkylenesilane-derived polycondensate (c) derived from the alkyltrialkoxysilane in the composite resin (ABC) is obtained. The amount of the siloxane segment (C) is preferably 5 to 50 parts by weight, and more preferably 10 to 30 parts by weight.

  Although the said composite resin (ABC) can be manufactured with various methods, it is preferable to manufacture in the process which consists of following (I)-(II) especially.

(I) A polymer (a ′) having both an acid group and a silicon atom-bonded hydroxyl group and / or hydrolyzable group, and an organoalkoxysilane (b) and / or a hydrolysis condensate thereof (b-1). Composite resin (A'B) formed by chemical condensation of polymer segment (A ') derived from polymer (a') and polysiloxane segment (B) derived from organoalkoxysilane (b) by hydrolytic condensation Obtaining a step,

(II) Next, the resulting composite resin (A′B) and the alkyltrialkoxysilane condensate (c) having 1 to 3 carbon atoms in the alkyl group are hydrolytically condensed to give the composite resin (A′B). The polysiloxane segment (B) and the polysiloxane segment (C) derived from the condensate (c) of alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group are bonded via a silicon-oxygen bond. A step of obtaining a composite resin (ABC) by neutralizing acid groups in the composite resin (A'BC) with a basic compound after the composite resin (A'BC) is obtained, or the obtained composite resin (A'BC) After the acid group in ′ B) is neutralized with a basic compound to form a composite resin (AB), the condensation product (c) of alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group is hydrolyzed and condensed. Polysiloxane segment of composite resin (AB) Composite resin (B) and a polysiloxane segment (C) derived from a condensate (c) of alkyltrialkoxysilane having 1 to 3 carbon atoms of an alkyl group bonded via a silicon-oxygen bond ( ABC).

  The hydrolysis-condensation reaction in the production process can be progressed by various methods, but a method in which the reaction is advanced by supplying water and a catalyst during the production process is simple and preferable.

  The hydrolysis condensation reaction refers to a condensation reaction in which part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then proceeds between the hydroxyl group or hydrolyzable group.

  The polymer (a ′) is a polymer having both an acid group and a silicon atom-bonded hydroxyl group and / or hydrolyzable group, and the neutralized acid except that the acid group is not neutralized. This is exactly the same as the polymer (a) having both a group and a silicon atom-bonded hydroxyl group and / or hydrolyzable group.

  When a vinyl polymer is used as the polymer (a ′), the vinyl polymer may be, for example, an acid group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer bonded to a silicon atom, and / or a silicon atom. The polymer can be produced by polymerizing a hydrolyzable group-containing vinyl monomer bonded to, and if necessary, another vinyl monomer.

  Examples of the acid group-containing vinyl monomer include various vinyl monomers containing an acid group such as a carboxyl group, a phosphoric acid group, an acidic phosphoric acid ester group, a phosphorous acid group, a sulfonic acid group, and a sulfinic acid group. Of these, a vinyl monomer containing a carboxyl group (which may be a carboxylic anhydride group) is preferred.

  Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid, fumaric acid and other unsaturated carboxylic acids; maleic anhydride, Unsaturated polycarboxylic acid anhydrides such as itaconic anhydride; unsaturated monocarboxylic acid anhydrides such as acrylic acid anhydride and methacrylic anhydride; unsaturated carboxylic acid such as acrylic acid and methacrylic acid; acetic acid and propion Acid, mixed acid anhydride with saturated carboxylic acid such as benzoic acid; monomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-fumarate Various monoesters (half-esters) of saturated dicarboxylic acids such as butyl and saturated monohydric alcohols; Monovinyl esters of saturated dicarboxylic acids such as monovinyl dipinate and monovinyl succinate; bonded to carbon atoms with anhydrides of saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride and trimellitic anhydride Addition reaction products with vinyl monomers containing hydroxyl groups; and various monomers obtained by addition reaction of the carboxyl group-containing monomers with lactones, among others. Unsaturated carboxylic acids such as (meth) acrylic acid are preferred because they can be easily introduced into the vinyl polymer.

  The carboxyl group may be blocked. Examples of the vinyl monomer having a blocked carboxyl group include trimethylsilyl (meth) acrylate, dimethyl-tert-butylsilyl (meth) acrylate, and trimethylsilylcroto. Silyl ester group-containing vinyl monomers such as nates; hemiacetal ester groups such as 1-ethoxyethyl (meth) acrylate, 2-methoxy-2- (meth) acryloyloxypropane, 2- (meth) acryloyloxytetrahydrofuran Or hemiketal ester group-containing monomers; tert-butyl ester group-containing monomers such as tert-butyl (meth) acrylate and tert-butyl crotonate.

  Examples of the hydroxyl group-containing vinyl monomer bonded to the silicon atom include trihydroxyvinylsilane, ethoxydihydroxyvinylsilane, diethoxyhydroxyvinylsilane, dichlorohydroxyvinylsilane, 3- (meth) acryloyloxypropyltrihydroxysilane, 3 -(Meth) acryloyloxypropylmethyldihydroxysilane and the like.

As the hydrolyzable group-containing vinyl monomer bonded to the silicon atom, for example, a vinyl monomer having a hydrolyzable group represented by the following general formula (S-7) can be used. [In the general formula (S-7), R ⁵ represents a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ⁶ represents a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group or an aryloxy group. , A mercapto group, an amino group, an amide group, an aminooxy group, an iminooxy group, or an alkenyloxy group, and b is an integer of 0-2. ]

  Examples of the vinyl monomer having a hydrolyzable group represented by the general formula (S-7) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, and vinyl. Triacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxy Silane, 3- (meth) acryloyloxypropyltrichlorosilane, and the like. Among them, the hydrolysis reaction can easily proceed, and by-products after the reaction can be easily removed. Silane, 3 (Meth) acryloyloxy propyl trimethoxy silane is preferred.

  Examples of the other vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert- Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; benzyl (meth) acrylate, 2-phenylethyl (meta ) Aralkyl (meth) acrylates such as acrylate; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylic Ω-alkoxyalkyl (meth) acrylates such as carbonates; aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene; vinyl acetate, vinyl propionate, pivalic acid Carboxylic acid vinyl esters such as vinyl and vinyl benzoate; alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; Unsaturation such as dimethyl malate, di-n-butyl malate, dimethyl fumarate and dimethyl itaconate Dialkyl esters of dibasic acids; α-olefins such as ethylene and propylene; fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene; alkyls such as ethyl vinyl ether and n-butyl vinyl ether Nyl ethers; Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; Tertiary amides such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine and N-vinylpyrrolidone Group-containing monomers;

Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; hydroxyl groups such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether -Containing vinyl ethers; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether and 2-hydroxybutyl allyl ether; vinyl monomers containing hydroxyl groups bonded to these carbon atoms and lactones such as ε-caprolactone; Addition reaction product of

2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) ) Tertiary amino group-containing (meth) acrylic acid esters such as acrylate and N- [2- (meth) acryloyloxy] ethylmorpholine; tertiary amino group-containing vinylpyridine, N-vinylcarbazole, N-vinylquinoline, etc. Aromatic vinyl monomers: N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide, N- (2-di-n-propylamino) ethyl ( Tertiary amino group-containing (meth) acrylamides such as (meth) acrylamide; Tertiary amino group-containing crotonic acid amides such as-(2-dimethylamino) ethylcrotonic acid amide, N- (4-dimethylamino) butylcrotonic acid amide; 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4 -Tertiary amino group-containing vinyl ethers such as dimethylaminobutyl vinyl ether.

  The kind and amount of the vinyl monomer can be appropriately selected within a range that does not impair the effects of the present invention, depending on the properties imparted to the aqueous coating agent for glass plates of the present invention.

  The polymer (a ′) is selected from the group consisting of an anionic group, a cationic group and a nonionic group for the purpose of improving the solubility or dispersibility of the composite resin (ABC) in an aqueous medium. Those having at least one hydrophilic group can be used.

  Examples of the vinyl polymer usable as the polymer (a ′) include acid group-containing vinyl monomers, hydroxyl group-containing vinyl monomers bonded to silicon atoms, and / or hydrolyzable bonded to silicon atoms. It can be produced by polymerizing a group-containing vinyl monomer and, if necessary, another vinyl monomer by a polymerization method such as a bulk radical polymerization method, a solution radical polymerization method or a non-aqueous dispersion radical polymerization method. Especially, since it is easy to manufacture, it is preferable to apply a so-called solution radical polymerization method in which a vinyl polymer is manufactured by radical polymerization of the vinyl monomer in an organic solvent.

  When the vinyl monomer is polymerized by the radical polymerization method, a polymerization initiator can be used as necessary. Examples of such polymerization initiators include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile). Azo compounds such as nitrile); tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, diisopropyl And peroxides such as peroxycarbonate.

  Examples of the organic solvent include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, and cyclopentane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. Alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Esters such as acetone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, cyclohexanone; diethylene glycol dimethyl ether, diethylene glycol dibutyl ether Polyalkylene glycol dialkyl ethers such as 1, ethers such as 1,2-dimethoxyethane, tetrahydrofuran, and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate, and the like. These may be used alone or in combination of two or more. Can be used in combination.

  The polymer (a ') preferably has a number average molecular weight in the range of 500 to 200,000, more preferably in the range of 700 to 100,000, and in the range of 1,000 to 50,000. Particularly preferred are those having By using the polymer (a ′) having a number average molecular weight within such a range, it is possible to prevent thickening and gelation when producing the composite resin (ABC), and to provide a coating film excellent in durability. Can be formed.

  Next, the organoalkoxysilane (b) and / or the hydrolysis condensate (b-1) thereof used for constituting the polysiloxane segment (B) in the production step (I) will be described.

  The organoalkoxysilane (b) is not particularly limited, but among them, since it can form a coating film excellent in stability and durability of the composite resin (ABC), it has 4 to 12 carbon atoms. A monoorganotrialkoxysilane having an organic group and a diorganodialkoxysilane having two methyl groups and / or ethyl groups are preferred.

  The hydrolyzed condensate (b-1) of the organoalkoxysilane (b) is not particularly limited as long as it is a hydrolyzed condensate of the organoalkoxysilane (b). A product obtained by hydrolytic condensation of a monoorganotrialkoxysilane having -12 organic groups and / or a diorganodialkoxysilane having two silicon-bonded methyl and / or ethyl groups is preferred.

  Examples of the monoorganotrialkoxysilane having a silicon atom-bonded organic group having 4 to 12 carbon atoms include iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- ( And (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and the like.

  Examples of the diorganodialkoxysilane having two silicon atom-bonded methyl groups and / or ethyl groups include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, dimethyldiacetoxysilane, and diethyldimethoxy. Silane, diethyl diacetoxysilane, etc. are mentioned.

  Among these organoalkoxysilanes (b), the hydrolysis reaction can easily proceed and the by-products after the reaction can be easily removed. Therefore, iso-butyltrimethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane are used. preferable. These organoalkoxysilanes (b) may be used alone or in combination of two or more.

  In addition, in the said manufacturing process (I), although it is also possible to use the hydrolysis-condensation product (b-1) of organoalkoxysilane (b) independently, of composite resin (A'B) by hydrolysis condensation is sufficient. Since it is easy to produce, it is preferable to use an organoalkoxysilane (b) alone or a combination of an organoalkoxysilane (b) and its hydrolysis condensate (b-1), and use an organoalkoxysilane (b) alone. Is particularly preferred. Here, the single use of the organoalkoxysilane (b) is to use only the organoalkoxysilane (b), and includes the case where two or more organoalkoxysilanes (b) are used in combination.

  The hydrolysis condensation reaction in the production step (I) can proceed by various methods, but there is a method in which the reaction is advanced by supplying water and a catalyst during the production step (I). Simple and preferred.

  Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate, tetra Titanate esters such as butyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4 -Compounds containing basic nitrogen atoms such as diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; tetramethylammonium salts , Quaternary anions such as tetrabutylammonium salt and dilauryldimethylammonium salt Quaternary ammonium salts having chloride, bromide, carboxylate, hydroxide, etc. as counter anions; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate, Tin carboxylates such as tin stearate can be used alone or in combination of two or more.

  The catalyst is preferably used in an amount of 0.0001 to 10 parts by weight with respect to 100 parts by weight of the organoalkoxysilane (b) and / or its hydrolysis condensate (b-1). It is more preferable to use in the range of ˜3 parts by weight, and it is particularly preferable to use in the range of 0.001 to 1 part by weight.

  The water used when the hydrolysis condensation reaction proceeds is based on 1 mol of the hydrolyzable group and hydroxyl group of the organoalkoxysilane (b) and / or the hydrolysis condensate (b-1) thereof. 0.05 mol or more is appropriate, preferably 0.1 mol or more, particularly preferably 0.5 to 3.0 mol.

  The catalyst and water may be supplied collectively or sequentially, or a mixture of the catalyst and water previously supplied may be supplied.

  The reaction temperature of the hydrolysis condensation reaction is suitably in the range of 0 to 150 ° C, and preferably in the range of 20 to 100 ° C. The reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure.

  Alcohol and water, which are by-products that can be generated in the hydrolysis-condensation reaction, may be removed by a method such as distillation when the stability of the resulting aqueous curable coating composition is reduced.

  Next, the alkyltrialkoxysilane condensate (c) having 1 to 3 carbon atoms in the alkyl group used for constituting the polysiloxane segment (C) in the production step (II) will be described in detail.

  Examples of the alkyltrialkoxysilane having 1 to 3 carbon atoms in the alkyl group include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and iso-propyl. Trimethoxysilane and the like can be mentioned. Among them, methyltrimethoxysilane and ethyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed. These alkyltrialkoxysilanes may be used alone or in combination of two or more.

  There are no particular limitations on the method for obtaining the condensate (c) from the alkyltrialkoxysilane, and various methods may be mentioned. A method for allowing the hydrolysis and condensation reaction to proceed by supplying water and a catalyst is simple. preferable.

  About the water and catalyst used in that case, it can be used on the same conditions as the hydrolysis-condensation reaction in the said manufacturing process (I).

  Moreover, in the said manufacturing process (II), in addition to the condensate (c) of alkyl trialkoxysilane whose alkyl group has 1 to 3 carbon atoms, other silane compounds and hydrolysis condensates thereof may be used in combination. it can.

  Examples of the other silane compounds include tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, and tetra n-propoxysilane; hydrolysis condensates of the tetrafunctional alkoxysilane compounds, and the like. These can be used in combination as long as the effects of the present invention are not impaired.

  When the tetrafunctional alkoxysilane compound or a hydrolysis condensate thereof is used in combination, the tetrafunctional alkoxy is used with respect to 100 mol% of all silicon atoms constituting the polysiloxane segment (B) and the polysiloxane segment (C). It is preferable to use together in the range which the silicon atom which a silane compound and its hydrolysis condensate does not exceed 20 mol%.

  Furthermore, the condensate (c) of the alkyltrialkoxysilane having 1 to 3 carbon atoms of the alkyl group is substituted with a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium or aluminum, and the effect of the present invention is impaired. Can be used in combination as long as there is no range. For example, the above-mentioned metal alkoxide compound should be used in combination within a range not exceeding 25 mol% with respect to 100 mol% of all silicon atoms constituting the polysiloxane segment (B) and the polysiloxane segment (C). Can do.

  The aqueous coating agent for glass plate of the present invention comprises an aqueous product of a composite resin (ABC) obtained by dispersing or dissolving the composite resin (ABC) in an aqueous medium, preferably an aqueous dispersion of the composite resin (ABC) The composite resin (ABC) curing agent (D) is contained, and the production method is not limited, and can be produced by various methods. Among them, the production steps (I) to (II) After the composite resin (ABC) is manufactured, it is preferably manufactured in the following step (III).

(III) After the composite resin (ABC) obtained in the production step (II) is mixed with an aqueous medium to disperse or dissolve the composite resin (ABC), an aqueous product of the obtained composite resin (ABC) A step of mixing the curing agent (D).

  Examples of the aqueous medium used in the present invention include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  Next, the curing agent (D) of the composite resin (ABC) used in the present invention may be a compound having a functional group that reacts with the acid group and / or the hydroxyl group bonded to the silicon atom of the composite resin (ABC). It can be used as appropriate. Examples of the functional group that reacts with a hydroxyl group bonded to an acid group and / or a silicon atom reacts with a carboxyl group such as an isocyanate group or a blocked isocyanate group, but also reacts with a hydroxyl group bonded to a silicon atom; epoxy Group, cyclocarbonate group, amide group, hydroxyl group, oxazoline group, carbodiimide group, hydrazino group and other functional groups that react with carboxyl groups; hydroxyl groups bonded to silicon atoms such as N-hydroxymethylamino groups and N-alkoxymethylamino groups A functional group that reacts with a carboxyl group; a hydroxyl group bonded to a silicon atom; a hydrolyzable group bonded to a silicon atom; a functional group that reacts with a hydroxyl group bonded to a silicon atom such as a carboxyl group;

  Specific examples of the curing agent (D) include a compound having a silicon atom-bonded hydroxyl group and / or hydrolyzable group, an isocyanate group and a silicon atom-bonded hydroxyl group and / or a hydrolyzable group, an epoxy group, Compounds having a silicon atom-bonded hydroxyl group and / or hydrolyzable group, polyisocyanate compound, block polyisocyanate compound, polyepoxy compound, polycyclocarbonate compound, amino resin, primary or secondary amide group-containing compound, polycarboxy compound , Polyhydroxy compounds, polyoxazoline compounds, polycarbodiimide compounds, polyhydrazide compounds, and the like. Among them, compounds having silicon atom-bonded hydroxyl groups and / or hydrolyzable groups, epoxy groups and silicon atom-bonded hydroxyl groups and / or Or a compound having a hydrolyzable group, Cyanate compound, blocked polyisocyanate compound, polyepoxy compound, a polyoxazoline compound is preferable. These can be used alone or in combination of two or more.

  Examples of the epoxy group and a hydroxyl group having a silicon atom bond and / or a hydrolyzable compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethyl. Ethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc., their hydrolysis condensates, vinyl groups having epoxy groups and hydrolyzable silyl groups And copolymers.

  Examples of the polyisocyanate compound include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate; meta-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-meta-xylyl Aralkyl diisocyanates such as range isocyanate; hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2-methyl-1,3-diisocyanate cyclohexane, 2-methyl-1,5-diisocyanate cyclohexane Aliphatic or cycloaliphatic diisocyanates such as isophorone diisocyanate:

Various prepolymers having an isocyanate group, obtained by addition reaction of the polyisocyanate compound with polyhydric alcohols; prepolymers having an isocyanurate ring obtained by cyclization and trimerization of the polyisocyanate compound A polyisocyanate having a biuret structure obtained by reacting the polyisocyanate compound with water; 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, (meth) Examples thereof include vinyl copolymers containing isocyanate groups obtained from vinyl monomers containing as an essential component a vinyl monomer having an isocyanate group such as acryloyl isocyanate.

  Examples of the block polyisocyanate compound include those obtained by blocking the polyisocyanate compound with various blocking agents. Examples of the blocking agent include alcohols such as methanol, ethanol, and lactic acid esters; phenolic hydroxyl group-containing compounds such as phenol and salicylic acid ester; amides such as ε-caprolactam and 2-pyrrolidone; acetone oxime, methyl ethyl ketoxime, and the like And active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, and acetylacetone.

  Examples of the polyepoxy compound include polyglycidyl ethers of aliphatic or alicyclic polyols such as ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, and hydrogenated bisphenol A; bisphenol A Polyglycidyl ethers of aromatic diols such as bisphenol S and bisphenol F; polyglycidyl ethers of polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; tris (2-hydroxyethyl) isocyanurate Polyglycidyl ethers; polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as adipic acid, butanetetracarboxylic acid, phthalic acid, terephthalic acid; Bisepoxides of hydrocarbon dienes such as crooctadiene and vinylcyclohexene; Alicyclic rings such as bis (3,4-epoxycyclohexylmethyl) adipate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate Formula polyepoxy compounds; vinyl copolymers containing two or more epoxy groups.

  Examples of the polyoxazoline compound include 2,2′-p-phenylene-bis- (1,3-oxazoline), 2,2′-tetramethylene-bis- (1,3-oxazoline), 2,2 ′. -Low molecular weight poly (1,3-oxazoline) compounds such as octamethylene-bis- (2-oxazoline); 1,3-oxazoline group-containing vinyl monomers such as 2-isopropenyl-1,3-oxazoline And a vinyl polymer containing a 1,3-oxazoline group obtained by copolymerizing a homopolymer of the above and a vinyl monomer copolymerizable therewith.

  Examples of the polyhydrazide compound include dihydrazide compounds of organic acids such as oxalic acid dihydrazide, malonic acid dihydrazide, and succinic acid dihydrazide.

  As the amino resin, for example, an alkylol group obtained by reacting an amino group-containing compound such as melamine, benzoguanamine, acetoguanamine, urea, glycouril or the like with an aldehyde compound (or aldehyde supplying substance) such as formaldehyde or acetaldehyde. Examples of the amino resin having an alkylol group include alkoxyalkyl group-containing amino resins obtained by reacting the amino resin having an alkylol group with a lower alcohol such as methanol, ethanol, n-butanol, and iso-butanol.

  The amount of the curing agent (D) used is, for example, a compound in which the curing agent (D) has a silicon atom-bonded hydroxyl group and / or hydrolyzable group, a block polyisocyanate compound, an amino resin, or a polycarboxy compound. In this case, the solid content of the curing agent (D) is preferably in the range of 0.1 to 200 parts by weight, and 0.5 to 150 parts by weight with respect to 100 parts by weight of the composite resin (ABC). More preferably, it is in the range of 1 part by weight, and particularly preferably in the range of 1 to 100 parts by weight.

  Further, for example, the curing agent (D) is a compound having an epoxy group and a silicon atom-bonded hydroxyl group and / or a hydrolyzable group, a polyepoxy compound, a polycyclocarbonate compound, a primary or secondary amide group-containing compound, poly When it is a compound having a group that reacts with a carboxyl group such as a hydroxy compound, a polyoxazoline compound, a polycarbodiimide compound, a polyhydrazide compound, and the composite resin (ABC) is a composite resin containing a carboxyl group, Groups (epoxy group, cyclocarbonate group, amide group, hydroxyl group, oxazoline group carbodiimide group, hydrazino group) that react with the carboxyl group in the curing agent (D) with respect to 1 equivalent of the carboxyl group in the composite resin (ABC). Etc.) is preferably in the range of 0.2 to 5.0 equivalents, 0 5 to 3.0, more preferably in the range of equivalents, and particularly preferably in the range of 0.7 to 2.0 equivalents.

  Further, for example, the curing agent (D) is a compound having a isocyanate group and a silicon atom-bonded hydroxyl group and / or a hydrolyzable group, or a polyisocyanate compound, and the composite resin (ABC) is a silicon atom-bonded hydroxyl group. And / or in the case of a composite resin having a hydrolyzable group, in the curing agent (D) with respect to 1 equivalent of a hydroxyl group and / or hydrolyzable group of a silicon atom bond in the composite resin (ABC). The amount of isocyanate group is preferably in the range of 0.1 to 10 equivalents, more preferably in the range of 0.3 to 5.0 equivalents, and in the range of 0.5 to 2.0 equivalents. It is particularly preferred.

  The curing agent (D) is preferably one that is not easily separated when mixed with an aqueous dispersion in which the composite resin (ABC) is dissolved or dispersed. For example, the curing agent (D) is dispersed or dissolved in the aqueous medium. Those having a possible level of hydrophilicity, uniformly dispersed or dissolved in the aqueous dispersion, and cannot be dispersed or dissolved alone in the aqueous medium, but are mixed with the aqueous dispersion when mixed with the aqueous dispersion ( (ABC) Intrusion, fusion, adsorption, etc. to the particles occur, and the particles are integrated. Examples of those that are uniformly dispersed or dissolved in the aqueous dispersion include, for example, an aqueous polyisocyanate compound “Bernock DNW-5000” manufactured by DIC Corporation (polyisocyanate compound having an isocyanate group content of 13.5% by weight). Aqueous dispersion, non-volatile content 80% by weight), Daiichi Kogyo Seiyaku Co., Ltd. blocked polyisocyanate “Elastolon BN-77” (aqueous self-emulsified blocked polyisocyanate compound, solid content 31% by weight), Nippon Shokubai 1,3-oxazoline group-containing water-soluble resin “Epocross WS-500” (an aqueous solution of 1,3-oxazoline group-containing water-soluble resin having an equivalent of 220 g / eq of oxazoline group, content: 40% by weight) Moreover, as what integrates with composite resin (ABC) particle | grains at the time of mixing with the said aqueous dispersion, for example, 3 Glycidoxypropyltrimethoxysilane (3GPTMS), polymethoxysiloxane “MKC silicate MS51” manufactured by Mitsubishi Chemical Corporation, epoxy compound “Denacol EX-614B” manufactured by Nagase ChemteX Corporation (epoxy having an epoxy equivalent of 173 g / eq) Compound) and the like.

  The aqueous coating agent for glass plate of the present invention can contain a thermosetting resin as required. Examples of such thermosetting resins include vinyl resins, polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, or modified resins thereof.

  In the aqueous coating agent for glass plate of the present invention, for example, a resin in which various particles are dispersed can be used as a coating layer for the purpose of reducing the visible light reflectance. Examples of such particles (fillers) include particles of titanium oxide, silicon oxide (silica), tin oxide, calcium carbonate, indium tin oxide, antimony oxide, and the like. The diameter of such particles is preferably in the range of 0.1 to 1000 nm. Examples of resins for dispersing such particles include polyester, cellulose derivatives, polyvinyl chloride, polystyrene, polyvinyl acetate, polybutene, poly (meth) acrylic acid and its ester compounds, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyamide, An ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, a urethane resin, an epoxy resin, a silicone resin, a fluorine resin, or the like can be used. The compounding ratio of the particles and the resin is not particularly limited, but is preferably in the range of 0.1 to 15 parts by weight with respect to 100 parts by weight of the resin. The thickness of the coating layer in which such various particles are dispersed is usually 0.1 to 100 μm, preferably about 0.5 to 10 μm.

  If necessary, the aqueous coating agent for glass plate of the present invention may further include inorganic pigments, organic pigments, extender pigments, dyes, waxes, surfactants, stabilizers, flow regulators, antifoaming agents, leveling agents, rheology. Known and commonly used additives such as a control agent, an ultraviolet absorber, an antioxidant, or a plasticizer can be used.

  Although there is no restriction | limiting in particular in the film thickness of the coating film formed using the aqueous coating agent for glass plates of this invention, It is preferable that it is 0.1-50 micrometers, and it is more preferable that it is 0.3-10 micrometers. . If it is the film thickness in the said range, the crack which may arise in a cured coating film can be suppressed and the cured coating film which has the outstanding antifouling property can be formed.

  Examples of the method for applying the aqueous coating agent for glass plate of the present invention to glass include spin coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, and brush coating. It is possible to apply various coating methods such as.

  After applying the aqueous coating agent for glass plate of the present invention to the glass surface by the above-mentioned coating method, it is allowed to stand at room temperature for about 1 to 10 days or heated at a temperature range of 60 to 600 ° C. for 10 seconds to 2 hours. A surface-treated glass having a coating film excellent in adhesion, rust prevention, lubricity, scratch resistance and the like can be obtained.

  The aqueous coating agent for glass plates of the present invention can be used for architectural glass plates, glass for vehicles such as automobiles, glass for lenses, glass for mirrors, glass for display panels, glass for solar cell modules, and the like. The solar cell module is not limited as long as it can apply the aqueous coating agent of the present invention to the glass on the light receiving surface side, and is a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell, a compound solar cell. The present invention can be applied to various solar cell modules such as a battery, a dye-sensitized solar cell, and an organic thin film solar cell.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, all parts and% are based on weight.

  The glass plate aqueous coating agent of the present invention was applied to a glass plate as described below and subjected to performance evaluation of each item.

  A glass plate aqueous coating agent was applied on a JIS R 3202 glass plate to a dry film thickness of 10 μm, dried at 150 ° C. for 20 minutes to obtain a surface-treated glass plate, and then measured for light transmittance and light resistance. The test, temperature cycle test, heat resistance test, moisture resistance test, and actual exposure test were carried out as follows.

Light transmittance measurement: JIS R 3106 solar transmittance (300-2100 nm)
Light resistance test: JIS C 8917 Annex 5 Light irradiation test A-5
The test time was 1000 hours.
Temperature cycle test: JIS C 8917 Annex 1 Temperature cycle test A-1
Heat resistance test: JIS C 8917 Annex 10 Heat resistance test B-1
Moisture resistance test: JIS C 8917 Annex 11 Moisture resistance test B-2
Actual exposure test: The coated plate was left outdoors for 6 months, and the degree of surface contamination was visually observed.

Synthesis example 1
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 1421 parts of methyltrimethoxysilane (MTMS) was charged and heated to 60 ° C. Subsequently, a mixture of 0.17 part of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 207 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the temperature in the reaction vessel was raised to 80 ° C. and stirred for 4 hours to conduct a hydrolysis condensation reaction. Subsequently, the obtained condensate is reduced under a reduced pressure of 300 to 10 mmHg (note that the reduced pressure condition at the start of the distillation of methanol is 300 mmHg and finally reduced to 10 mmHg. The same applies hereinafter). By removing the generated methanol and water within a temperature range of 40 to 60 ° C., a condensate of methyltrimethoxysilane having a number average molecular weight of 1,000 and an active ingredient of 70.0% in the reaction solution ( c-1) 1,000 parts were obtained. Next, 80 parts of isopropyl alcohol (IPA), 54 parts of phenyltrimethoxysilane (PTMS) and 32 parts of dimethyldimethoxysilane (DMDMS) were charged into the same reaction vessel as described above, and the temperature was raised to 80 ° C. Next, at the same temperature, 112 parts of methyl methacrylate (MMA), 92 parts of butyl methacrylate (BMA), 52 parts of butyl acrylate (BA), 16 parts of acrylic acid (AA), 3-methacryloxypropyltrimethoxysilane (MPTS) 8 Part, IPA 51 parts and tert-butylperoxy-2-ethylhexanoate (TBPEH) 14 parts of the mixture was dropped into the reaction vessel over 4 hours, and after the addition was completed, the reaction was further continued at the same temperature for 2 hours. After obtaining a polymer having both a carboxyl group and a hydrolyzable group bonded to a silicon atom, a mixture of 0.9 part of “A-3” and 25 parts of deionized water is added dropwise over 5 minutes. A polymer segment having both a carboxyl group and a hydrolyzable group bonded to a silicon atom, which undergoes a hydrolytic condensation reaction by stirring at the same temperature for 3 hours, and PT To obtain a composite resin composed of polysiloxane segments derived from S and DMDMS (A'B-1). Next, the reaction product was cooled to 60 ° C., 50 parts of propylene glycol-n-propyl ether (PnP) and 18 parts of triethylamine were added, and 93 parts of the condensate of methyltrimethoxysilane (c-1) was further added. Further, 580 parts of deionized water was further added, and the composite resin (AB-1) neutralized and the polysiloxane segment (C-1) derived from the condensate (c-1) of methyltrimethoxysilane were combined. A dispersion of resin (ABC-1) was obtained. Next, the obtained dispersion was distilled under reduced pressure of 300 to 10 mmHg for 3 hours under conditions of 40 to 60 ° C. to remove the generated methanol and IPA, and then the non-volatile content was adjusted with deionized water. 1,000 parts of an aqueous dispersion of a composite resin (ABC-1) having a nonvolatile content of 40.0% was obtained.

Example 1
100 parts of the aqueous dispersion of the composite resin (ABC-1) obtained in the synthesis example, 5 parts of 3-glycidoxypropyltrimethoxysilane (3GPTMS) as a curing agent (D) and 5 parts of PnP were mixed, and the present invention. A glass plate aqueous coating agent was obtained. Next, the obtained aqueous coating agent was applied on a JIS R 3202 glass plate so as to have a dry film thickness of 10 μm, and dried at 150 ° C. for 20 minutes to obtain a surface-treated glass plate (P-1). The physical property of the obtained surface-treated glass plate (P-1) was evaluated. The obtained results are shown in Table 1.

Comparative Example 1
Evaluation was performed in the same manner as in Example 1 on an untreated glass plate (the same substrate as used in Example 1 but without a coating agent applied). The obtained results are shown in Table 1.

In addition, the evaluation result in a table | surface represents the following state.
No change is observed; ○
Cloudiness occurred on the surface;
The surface condition has deteriorated significantly. ×

  Relative rate% = 100 × [(Example 1; coated glass) / (light transmittance of untreated glass)]

Claims (7)

The polysiloxane segment (B) of the composite resin (AB) in which the polymer segment (A) having a neutralized acid group and the polysiloxane segment (B) are chemically bonded, and the alkyl group has 1 carbon atom. A composite resin (ABC) in which the polysiloxane segment (C) derived from the condensate of alkyl trialkoxysilane (c) to 3 is bonded via a silicon-oxygen bond is dissolved or dispersed in an aqueous medium. An aqueous coating agent for a glass plate, comprising an aqueous product of a composite resin (ABC) and a curing agent (D) of the composite resin (ABC). The aqueous coating agent for glass plate according to claim 1, wherein the composite resin (ABC) is a composite resin containing 15 to 85% by weight of the polysiloxane segment (B) and the polysiloxane segment (C) in total. . The aqueous coating agent for glass plate according to claim 2, wherein the composite resin (ABC) is a composite resin containing 5 to 50% by weight of the polysiloxane segment (C). In the composite resin (ABC), the polymer segment (A) and the polysiloxane segment (B) are represented by the following structural formula (S-1).

[However, the carbon atom in the structural formula (S-1) constitutes a part of the polymer segment (A), and the silicon atom and the oxygen atom constitute a part of the polysiloxane segment (B). ]
The aqueous coating agent for glass plates according to claim 1, 2 or 3, which is a composite resin bonded through a bond represented by: The aqueous coating agent for glass plates according to claim 4, wherein the polymer segment (A) is a segment derived from a vinyl polymer. The aqueous solution for glass plates according to claim 1, 2 or 3, wherein the alkyltrialkoxysilane condensate (c) is a condensate obtained by hydrolytic condensation of methyltrimethoxysilane and / or methyltriethoxysilane. Coating agent. The curing agent (D) is a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, a compound having an isocyanate group and a hydrolyzable group bonded to a silicon atom in one molecule, Compound having hydrolyzable group bonded to epoxy group and silicon atom in one molecule, polyisocyanate compound, block isocyanate compound, polyepoxy compound, polycyclocarbonate compound, amino resin, primary or secondary amide group-containing compound, The aqueous coating agent for glass plates according to claim 1, 2 or 3, which is at least one compound selected from the group consisting of a polycarboxy compound and a polyhydroxy compound.