JP2009149798A - Aqueous resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous resin dispersion capable of serving as an aqueous coating agent excellent in adhesiveness to various old coating films, and having an aptitude as a top coating paint with water-proofness, alkali resistance and the like. <P>SOLUTION: This aqueous resin dispersion contains a vinyl copolymer emulsion A having a neutralized carboxyl group, a glycidyl group containing compound B having no radical-polymerizable unsaturated bond, and a compound C having a hydrolyzable silyl group and/or a silanol group and an amino group, preferably 0.2-10 pts.wt. of the glycidyl group containing compound B having no radical-polymerizable unsaturated bond, and 0.1-10 pts.wt. of the compound C having the hydrolyzable silyl group and/or the silanol group and the amino group, with respect to 100 pts.wt. of resin solid content in the vinyl copolymer emulsion A having the neutralized carboxyl group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aqueous resin dispersion having excellent adhesion to an old coating film and having water resistance, alkali resistance, etc., which are suitable as a top coating material.

In recent years, from the viewpoints of global environmental protection, occupational health, and the like, transition from solvent-based to water-based is being promoted in various coating materials. In the paint field, emulsion paints that are water-based have been widely used for architectural paints. However, since emulsion paints are inferior to solvent-based paints in adhesion to old paint films, solvent-based paints are often used in renovation applications. Under such circumstances, it is desired to develop an emulsion paint having excellent old film adhesion, particularly an emulsion paint having performance as a top coat, that is, durability such as water resistance and alkali resistance.
Therefore, development of an aqueous coating agent that is excellent in durability such as water resistance and alkali resistance as well as adhesion to the old coating film has been actively studied.

  For example, it is obtained by polymerizing (meth) acrylic acid alkyl ester and unsaturated carboxylic acid using alkyl diphenyl ether disulfonate as an emulsifier, and has a glass transition temperature (hereinafter abbreviated as Tg) of 15 to 50 ° C. Thus, it is disclosed that an aqueous coating agent using a synthetic resin emulsion having an average particle diameter of synthetic resin particles of 0.01 to 0.2 μm is excellent in adhesion to various old coating films (for example, Patent Document 1). reference.). Although this water-based coating has good adhesion to old coatings, especially old coatings composed of aqueous coatings, it is a solvent-based coating, particularly a coating consisting of a terpene-soluble coating or a solvent-based two-component coating. Adhesion to the film is not sufficient.

  Further, an aqueous coating agent containing a vinyl polymer emulsion having an alkoxysilyl group and a silanol compound having an amino group is known (for example, see Patent Document 2). However, this aqueous coating agent is also not sufficiently adherent to an old coating film composed of a two-component curable solvent-based coating agent.

JP 2001-342219 A JP 2002-105389 A

  The problem to be solved by the present invention is an aqueous resin dispersion that can be used as an aqueous coating agent that has excellent adhesion to various old coating films and that also has suitability as a top coating material such as water resistance and alkali resistance. Is to provide.

  As a result of intensive studies, the present inventors have found that a vinyl copolymer emulsion (A) containing a neutralized carboxyl group, a glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond, and By using the aqueous resin dispersion containing the compound (C) having a hydrolyzable silyl group and / or a silanol group and an amino group, the adhesion to the old coating film is excellent, and the performance as a top coating, It has been found that an aqueous coating agent having durability such as water resistance and alkali resistance can be easily obtained, and the present invention has been completed.

  That is, the present invention relates to a vinyl copolymer emulsion (A) containing a neutralized carboxyl group, a compound (B) having a glycidyl group having no radically polymerizable unsaturated bond, and a hydrolyzable silyl group. An aqueous resin dispersion comprising a compound (C) having a group and / or a silanol group and an amino group is provided.

  The aqueous resin dispersion of the present invention can be used as an aqueous coating agent that has excellent adhesion to an old coating film and also has performance as a top coating, that is, durability such as water resistance and alkali resistance.

  The vinyl copolymer emulsion (A) containing a neutralized carboxyl group used in the present invention is a vinyl copolymer obtained by neutralizing a carboxyl group in a vinyl copolymer containing a carboxyl group with a basic compound. The emulsion may be an emulsion in which a copolymer is dispersed, and can be obtained by adopting various techniques. In particular, vinyl monomers containing a carboxyl group-containing vinyl monomer (a1) (a Emulsion obtained by a method of neutralizing a vinyl copolymer emulsion containing a carboxyl group obtained by emulsion polymerization with a basic compound is preferred.

  Examples of the emulsion polymerization method of the vinyl monomers (a) include, for example, the vinyl monomers (a) in an aqueous medium in the presence of an emulsifier, preferably the presence of an emulsifier and a chain transfer agent. Below, the method of making it copolymerize using a radical polymerization initiator is mentioned.

  The vinyl monomers (a) used here are not particularly limited as long as they are vinyl monomers containing a carboxyl group-containing vinyl monomer (a1). Vinyl monomers containing the containing vinyl monomer (a1) and other vinyl monomers (a2) are used. Among the vinyl monomers (a), an aqueous coating agent capable of forming a coating film having excellent adhesion to the old coating film and excellent durability such as water resistance and alkali resistance is obtained. The group-containing vinyl monomer (a1) 0.1 to 10% by weight and the other vinyl monomer (a2) 99.9 to 90% by weight are preferred, and the carboxyl group-containing vinyl monomer ( It is more preferable that a1) 0.5 to 5% by weight and other vinyl monomer (a2) 99.5 to 95% by weight.

  The carboxyl group-containing vinyl monomer (a1) is not particularly limited. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid half ester, maleic acid half ester, Maleic anhydride, itaconic anhydride, 2-methacryloylpropionic acid and the like can be mentioned. These can be used in combination of a plurality of types. Of these, one or more of acrylic acid, methacrylic acid and itaconic acid are preferably used.

  The other vinyl monomer (a2) is a vinyl monomer other than the carboxyl group-containing vinyl monomer (a1), and includes a carboxyl group-containing vinyl monomer (a1) and a radical. Any copolymerizable monomer may be used. Specific examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate; methacrylic acid Methacrylic acid esters such as methyl, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate;

Maleic acid, fumaric acid, itaconic acid esters; vinyl esters such as vinyl acetate, vinyl propionate and vinyl tertiary carboxylate; aromatic vinyl compounds such as styrene and vinyltoluene; heterocyclic compounds such as vinylpyrrolidone Vinyl compounds; vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinyl amide; vinylidene halide compounds such as vinylidene chloride and vinylidene fluoride; α-olefins such as ethylene and propylene; dienes such as butadiene; acrylamide, methacrylamide and maleic acid Amides of α, β-ethylenically unsaturated acids such as amides;

Glycidyl group-containing monomers such as glycidyl methacrylate and allyl glycidyl ether; Hydroxyl group-containing monomers such as 2-hydroxylethyl methacrylate and 2-hydroxylethyl acrylate; Amino group-containing monomers such as dimethylaminoethyl methacrylate; N-methylol Substituted amides of unsaturated carboxylic acids such as acrylamide, N-methylol methacrylamide, diacetone acrylamide;

Vinyl having hydrolyzable silyl group and / or silanol group such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, and hydrolysates thereof Monomers such as diallyl phthalate, divinyl benzene, allyl acrylate, trimethylol propane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., monomers having a plurality of unsaturated groups. . These can be used alone or in combination of two or more.

  As the other vinyl monomer (a2), an acrylic coating and / or methacrylic acid can be obtained because an aqueous coating agent capable of forming a coating having excellent durability such as water resistance and alkali resistance can be obtained. A vinyl monomer containing an ester as an essential component is preferred.

  In addition, as the vinyl copolymer emulsion (A) containing the neutralized carboxyl group, a coating film having a good balance of adhesion to old coating film and durability such as water resistance and alkali resistance, among others. Is preferably a vinyl copolymer emulsion having a neutralized carboxyl group and hydrolyzable silyl group and / or silanol group, and the other vinyl monomer The body (a2) is preferably a vinyl monomer containing a vinyl monomer having a hydrolyzable silyl group and / or a silanol group.

  The amount of the vinyl monomer having a hydrolyzable silyl group and / or silanol group is 0.01 to 10% by weight with respect to 100% by weight of the vinyl monomers (a). It is preferably 0.05 to 2% by weight.

  Further, as the vinyl copolymer emulsion (A) containing a neutralized carboxyl group, an aqueous coating agent capable of forming a coating film excellent in adhesion to an old coating film can be obtained. Two or more types of vinyl copolymers having a transition temperature (Tg) difference of 5 ° C. or more (the difference in Tg is 5 ° C. or more even if any two of the two or more types of vinyl copolymers are compared) It is preferably an emulsion in which resin particles composed of a combination of vinyl copolymers are dispersed, and the difference in glass transition temperature (Tg) is 5 to 100 ° C. More preferably, it is an emulsion in which resin particles made of a copolymer are dispersed, and the resin particles made of 2 to 4 types of vinyl copolymers each having a difference in glass transition temperature (Tg) of 10 to 80 ° C. But And most preferably dispersed and formed by emulsion.

  A method for producing an emulsion in which resin particles composed of two or more kinds of vinyl copolymers having a glass transition temperature (Tg) difference of 5 ° C. or more are dispersed is not particularly limited. As the vinyl monomers (a) containing the vinyl monomer (a1), two or more vinyl monomers having a composition having a glass transition temperature (Tg) difference of 5 ° C. or more [provided that At least one vinyl monomer is a vinyl monomer containing a carboxyl group-containing vinyl monomer (a1). ], And a method of emulsion polymerization by sequentially supplying these vinyl monomers. In addition, there is no limitation in the supply order of 2 or more types of vinylic monomers used in this case.

  In the present invention, the glass transition temperature (Tg) of the vinyl copolymer is a value calculated by the following well-known Fox equation. The glass transition temperature (Tg) of the homopolymer used for the calculation is shown below. Values not described in the glass transition temperature (Tg) of homopolymers below can be values generally described in the literature. The glass transition temperature (Tg) of the homopolymer can also be determined by measuring using a differential scanning calorimetry method or a dynamic viscoelasticity measurement method.

[Fox's formula]
1 / Tg = Σ (Wn / Tgn)
Tg: Glass transition temperature of polymer (absolute temperature)
Wn: weight fraction of monomer n Tgn: glass transition temperature (absolute temperature) of homopolymer of monomer n

[Tg of homopolymer]
Homopolymer of 2-ethylhexyl acrylate (2EHA): −55.3 ° C.
Homopolymer of butyl acrylate (BA): −45.4 ° C.
Homopolymer of methyl methacrylate (MMA): 104.2 ° C
Styrene (St) homopolymer: 100.0 ° C
Methacrylic acid (MAA) homopolymer: 143.5 ° C
Homopolymer of acrylic acid (AA): 86.6 ° C
Homopolymer of glycidyl methacrylate (GMA): 46.3 ° C

  The emulsifier used in the emulsion polymerization of the vinyl monomers (a) is not particularly limited, and various emulsifiers can be used. Examples thereof include alkylbenzene sulfonates, alkylene disulfonates, alkyl diphenyl ethers. Disulfonates, alkyl sulfates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, dialkyl succinates Anionic emulsifiers containing sulfonic acid or sulfate ester skeletons such as sulfonates, monoalkyl succinates, salts of naphthalene sulfonic acid formalin condensate, etc .;

Fatty acid salts such as fatty acid sodium and fatty acid potassium, polyoxyethylene alkyl ether acetates, polycarboxylic acid surfactants, anionic emulsifiers having carboxyl groups or salts thereof such as alkylated succinic acid or salts thereof in the skeleton; An anionic emulsifier having a phosphate group or a salt thereof such as oxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, alkyl phosphate in the skeleton;

Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene glycol, polyoxyethylene alkate, sorbitan alkate, polyoxyethylene sorbitan alkate, polyoxy Nonionic emulsifiers such as ethylene polycyclic phenyl ether, polyoxyalkylene alkylphenyl ether, and polyoxyethylene-polyoxypropylene block copolymer are listed. These emulsifiers can be used alone or in combination of two or more.

  Furthermore, examples of the emulsifier include vinyl sulfonates, (meth) acryloyloxy polyoxyethylene sulfate esters, (meth) acryloyloxy polyoxyethylene sulfonates, polyoxyethylene alkenyl phenyl sulfonates, poly Anionic reactive emulsifiers such as oxyethylene alkenyl phenyl ether sulfates, sodium allyl alkyl sulfosuccinate, (meth) acryloyloxy polyoxypropylene sulfonates, polyoxyethylene alkenyl phenyl ether, polyoxyethylene methacryloyl ether, etc. Reactive emulsifiers such as nonionic reactive emulsifiers can also be used. These reactive emulsifiers can be used alone or in combination. In addition, as these emulsifiers, it is preferable to use an emulsifier having no alkylphenol skeleton from the viewpoint of environmental protection and occupational health.

  In addition, as the emulsion polymerization of the vinyl monomers (a), without using an emulsifier as described above, instead, in an aqueous medium in which a polymer having a neutralized carboxyl group is dissolved or dispersed. A method of emulsion polymerization of the vinyl monomers (a), that is, a soap-free polymerization method can also be employed. Of course, the emulsion polymerization method of the vinyl monomers (a) is not limited to these methods, as long as the vinyl monomers (a) can be emulsion polymerized. Any method can be adopted.

  Specific examples of the emulsion polymerization of the vinyl monomers (a) are 50 to 10,000 parts by weight, preferably 60 to 200 parts by weight based on 100 parts by weight of the vinyl monomers (a). In the presence of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight of an emulsifier, using 0.01 parts by weight and 0.01 to 10 parts by weight, preferably 0.05 to 1 part by weight of a radical polymerization initiator. 0 to 100 ° C., preferably 40 to 80 ° C. Moreover, it can carry out also in the redox polymerization which uses a radical polymerization initiator and a reducing agent together, and the usage-amount of the reducing agent in this case is 0.00 with respect to 100 weight part of vinyl-type monomers (a). 01 to 10 parts by weight, preferably 0.05 to 1 part by weight. In this case, a compound that generates a polyvalent metal salt ion such as iron ion or copper ion can be used in combination as an accelerator.

  Examples of the radical polymerization initiator used in the emulsion polymerization of the vinyl monomers (a) include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; azobisisobutyronitrile and its hydrochloride Azo initiators such as 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid); hydrogen peroxide, t-butyl hydroperoxide, cumene hydro Examples thereof include peroxide-based initiators such as peroxides.

  Examples of reducing agents that can be used in combination with these radical polymerization initiators include sodium sulfooxylate formaldehyde, sodium pyrosulfite, and isoascorbic acid sodium.

  Furthermore, in the emulsion polymerization of the vinyl monomers (a), it is preferable to use a chain transfer agent because an aqueous coating agent capable of forming a coating film excellent in adhesion to the old coating film is obtained. . However, it is preferable from the viewpoint of environmental protection and occupational health that the volatile organic solvent is not contained as much as possible. Examples of the chain transfer agent include alkyl mercaptans such as dodecyl mercaptan, alkyl thioglycolates such as octyl thioglycolate, alcohol-based organic solvents, aliphatic organic solvents, aromatic organic solvents, and the like. Of these, alkyl mercaptans and alkyl thioglycolates are preferred. The amount of the chain transfer agent used in the emulsion polymerization of the vinyl monomers (a) is, among other things, a coating film having a good balance of adhesion to the old coating film and durability such as water resistance and alkali resistance. Since an aqueous coating agent that can be formed is obtained, it is preferably 0.01 to 5 parts by weight, and 0.05 to 2 parts by weight with respect to 100 parts by weight of the vinyl monomers (a). Is more preferable.

  As the vinyl polymer emulsion (A) containing a neutralized carboxyl group used in the present invention, for example, after producing a vinyl polymer emulsion containing a carboxyl group, it contains a carboxyl group with a basic compound. Examples thereof include those obtained by neutralizing carboxyl groups in vinyl polymers. The basic compound used in this case is not particularly limited. For example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, 2- Organic amines such as amino-2-methyl-1-propamol, inorganic basic compounds such as ammonia, sodium hydroxide and potassium hydroxide, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium Hydroxide quaternary ammonium hydroxides, etc., among others, an aqueous coating agent capable of forming a coating film with excellent adhesion to the old coating film is obtained. Ethanolamine, diethanolamine, triethanolamine, water-soluble organic amine such as dimethyl ethanolamine 2-amino-2-methyl-1-propanol is preferred.

  In addition, as the vinyl polymer emulsion (A) containing the neutralized carboxyl group, an aqueous coating agent capable of forming a coating film having excellent adhesion to the old coating film can be obtained. It is preferably an emulsion in which resin particles having an average particle size of 0.05 to 0.2 μm measured using a measuring device (Microtrack UPA manufactured by Nikkiso Co., Ltd.) are dispersed, and the average particle size is 0.05 to It is more preferable that the emulsion is formed by dispersing 0.15 μm resin particles.

  The amount of the basic compound used is not particularly limited, but an aqueous coating that has good storage stability, low odor, and no occupational health problems can be obtained. It is preferable to prepare by using a water-soluble organic amine so that the pH is in the range of 7.0 to 10.0.

  Next, the glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond used in the present invention is a compound having a glycidyl group and having no radically polymerizable unsaturated bond. There is no particular limitation, and for example, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether , Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like, for example, “CR-5L” manufactured by Dainippon Ink & Chemicals, Inc. “Denacol EX-9” manufactured by Nagase ChemteX Corporation 31 ”,“ Denacol EX-841 ”,“ Denacol EX-411 ”,“ Denacol EX-252 ”,“ Denacol EX-314 ”,“ Denacol EX-614B ”,“ Denacol EX-201 ”. , Glycidyl ethers such as "denacol EX-211", alkyl glycidyl ethers, phenyl glycidyl ethers, phenyl glycidyl ethers, polyoxyethylene glycol diglycidyl ethers, glycidyl ethers of neopentyl polyol, and epoxy silanes. . Among these, sorbitol polyglycidyl ether and epoxy silane are preferably used.

  The amount of the glycidyl group-containing compound (B) having no radical polymerizable unsaturated bond is, among others, excellent in adhesion to the old coating film and excellent in durability such as water resistance and alkali resistance. Since an aqueous coating agent capable of forming a film is obtained, it is 0.2 to 10 parts by weight with respect to 100 parts by weight of the resin solid content of the neutralized carboxyl-containing vinyl polymer emulsion (A). It is preferably 0.5 to 5 parts by weight.

  The method for mixing the neutralized carboxyl group-containing vinyl copolymer emulsion (A) and the glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond is not particularly limited, Any method may be used. For example, a glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond after a vinyl copolymer emulsion (A) containing a neutralized carboxyl group is prepared in advance. And a vinyl copolymer emulsion (A) containing a neutralized carboxyl group in the presence of a glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond. The method of mixing etc. can be mentioned. Among them, a glycidyl group having no radically polymerizable unsaturated bond is obtained because an aqueous coating agent capable of forming a coating film having a good balance of durability such as adhesion to old coating film and water resistance and alkali resistance is obtained. A method of mixing by producing a vinyl copolymer emulsion (A) neutralized and containing a carboxyl group in the presence of the containing compound (B) is preferred.

  The compound (C) having a hydrolyzable silyl group and / or silanol group and amino group used in the present invention may be any compound having both a hydrolyzable silyl group and / or silanol group and an amino group, and is particularly limited. Specific examples are N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N -Phenyl-3-aminopropyltrimethoxysilane and the like can be mentioned. Among these, since an aqueous coating agent capable of forming a coating film having good miscibility with the neutralized carboxyl group-containing vinyl polymer emulsion (A) and excellent adhesion to the old coating film is obtained. (Aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyltrimethoxysilane are preferred.

  As the use amount of the hydrolyzable silyl group and / or the compound (C) having a silanol group and an amino group, the balance between adhesion to the old coating film and durability such as water resistance and alkali resistance is particularly good. Since an aqueous coating agent capable of forming a coating film is obtained, it is 0.1 to 10 parts by weight relative to 100 parts by weight of the resin solid content of the neutralized vinyl polymer emulsion (A) containing a carboxyl group. It is preferable that it is 0.5 to 5 parts by weight.

  The method of mixing the hydrolyzable silyl group and / or the compound (C) having a silanol group and an amino group into the aqueous resin dispersion is not particularly limited, and any method may be used. A method of mixing a hydrolyzable silyl group and / or a compound having a silanol group and an amino group (C) after producing a vinyl copolymer emulsion (A) containing a group in advance; Or the method of mixing by manufacturing the vinyl-type copolymer emulsion (A) containing the neutralized carboxyl group in presence of the compound (C) which has a silanol group and an amino group can be mentioned. In particular, since a water-based coating agent capable of forming a coating film excellent in adhesion to the old coating film is obtained, after the vinyl copolymer emulsion (A) containing a neutralized carboxyl group is produced in advance, hydrolysis is performed. The method of mixing with the compound (C) having a reactive silyl group and / or silanol group and an amino group is preferred.

  If necessary, the aqueous resin dispersion of the present invention may contain pigments, fillers, aggregates, dispersants, wetting agents, thickeners, rheology control agents, antifoaming agents, antiseptics, antifungal agents, and pH adjusters. It is also possible to add a rust inhibitor, an ultraviolet absorber, an antioxidant and the like.

  The aqueous resin dispersion of the present invention can be applied to various uses such as coatings, adhesives, textile processing, industrial building materials, civil engineering, and paper processing. Especially, since it is excellent in the adhesiveness with respect to an old coating film, it is useful for coating materials, especially an architectural coating material. Further, since it has durability such as water resistance and alkali resistance, it can be used as a top coating, but it is also useful for various architectural coatings such as a sealer and a base preparation.

  Hereinafter, the present invention will be described in detail with reference to production examples, comparative production examples, examples, comparative examples, test examples, and comparative test examples. However, the present invention is not limited to the following examples. The following “parts” and “%” are based on weight.

Production Example 1
80 parts of styrene (hereinafter abbreviated as SM), 132 parts of 2-ethylhexyl acrylate (hereinafter abbreviated as 2-EHA), 184 parts of methyl methacrylate (hereinafter abbreviated as MMA) and acrylic acid (hereinafter referred to as AA) 4 parts were emulsified with an aqueous emulsifier solution in which 45 parts of New Coal 707SF [anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd .: active ingredient 30%] was dissolved in 80 parts of ion-exchanged water to prepare a monomer emulsion. . Further, 1.2 parts of sodium persulfate (hereinafter abbreviated as “NAPS”) was dissolved in 32 parts of ion-exchanged water to prepare a radical polymerization initiator aqueous solution.

  In a 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, 300 parts of ion exchange water was charged, and the temperature in the reaction vessel was raised to 80 ° C. while stirring while feeding nitrogen gas. After the temperature increase, the monomer emulsion and the radical polymerization initiator aqueous solution were respectively added dropwise to the reaction vessel over 3 hours to carry out emulsion polymerization. After completion of the dropwise addition, 0.2 parts of NAPS was added, and the mixture was further stirred for 2 hours and kept at 80 ° C., then cooled to room temperature, adjusted to pH 9.0 to 9.5 with 12% ammonia water, and then ion exchanged. The nonvolatile content was adjusted to 45% with water to obtain a vinyl copolymer emulsion.

Production Example 2
Using an emulsifier aqueous solution in which 80 parts of SM, 132 parts of 2-EHA, 184 parts of MMA, 4 parts of AA and 1.2 parts of dodecyl mercaptan (hereinafter abbreviated as D-SH) are dissolved in 45 parts of Newcol 707SF in 80 parts of ion-exchanged water. Emulsification was performed to prepare a monomer emulsion. Thereafter, a vinyl copolymer emulsion was obtained in the same manner as in Production Example 1 except that this monomer emulsion was used.

Production Example 3
An emulsifier aqueous solution in which 80 parts of SM, 132 parts of 2-EHA, 184 parts of MMA, 4 parts of AA and 0.4 parts of γ-methacryloylpropyltrimethoxysilane (hereinafter abbreviated as MTMS) are dissolved in 45 parts of Newcol 707SF in 80 parts of ion-exchanged water. Was emulsified to prepare a monomer emulsion. Thereafter, a vinyl copolymer emulsion was obtained in the same manner as in Production Example 1 except that this monomer emulsion was used.

Production Example 4
80 parts of SM, 132 parts of 2-EHA, 184 parts of MMA, 4 parts of AA, 1.2 parts of MTMS and 1.2 parts of D-SH are emulsified using an emulsifier aqueous solution in which 45 parts of New Coal 707SF are dissolved in 80 parts of ion-exchanged water, and monomer emulsion Was made. Thereafter, a vinyl copolymer emulsion was obtained in the same manner as in Production Example 1 except that this monomer emulsion was used.

Production Example 5
80 parts of SM, 132 parts of 2-EHA, 184 parts of MMA, 4 parts of AA, 0.4 part of MTMS and 1.2 parts of D-SH are emulsified using an emulsifier aqueous solution in which 13 parts of New Coal 707SF are dissolved in 80 parts of ion-exchanged water, and monomer emulsion Was made. In addition, 1.2 parts of NAPS was dissolved in 32 parts of ion-exchanged water to prepare a radical polymerization initiator aqueous solution.

  In a 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, 300 parts of ion exchange water and 32 parts of New Coal 707SF were charged, and the inside of the reaction vessel was heated to 80 ° C. while stirring while feeding nitrogen gas. After the temperature increase, 24.7 parts of the monomer emulsion was charged into the reaction vessel, and then 6.6 parts of the radical polymerization initiator aqueous solution was charged. After the addition, the mixture was kept at 80 ° C. with stirring for 15 minutes, and then the remaining monomer emulsion and the remaining aqueous solution of radical polymerization initiator were added dropwise into the reaction vessel over 3 hours to perform emulsion polymerization. After completion of the dropwise addition, 0.2 parts of NAPS was added, and the mixture was further stirred for 2 hours and kept at 80 ° C., then cooled to room temperature, adjusted to pH 9.0 to 9.5 with 12% ammonia water, and then ion exchanged. The nonvolatile content was adjusted to 45% with water to obtain a vinyl copolymer emulsion.

Production Example 6
A vinyl copolymer emulsion was obtained in the same manner as in Production Example 5 except that a 50% aqueous solution of 2-amino-2-methyl-1-propanol (hereinafter abbreviated as AMP) was used instead of 12% ammonia water. It was.

Production Example 7
80 parts of cyclohexyl methacrylate (hereinafter abbreviated as CHMA), 138 parts of 2-EHA, 178 parts of MMA, 4 parts of AA, 0.4 part of MTMS and 1.2 parts of D-SH, and 13 parts of New Coal 707SF are dissolved in 80 parts of ion-exchanged water. A monomer emulsion was prepared by emulsification using the resulting emulsifier aqueous solution. Thereafter, a vinyl copolymer emulsion was obtained in the same manner as in Production Example 5 except that this monomer emulsion was used and a 50% aqueous solution of AMP was used instead of 12% aqueous ammonia.

Production Example 8
80 parts of SM, 60 parts of 2-EHA, 184 parts of MMA, 4 parts of AA, 0.4 parts of MTMS and 1.2 parts of D-SH are emulsified using an emulsifier aqueous solution in which 13 parts of New Coal 707SF are dissolved in 80 parts of ion-exchanged water, and monomer emulsion (1) was produced. Further, 1.6 parts of potassium persulfate (hereinafter abbreviated as KPS) was dissolved in 32 parts of ion-exchanged water to prepare a radical polymerization initiator aqueous solution.

  In a 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, 300 parts of ion exchange water and 32 parts of New Coal 707SF were charged, and the inside of the reaction vessel was heated to 80 ° C. while stirring while feeding nitrogen gas. After the temperature rise, 24.7 parts by weight of the monomer emulsion (1) was charged into the reaction vessel, and then 6.7 parts of the radical polymerization initiator aqueous solution was charged. After the addition, the mixture was kept at 80 ° C. with stirring for 15 minutes, and then dropwise addition of the monomer emulsion (1) and the radical polymerization initiator aqueous solution was started. The monomer emulsion was dropped into 140.2 parts in the first hour to effect emulsion polymerization. At this point, 36 parts of 2-EHA was added to the monomer emulsion (1) and stirred to obtain a monomer emulsion (2). Subsequently, 164.9 parts of the monomer emulsion (2) was dropped into the emulsion in one hour to effect emulsion polymerization. At this point, 36 parts of 2-EHA was further added to the monomer emulsion (2), and the mixture was stirred to prepare the monomer emulsion (3). Obtained. Subsequently, the monomer emulsion (3) was added dropwise over 1 hour to effect emulsion polymerization, and the monomer emulsions (1) to (3) were added dropwise over a period of 3 hours for emulsion polymerization. Further, the radical polymerization initiator aqueous solution was also added in parallel for 3 hours in parallel. After completion of the dropwise addition, 0.2 parts of NAPS was added, and the mixture was further maintained at 80 ° C. with stirring for 2 hours, then cooled to room temperature, adjusted to pH 9.0 to 9.5 with a 50% aqueous solution of AMP, and then ion The non-volatile content was adjusted to 45% with exchange water to obtain a vinyl copolymer emulsion.

  The glass transition temperatures (Tg) of the vinyl copolymers composed of the monomer emulsions (1), (2), and (3) are 59 ° C., 34 ° C., and 5 ° C., respectively. ) Difference (ΔTg) was 5 ° C. or more.

Production Example 9
80 parts of SM, 100 parts of 2-EHA, 184 parts of MMA, 4 parts of AA, 0.4 parts of MTMS and 1.2 parts of D-SH are emulsified using an emulsifier aqueous solution in which 41 parts of New Coal 707SF are dissolved in 80 parts of ion-exchanged water, and monomer emulsion (1) was produced. Further, 1.6 parts of KPS was dissolved in 32 parts of ion-exchanged water to prepare a radical polymerization initiator aqueous solution.

  In a 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, 300 parts of ion exchange water and 4 parts of New Coal 707SF were charged, and the inside of the reaction vessel was heated to 80 ° C. while stirring while feeding nitrogen gas. After the temperature rise, 24.7 parts by weight of the monomer emulsion (1) was charged into the reaction vessel, and then 6.7 parts of the radical polymerization initiator aqueous solution was charged. After the addition, the mixture was kept at 80 ° C. with stirring for 15 minutes, and then dropping of the monomer emulsion (1) and the aqueous radical polymerization initiator solution was started. 149.5 parts of monomer emulsion was dropped into the monomer emulsion in the first hour to effect emulsion polymerization. At this point, 16 parts of 2-EHA was added to the monomer emulsion (1) and stirred to obtain monomer emulsion (2). Subsequently, 174.2 parts of the monomer emulsion (2) was added dropwise in one hour to effect emulsion polymerization. At this point, 16 parts of 2-EHA was further added to the monomer emulsion (2), and the mixture was stirred to prepare the monomer emulsion (3). Obtained. Thereafter, a vinyl copolymer emulsion was obtained in the same manner as in Production Example 8 except that this monomer emulsion (3) was used. The glass transition temperatures (Tg) of the vinyl copolymers comprising the monomer emulsions (1), (2), and (3) are 41 ° C., 32 ° C., and 19 ° C., respectively. ) Difference (ΔTg) was 5 ° C. or more.

Production Example 10
A 1 liter reaction vessel equipped with a stirrer, a thermometer, and a condenser is charged with 300 parts of ion exchange water, 32 parts of Newcol 707SF, and 8 parts of CR-5L (polyhydroxyalkane polyglycidyl ether manufactured by Dainippon Ink & Chemicals, Inc.). A vinyl copolymer emulsion was obtained in the same manner as in Example 8 except that. The glass transition temperatures (Tg) of the vinyl copolymers composed of the monomer emulsions (1), (2), and (3) are 59 ° C., 34 ° C., and 5 ° C., respectively. ) Difference (ΔTg) was 5 ° C. or more.

Comparative production example 1
80 parts of SM, 132 parts of 2-EHA, 176 parts of MMA, 8 parts of glycidyl methacrylate (hereinafter abbreviated as GMA), 4 parts of AA, 0.4 parts of MTMS and 1.2 parts of D-SH, 45 parts of New Coal 707SF and 80 parts of ion-exchanged water A monomer emulsion was prepared by emulsification using an aqueous emulsifier solution dissolved in part. Thereafter, a vinyl copolymer emulsion was obtained in the same manner as in Production Example 1 except that this monomer emulsion was used.

Comparative production example 2
120 parts of SM, 160 parts of butyl acrylate (hereinafter abbreviated as BA), 106 parts of MMA, 4 parts of GMA and 10 parts of methacrylic acid (hereinafter abbreviated as MAA), 22 parts of New Coal 707SF and 2D-1 Fax Anion emulsifier manufactured by Co., Ltd .: alkyldiphenyl ether disulfonate] was emulsified using an aqueous emulsifier solution prepared by dissolving 6 parts of ion-exchanged water in 80 parts to prepare a monomer emulsion. In addition, 1.2 parts of NAPS was dissolved in 32 parts of ion-exchanged water to prepare a radical polymerization initiator aqueous solution.

  In a 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler, 300 parts of ion exchange water and 4 parts of New Coal 707SF were charged, and the inside of the reaction vessel was heated to 80 ° C. while stirring while feeding nitrogen gas. Thereafter, a vinyl copolymer emulsion was obtained in the same manner as in Production Example 5.

Footnotes of Table 1 (1) to (3) * 1) 707SF: New Coal 707SF [Anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd .: 30% active ingredient]
* 2) 2A-1: Dowfax 2A-1 [Nippon Emulsifier Co., Ltd. anionic emulsifier: alkyl diphenyl ether disulfonate]
* 3) CR-5L: Polyhydroxyalkane polyglycidyl ether manufactured by Dainippon Ink & Chemicals, Inc.

Examples 1-11 and Comparative Examples 1-7
Vinyl copolymer emulsion obtained in Production Examples 1 to 10 or Comparative Production Examples 1 and 2, CR-5L [Dainippon Ink Chemical Co., Ltd. polyhydroxyalkane polyglycidyl ether], KBM-403 [Shin-Etsu Chemical Industry Co., Ltd. 3-glycidoxypropyltrimethoxysilane], KBM-602 [Shin-Etsu Chemical Co., Ltd. N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane], and AY- Using 43-040 [Phenyltrimethoxysilane manufactured by Toray Dow Corning Co., Ltd.], the mixture composition was stirred and mixed with the blending compositions shown in Tables 2 (1) to (4) below to obtain an aqueous resin dispersion.

Test Examples 1-11 and Comparative Test Examples 1-7
Using a disper, the following pigment paste composition was dispersed at 3000 rpm for 1 hour to obtain 291.5 parts of pigment paste, and then blended with the following aqueous paint composition to obtain an aqueous paint. A water-based paint adhesion test, water resistance test, water resistance test, and alkali resistance test were carried out by the following test methods. The test results are shown in Tables (1) to (4).

-Pigment paste formulation water 62.0 parts Orotan SG-1 ^{* 4)} 5.7 parts 10% sodium tripolyphosphate 4.1 parts 50% Emulgen A-60 ^{* 5)} 3.7 parts propylene glycol 14.4 parts Best Side 500 ^{* 6)} 0.8 part R-930 ^{* 7)} 200.2 part SN deformer 380 ^{* 8)} 0.4 part 28% ammonia water 0.2 part Subtotal 291.5 parts

Aqueous paint blending composition Pigment paste 291.5 parts Resin aqueous dispersion 634.4 parts (obtained in Examples 1 to 10 and Comparative Examples 1 to 7)
Texanol ^{* 9)} 63.4 parts 3% cellosize QP-4400H ^{* 10)} 13.4 parts 15% adecanol UH-438 ^{* 11)} 3.3 parts BYK-028 ^{* 12)} 0.4 parts Total 1006.4 parts

* 4) Orotan SG-1: Pigment dispersant manufactured by Rohm & Haas * 5) Emulgen A-60: Nonionic emulsifier manufactured by Kao Corporation * 6) Best Side 500: Preservative manufactured by Nippon Soda Co., Ltd. * 7) R -930: Titanium oxide manufactured by Ishihara Sangyo Co., Ltd. * 8) SN deformer 380: Antifoaming agent manufactured by San Nopco Co., Ltd. Thickener * 11) Adecanol UH-438: Thickener manufactured by Adeka Co., Ltd. * 12) BYK-028: Defoamer manufactured by BYK

[Test method]
-Preparation of base material for adhesion and water resistance test: Diamond Depol [waterproof exterior synthetic resin emulsion-based thin finish paint manufactured by Hengwa Chemical Industry Co., Ltd .; hereinafter abbreviated as paint (1). ], Kikusui tile color finishing material [solvent type acrylic resin enamel paint manufactured by Kikusui Chemical Co., Ltd .; hereinafter abbreviated as paint (2). ], Fine coat [Turpen soluble acrylic resin paint manufactured by Kikusui Chemical Co., Ltd .; hereinafter abbreviated as paint (3). ] Fine coat urethane [Kikusui Chemical Co., Ltd. weak solvent type two-component urethane paint; hereinafter abbreviated as paint (4). Each of the above is brush-coated on a slate plate so that the coating amount is 300 g / m ² , dried at 23 ° C. for 14 days, and then dried at 50 ° C. for 3 days to form a substrate for adhesion and water resistance test. Got.

· Adhesion test: on the coating film of the adhesion and water resistance adhesion test substrate, after brushed so that the amount of coating of aqueous paint is 300 g / m ^2, and dried for 7 days at 23 ° C., The coating film was cut with a cutter knife at intervals of 2 mm to produce 5 × 5 = 25 grids, subjected to a cellophane tape peeling test, and evaluated according to the following evaluation criteria.
Evaluation criteria A: 25 adhered ○-◎: 23-24 adhered ○: 20-22 adhered Δ- ○: 15-19 adhered Δ: 10-14 adhered × ˜Δ: 5-9 adhered ×: Less than 4 sticks

Water resistance test: After applying a water-based paint on the coating film of the adhesion and water resistance test base material so that the coating amount is 300 g / m ² and drying at 23 ° C. for 7 days. Soaked in water for 1 day, taken out and dried at 23 ° C. for 24 hours, then cut 2mm intervals with a cutter knife into the coating film to make 5 × 5 = 25 grids and peel off cellophane tape A test was conducted and the adhesion test was evaluated according to the same criteria.

  Water resistance test: Performed according to JIS K 5660.

  -Alkali resistance test: conducted in accordance with JIS K 5660.

Claims (8)

A vinyl copolymer emulsion (A) containing a neutralized carboxyl group, a glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond, a hydrolyzable silyl group and / or a silanol group, An aqueous resin dispersion comprising a compound (C) having an amino group. In the presence of a chain transfer agent, the vinyl copolymer emulsion (A) containing a neutralized carboxyl group is a vinyl monomer containing a carboxyl group-containing vinyl monomer (a1) (a 2. The aqueous resin dispersion according to claim 1, which is obtained by neutralizing a vinyl copolymer emulsion containing a carboxyl group by emulsion polymerization with a basic compound. The vinyl copolymer emulsion (A) containing a neutralized carboxyl group is a vinyl copolymer emulsion containing a neutralized carboxyl group and a hydrolyzable silyl group and / or silanol group. The aqueous resin dispersion according to 1 or 2. The vinyl copolymer emulsion (A) containing a neutralized carboxyl group is obtained by neutralizing a vinyl copolymer emulsion containing a carboxyl group with a water-soluble organic amine. Or 3. The aqueous resin dispersion according to 3. Resin particles composed of two or more types of vinyl copolymers having a glass transition temperature (Tg) difference of 5 ° C. or higher are dispersed in the vinyl copolymer emulsion (A) containing neutralized carboxyl groups. The aqueous resin dispersion according to claim 1, 2 or 3, which is an emulsion formed as described above. The vinyl copolymer emulsion (A) containing a neutralized carboxyl group is an emulsion in which resin particles having an average particle diameter of 0.05 to 0.15 μm are dispersed. The resin aqueous dispersion as described. The resin aqueous dispersion according to any one of claims 1 to 6, wherein the glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond is polyglycidyl ether and / or epoxysilane. The glycidyl group-containing compound (B) having no radically polymerizable unsaturated bond is added to the resin solid content in the vinyl copolymer emulsion (A) containing a neutralized carboxyl group (A) by 100 parts by weight. The resin aqueous solution according to any one of claims 1 to 7, comprising 0.1 to 10 parts by weight of a compound (C) having 2 to 10 parts by weight, a hydrolyzable silyl group and / or a silanol group and an amino group. Dispersion.