JP2008274084A - Aqueous resin dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous resin dispersion capable of being formed into a water-based coating agent excellent in adhesion to various old coating films and possessing suitability as a top coating material resistant to water, alkalis, etc. <P>SOLUTION: The aqueous resin dispersion is prepared by the emulsion-polymerization of an ethylenically unsaturated monomer mixture (A) containing an amino-containing ethylenically unsaturated monomer (a-1), a carboxyl-containing ethylenically unsaturated monomer (a-2), and other ethylenically unsaturated monomers (a-3), desirably a monomer mixture in which 0.1-5 pts.wt. monomer (a-1) and 0.1-5 pts.wt. monomer (a-2) are used per 100 pts.wt. ethylenically unsaturated monomer (A), and the total amount of these monomers (a-1) and (a-2) used is 0.5-6 pts.wt. in the presence of an alkylene oxide skeleton emulsifier (B), desirably a polyoxyethylene alkyl ether skeleton emulsifier. <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 building paint field, emulsion paints that have been water-based have long been the mainstream. 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 0.12 μm is excellent in adhesion to various old coating films (for example, Patent Document 1). reference.). According to this method, although it shows good adhesion to old paint films, especially old paint films made of aqueous coating agents, solvent paints, especially paint films made of terpene-soluble paints and solvent-type two-component paints. Adhesion to is not sufficient.

  Further, it is disclosed that an aqueous coating agent comprising an emulsion obtained by emulsion polymerization using a reactive surfactant having a surface tension of 40 mN / m or less is excellent in adhesion to an old coating film (for example, , See Patent Document 2). However, even in this method, the adhesion to a coating film made of a solvent-based coating, particularly an old coating film made of a terpene-soluble paint or a two-component curable solvent-based coating, is not sufficient.

JP 2001-342219 A JP 2002-194292 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 paint films and that also has suitability as a top coating such as water resistance and alcal resistance. To provide a body.

  As a result of intensive studies, the inventors of the present invention have reported that an amino group-containing ethylenically unsaturated monomer and a carboxyl group-containing ethylenically unsaturated monomer, which are usually difficult to copolymerize due to aggregation. Copolymerization is possible without agglomeration in the presence of an emulsifier having an alkylene oxide skeleton, and an amino group-containing ethylenically unsaturated monomer and a carboxyl group-containing ethylene in the presence of an emulsifier having an alkylene oxide skeleton. By using a resin aqueous dispersion obtained by copolymerizing a photopolymerizable unsaturated monomer, it 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 inventors have found that a water-based coating agent can be easily obtained, and have completed the present invention.

  That is, the present invention relates to an amino group-containing ethylenically unsaturated monomer (a-1), a carboxyl group-containing ethylenically unsaturated monomer (a-2), and other ethylenically unsaturated monomers (a- An aqueous resin dispersion characterized by being obtained by emulsion polymerization of an ethylenically unsaturated monomer (A) containing 3) in the presence of an emulsifier (B) having an alkylene oxide skeleton. Is.

  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.

  In the present invention, the amino group-containing ethylenically unsaturated monomer (a-1) and carboxyl are used as the ethylenically unsaturated monomer (A) that undergoes emulsion polymerization in the presence of the emulsifier (B) having an alkylene oxide skeleton. It is necessary to use what contains group-containing ethylenically unsaturated monomer (a-2) as an essential component with another ethylenically unsaturated monomer (a-3).

  The amino group-containing ethylenically unsaturated monomer (a-1) is not particularly limited and may be any amino group-containing ethylenically unsaturated group as long as it has an amino group and an ethylenically unsaturated group. Any of group, secondary amino group, tertiary amino group, and quaternary amino group may be used. Specific examples include alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, vinylamine, dimethylaminoethyl hydrochloride (meth) acrylate, and 3- (meth) acryloyl-2-hydroxypropyltrimethyl. Examples include ammonium chloride. Among these amino group-containing ethylenically unsaturated monomers (a-1), dimethylaminoethyl (meth) acrylate is easy to produce and can be used to produce an aqueous resin dispersion that provides an aqueous coating agent that is superior in adhesion. Alkylaminoalkyl (meth) acrylates such as

  In addition, the carboxyl group-containing ethylenically unsaturated monomer (a-2) is not particularly limited and may be any one having a carboxyl group and an ethylenically unsaturated bond. 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. Among these carboxyl group-containing ethylenically unsaturated monomers (a-2), (meth) acrylic acid, itacon can be produced because it is easy to produce and can produce an aqueous resin dispersion that provides an aqueous coating agent that is superior in adhesion. Acid is preferred.

  As other ethylenically unsaturated monomers (a-3) used in combination with these amino group-containing ethylenically unsaturated monomers (a-1) and carboxyl group-containing ethylenically unsaturated monomers (a-2) There are no particular restrictions, and any material can be used. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid-2. -(Meth) acrylic acid esters such as ethylhexyl and cyclohexyl (meth) acrylate; esters of unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid; vinyl acetate, vinyl propionate and tertiary carboxylic acid vinyl , Vinyl esters such as Veova; aromatic vinyl monomers such as styrene and vinyl toluene; heterocyclic vinyl monomers such as vinyl pyrrolidone; salts Vinyl, 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; and (meth) acrylamides and maleic amides Amides of saturated carboxylic acids; Glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate and allyl glycidyl ether; Hydroxyl group-containing vinyl monomers such as 2-hydroxylethyl (meth) acrylate; N-methylol (meta ) Substituted amides of unsaturated carboxylic acids such as acrylamide and diacetone acrylamide; Unsaturated bond-containing silane compounds such as γ-methacryloxypropyltrimethoxysilane; diallyl phthalate, divinylbenzene, allyl acrylate Trimethylolpropane trimethacrylate, vinyl monomers having two or more unsaturated bonds in one molecule such as ethylene glycol dimethacrylate and the like. Of course, it is not limited to these, and any ethylenically unsaturated monomer that can be used for radical polymerization can be used.

  These other ethylenically unsaturated monomers (a-3) contain a (meth) acrylic acid ester and / or styrene since an aqueous resin dispersion can be produced from which an aqueous coating agent having better adhesion can be obtained. It is preferable to use those, and it is more preferable to use those containing (meth) acrylic acid ester and / or styrene having a solubility in water at 20 ° C. of 0.1% or less. As the amount used, the amount used per 100 parts by weight of the ethylenically unsaturated monomer (A) is preferably 80 parts by weight or more, and more preferably 90 to 97 parts by weight. Specific examples of the (meth) acrylic acid ester having a solubility in water at 20 ° C. of 0.1% or less include 2-ethylhexyl acrylate, n-butyl methacrylate, t-butyl methacrylate, i-butyl methacrylate, methacrylic acid. Examples thereof include cyclohexyl acid and stearyl methacrylate.

  The amount of each of the amino group-containing ethylenically unsaturated monomer (a-1) and the carboxyl group-containing ethylenically unsaturated monomer (a-2) is not particularly limited and is used in any amount. Can do. However, the amount of the amino group-containing ethylenically unsaturated monomer (a-1) used is an aqueous resin dispersion that is easy to polymerize and provides an aqueous coating agent that is superior in adhesion, water resistance, alkali resistance, and the like. Since it can manufacture, it is preferable that it is 0.1-5 weight part per 100 weight part of ethylenically unsaturated monomers (A), and it is more preferable that it is 0.5-2 weight part especially. In addition, the amount of the carboxyl group-containing ethylenically unsaturated monomer (a-2) used is an aqueous resin dispersion that can be easily polymerized and provides an aqueous coating agent that is superior in adhesion, water resistance, alkali resistance, and the like. Since it can manufacture, it is preferable that it is 0.1-5 weight% per 100 weight part of ethylenically unsaturated monomers (A), and it is more preferable that it is 0.5-4 weight part especially. Furthermore, the total amount of the monomer (a-1) and the monomer (a-2) used is easy to polymerize, and an aqueous coating agent that is superior in adhesion, water resistance, alkali resistance and the like is obtained. Since an aqueous resin dispersion can be produced, the amount is preferably 0.5 to 6 parts by weight, more preferably 1 to 4 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer (A). .

  The emulsion polymerization of the ethylenically unsaturated monomer (A) is essential in the presence of an emulsifier, and specifically, it is essential to use an emulsifier (B) having an alkylene oxide skeleton. That is, it is usually difficult to copolymerize the amino group-containing ethylenically unsaturated monomer (a-1) and the carboxyl group-containing ethylenically unsaturated monomer (a-2) because aggregation occurs. However, by using the emulsifier (B) having an alkylene oxide skeleton, the monomer (a-1) and the monomer (a-2) can be copolymerized.

  The emulsifier (B) having an alkylene oxide skeleton is not particularly limited, and any emulsifier having an alkylene oxide skeleton can be used. Specific examples include anionic emulsifiers such as polyoxyethylene alkylphenyl sulfonates and polyoxyethylene alkyl ether sulfates; polyoxyethylene distyrenated phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether , Nonionic emulsifiers such as polyoxyethylene-polyoxypropylene block copolymers, and the like, and polyoxyethylene sulfonates of methacrylic acid, polyoxyethylene alkenyl phenyl sulfonates, polyoxyethylene alkenyl phenyl sulfates , Anionic reactive emulsifiers such as polyoxypropylene sulfonates of methacrylic acid; polyoxyethylene alkenyl phenyl ether, polyoxyethylene methacryloyl Reactive emulsifiers such as nonionic reactive emulsifier such as ether can be used. Of course, these emulsifiers can be used in combination. The type of emulsifier is not limited by the above structure, but is commercially available, specifically, Aqualon HS series, KH series, BC series (Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE series , NE series, SR series, ER series [Asahi Denka Kogyo Co., Ltd.] and the like. Among these emulsifiers (B) having an alkylene oxide skeleton, it is preferable to use an emulsifier having a polyoxyethylene alkyl ether skeleton such as polyoxyethylene alkyl ether or polyoxyethylene alkyl ether sulfate.

  Although there is no restriction | limiting in particular in the usage-amount of these emulsifiers (B) which have these alkylene oxide frame | skeletons, since it can superpose | polymerize easily and can manufacture the resin aqueous dispersion from which the aqueous | water-based coating agent which is excellent by adhesiveness, water resistance, alkali resistance, etc. is obtained. The amount is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer (A). Further, in emulsion polymerization of the ethylenically unsaturated monomer (A), the emulsifier (B) having the alkylene oxide skeleton is essential, but other emulsifiers having other skeletons may be used in combination. . In using together, there is no restriction | limiting in particular in another emulsifier, What can be used can be used if it can be used by emulsion polymerization. Specific examples of other emulsifiers include alkylbenzene sulfonates, alkyl sulfates, alkyl diphenyl ether disulfonates, dialkyl sulfosuccinate salts, vinyl sulfonates, styrene sulfonate soda It is also possible to use a reactive emulsifier such as sodium allylalkylsulfosuccinate. Of course, a plurality of types can be used in combination.

  The aqueous resin dispersion of the present invention is an aqueous dispersion obtained by emulsion polymerization of an ethylenically unsaturated monomer (A), and the emulsion polymerization method is not particularly limited, and can be carried out by various emulsion polymerization methods. it can. When the specific example of an emulsion polymerization method is given, 0.01-10 weight part of radical polymerization initiator (C) with respect to 100 weight part of whole quantity of an ethylenically unsaturated monomer (A), Preferably 0.05- 1 part by weight and 50 to 10,000 parts by weight, preferably 60 to 200 parts by weight of an aqueous medium, and 0 to 100 ° C., preferably 40 to 80 in the presence of an emulsifier (B) having an alkylene oxide skeleton. Polymerization can be carried out at 0 ° 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 a reducing agent in this case is 0.01 with respect to 100 weight part of ethylenically unsaturated monomers (A). -10 parts by weight, preferably 0.05-1 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. Moreover, it can also be set as heterophasic structure emulsions, such as core-shell polymerization and seed polymerization.

  Examples of the radical polymerization initiator (C) include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; azobisisobutyronitrile and its hydrochloride, 2,2′-azobis (2-amidino Propane) dihydrochloride, azo initiators such as 4,4'-azobis (4-cyanovaleric acid); peroxide initiators such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. Is mentioned. Among these, peroxide-based initiators, particularly organic peroxide-based initiators, are particularly preferable because an aqueous resin dispersion that can provide an aqueous coating agent that is superior in adhesion, water resistance, alkali resistance, and the like can be produced. Butyl hydroperoxide is preferred. Examples of the reducing agent that can be used in combination with the radical polymerization initiator (C) include sodium sulfooxylate formaldehyde, sodium pyrosulfite, and isoascorbic acid sodium.

  Furthermore, in the emulsion polymerization method for obtaining the aqueous resin dispersion of the present invention, a chain transfer agent (D), for example, a mercaptan, an alcohol organic solvent, an aliphatic organic solvent, an aromatic organic solvent, or the like is used. It is also possible. However, it is preferable that the volatile organic solvent is not contained as much as possible from the viewpoints of environmental protection and occupational health. Further, since the adhesion is improved, the chain transfer agent has a solubility in water at 20 ° C. of 5% or less as a chain transfer agent. It is more preferable to use Specific examples of the chain transfer agent having a solubility in water at 20 ° C. of 5% or less include alkyl mercaptans such as lauryl mercaptan and alkyl thioglycolates such as octyl thioglycolate.

  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 Examples and Comparative Examples, but the present invention is not limited only to the following Examples. The following “parts” and “%” are based on weight.

Example 1
4 parts dimethylaminoethyl methacrylate (hereinafter abbreviated as DMAEMA), 2 parts methacrylic acid (hereinafter abbreviated as MAA), 120 parts styrene (hereinafter abbreviated as SM), 2-ethylhexyl acrylate (hereinafter referred to as 2 -Abbreviated as EHA.) Ethyl unsaturated monomer consisting of 140 parts and methyl methacrylate (hereinafter abbreviated as MMA) 134 parts was converted into New Coal 707SF [Emulsifier manufactured by Nippon Emulsifier Co., Ltd .; active ingredient 30%] 40 parts of Neugen ET-102 (polyoxyethylene alkyl ether skeleton-containing emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was emulsified using an aqueous emulsifier solution in 120 parts of ion-exchanged water to prepare a monomer emulsion. did. Further, 1.2 parts of sodium persulfate (hereinafter abbreviated as NAPS) was dissolved in 24 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, 310 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 elevation, the monomer emulsion and the radical polymerization initiator aqueous solution were dropped into the reaction vessel over 3 hours, respectively, to carry out emulsion polymerization. After completion of the dropwise addition, 0.2 part of NAPS was added, and the mixture was further stirred for 2 hours, kept at 80 ° C., cooled to room temperature, adjusted to pH 8.5 with 14% ammonia water, and then non-volatile with ion-exchanged water. Was adjusted to 45% and then taken out to obtain an aqueous resin dispersion.

Examples 2-4
A resin aqueous dispersion was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were used.

Example 5
DMAEMA 4 parts, MAA 2 parts, SM145 parts, 2-EHA 115 parts, MMA 20 parts, i-BMA 114 parts and dodecyl mercaptan 2 parts, ethylenic 707SF 40 parts and Neugen ET-102 4 parts were emulsified using an aqueous emulsifier solution dissolved in 120 parts of ion-exchanged water to prepare a monomer emulsion. In addition, 2.4 parts of t-butyl hydroperoxide (active ingredient 69%, hereinafter abbreviated as PB-H) is dissolved in 24 parts of ion-exchanged water to prepare a radical polymerization initiator aqueous solution and isoascorbic acid sodium 2 Part was dissolved in 24 parts of ion-exchanged water to prepare a reducing agent aqueous solution.

  A 1 liter reaction vessel equipped with a stirrer, a thermometer, and a cooler was charged with 290 parts of ion-exchanged water and 0.7 part of 1% aqueous ferric chloride solution, and the inside of the reaction vessel was stirred while feeding nitrogen gas while stirring. The temperature was raised to ° C. After the temperature increase, the monomer emulsion, the radical polymerization initiator aqueous solution, and the reducing agent aqueous solution were dropped into the reaction vessel over 3 hours, respectively, 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 70 ° C., then cooled to room temperature, adjusted to pH 8.5 with 14% ammonia water, and then non-volatile with ion-exchanged water. Was adjusted to 45% and then taken out to obtain an aqueous resin dispersion.

Example 6
In preparing the monomer emulsion, Examples were used except that 16 parts of Aqualon KH-10 (Ethylene Oxide Skeleton-containing reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were used as emulsifiers instead of Neucor 707SF and Neugen ET-102. In the same manner as in No. 5, an aqueous resin dispersion was obtained.

Comparative Examples 1 and 2
A resin aqueous dispersion was obtained in the same manner as in Example 1 except that the raw materials shown in Table 2 were used.

Comparative Example 3
An ethylenically unsaturated monomer consisting of 140 parts of 2-EHA, 128 parts of MMA, 120 parts of SM, 6 parts of acrylic acid (hereinafter abbreviated as AA) and 6 parts of hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) -2 [anionic reactive emulsifier manufactured by Sanyo Chemical Industries, Ltd .: alkylallylsulfosuccinic acid sodium salt; active ingredient 38%] 21 parts and Aqualon HS-10 [anionic reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt] Example 1 except that a monomer emulsion was prepared by emulsifying using 4 parts of an emulsifier aqueous solution in which 120 parts of ion-exchanged water was dissolved. A resin aqueous dispersion was obtained in the same manner.

Comparative Example 4
An ethylenically unsaturated monomer consisting of 120 parts of SM, 160 parts of butyl acrylate (hereinafter abbreviated as BA), 106 parts of MMA, 10 parts of MAA, and 4 parts of glycidyl methacrylate (hereinafter abbreviated as GMA) was added to Newcol 707SF22. And 6 parts of Dowfax 2A-1 [anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd., sodium alkyldiphenyl ether disulfonate 50% aqueous solution] were emulsified using an aqueous emulsifier solution in 120 parts of ion-exchanged water, Produced. Further, 1.2 parts of NAPS was dissolved in 24 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, 4 parts of Neucor 707SF and 315 parts of ion-exchanged water were charged, and the inside of the reaction vessel was heated to 80 ° C. while stirring while feeding nitrogen gas. After the temperature elevation, the monomer emulsion and the radical polymerization initiator aqueous solution were dropped into the reaction vessel over 3 hours, respectively, to carry out emulsion polymerization. After completion of the dropwise addition, 0.2 part of NAPS was added, and the mixture was further stirred for 2 hours, kept at 80 ° C., cooled to room temperature, adjusted to pH 8.5 with 14% ammonia water, and then non-volatile with ion-exchanged water. Was adjusted to 45% and then taken out to obtain an aqueous resin dispersion. The obtained aqueous resin dispersion had an average particle size of 0.12 μm (measured with a light scattering particle size distribution analyzer).

Footnotes in Tables 1 and 2 * 1) i-BMA: Isobutyl methacrylate

Test Examples 1-6 and Comparative Test Examples 1-4
Using a disper, the following pigment paste composition was dispersed at 3000 rpm for 1 hour to obtain 291.4 parts of pigment paste, and then blended with the following paint composition to obtain an aqueous paint. An adhesion test, a water adhesion test, a water resistance test, and an alkali resistance test of the water-based paint were conducted by the following test methods. Table 4 shows the test results.

-Pigment paste formulation water 62.0 parts Orotan SG-1 ^{* 2)} 5.7 parts 10% sodium tripolyphosphate 4.1 parts 50% Emulgen A-60 ^{* 3)} 3.7 parts propylene glycol 14.4 parts Best Side 500 ^{* 4)} 0.8 part R-930 ^{* 5)} 200.2 part SN deformer 380 ^{* 6)} 0.4 part 28% ammonia water 0.2 part
Subtotal 291.4 parts

-Paint blending composition Pigment paste 291.4 parts Resin aqueous dispersion 634.4 parts (obtained in Examples 1-6 or Comparative Examples 1-4)
Texanol ^{* 7)} 57.1 parts 3% celloca size QP-4400H ^{* 8)} 13.4 parts 15% adecanol UH-438 ^{* 9)} 3.3 parts BYK-028 ^{* 10)} 0.4 parts
Total 1000.0 parts

* 2) Orotan SG-1: Pigment dispersant manufactured by Rohm & Haas Co., Ltd. * 3) Emulgen A-60: Nonionic emulsifier manufactured by Kao Co., Ltd. * 4) Best Side 500: Preservative manufactured by Nippon Soda Co., Ltd. * 5) R-930: Titanium oxide manufactured by Ishihara Sangyo Co., Ltd. * 6) SN deformer 380: Antifoaming agent manufactured by San Nopco Co., Ltd. * 7) Texanol: Film auxiliary agent manufactured by Eastman Chemical Co., Ltd. * 8) Celloca size QP-4400H: Thickener manufactured by Dow Chemical Co., Ltd. * 9) Adecanol UH-438: Thickener manufactured by Asahi Denka Co., Ltd. * 10) BYK-028: Defoamer manufactured by BYK

〔Test method〕
-Manufacture of base material for adhesion and water resistance test: Diamond New Paul [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 was coated with a brush on a slate plate so that the coating amount was 300 g / m ² , dried at 25 ° C. for 14 days, and then dried at 50 ° C. for 3 days to obtain a substrate for adhesion and water resistance test. Obtained.

-Adhesion test: A water-based paint is applied onto the coating film of the adhesion test substrate so that the coating amount is 300 g / m ² , dried at 25 ° C. for 7 days, and then applied to the coating film with a cutter knife. After making 5 × 5 = 25 grids with 2 mm intervals, a cellophane tape peeling test was performed and evaluated according to the following evaluation criteria.
Evaluation criteria ○: 20 or more attached Δ- ○: 15 to 19 attached Δ: 10 to 14 attached × to Δ: 5 to 9 attached ×: 4 or less attached

Water-resistant adhesion test: A water-based paint was applied onto the coating film of the test substrate for water-resistant adhesion test with a brush so that the coating amount was 300 g / m ² , dried at 25 ° C. for 7 days, and then 1 in water. After immersing for days, taking out and drying at 25 ° C. for 24 hours, the coating film was cut with a cutter knife at intervals of 2 mm to prepare 5 × 5 = 25 grids, and then a cellophane tape peeling test was performed. Evaluation was performed based on the same evaluation criteria as the adhesion test.

  -Water resistance test: It was performed according to JIS K 5660.

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

Claims (8)

Ethylene containing amino group-containing ethylenically unsaturated monomer (a-1), carboxyl group-containing ethylenically unsaturated monomer (a-2) and other ethylenically unsaturated monomers (a-3) An aqueous resin dispersion obtained by emulsion polymerization of a polymerizable unsaturated monomer (A) in the presence of an emulsifier (B) having an alkylene oxide skeleton. The amount of the amino group-containing ethylenically unsaturated monomer (a-1) used is 0.1 to 5 parts by weight per 100 parts by weight of the ethylenically unsaturated monomer (A), and the carboxyl group-containing ethylenically unsaturated monomer The amount of the monomer (a-2) used is 0.1 to 5 parts by weight, and the total amount of these monomers (a-1) and monomer (a-2) used is 0.5 to 6 The resin aqueous dispersion according to claim 1, which is part by weight. The other ethylenically unsaturated monomer (a-3) contains (meth) acrylic acid ester and / or styrene having a solubility in water at 20 ° C of 0.1% or less. Resin aqueous dispersion. The amount of (meth) acrylic acid alkyl ester and / or styrene having a solubility in water at 20 ° C. of 0.1% or less is 80 parts by weight or more per 100 parts by weight of ethylenically unsaturated monomer (A) Item 4. The aqueous resin dispersion according to Item 3. The aqueous resin dispersion according to claim 1, wherein the emulsifier (B) having an alkylene oxide skeleton is an emulsifier having a polyoxyethylene alkyl ether skeleton. The resin aqueous dispersion according to any one of claims 1 to 5, which is obtained by emulsion polymerization of an ethylenically unsaturated monomer (A) using an organic peroxide as a radical polymerization initiator (C). body. The aqueous resin dispersion according to any one of claims 1 to 5, which is obtained by emulsion polymerization of an ethylenically unsaturated monomer (A) in the presence of a chain transfer agent (D). The aqueous resin dispersion according to claim 6, wherein the chain transfer agent (D) has a solubility in water at 20 ° C of 5% by weight or less.