JP2753158B2 - Crosslinkable waterborne emulsion paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable aqueous emulsion paint suitable for coating indoors such as indoor walls and ceilings which are contaminated with tobacco smoke, oily smoke, hand marks and the like.

[0002]

2. Description of the Related Art Water-based emulsion paints are generally used for painting interior walls such as buildings, general houses, and vehicles, such as repainting, etc., from the viewpoints of environmental hygiene and the Fire Service Law. There are many. However, their interior surfaces are often contaminated with tobacco smoke, oily smoke, hand marks, etc.
After painting, these contaminants may seep out onto the painted surface and impair the aesthetic appearance. In particular, contaminants having a large amount of water-soluble components such as cigarette smoke become remarkable when an aqueous emulsion paint is applied.

Therefore, when a surface to be coated contaminated with tobacco smoke or the like is coated with white or light-color paint, it is practically difficult to use water-based paint, and organic solvent-based paint is unavoidably used. It is the current situation.

[0004]

Means for Solving the Problems From the viewpoint of improving the coating work environment, the present inventors have made intensive studies to prevent the seepage of contaminants in aqueous emulsion paints. It has been found that the incorporation of a special pigment can prevent seepage of the contaminants, and the present invention has been completed.

That is, the present invention provides a copolymer aqueous emulsion containing a carbonyl group-containing .alpha.,. Beta.-ethylenically unsaturated monomer as a monomer component in an amount of 0.1 to 30% by weight in a monomer composition, and one molecule as a crosslinking agent. A resin dispersion containing a polyhydrazide compound having at least two hydrazide groups per 1 equivalent of the carbonyl group in the emulsion particles has an amount of the hydrazide group of 0.02 to 3.0 equivalent. An aqueous emulsion paint characterized by containing activated alumina and / or activated clay as a pigment component.

The paint of the present invention contains, as a main component, a resin dispersion liquid capable of being crosslinked by the reaction of a carbonyl group-containing emulsion with a polyhydrazide compound. When it becomes
The diffusion of contaminants on the object to be coated onto the coating film is suppressed, and the coating contains activated alumina and / or activated clay having an adsorbing ability. The contaminants are adsorbed on the contaminants, and the combined effect of the two prevents the contaminants from seeping onto the coating film surface.

[0007] The paint of the present invention essentially contains, as vehicle components, a resin of a copolymer aqueous emulsion containing a carbonyl group and a polyhydrazide compound.

[0008] The copolymer aqueous emulsion is used as a monomer component of the copolymer forming emulsion particles.
Any stable copolymer aqueous emulsion containing 1 to 30% by weight of a carbonyl group-containing α, β-ethylenically unsaturated monomer in the monomer composition can be used.

The above-mentioned stable aqueous emulsion of the copolymer is, for example, 0.1 to 30% by weight of an α, β-ethylenically unsaturated monomer having a carbonyl group, and (b) an aqueous solution copolymerizable with the monomer (a). 0 to 10% by weight of an ethylenically unsaturated monomer and (c) an ethylenically unsaturated monomer other than the monomer (a) and the monomer (b) copolymerizable with the monomer (a) and the monomer (b)
It can be obtained by emulsion polymerization of a monomer mixture containing 99.9% by weight in the presence of a dispersion stabilizer.

Examples of the monomer (a) include vinyl alkyl having 4 to 7 carbon atoms such as acrolein, diacetone acrylamide, diacetone methacrylamide, formylstyrene and vinyl methyl ketone, vinyl ethyl ketone and vinyl butyl ketone. Ketone and the like. Of these, particularly preferred are diacetone acrylamide and diacetone methacrylamide.

The monomer (b) is a monomer which can be copolymerized with the monomer (a) and shows a strong hydrophilicity by itself or by neutralization or quaternary salification, and is anionic, cationic or nonionic. May be any monomer. The monomer (b) is used for imparting hydrophilicity to the copolymer emulsion particles. By imparting hydrophilicity, the stability of the emulsion particles can be increased.

Representative examples of the monomer (b) include acrylic acid, methacrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, Sodium styrenesulfonate, etc .; cationic systems include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, acrylamide, methacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, and glycidyl (meth) acrylate. Adducts with amines and the like: In the case of nonionics, (meth) acrylates having a polyoxyethylene chain are exemplified.

The monomer (c) is not particularly limited as long as it is copolymerizable with the monomers (a) and (b) and is an ethylenically unsaturated monomer other than the monomers (a) and (b). Can be used without.

Representative examples of the monomer (c) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, acryl Lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate,
C ₁ of (meth) acrylic acid such as stearyl methacrylate
Alkyl or cycloalkyl esters -C _24; methoxybutyl acrylate, methacrylic acid methoxybutyl, methoxyethyl acrylate, methacrylic acid methoxy ethyl, ethoxy butyl acrylate, C ₁ ~ of (meth) acrylic acid such as ethoxy butyl methacrylate C ₁₈ alkoxyalkyl ester; C ₂ -C ₈ hydroxyalkyl ester of (meth) acrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; styrene, vinyltoluene, α-methylstyrene, N- Aromatic unsaturated monomers such as vinylpyrrolidone and vinylpyridine; olefins such as ethylene, propylene, butylene and pentene; diene compounds such as butadiene, isoprene and chloroprene A vinyl propionate, a vinyl acetate, an acrylonitrile, a methacrylonitrile, a vinyl pivalate, a beoba monomer (a product of Shell Chemical Co., Ltd.), and the like, which are appropriately used depending on desired performance.

The proportion of the monomers (a), (b) and (c) occupying the entire monomer component is within the following range. Monomer (a): 0.1 to 30% by weight, preferably 2 to 30% by weight
20% by weight, monomer (b): 0 to 10% by weight, preferably 0 to 3% by weight, monomer (c): 60 to 99.9% by weight, preferably 7
7 to 98% by weight

If the amount of the monomer (a) is less than 0.1% by weight, the crosslinking point with the polyhydrazide compound as a crosslinking agent is too small to perform sufficient crosslinking, resulting in insufficient strength of the coating film. The effect of preventing seepage of contaminants is not sufficient. On the other hand, if the amount of the monomer (a) is more than 30% by weight, the storage stability of the paint will be poor. When the amount of the monomer (b) is increased, the hydrophilicity of the obtained emulsion becomes stronger, and the water resistance of the resulting coating film tends to deteriorate. Therefore, the amount of the monomer (b) is limited to 10% by weight. Is preferred.

In the present invention, the copolymer aqueous emulsion can be obtained by a known method. For example, it can be easily obtained by emulsion polymerization of the above monomer component in the presence of a dispersion stabilizer. Examples of the dispersion stabilizer include an anionic surfactant, a nonionic surfactant, and a cationic surfactant. Of these,
In particular, when there is a monomer having an acid group such as a carboxyl group in the monomer component, it is an anionic surfactant and a polyoxyethylene or polyoxypropylene chain between a hydrophobic portion and a hydrophilic anion portion. Anionic surfactants having a nonionic moiety such as are preferred.

When the anionic surfactant having a nonionic portion adheres to the particle surface, there is a hydrophilic nonionic surface active portion between the polymer phase of the particle and the anion in water, and the nonionic surfactant on the particle surface during storage. Prevents anions from promoting crosslinking. Examples of such surfactants include Newcol 560SN, Newcol5
60SF, Newcol 707SF, Newcol
861SE, Newcol 1305SN (manufactured by Nippon Emulsifier), Hytenol series (manufactured by Daiichi Kogyo Seiyaku),
Latemul WX, Emar NC-35, Lebenol WZ
(Made by Kao). The amount used is 0.1 to 6% by weight, preferably 0.2 to 5% by weight. 0.1% by weight
If it is less than 10, it is difficult to obtain emulsion polymerization stability,
If the amount is more than 10% by weight, the water resistance of the coating film is reduced, and the tackiness is apt to remain.

The copolymer aqueous emulsion used in the paint of the present invention can be obtained by emulsion polymerization as described above, but can also be obtained by other methods. For example, in a hydrophilic organic solvent, the monomers (a), (b),
In this method, the monomer component (c) is copolymerized and then water-dispersed, and the water-dispersible ability is imparted by the contribution of the water-soluble ethylenically unsaturated monomer (b). When the monomer (b) is anionic, neutralization is performed with ammonia and amines. When the monomer (b) is cationic, neutralization is performed with an organic acid such as acetic acid, propionic acid, and lactic acid. By quaternary salification, the ability to disperse in water can be increased.

The crosslinking agent used in the method of the present invention comprises a hydrazide group capable of reacting with a carbonyl group in the above-mentioned copolymer aqueous emulsion particles.

[0021]

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Is a polyhydrazide compound having at least two in one molecule.

Examples of the polyhydrazide compound include saturated aliphatic carboxylic acid dihydrazides having 2 to 18 carbon atoms, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide. Dihydrazide, sebacic acid; dihydrazides of monoolefinically unsaturated dicarboxylic acids, such as maleic dihydrazide, fumaric acid dihydrazide and itaconic acid dihydrazide; carbonic acid polyhydrazide, such as carbonic acid dihydrazide;

[0024]

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A compound represented by the formula (wherein x represents an integer of 1 to 5, preferably 1 to 3); bissemicarbazide, in particular, a compound of the general formula

[0026]

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Wherein the group —R— is a divalent linear or branched aliphatic residue having 2 to 7 carbon atoms or 6
Carbocyclic residues having up to 8 carbon atoms, such as o-,
m- or p-phenylene group, tolylene group, cyclohexylene group or methylcyclohexylene group)
An aliphatic, alicyclic or aromatic bissemicarbazide represented by the following: polyhydrazide of an aromatic polycarboxylic acid, for example, dihydrazide of phthalic acid, terephthalic acid or isophthalic acid, and dihydrazide, trihydrazide or tetrahydrazide of pyromellitic acid; Aliphatic trihydrazide, for example, nitrilotriacetic trihydrazide; tetrahydrazide, for example, ethylenediaminetetraacetic acid tetrahydrazide; polyhydrazide obtained by reacting a low polymer having a lower alkyl ester group of carboxylic acid with hydrazine or hydrazine hydrate (hydrazine hydride). (See Japanese Patent Publication No. 52-22878).

When the above-mentioned polyhydrazide compound is too strong in hydrophobicity, it is difficult to disperse in water and a uniform cross-linked coating film cannot be obtained. Therefore, a relatively low molecular weight (approximately 300 or less) having moderate hydrophilicity is obtained. It is preferred to use compounds. One preferred representative examples, such as succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, C ₄ dihydrazide compound of dicarboxylic acids -C ₁₂ as such sebacic acid dihydrazide and the like.

When the paint of the present invention is cured, the crosslinking reaction between the carbonyl group and the hydrazide group occurs according to the following formula.

[0030]

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In the paint of the present invention, the amount of the polyhydrazide compound as a cross-linking agent is such that the amount of the hydrazide group is from 0.02 to 3.0 equivalents to 1 equivalent of the carbonyl group in the particles of the aqueous copolymer emulsion. , Preferably 0.1 to
It is an amount equivalent to 2.0 equivalents.

The vehicle component of the coating composition of the present invention comprises the solid content of the aqueous dispersion of the carbonyl group-containing copolymer and the resin dispersion containing the polyhydrazide compound. The resin dispersion comprises the aqueous emulsion of the copolymer and It may consist of only a polyhydrazide compound,
In addition, known emulsions which do not perform interparticle crosslinking, such as vinyl acetate emulsions, acrylic resin emulsions, vinyl acetate-acryl emulsions, ethylene-vinyl acetate emulsions, and epoxy resin emulsions, which are conventionally used in the field of coatings, are not used. , A urethane resin emulsion, an alkyd resin emulsion, a natural or synthetic rubber latex or the like may be blended in such an amount that the solid content in the total vehicle components is 50% by weight or less. Among these emulsions, an acrylic resin emulsion is suitable as a non-crosslinkable resin dispersion. The acrylic resin emulsion is the monomer listed in the description of the carbonyl group-containing copolymer aqueous emulsion.
It can be obtained by emulsion polymerization of a monomer component selected from (b) and (c) in the presence of a dispersion stabilizer.

In the present invention, activated alumina and activated clay are contained as essential components as pigment components in the resin dispersion in which the solid content is a vehicle component. Activated alumina and activated clay are compounds having a porous structure having a large adsorptivity, and are industrially used for decolorization and purification of fats and oils and petroleum mineral oils.

Activated alumina is an intermediate alumina having a pore structure obtained by calcining alumina hydrate such as gypsite, boehmite, bayerite, amorphous hydrated gel at a suitable temperature, usually 200 to 1000 ° C. Transition alumina). Activated alumina is also called gamma-alumina. As commercially available products, activated alumina KC-501, KC-503 and gamma-alumina A-manufactured by Sumitomo Chemical Co., Ltd.
11; DN-1A manufactured by Mizusawa Chemical Co., Ltd., and the like. Activated clay is obtained by treating acidic clay, which is a kind of clay containing a montmorillonite group clay mineral and soluble silicic acid as main components, with an acid to elute a part of basic components. Activated clay made by Nippon Activated Shirato Co., Ltd.
Galleon Earth NV manufactured by Mizusawa Chemical Co., Ltd.
And the like.

Incidentally, before reaching the present invention, inorganic compounds containing elements of aluminum and silicon as well as activated alumina and activated clay, specifically, silicon dioxide, aluminum oxide, diatomaceous earth, talc, clay, mica These were also examined, but these were poor in the effect of adsorbing pollutants.

Activated alumina and / or
Alternatively, the amount of the activated clay is a total of the two, and is suitably in the range of 10 to 300 parts by weight with respect to the vehicle component in the paint, that is, 100 parts by weight of the solid content of the resin dispersion. More preferably, it is in the range of parts by weight. When the amount is less than 10 parts by weight, the ability to adsorb contaminants cannot be sufficiently exhibited. On the other hand, when the amount is more than 300 parts by weight, problems such as storability and adhesion tend to occur.

The coating composition of the present invention may further comprise, in addition to the resin dispersion, activated alumina and / or activated clay, if necessary,
Coloring pigments such as titanium white, red iron black, carbon black, phthalocyanine blue, phthalocyanine green, and azo red; calcium carbonate, talc, clay,
Extenders such as silica, barita and mica which are usually used in the field of coatings; solvents; additives for coatings such as dispersants, thickeners, defoamers, film-forming aids, preservatives, antifreezing agents, etc. Can be contained.

In the paint of the present invention, the volume ratio (PVC) of all pigments (including activated alumina and / or activated clay) to the total solid content in the paint is preferably 70% or less. A range of 60% is more preferred. As the PVC becomes larger than 70%, the denseness of the coating film decreases, and when applied on the object to be coated with the contaminants, a sufficient stain stopping effect cannot be exhibited.

The method for producing the paint of the present invention is not particularly limited, and can be carried out by a method known per se. For example, it can be carried out by adding a pigment content and, if necessary, a solvent or a coating additive to the resin dispersion, and uniformly dispersing the mixture by a known means such as a stirrer. The paint of the present invention can be used as an overcoat or undercoat as appropriate.

[0040]

Since the paint of the present invention contains activated alumina and / or activated clay having an adsorbing ability in the paint, when the paint film is formed on an object to which contaminants are adhered, the paint film is formed. The activated alumina and / or activated clay adsorb the contaminants dissolved therein, and the paint of the present invention contains, as a main component, a resin dispersion liquid which can be crosslinked by a reaction between a carbonyl group-containing emulsion and a polyhydrazide compound. A tough three-dimensional crosslinked film is formed to suppress the diffusion of contaminants onto the coating film, and the combined effect of these two can prevent seepage of contaminants onto the coating film surface.

Further, since the paint of the present invention is water-based, it is possible to repaint walls and ceilings of rooms and the like contaminated with tobacco smoke and the like without impairing the painting work environment.

[0042]

The present invention will be described more specifically with reference to the following examples. Hereinafter, “parts” and “%” are based on weight unless otherwise specified.

Production of Resin Dispersion Production Example 1 Deionized water 232 was placed in a two-liter four-necked flask.
Part, Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd.)
An anionic surfactant having a polyoxyethylene chain,
2.3 parts of a nonvolatile component (30%), 80 ° C. after nitrogen replacement.
Kept. 0.7 parts of ammonium persulfate was added thereto, and 15 minutes after the addition, a pre-emulsion obtained by emulsifying the following composition was added dropwise over 3 hours. Deionized water 338 parts Diacetone acrylamide 32 parts Acrylic acid 3.2 parts Styrene 97 parts Methyl methacrylate 260 parts 2-ethylhexyl acrylate 100 parts n-butyl acrylate 150 parts Newcol 707SF 62 parts Ammonium persulfate 1.2 parts

After a lapse of 30 minutes from the end of the dropping, 7.7 parts of a solution in which 0.7 part of ammonium persulfate was dissolved in 7 parts of deionized water were started to be dropped, and the drop was completed over 30 minutes. Then, after maintaining at 80 ° C. for another 2 hours,
The temperature dropped. In this, adipic dihydrazide 4.9
Was mixed with 25 parts of deionized water, and adjusted to pH 8.5 with aqueous ammonia to obtain a solid content of 5 parts.
A 0.7% crosslinkable resin dispersion (1) was obtained.

Production Example 2 Deionized water 242 was placed in a two-liter four-necked flask.
And 2.4 parts of Newcol 707SF, and the mixture was maintained at 80 ° C. after nitrogen replacement. 0.7 parts of ammonium persulfate was added thereto, and 15 minutes after the addition, a pre-emulsion having the following composition was added dropwise over 3 hours. Deionized water 352 parts Diacetone acrylamide 13.4 parts Acrylic acid 13.4 parts Styrene 268 parts Methyl methacrylate 174 parts 2-ethylhexyl acrylate 201 parts Newcol 707SF 64.5 parts Ammonium persulfate 1.3 parts

After a lapse of 30 minutes from the end of the dropping, 7.7 parts of a solution in which 0.7 part of ammonium persulfate was dissolved in 7 parts of deionized water were started to be dropped, and the drop was completed over 30 minutes. Then, after maintaining at 80 ° C. for another 2 hours,
The temperature dropped. In this, adipic acid dihydrazide 6.7
Was dissolved in 34 parts of deionized water, adjusted to pH 8.5 with aqueous ammonia, and adjusted to a solid content of 5%.
A 0.7% crosslinkable resin dispersion (2) was obtained.

Production Example 3 242 parts of deionized water and N
2.4 parts of ewcol 707SF (manufactured by Nippon Emulsifier Co., Ltd., anionic surfactant having a polyoxyethylene chain, solid content: 30%) was added, and the mixture was replaced with nitrogen and kept at 80 ° C. 0.7 parts of ammonium persulfate was added thereto, and 15 minutes after the addition, a pre-emulsion having the following composition was added dropwise over 3 hours.

Deionized water 352 parts Newcol 707SF 62.5 parts Methyl methacrylate 201 parts Styrene 134 parts n-butyl acrylate 321 parts Acrylic acid 13.4 parts Ammonium persulfate 1.3 parts After 30 minutes from the completion of dropping, ammonium persulfate 7.7 parts of a solution prepared by dissolving 0.7 parts in 7 parts of deionized water was added dropwise over 30 minutes.
After the temperature was kept at 45 ° C., the mixture was cooled to 45 ° C., and the pH was adjusted to 9 by further adding aqueous ammonia to obtain a non-crosslinkable resin dispersion liquid (3) having a solid content of 50.8%.

Example 1 The following composition was blended in a stainless steel container having a capacity of 0.5 liter and stirred with a stirrer for 20 to 40 minutes to obtain a pigment paste. Water 100 parts Ethylene glycol 5 parts Nopcospars 44C (Note 1) 2 parts SN deformer 364 (Note 2) 2 parts Fujichemi HEC KF-100 (Note 3) 1 part Titanium white 140 parts Activated alumina KC-503 (Note 4) 50 Department Tancar (Note 5) 80 parts (Note 1) Pigment dispersant manufactured by San Nopco Co., Ltd. (Note 2) Defoamer manufactured by San Nopco Co., Ltd. (Note 3) Thickener manufactured by Fuji Chemical Co., Ltd. (Note 4) Sumitomo Adsorbent pigment, activated alumina manufactured by Chemical Co., Ltd. (* 5) Extender pigment, calcium carbonate manufactured by Takehara Chemical Industry Co., Ltd.

With respect to 380 parts of the obtained pigment paste,
200 parts of the crosslinkable resin dispersion liquid (1) having a solid content of 50.7% obtained in Production Example 1 and 200 parts of isopropionic acid (2,2,4)
-Trimethyl-3-hydroxypentyl) ester 12
Parts were blended and stirred for 10 to 20 minutes to obtain Paint A.

Examples 2 to 6 and Comparative Examples 1 to 2 In the same manner as in Example 1, except that the pigment composition and the resin dispersion in producing the pigment paste were as shown in Table 1 below, the coating was performed in the same manner as in Example 1. B, C, D,
E, F, G and H were obtained.

[0052]

[Table 1]

Comparative Examples 3 and 4 Vinyl deluxe 300 white (non-crosslinked water-based acrylic resin emulsion paint, white, manufactured by Kansai Paint Co., Ltd.) was used as Comparative Example 3 and EP Sealer White (Kansai Paint Co., Ltd.)
(Water-based acrylic resin-based non-crosslinking type emulsion paint for undercoating, white) was used as Comparative Example 4.

Test Example 1 Flexible board of 4 × 70 × 150 mm (JIS A54
03 compliant product), coated twice with a brush with VINYDELUX 300 white diluted 10% with tap water to obtain a dry coating amount of about 100 g /
It was painted in such a way as to provide a m ^2. This painted plate is 20 ℃ -65% R
After drying for 1 week under the condition of H, a coated plate for test was obtained. Three test coated plates were prepared, and a circle having a diameter of 4 cm was placed in the center of one of the test coated plates with an oil-based marking pen black (JIS S6037).
Compatible product) and painted inside the circle. A circle was painted in the same manner on the other coated plate except that a water-based marking pen black (a product conforming to JIS S6037) was used instead of the oil-based marking pen black. On the last painted plate,
500 cc of methanol was added to 50 g of the dried tobacco leaves, and a circle was painted in the same manner except that the nicotine-containing extract extracted by standing at room temperature for 24 hours was used instead of the oil-based marking pen black.

The three types of contaminated coated plates obtained as described above were coated with a coating A diluted to a coating viscosity with tap water to a dry coating amount of about 50.
After brush-coating to a g / m ² and drying at room temperature for 48 hours, the degree of seepage of contaminants on each coated plate (stain resistance) was visually determined. Table 2 shows the results.

Test Examples 2 to 6 and Comparative Test Examples 1 to 4 In the above Test Example 1, except that the paints of Examples and Comparative Examples were used instead of Paint A as shown in Table 2, The same was done. Table 2 shows the results.

Test Example 7 Paint A was applied in Test Example 1, dried at room temperature for 48 hours, and further painted with Vinylidex 300 white so that the dry coating amount was about 50 g / m ² . 4 at room temperature
After drying for 8 hours, the same procedure as in Test Example 1 was carried out except that the stain resistance was evaluated. Table 2 shows the results.

Comparative Test Example 5 A test was conducted in the same manner as in Test Example 7 except that EP Sealer White was used instead of Paint A in Test Example 7. Table 2 shows the results.

[0059]

[Table 2]

(Note 8) In Table 2, the evaluation of stain resistance was carried out according to the following criteria. ：: No or almost no seepage of contaminants was observed. ：: Light seepage was recognized but no problem in practical use. Δ: Considerable exudation can be confirmed. X: Exudation is seen on the entire surface, and the discoloration of the painted surface is remarkable.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09D 5/02 C09D 7/12 C09D 133/00-133/26 C09D 129/00-129/12

Claims (5)

(57) [Claims] 1. A copolymer aqueous emulsion containing a carbonyl group-containing α, β-ethylenically unsaturated monomer as a monomer component in an amount of 0.1 to 30% by weight in the monomer composition, and a crosslinking agent per molecule. The pigment dispersion is contained in a resin dispersion containing a polyhydrazide compound having at least two hydrazide groups in an amount such that the amount of hydrazide groups is 0.02 to 3.0 equivalents relative to 1 equivalent of carbonyl groups in the emulsion particles. An aqueous emulsion paint characterized by containing activated alumina and / or activated clay as a component. 2. The aqueous emulsion coating composition according to claim 1, wherein the resin dispersion is blended with an emulsion which does not carry out cross-linking between particles in such an amount that the proportion of the solid content in all vehicle components is 50% by weight or less. 3. The water-based emulsion paint according to claim 2, wherein the emulsion that does not perform interparticle crosslinking is an acrylic resin emulsion. 4. A vehicle component (solid content) 100 in a coating material.
The aqueous emulsion paint according to any one of claims 1 to 3, wherein the amount of activated alumina and / or activated clay is 10 to 300 parts by weight with respect to parts by weight. 5. The aqueous emulsion paint according to claim 1, wherein a volume ratio (PVC) of the total pigment to the total solid content in the paint is 70% or less.