JPH06207125A - Cross-linkable water-based emulsion coating - Google Patents

Abstract

PURPOSE:To obtain a cross-linkable water-based emulsion coating, excellent in antifouling properties without deteriorating the working environment and suitable for indoor coating, etc., by including hydrotalcites in a specific resin dispersion. CONSTITUTION:The coating is obtained by including (B) hydrotalcites as a pigment component in an amount of preferably 2-250 pts.wt. [based on 100 pts.wt. vehicle component (solid content) in the coating] in (A) a resin dispersion containing (i) an aqueous emulsion of a copolymer containing a carbonyl group- containing alpha,beta-ethylenically unsaturated monomer as a monomer component in an amount of 0.1-30wt.% in the monomer composition and (ii) a polyhydrazide compound having >=2 hydrazide groups per molecule as a cross-linking agent in an amount so as to provide 0.02-3.0 equiv. amount of the hydrazide group based on 1 equiv. carbonyl group in the resultant emulsion particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable water-based emulsion paint suitable for painting indoor surfaces such as indoor wall surfaces and ceilings contaminated with cigarette smoke, oil smoke, hand dust, writing instruments and the like.

[0002]

2. Description of the Related Art Aqueous emulsion paints are generally used for repainting walls, ceilings, etc. of buildings, general houses, vehicles, etc., from the viewpoint of environmental hygiene and the Fire Service Act. There are many. However, these indoor surfaces are often contaminated with cigarette smoke, oil smoke, hand dust, writing instruments, etc., and after coating, these contaminants may exude to the painted surface and spoil the appearance. In particular, contaminants such as cigarette smoke, which have a large amount of water-soluble components, become remarkable when an aqueous emulsion paint is applied.

Therefore, it is practically difficult to use a water-based paint when a white or light-colored paint finish is applied to a surface to be coated which is contaminated by cigarette smoke or the like, and an organic solvent-based paint is unavoidably used. The current situation.

[0004]

Means for Solving the Problems From the viewpoint of improving the coating work environment, the present inventors have diligently studied to prevent the leaching of contaminants in an aqueous emulsion paint, and as a result, a specific crosslinkable aqueous emulsion dispersion was obtained. The inventors have found that blending a special pigment can prevent the contaminants from seeping out, and have completed the present invention.

That is, the present invention provides 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 one molecule as a crosslinking agent. In a resin dispersion liquid containing a polyhydrazide compound having at least two hydrazide groups per 1 carbonyl group in the emulsion particles in an amount of 0.02 to 3.0 equivalents of hydrazide groups, The present invention provides a crosslinkable aqueous emulsion paint characterized by containing hydrotalcites as a pigment component.

Since the coating composition 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, it quickly forms a tough three-dimensional crosslinked film, and a coating film When
It suppresses the diffusion of contaminants on the coated object onto the coating film, and since the coating contains hydrotalcites that have adsorption ability, it prevents contaminants dissolved in the coating film with the coating solvent. They are adsorbed on these, and the combined effect of both of them prevents the exudation of contaminants on the surface of the coating film.

In the coating material of the present invention, as a vehicle component, a resin of a copolymer aqueous emulsion containing a carbonyl group and a polyhydrazide compound are essentially contained.

The above 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 the carbonyl group-containing α, β-ethylenically unsaturated monomer in the monomer composition can be used.

The stable copolymer aqueous emulsion is, for example, (a) 0.1 to 30% by weight of a carbonyl group-containing α, β-ethylenically unsaturated monomer, (b) an aqueous solution copolymerizable with the monomer (a). 0-10% by weight and (c) ethylenically unsaturated monomer other than the monomer (a) and the monomer (b) copolymerizable with the monomer (a) and the monomer (b) 60-
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 acrolein, diacetone acrylamide, diacetone methacrylamide, formyl styrene and vinyl alkyl having 4 to 7 carbon atoms such as vinyl methyl ketone, vinyl ethyl ketone and vinyl butyl ketone. Examples include ketones. Of these, particularly preferred are diacetone acrylamide and diacetone methacrylamide.

The above-mentioned monomer (b) is a monomer which is copolymerizable with the monomer (a) and shows strong hydrophilicity as it is or by neutralization or quaternary chlorination, and is anionic, cationic or nonionic. It may be any of the above monomers. The monomer (b) is used for imparting hydrophilicity to the copolymer emulsion particles, and by imparting hydrophilicity, the stability of the emulsion particles can be increased.

Typical examples of the monomer (b) include acrylic acid, methacrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, and the like in the anionic type. Sodium styrenesulfonate, etc .; in the cationic system, with dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, acrylamide, methacrylamide, dimethylaminopropyl acrylamide and dimethylaminopropyl methacrylamide, and further with glycidyl (meth) acrylate. Addition products with amines and the like; examples of nonionic compounds include (meth) acrylates having a polyoxyethylene chain.

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

Typical examples of the monomer (c) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and acrylic. Lauryl acid, 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
To C ₂₄ alkyl or cycloalkyl ester; C ₁ to (meth) acrylic acid such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate and ethoxybutyl 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 Vinyl propionate, vinyl acetate, acrylonitrile, methacrylonitrile, vinyl pivalate, Veova monomer (manufactured by Shell Chemical Co., Ltd.) and the like can be mentioned, and these are appropriately used depending on the desired performance.

The ratio of the above monomers (a), (b) and (c) to the total monomer components is within the following range. Monomer (a): 0.1 to 30 weight, preferably 2 to 2
0% 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
7-98% by weight

When the amount of the monomer (a) is less than 0.1% by weight, the number of crosslinking points with the polyhydrazide compound which is a crosslinking agent is too small to effect sufficient crosslinking, resulting in insufficient strength of the coating film. The effect of preventing the exudation of contaminants becomes insufficient. On the other hand, when the amount of the monomer (a) exceeds 30% by weight, the storage stability of the paint becomes poor. When the amount of the monomer (b) increases, the hydrophilicity of the obtained emulsion becomes stronger, and accordingly, the water resistance of the coating film obtained tends to deteriorate, so that the amount of the monomer (b) is limited to 10% by weight or less. It is preferable.

In the present invention, the aqueous copolymer 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 anionic surfactants, nonionic surfactants, and cationic surfactants. Of these,
In particular, when the monomer component has a monomer having an acid group such as a carboxyl group, it is an anionic surfactant and is a polyoxyethylene or polyoxypropylene chain between the hydrophobic portion and the hydrophilic anion portion. Anionic surfactants having nonionic moieties such as

When the above-mentioned anionic surfactant having a nonionic moiety is attached to the surface of the particle, there is a hydrophilic nonionic surface active moiety between the polymer phase of the particle and the anion in the water, and the Prevents anions from promoting cross-linking. Examples of such a surfactant include Newcol 560SN and Newcol 5
60SF, Newcol 707SF, Newcol
831SE, Newcol 1305SN (made by Nippon Emulsifier), Hitenol series (made by Dai-ichi Kogyo Seiyaku),
Latemur WX, Emar NC-35, Rebenol 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 6, it is difficult to obtain emulsion polymerization stability, and 6
When the content exceeds the weight%, the water resistance of the coating film is lowered and the tackiness tends to remain.

The aqueous copolymer emulsion used in the coating composition 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),
This is a method in which the monomer component of (c) is copolymerized and then water-dispersed, and water-dispersing ability is imparted by the contribution of the water-soluble ethylenically unsaturated monomer (b). When the monomer (b) is anionic, it is neutralized with ammonia and amines. When the monomer (b) is cationic, it is neutralized with organic acids such as acetic acid, propionic acid and lactic acid. The water dispersibility can be increased by quaternary salification.

The cross-linking agent used in the method of the present invention is a hydrazide group capable of reacting with the carbonyl group in the aqueous copolymer emulsion particles.

[0021]

[Chemical 1]

It is a polyhydrazide compound having at least two in one molecule.

Specific examples of the polyhydrazide compound include saturated aliphatic carboxylic acid dihydrazides having 2 to 18 carbon atoms, such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, and adipic acid dihydrazide. , Sebacic acid dihydrazide; dihydrazides of monoolefinically unsaturated dicarboxylic acids, such as maleic acid dihydrazide, fumaric acid dihydrazide and itaconic acid dihydrazide; polyhydrazides of carbonic acid, such as carbonic acid dihydrazide and general formula

[0024]

[Chemical 2]

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

[0026]

[Chemical 3]

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

If the above polyhydrazide compound is too hydrophobic, it becomes difficult to disperse it in water, and a uniform crosslinked coating film cannot be obtained. Therefore, a relatively low molecular weight (about 300 or less) having appropriate hydrophilicity is obtained. Preference is given to using 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 coating composition of the present invention is cured, the crosslinking reaction between the carbonyl group and the hydrazide group occurs according to the following formula.

[0030]

[Chemical 4]

In the coating composition of the present invention, the amount of the polyhydrazide compound as a crosslinking agent added is such that the amount of hydrazide groups is 0.02 to 3.0 equivalents relative to 1 equivalent of carbonyl groups in the particles of the aqueous copolymer emulsion. , Preferably 0.1
The amount is 2.0 equivalents.

The vehicle component of the coating composition of the present invention comprises the solid content of the carbonyl group-containing copolymer aqueous emulsion and the resin dispersion containing the polyhydrazide compound, and the resin dispersion contains the copolymer aqueous emulsion and the solid content of the resin dispersion. It may be composed of only a polyhydrazide compound,
Known emulsions which have not been used in the field of paints and which do not undergo interparticle cross-linking, such as vinyl acetate emulsion, acrylic resin emulsion, vinyl acetate-acrylic emulsion, ethylene-vinyl acetate emulsion, and epoxy resin emulsion. , Urethane resin emulsion, alkyd resin emulsion, natural or synthetic rubber latex, etc. may be blended in such an amount that the proportion of solid content in all vehicle components is 50% by weight or less.

In the present invention, hydrotalcites are contained as an essential component as a pigment component in the above resin dispersion liquid whose solid content is the vehicle component. The hydrotalcites are a general term for compounds mainly composed of Mg and Al and mainly represented by the following general formula. Mg _yx Al _x (OH) _2y · A _{x / n} ^n- · mH ₂ O (In the formula, A ^n- is an n-valent anion such as OH ⁻ and Cl.
^- , NO ₃ ⁻ , CO ₃ ²⁻ , SO ₄ ^2−, and other 1 to 4 valent anions, x is 0 <x, y is 2x ≦ y, and m is a number satisfying 0 <m.

Such hydrotalcites are compounds having a layered structure having a large adsorptive ability, and are industrially used as an antacid, a heat stabilizer and the like. Specific examples of the hydrotalcites include Mg ₆ Al ₂ (O
_{H) 16 CO 3 · 4H 2} O, Mg 4.5 Al 2 (OH) 13 C
O ₃ · 3.5H ₂ O, Mg ₄ Al ₂ (OH) ₁₂ CO ₃ ·
In addition to 3H ₂ O, Mg _0.7 Al _0.3 O _{1.15 and the} like can be mentioned. As commercial products, Kyoward 500, 1000, 2
000, 2100, 2200 (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) and the like, and these can be used alone or in combination.

Prior to the present invention, like the hydrotalcites, inorganic compounds containing Al and Mg elements which have been used in the field of conventional coating materials, specifically, aluminum oxide, talc and clay. , Mica, etc. were also examined, but they had a poor effect of adsorbing pollutants.

In the present invention, activated alumina and / or activated clay can be used in combination with the above-mentioned hydrotalcites as a pigment. Such activated alumina and activated clay are also compounds having a porous structure having adsorption ability, and are industrially used for decolorizing and refining fats and oils and petroleum mineral oils.

The activated alumina is an intermediate having a pore structure obtained by calcining an alumina hydrate such as gypsite, boehmite, bayerite, and amorphous hydrated gel at an appropriate temperature, usually 200 to 1,000 ° C. Alumina (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; such as DN-1A manufactured by Mizusawa Chemical Co., Ltd. The activated clay is obtained by treating acid clay, which is a kind of clay containing montmorillonite group clay minerals and soluble silicic acid as main components, with an acid to elute a part of basic components. As commercially available products, activated clay produced by Japan Activated Soil Co., Ltd. and Galleon Earth produced by Mizusawa Chemical Co., Ltd.
NV etc. are mentioned.

The blending amount of hydrotalcites in the coating composition of the present invention is appropriately in the range of 2 to 250 parts by weight with respect to 100 parts by weight of the solid content of the vehicle component in the coating composition, that is, the resin dispersion, and further, It is more preferably in the range of 5 to 200 parts by weight. If the blending amount is less than 2 parts by weight, the ability to adsorb pollutants cannot be sufficiently exhibited, while if the blending amount exceeds 250 parts by weight, problems are likely to occur in the storage properties of the paint and the adhesion of the coating film formed.

When hydrotalcites are used in combination with activated alumina and / or activated clay as a pigment component, the mixing ratio is not particularly limited, but preferably 1:10 to 10 by weight. Suitably it is used in a ratio of 1: 1. These are suitable because the target of the pollutants that can be adsorbed by the combined use is further expanded.

The coating composition of the present invention comprises a pigment such as titanium white, red iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, and azo red; Extenders commonly used in the paint field such as calcium, talc, clay, silica, barita, and mica; solvents; dispersants, thickeners, defoamers, film-forming aids, preservatives, antifreeze agents, etc. It may contain additives for paints.

In the coating composition of the present invention, the volume ratio (PVC) of all pigments (including hydrotalcites) to the total solid content in the coating composition is preferably 70% or less, preferably 10 to 60%. A range is more preferable. 7 PVC
As it becomes larger than 0%, the denseness of the coating film deteriorates, and when it is applied onto the coated object on which the contaminants are present, a sufficient stain-proofing effect cannot be exerted.

The method for producing the coating composition of the present invention is not special and can be carried out by a method known per se. For example, it can be carried out by adding a pigment component and, if necessary, a solvent and a paint additive to the resin dispersion liquid and uniformly dispersing the dispersion liquid by a known means such as a stirrer. The coating composition of the present invention can be appropriately used as the top coating composition and the undercoat coating composition.

[0043]

FUNCTION AND EFFECTS OF THE INVENTION Since the coating composition of the present invention contains hydrotalcites having adsorption ability in the coating composition, when a coating film is formed on an article to which contaminants are attached, it dissolves in the coating film. Hydrotalcites adsorb pollutants that have
Further, since the coating composition of the present invention contains as a main component a resin dispersion liquid which can be cross-linked by the reaction of a carbonyl group-containing emulsion and a polyhydrazide compound, it forms a tough three-dimensional cross-linked film to prevent contaminants on the coating film. It suppresses diffusion, and the combined effect of both of these can prevent the exudation of contaminants on the surface of the coating film. Further, in the coating material of the present invention, by using activated alumina and / or activated clay in combination with hydrotalcites, the target of contaminants that can be adsorbed is widened, and it is possible to effectively prevent the contaminants from leaching out by selecting an appropriate composition. .

Furthermore, since the coating composition of the present invention is water-based, it is possible to repaint the walls, ceiling, etc. of a room or the like contaminated with cigarette smoke or the like without impairing the coating work environment.

[0045]

The present invention will be described in more detail with reference to the following examples. In the following, "parts" and "%" are based on weight unless otherwise specified.

Production of Resin Dispersion Production Example 1 Deionized water 232 was placed in a 2-necked four-necked flask.
Part, Newcol 707SF (manufactured by Nippon Emulsifier Co., Ltd.,
An anionic surfactant having a polyoxyethylene chain,
Non-volatile content 30%) 2.3 parts, and after nitrogen substitution, 80 ℃
Kept at. To this, 0.7 part of ammonium persulfate was added, 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

Thirty minutes after the completion of the dropping, 7.7 parts of a solution prepared by dissolving 0.7 parts of ammonium persulfate in 7 parts of deionized water was started to be added, and the addition was completed over 30 minutes. Then, after holding at 80 ℃ for another 2 hours, 45 ℃
The temperature dropped to. In this, adipic acid dihydrazide 4.9
29.9 parts of a solution prepared by dissolving 25 parts of deionized water in 25 parts of deionized water, adjusted to pH 8.5 with aqueous ammonia, and solid content of 5
A 0.7% crosslinkable resin dispersion (1) was obtained.

Production Example 2 Deionized water 242 was placed in a 4-necked flask having a capacity of 2 liters.
And 2.4 parts of Newcol 707SF were added, and the atmosphere was replaced with nitrogen, and the temperature was maintained at 80 ° C. 0.7 part 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

Thirty minutes after the completion of the dropping, 7.7 parts of a solution prepared by dissolving 0.7 parts of ammonium persulfate in 7 parts of deionized water was started to be added, and the addition was completed over 30 minutes. Then, after holding at 80 ℃ for another 2 hours, 45 ℃
The temperature dropped to. In this, adipic acid dihydrazide 6.7
40.7 parts of a solution obtained by dissolving 34 parts of deionized water in 34 parts of deionized water was added, and the pH was adjusted to 8.5 with aqueous ammonia.
A 0.7% crosslinkable resin dispersion (2) was obtained.

Production Example 3 242 parts of deionized water and N in a 2-liter four-necked flask.
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 temperature was maintained at 80 ° C. after nitrogen substitution. 0.7 part 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 had elapsed from the end of the dropping, 7.7 parts of a solution prepared by dissolving 0.7 parts of ammonium persulfate in 7 parts of deionized water was added dropwise over 30 minutes, and after the completion of the dropping, it was further heated at 80 ° C. for 2 hours. After that, the mixture was cooled to 45 ° C. and further adjusted to pH 9 by adding aqueous ammonia to obtain a non-crosslinkable resin dispersion liquid (3) having a solid content of 50.8%.

Example 1 A stainless steel container having a volume of 0.5 liter was mixed with the following composition and stirred with a stirrer for 20 to 40 minutes to obtain a pigment paste. Water supply 100 parts Ethylene glycol 5 parts Nopco spar 44C (Note 1) 2 parts SN deformer 364 (Note 2) 2 parts Fuji Chemi HEC KF-100 (Note 3) 1 part Titanium white 140 parts Kyoward 500 (* 4) 30 parts Tankal (Note 5) 80 parts (Note 1) Pigment dispersant manufactured by San Nopco Ltd. (Note 2) Defoaming agent manufactured by San Nopco Ltd. (Note 3) Thickener manufactured by Fuji Chemical Co., Ltd. (Note 4) Kyowa Chemical Industry Hydrotalcite, manufactured by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O (Note 5) Extender pigment, manufactured by Takehara Chemical Industry Co., Ltd., calcium carbonate

With respect to 360 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 isopropionic acid (2, 2, 4
-Trimethyl-3-hydroxypentyl) ester 12
Parts were mixed and stirred for 10 to 20 minutes to obtain a coating material A.

Examples 2 to 8 and Comparative Examples 1 and 2 A coating composition was prepared in the same manner as in Example 1 except that the pigment composition and the resin dispersion liquid in the production of the pigment paste were as shown in Table 1 below. B, C, D,
E, F, G, H, I and J were obtained.

[0055]

[Table 1] (Note 6) Synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd., Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O (Note 7) Adsorbent pigment manufactured by Sumitomo Chemical Co., Ltd., activated alumina (Note 8) Adsorbent pigment manufactured by Nippon Activated Shirado Co., Ltd. (Note 9) Aluminum silicate manufactured by Fujilite Co., Ltd., volume pigment

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

Test Example 1 4 × 70 × 150 mm flexible plate (JIS A54
(03 compatible product), 10% diluted with deionized water of VINYDELUX 300 white is applied twice with a brush to give a dry coating amount of about 100 g /
Painted to be m ² . This coated plate is 20 ℃ -65% R
The coated plate for a test was obtained by drying for 1 week under the condition of H. Three coated plates for this test were prepared, and a circle with a diameter of 4 cm was placed in the center of one of them to make an oil-based marking pen black (JIS S6037).
(Compatible product) and filled in the circle. A circle was filled in the same manner as the other coated plate except that an aqueous marking pen black (JIS S6037 compliant product) was used instead of the oil-based marking pen black. The last remaining coated plate is
To 50 g of dried tobacco leaves, 500 cc of methanol was added, and the nicotine-containing extract extracted by leaving it at room temperature for one day was used in the same manner except that the oil-based marking pen black was used instead of the black ink.

The three types of contaminated coated plates obtained as described above were coated with a coating material A diluted with tap water to a coating viscosity to give a dry coating amount of about 50.
After applying a brush so as to be g / m ² and drying at room temperature for 48 hours, the degree of exudation (contamination resistance) of contaminants on each coated plate was visually determined. The results are shown in Table 2.

Test Examples 2 to 8 and Comparative Test Examples 1 to 4 In Test Example 1 described above, instead of the paint A, the paints of Examples and Comparative Examples as shown in Table 2 were used, respectively. The same was done. The results are shown in Table 2.

Test Example 9 The paint A was applied in Test Example 1 and dried at room temperature for 48 hours, and then a vinyl deluxe 300 white was further brush-coated 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 performed except that the stain-proof property was determined. The results are shown in Table 2.

Comparative Test Example 5 Test Example 9 was repeated except that EP Sealer White was used in place of Paint A in Test Example 9. The results are shown in Table 2.

[0062]

[Table 2]

(Note 10) In Table 2, the stain resistance was evaluated according to the following criteria. ⊚: No or almost no exudation of contaminants is observed. ◯: Light bleeding is recognized, but there is no practical problem. Δ: Significant bleeding can be confirmed. X: Exudation was observed all over the surface and the discoloration of the painted surface was remarkable.

Claims (4)

[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 at least two per molecule as a crosslinking agent. A polyhydrazide compound having a hydrazide group of 1 as a pigment component in a resin dispersion containing an amount of the hydrazide group of 0.02 to 3.0 equivalents with respect to 1 equivalent of a carbonyl group in the emulsion particles, A crosslinkable water-based emulsion paint characterized by containing hydrotalcites. 2. The aqueous emulsion paint according to claim 1, further comprising activated alumina and / or activated clay as the pigment component. 3. A vehicle component (solid content) 100 in a paint.
The amount of hydrotalcites is 2 to 25 parts by weight.
The water-based emulsion paint according to claim 1 or 2, which is 0 part by weight. 4. The volume ratio (PVC) of all pigments to the total solid content in the coating composition is 70% or less.
The water-based emulsion paint described.