CN108699380B - Granulating stabilizer for multi-color pattern coating - Google Patents

Abstract

The present invention aims to provide a granulation stabilizer capable of stably storing a multicolor paint, that is, a granulation stabilizer having excellent stability of color particles, and a method for easily producing a multicolor paint having excellent storage stability. The present invention is a granulation stabilizer for a multicolor pattern coating material, characterized by containing a (co) polymer (A) having an ethylenically unsaturated carboxylic acid (salt) as an essential constituent monomer and having a weight-average molecular weight of 5 to 100 million. The ethylenically unsaturated carboxylic acid salt is preferably an alkali metal salt, an amine salt, or an organic quaternary ammonium salt. The (co) polymer (A) preferably has a molecular weight distribution (Mw/Mn) of 2.5 to 6.0. Preferably further comprises a water-soluble polyol (B).

Description

Granulating stabilizer for multi-color pattern coating

Technical Field

The invention relates to a granulation stabilizer for a multicolor pattern coating.

Background

As a method for producing a multicolor pattern paint, "a method for producing a granular gel (C), characterized by being a method for producing a granular gel (C), comprising: an aqueous liquid composition (a) containing an aqueous resin (a), a colorant (B) and a water-soluble polysaccharide (c) is brought into contact with an aqueous medium (B) containing a metal compound (d) containing an organic acid metal salt (d1) "as a part of its components (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2008-202037 (corresponding publication of the people's republic of China: CN101230141A)

Disclosure of Invention

Problems to be solved by the invention

The multicolor pattern paint obtained by the prior manufacturing method has the following problems: due to insufficient stability of the color particles, color particles of different colors may be united with each other to cause color mixing, or the color particles may be aggregated with each other.

The present invention aims to provide a granulation stabilizer capable of stably storing a multicolor paint, that is, a granulation stabilizer having excellent stability of color particles, and a method for easily producing a multicolor paint having excellent storage stability.

Means for solving the problems

The pellet stabilizer for a multicolor pattern coating material of the present invention is characterized by mainly containing a (co) polymer (a) containing an ethylenically unsaturated carboxylic acid (salt) as an essential constituent monomer and having a weight average molecular weight of 5 to 100 million.

The method for producing a multicolor paint pattern of the present invention is characterized by mainly comprising the following steps:

a matrix coating step (1) for obtaining a matrix coating by mixing a binder, a granulating agent, a coloring agent, water and the granulation stabilizer for a multicolor pattern coating; and

and (2) a granulation step in which a slurry containing particles having a number average particle diameter of 1mm to 20mm is obtained by mixing the aqueous granulating agent solution with the matrix coating material.

ADVANTAGEOUS EFFECTS OF INVENTION

The granulation stabilizer for a multicolor paint of the present invention is excellent in stability of color particles, and therefore can stably store a multicolor paint. Namely, the multicolor pattern paint is excellent in storage stability.

The method for producing a multicolor paint according to the present invention uses the above-mentioned granulation stabilizer for multicolor paints, and therefore, a multicolor paint having excellent storage stability can be easily produced.

Detailed Description

As the ethylenically unsaturated carboxylic acid (salt), ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids, salts thereof and the like are included.

As the ethylenically unsaturated monocarboxylic acid, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, aromatic monocarboxylic acids, and the like can be used.

Examples of the aliphatic monocarboxylic acid include (meth) acrylic acid, crotonic acid, 3-butenoic acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, 3-methyl-2-butenoic acid, 3-methyl-3-butenoic acid, 2-methyl-2-butenoic acid, 2-ethyl-2-acrylic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-heptenoic acid, 4-dimethyl-2-pentenoic acid, 2-octenoic acid, 3-methyl-2-heptenoic acid, 2-nonenoic acid, 3-methyl-2-octenoic acid, 3-methyl-2-heptenoic acid, 2-pentenoic acid, and 3-methyl-2-octenoic acid, 2-decenoic acid and 2-hydroxyacrylic acid, and the like.

"(meth) propene …" means (the same applies hereinafter) a methylpropene … and propene ….

Examples of the alicyclic monocarboxylic acid include 1-cyclopentenecarboxylic acid, 3-cyclopentenecarboxylic acid, 4-cyclopentenecarboxylic acid, 1-cyclohexene carboxylic acid, 3-cyclohexene carboxylic acid, 4-cyclohexene carboxylic acid, 1-cycloheptene carboxylic acid, 3-cycloheptene carboxylic acid, 4-cycloheptene carboxylic acid, 5-cycloheptene carboxylic acid, 1-cyclooctene carboxylic acid, 3-cyclooctene carboxylic acid, 4-cyclooctene carboxylic acid, 5-cyclooctene carboxylic acid, 1-cyclononene carboxylic acid, 3-cyclononene carboxylic acid, 4-cyclononene carboxylic acid, 5-cyclononene carboxylic acid, 1-cyclodecene carboxylic acid, 3-cyclodecene carboxylic acid, 4-cyclodecene carboxylic acid, and 5-cyclodecene carboxylic acid.

Examples of the aromatic monocarboxylic acid include orthophthalenecarboxylic acid, paraphenylenecarboxylic acid, cinnamic acid, atropic acid, 5-vinyl-1-naphthalenecarboxylic acid, 4-vinyl-1-naphthalenecarboxylic acid, and 4-vinyl-1-anthraquinone carboxylic acid.

As the unsaturated dicarboxylic acid, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, intramolecular anhydrides thereof, and the like can be used.

Examples of the aliphatic dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, butenedioic acid, 2-pentenedioic acid, 3-pentenoic acid, 4-pentenoic acid, 2-methyl-2-butenedioic acid, 2-ethyl-2-acrylic acid, 2-hexenedioic acid, 2-heptenedioic acid, 2-octenoic acid, 3-methyl-2-heptenedioic acid, 2-nonenedioic acid, 2-decenedioic acid, and 2-hydroxybutenedioic acid.

Examples of the alicyclic dicarboxylic acid include 1, 2-cyclopentenedicarboxylic acid, 1, 3-cyclopentenedicarboxylic acid, 1, 4-cyclopentenedicarboxylic acid, 1, 2-cyclohexenedicarboxylic acid, 1, 3-cyclohexenedicarboxylic acid, 1, 4-cyclohexenedicarboxylic acid, 1, 2-cycloheptenedicarboxylic acid, 1, 3-cycloheptenedicarboxylic acid, 1, 4-cycloheptenedicarboxylic acid, 1, 5-cycloheptenedicarboxylic acid, 1, 2-cyclooctenedicarboxylic acid, 1, 3-cyclooctenedicarboxylic acid, 1, 4-cyclooctenedicarboxylic acid, 1, 5-cyclooctenedicarboxylic acid, 1, 2-cyclononenedicarboxylic acid, 1, 3-cyclononenedicarboxylic acid, 1, 4-cyclononenedicarboxylic acid, 1, 5-cyclononenedicarboxylic acid, 1, 2-cyclodecenedicarboxylic acid, 1, 4-cyclononenedicarboxylic acid, 1, 5-cyclononenedicarboxylic acid, 1, 2-cycloecenedicarboxylic acid, 1, 4-cyclononenedicarboxylic acid, 1, 2-cycloecenedicarboxylic acid, 1, 4-cyclononenedicarboxylic acid, and the like, 1, 3-cyclodecene dicarboxylic acid, 1, 4-cyclodecene dicarboxylic acid, 1, 5-cyclodecene dicarboxylic acid, and the like.

Examples of the aromatic dicarboxylic acid include 4-vinyl-1, 3-benzenedicarboxylic acid, orthophthalenedicarboxylic acid, paraphenylenedicarboxylic acid, 4-vinyl-1, 2-naphthalenedicarboxylic acid, and 4-vinyl-1, 3-anthraquinone dicarboxylic acid.

Examples of the intramolecular acid anhydride of the unsaturated dicarboxylic acid include maleic anhydride, itaconic anhydride, and citraconic anhydride.

Among these ethylenically unsaturated carboxylic acids, from the viewpoint of stability of the color particles, aliphatic monocarboxylic acids and aliphatic dicarboxylic acids are preferable, further (meth) acrylic acid and maleic anhydride are preferable, and (meth) acrylic acid is particularly preferable.

As their salts, metal salts, amine salts, ammonium salts or the like of ethylenically unsaturated carboxylic acids are included.

As the metal salt, a salt of an alkali metal or an alkaline earth metal, or the like can be used.

Examples of the alkali metal include lithium, potassium, and sodium.

Examples of the alkaline earth metal include calcium and magnesium.

As the amine salt, salts of aliphatic amines having 2 to 6 carbon atoms, alicyclic amines having 3 to 6 carbon atoms, aromatic amines having 6 to 8 carbon atoms, and the like can be used.

Examples of the aliphatic amine include ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, dimethylethanolamine, diethylethanolamine, and ethylenediamine.

Examples of the alicyclic amine include cyclopropylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine.

Examples of the aromatic amine include aniline, pyridine, piperidine, benzylamine, phenylenediamine, and the like.

As the ammonium salt, inorganic ammonium (NH) may be used₄ ⁺) Salts and organic quaternary ammonium salts.

As the organic quaternary ammonium salt, organic ammonium salts having 4 to 8 carbon atoms can be used, and examples thereof include tetramethylammonium salt, tetraethylammonium salt, trimethylethylammonium salt, N-methylpyridinium salt, and N-methylimidazolium salt.

Among these salts, from the viewpoint of stability of the color particles, alkali metal salts, amine salts, and organic quaternary ammonium salts are preferable, lithium salts, potassium salts, sodium salts, and organic quaternary ammonium salts are more preferable, and sodium salts and organic quaternary ammonium salts are particularly preferable.

The content (mol%) of the ethylenically unsaturated carboxylic acid unit is preferably 0 to 90, more preferably 0 to 50, particularly preferably 0 to 20, and most preferably 0 to 10 based on the number of moles of the ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic acid salt. If the amount is within this range, the stability of the color particles becomes further excellent.

The content (mol%) of the ethylenically unsaturated carboxylic acid salt unit is preferably 10 to 100, more preferably 50 to 100, particularly preferably 80 to 100, and most preferably 90 to 100 based on the number of moles of the ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic acid salt. If the amount is within this range, the stability of the color particles becomes further excellent.

In the (co) polymer (a), as the constituent monomer, other monomers than the ethylenically unsaturated carboxylic acid (salt) may be contained.

The other monomer is not particularly limited as long as it can be copolymerized with the ethylenically unsaturated carboxylic acid (salt), and includes olefins, ethylenically unsaturated nitriles, ethylenically unsaturated amides, and the like.

Examples of the olefin include α -olefins having 2 to 20 carbon atoms (e.g., ethylene, propylene, butene, hexene, octene, undecene, tetradecene, and nonadecene), diisobutylene, butadiene, piperylene, chloroprene, pinene, limonene, indene, cyclopentadiene, dicyclopentadiene, and ethylidene norbornene.

Examples of the ethylenically unsaturated nitrile include (meth) acrylonitrile, cyanopropene, and cyanopentene.

Examples of the ethylenically unsaturated amide include (meth) acrylamide, N-methyl (meth) acrylamide, N-2-hydroxymethyl (meth) acrylamide, N- (2-aminoethyl) (meth) acrylamide, and N- (2-dimethylaminoethyl) (meth) acrylamide.

When other monomers are contained as constituent monomers, the content (mol%) of the other monomer units is preferably 1 to 90, more preferably 2 to 70, particularly preferably 5 to 50, and most preferably 8 to 20 based on the number of moles of the ethylenically unsaturated carboxylic acid unit and the ethylenically unsaturated carboxylic acid salt unit.

From the viewpoint of stability of the color particles, the weight average molecular weight (Mw) of the (co) polymer (a) is preferably 5 to 100 ten thousand, more preferably 10 to 70 ten thousand, particularly preferably 15 to 50 ten thousand, and most preferably 20 to 40 ten thousand. The molecular weight distribution (Mw/Mn) is preferably 2.5 to 6.0, more preferably 3.0 to 5.0, and particularly preferably 3.5 to 4.5.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by Gel Permeation Chromatography (GPC) using (poly) ethylene glycol having a known molecular weight as a standard substance (column temperature 40 ℃, eluent methanol, ion-exchanged water, sodium acetate 800: 1200: 15 (weight ratio), flow rate 0.8 ml/min, sample concentration 0.4 wt% eluent solution).

The (co) polymer (a) can be obtained by a general polymerization method of a vinyl monomer, and as the polymerization method, suspension polymerization, bulk polymerization, solution polymerization, and the like can be applied, and solution polymerization is preferable from the viewpoint of productivity and the like.

The (co) polymer (a) can be obtained by: a method (method 1) for producing an ethylenically unsaturated carboxylic acid by polymerizing an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid salt, and, if necessary, another monomer; a method (method 2) in which an ethylenically unsaturated carboxylic acid and, if necessary, another monomer are polymerized and then neutralized with a base (an alkali metal hydroxide, ammonia, or the like); and a method (method 3) in which these (method 1) and (method 2) are used in combination.

The polymerization may use a polymerization catalyst. As the polymerization catalyst, usual polymerization catalysts and the like can be used, including azo compounds, persulfates, inorganic peroxides, redox catalysts, organic peroxides and the like. Examples of the azo compound include 2, 2 ' -azobisisobutyronitrile, 4, 4 ' -azobis-4-cyanovaleric acid, 2 ' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane-1-carbonitrile), 2 ' -azobis (2, 4, 4-trimethylpentane), dimethyl-2, 2 ' -azobis (2-methylpropionate), 2 ' -azobis [2- (hydroxymethyl) propionitrile ], and 1, 1 ' -azobis (1-acetoxy-1-phenylethane). Examples of the persulfate include ammonium persulfate, potassium persulfate, and sodium persulfate. Examples of the inorganic peroxide include perborate and hydrogen peroxide. Examples of the redox catalyst include ascorbic acid-hydrogen peroxide. Examples of the organic peroxide include benzoyl peroxide. These polymerization catalysts may be used alone or in combination. Among these, persulfate and azo compounds are preferable, persulfate and 2, 2' -azobisisobutyronitrile are more preferable, and ammonium persulfate, potassium persulfate and sodium persulfate are particularly preferable.

When a polymerization catalyst is used, the amount (% by weight) of the polymerization catalyst used is preferably 0.1 to 10, more preferably 0.3 to 5, and particularly preferably 0.5 to 3 based on the weight of the constituent monomers.

Further, a chain transfer agent for radical polymerization may be used as needed. Examples of the chain transfer agent include thiocarboxylic acids (e.g., n-lauryl mercaptan, mercaptoethanol, and mercaptopropanol), mercaptoacids (e.g., mercaptoacetic acid and thiomalic acid), secondary alcohols (e.g., isopropanol), amines (e.g., dibutylamine), and hypophosphites (e.g., sodium hypophosphite).

When a chain transfer agent is used, the amount of the chain transfer agent used (% by weight) is preferably 0.01 to 10, more preferably 0.05 to 5, and particularly preferably 0.1 to 1 based on the weight of the constituent monomer.

In the case of solution polymerization and suspension polymerization, as the solvent, water (tap water, ion-exchanged water, industrial water, and the like), an alcohol solvent (methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, and the like), and/or an aromatic solvent (toluene, xylene, and the like) and the like can be used. Among these, water and a mixed solvent of water and an alcohol solvent are preferable, a mixed solvent of water and an alcohol is more preferable, and a mixed solvent of ion-exchanged water and isopropyl alcohol is particularly preferable.

When the solvent is used, the amount thereof is preferably 50 to 900 parts by weight, more preferably 100 to 700 parts by weight, and particularly preferably 200 to 500 parts by weight, based on 100 parts by weight of the constituent monomer.

The polymerization temperature is preferably about 40 to 130 ℃, and the polymerization time is preferably about 1 to 15 hours.

The polymerization may be carried out while dropping all or a part of the constituent monomers. Further, the polymerization may be carried out while dropping all or a part of the polymerization catalyst. Further, the polymerization may be carried out while dropping all or a part of the solvent together with the constituent monomer or the polymerization catalyst. On the other hand, the entire amount of the solvent may be charged into the polymerization vessel in advance, and polymerization may be carried out while removing the solvent. Among these, from the viewpoint of productivity and the like, a method of dropping the whole of the constituent monomer and the polymerization catalyst and a method of dropping a part of the solvent together with the constituent monomer or the polymerization catalyst are preferable, and a method of dropping the whole of the constituent monomer and the polymerization catalyst together with a part of the solvent is more preferable.

The form of the (co) polymer (a) is not particularly limited, and may be liquid or solid.

The case where the (co) polymer (a) is in a liquid state means a state where the (co) polymer (a) is dissolved or dispersed in a solvent. In this case, the (co) polymer (a) may be obtained by suspension polymerization, solution polymerization or the like, and may be obtained without removing all of the solvent, or may be obtained by dissolving or dispersing the (co) polymer (a) obtained by bulk polymerization or the like in a solvent.

When the (co) polymer (a) obtained by bulk polymerization or the like is dissolved or dispersed in a solvent, examples of the solvent include water and an alcohol solvent, and ketones having 1 to 6 carbon atoms (methyl isobutyl ketone, acetone, and the like) may be used alone or in combination.

On the other hand, when the (co) polymer (a) is in a solid state, it may be a solid formed of the (co) polymer (a).

In the case of a solid formed of the (co) polymer (a), it may be obtained by bulk polymerization, or may be obtained by removing the solvent after obtaining a solution or dispersion containing the (co) polymer (a) by suspension polymerization, solution polymerization, or the like.

As a method for removing the solvent from the solution or dispersion containing the (co) polymer (a), a known method such as a freeze drying method, a spray drying method, a drum drying method, or the like can be used.

From the viewpoint of solubility of the granulation stabilizer of the present invention, the size (mm; maximum length) of the solid (co) polymer (A) is preferably 0.01 to 5, more preferably 0.05 to 3, and particularly preferably 0.08 to 1.

Among the forms of the (co) polymer (a), the (co) polymer (a) is preferably in a liquid state, and more preferably in a state of being dissolved in a solvent.

The granulation stabilizer for multicolor pattern coating of the present invention preferably contains a water-soluble polyol (B).

Examples of the water-soluble polyol (B) include water-soluble compounds having at least 2 hydroxyl groups in the molecule, such as glycols { ethylene glycol, polyethylene glycol (number average molecular weight of 88 to 600), propylene glycol, polypropylene glycol (number average molecular weight of 116 to 950), isoprene glycol, and 1, 3-butylene glycol }, triols { glycerol, glycerol ethylene oxide adducts (1 to 20 moles per 1 mole of glycerol), glycerol propylene oxide adducts (1 to 10 moles per 1 mole of glycerol), trimethylolpropane, etc }, tetraols { diglycerol, sorbitan ethylene oxide adducts (1 to 20 moles per 1 mole of sorbitan), alkyl glycosides (1 to 10 carbons in the alkyl group), and hexaols { sorbitol, sorbitol propylene oxide adducts (1 to 10 moles per 1 mole of sorbitol) } Nonalcoholic { maltitol, etc. }. In addition to the above, as the water-soluble polyol (B), a water-soluble polyoxyalkylene compound having at least 2 hydroxyl groups in the molecule may also be used. Among these, diols, triols and tetraols are preferable, and diols and triols are more preferable.

When the water-soluble polyol (B) is contained, the content (% by weight) of the water-soluble polyol (B) is preferably 0.1 to 10, more preferably 0.5 to 8, and particularly preferably 0.8 to 5 based on the weight of the (co) polymer (A). When the amount is in this range, the stability of the color particles is more excellent.

The granulation stabilizer of the present invention may contain known additives (granulating agent, thickener, dispersant, wetting agent, film-forming aid, defoaming agent, anti-freezing agent, etc.) used together with the multicolor pattern paint. They may be used alone or in combination.

When these known additives are contained, the content (% by weight) thereof is preferably 1 to 25, more preferably 2 to 20, and particularly preferably 3 to 11 based on the weight of the (co) polymer (A).

When the water-soluble polyol (B) is contained in the granulation stabilizer for multicolor pattern coating materials of the present invention, the form of the granulation stabilizer of the present invention may be (1) (co) polymer (a) in the form of a liquid or solid together with the water-soluble polyol (B), or (a) and (B) may be reacted. Either (2) or (2) (co) polymer (A) and water-soluble polyol (B) are present in the form { either liquid or solid, respectively. And, they are mixed in the multicolor pattern paint, respectively. Any of them. In the case of (2), additives to be contained as needed may be contained individually or in any combination.

The granulation stabilizer for multicolor pattern coating of the present invention may be liquid or solid, and in the case of solid, it may be powder obtained by loading a powder with a liquid (co) polymer (a) or a mixed liquid thereof (which may contain an additive as required) with a water-soluble polyol (B); the (co) polymer (A) in a solid state or a mixed solid thereof with the water-soluble polyol (B) (which may contain additives as required).

When the liquid granulation stabilizer for multicolor pattern paint is supported on the powder, examples of the powder include activated carbon, calcium carbonate, silica, zeolite, Shirasu balloon (Shirasu balloon), bentonite, and the like.

As a method for supporting the powder, there can be applied: a method of stirring and mixing the powder and the liquid granulation stabilizer for the multicolor pattern paint using a known stirring mixer (ribbon mixer, henschel mixer, etc.).

The granulation stabilizer of the present invention is not limited in its production method as long as the (co) polymer (a), the water-soluble polyol (B), and, if necessary, additives are uniformly mixed in the form in which the (co) polymer (a) and the water-soluble polyol (B) are present together in the (1) granulation stabilizer.

The granulation stabilizer of the present invention can be obtained by a method of uniformly mixing the (co) polymer (a) or the water-soluble polyol (B) with an additive in a form in which the (co) polymer (a) and the water-soluble polyol (B) are present separately from each other and in a form in which the additive is contained in (a) and/or (B).

The method for producing the multicolor paint of the present invention will be described.

The binder is not limited as long as it is a binder for a multicolor pattern coating material, and examples thereof include acrylic resins, polyolefin resins, silicone resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, alkyd resins, polycarbonate resins, and the like. Among these, acrylic resins are preferable.

The amount (wt%) of the binder is preferably 35 to 70, and more preferably 45 to 60 based on the weight of the binder, the granulating agent, the coloring agent, water and the (co) polymer (A).

The granulating agent is not limited as long as it is a granulating agent (i.e., a protective colloid) for a multicolor pattern coating material, and examples thereof include organic granulating agents (methyl cellulose, ethyl cellulose, polyvinyl alcohol, casein, tragacanth gum, Carbarium Rubber (Japanese: カーバリウ ゴ ), cellulose acetate phthalate, hydroxyethyl cellulose, polymethacrylic acid, gum arabic, carrageenan, gelatin, sodium alginate, albumin, pectin, xanthan gum, starch, water-soluble urea-formaldehyde, and the like), and inorganic granulating agents (bentonite, modified metal silicate salts, and the like).

The amount (wt%) of the granulating agent is preferably 0.3 to 2.5, more preferably 0.5 to 1.5 based on the weight of the binder, granulating agent, colorant, water and (co) polymer (A).

The colorant is not limited AS long AS it is a pigment or dye for a multicolor pattern coating material, and examples of the pigment include a white pigment (e.g., titanium dioxide), a black pigment (e.g., carbon black, acetylene black, lamp black, bone black, graphite, iron black, and aniline black), a yellow pigment (e.g., yellow iron oxide, titanium yellow, monoazo yellow, condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, and permanent yellow), an orange pigment (e.g., permanent orange), a red pigment (e.g., red iron oxide, naphthol AS azo red, anthanthrone, anthraquinone red, perylene chestnut, quinacridone red, diketopyrrolopyrrole, indicator red, and permanent red), a violet pigment (e.g., cobalt violet, quinacridone violet, and dioxazine violet), a blue pigment (e.g., cobalt blue, phthalocyanine blue, and phthalocyanine blue), a green pigment (e.g., phthalocyanine green), a black pigment (e.g., carbon black, acetylene black, bone black, graphite black, aniline yellow, and aniline yellow), and permanent yellow, and the like), a yellow pigment (e.g., a pigment, Metallic pigments (aluminum powder, bronze powder, copper powder, tin powder, iron phosphide, zinc powder, and the like), pearl luster pigments (metal oxide-coated mica powder, mica-like iron oxide, and the like), extender pigments (barium oxide powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, and aluminobarium white (gloss white), and the like.

Examples of the dye include azo dyes (monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes, thiazole azo dyes, etc.), anthraquinone dyes (anthraquinone derivatives, anthrone derivatives, etc.), indigo dyes (indigo derivatives, thioindigo derivatives, etc.), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinonimine dyes (azine dyes, oxazine dyes, thiazine dyes, etc.), methine dyes (polymethine (or cyanine) dyes, azomethine dyes, etc.), quinoline dyes, nitro dyes, nitroso dyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes, and perinone dyes.

From the viewpoint of handling properties and the like, a commercially available color paste may be used as it is, or a color paste may be prepared by mixing a pigment or dye with water and used. When preparing a color paste from a pigment or dye, a dispersant may be used as needed. The water content in the color paste is about 50 to 95 wt%.

The amount (% by weight) of the coloring agent is preferably 29.5 to 60.2, and more preferably 39 to 52, based on the weight of the binder, the granulating agent, the coloring agent and the (co) polymer (A).

The amount of water used (% by weight) is preferably 100 to 300, and more preferably 150 to 250, based on the weight of the binder, granulating agent, coloring agent and (co) polymer (A).

The amount of the granulation stabilizer to be used is preferably 0.2 to 2.3, more preferably 0.5 to 1.5, in terms of the weight% of the (co) polymer (a), based on the weight of the binder, granulating agent, coloring agent and (co) polymer (a), from the viewpoint of stability of the color particles.

In the substrate coating step (1), the mixing method is not particularly limited, and mixing can be performed by a known method. As the mixing device, a disperser, a twin-screw mixer, a butterfly mixer, a planetary mixer, and the like can be used.

In the granulation step (2), the aqueous granulating agent solution is not limited as long as it contains the granulating agent and water, and the concentration of the granulating agent is preferably about 2 to 15 wt%.

The method for mixing the aqueous granulating agent solution and the matrix coating material is not particularly limited, and the addition and mixing can be performed by a known method. As the mixing device, a disperser, a metal mesh, a twin-screw mixer, a butterfly mixer, a planetary mixer, and the like can be used, and a disperser is preferable.

The amount (wt%) of the granulating agent aqueous solution is preferably 30 to 70, and more preferably 40 to 60 based on the weight of the matrix coating and the granulating agent aqueous solution. The amount (wt%) of the matrix coating is preferably 30 to 70, and more preferably 40 to 60 based on the weight of the matrix coating and the aqueous granulating agent solution.

The shortest particle diameter of the particles contained in the slurry was determined by visual observation, and the number average particle diameter of the particles contained in the slurry was a number average of at least 20 of them.

As the multicolor pattern paint, it can be obtained by mixing a clear paint with a slurry of at least two of the above-described color particles.

The clear coat can be obtained by mixing a binder with water.

The binder is not limited as long as it can be used in the multicolor pattern coating material, and may be the same as or different from the binder used in the above-mentioned base coating material.

The content of the binder is preferably 30 to 65 wt% based on the weight of the binder and water. In addition, the content of water is preferably 35 to 70 wt% based on the weight of the binder and water.

The amount of the color particle paste is preferably about 40 to 70 wt% based on the weight of the color particle paste and the clear coating material. The amount of the clear coating is preferably about 30 to 60 wt% based on the weight of the color particle slurry and the clear coating.

The method for mixing the clear coat material with the slurry of at least two kinds of color particles is not particularly limited, and a known method can be applied. As the mixing device, a disperser, a twin-screw mixer, a butterfly mixer, a planetary mixer, and the like can be used.

The multi-color pattern coating can be properly mixed with a flatting agent, a viscosity regulator, a pH regulator, a dispersing agent, a defoaming agent, a preservative, a film-forming assistant and/or an anti-freezing agent and the like according to the needs.

Examples

The present invention will be further described with reference to examples, but the present invention is not limited thereto. In the following description, unless otherwise specified, parts means parts by weight and% means% by weight.

< example 1>

80 parts of ion-exchanged water and 20 parts of isopropyl alcohol were put into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, and 200 parts of acrylic acid and 50 parts of a 40% aqueous solution of sodium persulfate were added dropwise from the respective dropping lines at a constant rate over 3 hours under stirring, and the reaction was carried out under a closed condition. The reaction temperature is kept at 80-100 ℃. After completion of the dropwise addition, the mixture was held at 95 to 100 ℃ for 2 hours, and then 200 parts of ion-exchanged water (hereinafter, the operation of dropwise addition of ion-exchanged water will be abbreviated as "water addition") was added dropwise while removing isopropanol under reduced pressure, and then the mixture was cooled to 30 ℃ and, while keeping the temperature at 40 ℃ or lower, 231.1 parts of a 48% aqueous sodium hydroxide solution (reagent grade, Kanto chemical Co., Ltd.) was gradually added thereto in portions while stirring. Then, water was added to adjust the concentration to 30% to obtain the granulation stabilizer (1) [ acrylic acid sodium salt polymer ] for multicolor pattern paint of the present invention. The weight average molecular weight was 5 ten thousand, and the molecular weight distribution (Mw/Mn) was 2.5.

< example 2>

A granulation stabilizer (2) [ acrylic acid sodium salt (90 mol%) -acrylic acid (10 mol%) copolymer for multicolor pattern coating of the present invention was obtained in the same manner as in example 1 except that "ion-exchanged water 80 parts", "isopropanol 20 parts", "40% sodium persulfate aqueous solution 50 parts" and "48% sodium hydroxide aqueous solution 231.1 parts" were changed to "ion-exchanged water 390 parts", "isopropanol 10 parts", "40% sodium persulfate aqueous solution 25 parts" and "48% sodium hydroxide aqueous solution 208 parts", respectively; concentration 30% ]. The weight average molecular weight was 10 ten thousand, and the molecular weight distribution (Mw/Mn) was 3.

< example 3>

A granulation stabilizer (3) [ acrylic acid sodium salt (95 mol%) -acrylic acid (5 mol%) copolymer for multicolor pattern coating of the present invention was obtained in the same manner as in example 1 except that "ion-exchanged water 80 parts", "isopropyl alcohol 20 parts", "40% sodium persulfate aqueous solution 50 parts" and "48% sodium hydroxide aqueous solution 231.1 parts" were changed to "ion-exchanged water 199.9 parts", "isopropyl alcohol 0.1 parts", "40% sodium persulfate aqueous solution 15 parts" and "48% sodium hydroxide aqueous solution 219.5 parts", respectively; concentration 30% ]. The weight average molecular weight was 20 ten thousand, and the molecular weight distribution (Mw/Mn) was 3.5.

< example 4>

A granulation stabilizer (4) [ acrylic acid sodium salt (80 mol%) -acrylic acid (20 mol%) copolymer for multicolor pattern coating of the present invention was obtained in the same manner as in example 1 except that "ion-exchanged water 80 parts", "isopropanol 20 parts", "40% sodium persulfate aqueous solution 50 parts" and "48% sodium hydroxide aqueous solution 231.1 parts" were changed to "ion-exchanged water 720 parts", "isopropanol 80 parts", "10% sodium persulfate aqueous solution 10 parts" and "48% sodium hydroxide aqueous solution 184.9 parts", respectively; concentration 30% ]. The weight average molecular weight was 40 ten thousand, and the molecular weight distribution (Mw/Mn) was 4.5.

< example 5>

The procedure of example 1 was repeated except for changing "ion-exchanged water 80 parts", "isopropyl alcohol 20 parts", "40% aqueous sodium persulfate solution 50 parts" and "48% aqueous sodium hydroxide solution 231.1 parts" to "ion-exchanged water 999.9 parts", "isopropyl alcohol 0.1 parts", "10% aqueous sodium persulfate solution 10 parts" and "48% aqueous sodium hydroxide solution 23.1 parts", respectively, to obtain a stabilizer for multicolor pattern paint (5) [ acrylic acid sodium salt (10 mol%) -acrylic acid (90 mol%) copolymer; concentration 30% ]. The weight average molecular weight was 50 ten thousand, and the molecular weight distribution (Mw/Mn) was 5.5.

< example 6>

A granulation stabilizer (6) [ ammonium acrylate salt (50 mol%) -acrylic acid (50 mol%) copolymer for multicolor pattern coating of the present invention was obtained in the same manner as in example 1 except that "ion-exchanged water 80 parts", "isopropanol 20 parts", "40% aqueous sodium persulfate solution 50 parts" and "48% aqueous sodium hydroxide solution 231.1 parts" were changed to "ion-exchanged water 599.6 parts", "isopropanol 0.6 part", "10% aqueous ammonium persulfate solution 20 parts" and "28% aqueous ammonium solution 84.2 parts", respectively; concentration 30% ]. The weight average molecular weight was 30 ten thousand, and the molecular weight distribution (Mw/Mn) was 4.

< example 7>

1050 parts of ion-exchanged water and 100 parts of maleic anhydride were put into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, and 50 parts of acrylic acid and 4.5 parts of a 10% aqueous solution of sodium persulfate were added dropwise from the respective dropping lines at a constant rate over 2 hours under stirring, and the mixture was reacted under a closed condition. The reaction temperature is kept at 80-90 ℃. After the completion of the dropwise addition, the mixture was held at 95 to 100 ℃ for 2 hours, cooled to 30 ℃ and gradually charged with 273.3 parts of 40% sodium hydroxide while being kept at 40 ℃ or lower under stirring. Then, water was added to adjust the concentration to 30% to obtain a granulation stabilizer (7) [ acrylic acid sodium salt (40 mol%) -maleic acid sodium salt (60 mol%) copolymer ] for multicolor pattern paint of the present invention. The weight average molecular weight was 70 ten thousand, and the molecular weight distribution (Mw/Mn) was 5.5.

< example 8>

900 parts of ion-exchanged water was put into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, and 99.2 parts of acrylic acid, 0.8 part of acrylonitrile and 1 part of a 10% sodium persulfate aqueous solution were added dropwise from the respective dropping lines at a constant rate over 2 hours under stirring, and the reaction was carried out under a closed condition. The reaction temperature is kept at 80-90 ℃. After the completion of the dropwise addition, the mixture was held at 95 to 100 ℃ for 2 hours, and then cooled to 30 ℃ and, while being kept at 40 ℃ or lower, 174.4 parts of 40% sodium hydroxide was gradually added thereto in portions while stirring. Then, water was added to adjust the concentration to 30% to obtain a granulation stabilizer (8) [ acrylic acid sodium salt (99 mol%) -acrylonitrile (1 mol%) copolymer ] for multicolor pattern paint of the present invention. The weight average molecular weight was 100 ten thousand, and the molecular weight distribution (Mw/Mn) was 6.

< example 9>

A pelletization stabilizer (9) [ sodium acrylate salt (53 mol%) -acrylamide (47 mol%) copolymer for multicolor pattern coating according to the present invention was obtained in the same manner as in example 8 except that "900 parts of ion-exchanged water", "99.2 parts of acrylic acid", "0.8 part of acrylonitrile", "1 part of 10% sodium persulfate aqueous solution" and "174.4 parts of 40% sodium hydroxide" were changed to "600 parts of ion-exchanged water", "106 parts of acrylic acid", "94 parts of acrylamide", "20 parts of 10% sodium persulfate aqueous solution" and "279.3 parts of 40% sodium hydroxide"; concentration 30% ]. The weight average molecular weight was 35 ten thousand, and the molecular weight distribution (Mw/Mn) was 4.2.

< example 10>

100 parts of the granulation stabilizer (1) [ acrylic acid sodium salt polymer ] obtained in example 1 and 0.1 part of dipropylene glycol (B1) were heated to 40 ℃ with stirring, and were uniformly stirred and mixed at the temperature to obtain a granulation stabilizer (10) for a multicolor pattern coating material of the present invention.

< example 11>

100 parts of the granulation stabilizer (3) [ acrylic acid sodium salt (95 mol%) -acrylic acid (5 mol%) copolymer ] obtained in example 3 and 10 parts of polyethylene glycol (B2) (number average molecular weight 400) were stirred and heated to 40 ℃ and uniformly stirred and mixed at the temperature to obtain the granulation stabilizer (11) for a multicolor pattern paint of the present invention.

< example 12>

100 parts of the granulation stabilizer (5) [ acrylic acid sodium salt (10 mol%) -acrylic acid (90 mol%) copolymer ] obtained in example 5 and 0.8 part of glycerin (B3) were heated to 40 ℃ with stirring, and then uniformly stirred and mixed at the temperature to obtain the granulation stabilizer (12) for multicolor pattern paint of the present invention.

< example 13>

A granulation stabilizer (13) for a multicolor pattern coating material of the present invention was obtained in the same manner as in example 12, except that "0.8 part of glycerin (B3)" was changed to "5 parts of glycerin (B3)".

< example 14>

100 parts of the granulation stabilizer (7) [ acrylic acid sodium salt (40 mol%) -maleic acid sodium salt (60 mol%) copolymer ] obtained in example 7 and 8 parts of diglycerin (B4) were heated to 40 ℃ with stirring, and were uniformly stirred and mixed at the temperature to obtain the granulation stabilizer (14) for multicolor pattern paint of the present invention.

< example 15>

100 parts of the granulation stabilizer (9) [ acrylic acid sodium salt (53 mol%) -acrylamide (47 mol%) copolymer ] obtained in example 9 and 0.5 part of isoprene glycol (B5) were stirred and heated to 40 ℃ and uniformly stirred at that temperature to obtain the granulation stabilizer (15) for a multicolor pattern paint of the present invention.

< comparative example 1>

100 parts of ion-exchanged water and 100 parts of isopropyl alcohol were put into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, and 300 parts of acrylic acid and 90 parts of a 40% aqueous solution of sodium persulfate were added dropwise from the respective dropping lines at a constant rate over 2 hours under stirring, and the reaction was carried out under a closed condition. The reaction temperature is kept at 80-100 ℃. After the completion of the dropwise addition, the mixture was kept at 95 to 100 ℃ for 2 hours, and then 200 parts of ion exchange water (water) was added dropwise while removing isopropanol under reduced pressure, and then the mixture was cooled to 30 ℃ and added with water to adjust the concentration to 30% to obtain a comparative granulation stabilizer (16) [ acrylic acid polymer ]. The weight average molecular weight was 2.5 ten thousand, and the molecular weight distribution (Mw/Mn) was 1.8.

< comparative example 2>

The "ion-exchanged water 100 parts", "isopropyl alcohol 100 parts", "acrylic acid 300 parts" and "40% sodium persulfate aqueous solution 90 parts" were changed to "ion-exchanged water 60 parts", "isopropyl alcohol 140 parts", "acrylic acid 300 parts" and "40% sodium persulfate aqueous solution 90 parts", respectively, and "cooled to 30 ℃ and added with water to adjust the concentration to 30%" changed to "30 ℃ and then slowly added with 395.3 parts of 48% sodium hydroxide aqueous solution in portions while keeping at 40 ℃ or lower under stirring. A granulation stabilizer (17) [ acrylic acid (5 mol%) -acrylic acid sodium salt (95 mol%) copolymer ] for comparison was obtained in the same manner as in comparative example 1, except that water was added to adjust the concentration to 30% ". The weight average molecular weight was 1.5 ten thousand, and the molecular weight distribution (Mw/Mn) was 1.3.

< comparative example 3>

500 parts of ion-exchanged water and 10 parts of isopropyl alcohol were put into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer and a thermometer, and 50 parts of acrylic acid and 5 parts of 50% sodium persulfate aqueous solution were added dropwise from the respective dropping lines at a constant rate over 1 hour under stirring, and the reaction was carried out under a closed condition. The reaction temperature is kept at 80-100 ℃. After completion of the dropwise addition, the mixture was held at 95 to 100 ℃ for 1 hour, 200 parts of ion exchange water (water) was added dropwise while removing isopropanol under reduced pressure, the mixture was cooled to 30 ℃ and 69.3 parts of a 48% aqueous sodium hydroxide solution was gradually added thereto in portions while keeping the temperature at 40 ℃ or lower under stirring. Water was added to adjust the concentration to 30% to obtain a granulation stabilizer (18) [ acrylic acid sodium salt polymer ] for comparison. The weight average molecular weight was 130 ten thousand, and the molecular weight distribution (Mw/Mn) was 6.5.

< comparative example 4>

100 parts of the comparative granulation stabilizer (16) [ acrylic polymer ] obtained in comparative example 1 and 15 parts of dipropylene glycol (B1) were heated to 40 ℃ with stirring, and uniformly stirred and mixed at the temperature to obtain a comparative granulation stabilizer (19).

Using the granulation stabilizers (1) to (19) obtained in examples and comparative examples, color particle slurries for evaluation were prepared in the following manner, and the stability of the color particles was performed, and the results thereof are shown below.

< preparation of base coating Material (1) >

The compounding ingredients shown in Table 1 were mixed with a bench-top dispenser to obtain a base coating material (C1-19).

[ Table 1]

Compounding ingredients	Compounding amount (parts)
		Binder (note 1)	350
Granulating agent (Note 2)	3
		Red paste (note 3)	250
Granulation stabilizer (1) to (19)	10
		Thickening agent (Note 5)	20
Dispersant (Note 6)	15
		Antifoaming agent (Note 7)	5
Film-forming aid (Note 8)	20
		Water (W)	327

(note 1) binder: acrylic resin emulsion (water concentration 50%): BONCOAT CE-6400, DIC corporation, "BONCOAT" is a registered trademark of this company.

(Note 2) granulating agent: modified silicate, Laponite S482, BYK Chemie JAPAN Co., Ltd

(Note 3) Red paste: the concentrated colorant unirant red, yokohama chemical company, "unirant" is a registered trademark of this company. The concentration of water is 50%

(Note 4) thickener: SN-thickener 640, San Nopco Kabushiki Kaisha

(Note 5) dispersant: nopcol 5200, San Nopco corporation, "Nopcol" is a registered trademark of this company.

(Note 6) defoaming agent: nopco NXZ, San Nopco, Inc. "NXZ" is a registered trademark of this company.

(Note 7) film-Forming aid: TEXANOL, Eastman Chemical Japan K.K. "TEXANOL" is a registered trademark of Jimura oil Chemical Co.

< preparation of base coating Material (2) >

The same procedure as in the preparation (1) of the base coating was carried out except that "red paste" and "granulation stabilizers (1) to (19)" were changed to "yellow paste (concentrated colorant for aqueous coating, uniant yellow, yokohama, water concentration: 50%)" and "granulation stabilizers (3), (4) and (19)", thereby obtaining base coatings (C20 to 22).

< preparation of base coating Material (3) >

Substrate coatings (C23-25) were obtained in the same manner as in the preparation (1) of the substrate coating except that the "red paste" and the "granulation stabilizers (1-19)" were changed to "black paste (concentrated colorant for aqueous coating, uniant black, Duhamama Kabushiki Kaisha, concentration of water 60%)" and "granulation stabilizers (3), (4), and (19)".

< preparation of base coating Material (4) >

A substrate coating material (blank control, C26) was obtained in the same manner as in the preparation (1) of the substrate coating material except that the "granulation stabilizers (1) to (19)" were not used.

< preparation of color particle slurry >

200g of each of the above-mentioned base paints (C1 to 26) and 200g of a 10% aqueous solution of a granulating agent (Laponite S482, BYK Chemie JAPAN Co., Ltd.) were stirred and mixed with a bench-top disperser (ED-11, 400rpm, 3 minutes, manufactured by Nippon Seiki Seisaku-Sho Ltd.) to obtain a color particle slurry for evaluation.

< evaluation of color particle stability >

(1) The shortest particle size of the particles contained in the color particle slurry was measured by visual observation immediately after (a) production, (b) standing at 50 ℃ for 1 day in a closed vessel, and (c) standing at 50 ℃ for 1 week in a closed vessel, and the number average value (number average particle size) of 20 particles was calculated.

(2) Immediately after the preparation of the color particle slurry, the color particle slurry was transferred to a 500ml measuring cylinder, and after being left in a closed vessel at 50 ℃ for 1 week, the state of separation of the color particle slurry was visually observed, and the volume% (degree of separation) of the volume of the upper layer solution portion with respect to the entire volume of the color particle slurry was calculated.

[ Table 2]

"-": the particles showed a shape collapse (the shortest particle diameter could not be measured), and were separated into a colored layer (lower layer) and a transparent water layer (upper layer) (the same applies hereinafter).

[ Table 3]

As shown in the above results, the granulation stabilizer for multicolor pattern coating of the present invention is superior in color particle stability to the granulation stabilizer for comparison.

< example 16>

A clear coating material was prepared by uniformly mixing 900 parts of a binder (UCOAT UWS-145, Sanyo Chemical Co., Ltd., "UCOAT" is a registered trademark of the same Co., Ltd.), 20 parts of a film-forming aid (TEXANOL, Eastman Chemical Japan Co., Ltd.) and 80 parts of water with a desk top dispenser (ED-11, manufactured by Nippon Seiki Seisaku-Sho Co., Ltd.).

50g of each of the color particle slurries (C3), (C20) and (C23) obtained in the above preparation of color particle slurry and 200g of clear paint were mixed with stirring using a desk top disperser (ED-11, 400rpm, 5 minutes, manufactured by Nippon Seiko Seisakusho Co., Ltd.) to obtain a multicolor pattern paint (1).

< example 17>

A multicolor pattern paint (2) was obtained in the same manner as in example 16, except that "50 g each of the color particle slurries (C3), (C20) and (C23)" was changed to "80 g each of the color particle slurries (C4), (C21) and (C24)".

< comparative example 5>

A multicolor pattern paint for comparison was obtained in the same manner as in example 16, except that "color particle pastes (C3), (C20) and (23)" were changed to "color particle pastes (C19), (C22) and (C25)".

< evaluation of stability of multicolor Pattern coating >

(1) The shortest particle size of the particles contained in the multicolor paint was measured by visual observation immediately after (a) production and after (b) leaving at 50 ℃ for 1 week in a closed vessel, and the number average (number average particle size) of 20 particles was calculated.

(2) Immediately after (a) production and (b) leaving at 50 ℃ for 1 week in a closed vessel, the color mixture (presence or absence of color mixture) of red, yellow and black particles was visually observed.

[ Table 4]

As shown in the above results, the granulated stabilizer for a multicolor pattern coating material of the present invention is superior in stability of color particles to the comparative granulated stabilizer, and therefore can stably store a multicolor pattern coating material.

Claims (7)

1. A granulation stabilizer for a multicolor pattern coating, characterized by comprising a polymer A or a copolymer A which contains an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic acid salt as an essential constituent monomer and has a weight-average molecular weight of 5 to 100 ten thousand,

the molecular weight distribution Mw/Mn of the polymer A or the copolymer A is 2.5-6.0,

the granulation stabilizer further comprises a water-soluble polyol B.

2. The granulation stabilizer of claim 1, wherein the ethylenically unsaturated carboxylic acid salt is an alkali metal salt, an amine salt, or an organic quaternary ammonium salt.

3. The granulation stabilizer as claimed in claim 1 or 2, wherein the content of the ethylenically unsaturated carboxylic acid unit is from 0 mol% to 90 mol% and the content of the ethylenically unsaturated carboxylic acid salt unit is from 10 mol% to 100 mol%, based on the number of moles of the ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic acid salt.

4. The granulation stabilizer as claimed in claim 1 or 2, wherein the molecular weight distribution Mw/Mn of the polymer A or the copolymer A is 2.5 to 5.5.

5. The granulation stabilizer as claimed in claim 3, wherein the molecular weight distribution Mw/Mn of the polymer A or the copolymer A is 2.5 to 5.5.

6. The granulation stabilizer as claimed in claim 1, wherein the water-soluble polyol B is contained in an amount of 0.1 to 10% by weight based on the weight of the polymer A or the copolymer A.

7. A method for manufacturing a multicolor pattern paint is characterized by comprising the following steps:

a matrix coating step (1) of mixing a binder, a granulating agent, a coloring agent, water and the granulation stabilizer for a multicolor pattern coating material according to any one of claims 1 to 6 to obtain a matrix coating material; and

and (2) a granulation step in which a slurry containing particles having a number average particle diameter of 1mm to 20mm is obtained by mixing the aqueous granulating agent solution with the matrix coating material.