KR20190008534A - Granulation stabilizer for multicolor coating material - Google Patents

Abstract

It is an object of the present invention to provide a granulation stabilizer capable of stably storing a multicolored coating material, that is, a granulation stabilizer excellent in the stability of color particles, and a method for easily producing a multicolored coating material having excellent storage stability .
The present invention relates to an assembly for a multicolored paint, which comprises a (co) polymer (A) having an ethylenically unsaturated carboxylic acid (salt) as an essential constituent monomer and having a weight average molecular weight of 50,000 to 1,000,000 It is a stabilizer. The ethylenically unsaturated carboxylic acid salt is preferably an alkali metal salt, an amine salt or a quaternary organic ammonium salt. (Co) polymer (A) preferably has a molecular weight distribution (Mw / Mn) of 2.5 to 6.0. It is also preferable that the water-soluble polyhydric alcohol (B) is contained.

Description

{GRANULATION STABILIZER FOR MULTICOLOR COATING MATERIAL}

The present invention relates to a granulation stabilizer for a multicolor paint.

(A) containing a water-soluble resin (a), a colorant (b) and a water-soluble polysaccharide (c) is contacted with an aqueous medium (B) containing a metal compound (C), which is characterized in that the metal compound (d) contains an organic acid metal salt (d1) as a part of its component, is known as a method for producing a granular gel (C) (Patent Document 1).

Japanese Patent Application Laid-Open No. 2008-202037 (corresponding to Chinese Official Gazette: CN101230141A)

In the case of the color form paint obtained by the conventional production method, there is a problem in that the stability of the color particles is insufficient, so that the color particles of different colors are combined to cause color mixing, or the color particles are agglomerated.

An object of the present invention is to provide a granulation stabilizer capable of stably storing a multicolored coating material, that is, a granulation stabilizer having excellent stability of color granules, and to provide a granular stabilizer capable of easily producing a multicolored coating material having excellent storage stability It is a way to provide.

The granulation stabilizer for a multicolor paint of the present invention is 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 50,000 to 1,000,000 This is the point that is made.

A feature of the method for producing a multicolored paint of the present invention is a base painting step (1) for obtaining a base paint by mixing a binder, a granulating agent, a colorant, water and a granulation stabilizer for the multicolored paint, and

(2) in which a slurry containing particles having a number average particle diameter of 1 to 20 mm is obtained by mixing an aqueous granule solution and a base paint.

The granulation stabilizer for a multicolored paint of the present invention is capable of stably storing a multicolored paint because the stability of color particles is excellent. That is, the storage stability of the multicolor paint is excellent.

Since the method for producing a multicolored paint of the present invention uses the granulation stabilizer for the multicolor paint, it is possible to easily produce a multicolor paint having excellent storage stability.

Examples of the ethylenically unsaturated carboxylic acid (salt) include ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids, and salts thereof.

As the ethylenically unsaturated monocarboxylic acid, an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, and an aromatic monocarboxylic acid 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- 2-pentenoic acid, 2-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 2-pentenoic acid, 2-octenoic acid, 3-methyl-2-heptenoic acid, 2-nonenoic acid, 3-methyl- And 2-hydroxypropenoic acid.

The term " (meth) acrylate " means methacrylate, acrylate (hereinafter the same).

Examples of the alicyclic monocarboxylic acid include 1-cyclopentenecarboxylic acid, 3-cyclopentenecarboxylic acid, 4-cyclopentenecarboxylic acid, 1-cyclohexenecarboxylic acid, 3-cyclohexenecarboxylic acid, 3-cycloheptenecarboxylic acid, 3-cycloheptenecarboxylic acid, 4-cycloheptenecarboxylic acid, 5-cycloheptenecarboxylic acid, 1-cycloheptenecarboxylic acid, 3-cycloheptenecarboxylic acid, But are not limited to, carboxylic acid, 4-cyclooctene carboxylic acid, 5-cyclooctenecarboxylic acid, 1-cyclononenecarboxylic acid, 3-cyclononenecarboxylic acid, 4-cyclononenecarboxylic acid, , 1-cyclodecenecarboxylic acid, 3-cyclodecenecarboxylic acid, 4-cyclodecenecarboxylic acid, and 5-cyclodecenecarboxylic acid.

Examples of the aromatic monocarboxylic acid include o-styrene carboxylic acid, p-styrenecarboxylic acid, cinnamic acid, atropic acid, 5-vinyl-1-naphthalenecarboxylic acid, 4- Vinyl-1-anthraquinone carboxylic acid, and the like.

As the unsaturated dicarboxylic acid, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid and a molecular acid anhydride thereof can be used.

Examples of the aliphatic dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, butenoic acid, 2-pentenoic acid, 3- 2-hexenoic acid, 2-hexenoic acid, 2-octenoic acid, 3-methyl-2-heptenoic acid, 2-nonenoic acid, 2-decenoic acid and 2- .

Examples of the alicyclic dicarboxylic acid include 1,2-cyclopentene dicarboxylic acid, 1,3-cyclopentene dicarboxylic acid, 1,4-cyclopentene dicarboxylic acid, 1,2-cyclohexene dicarboxylic acid , 1,3-cyclohexene dicarboxylic acid, 1,4-cyclohexene dicarboxylic acid, 1,2-cycloheptene dicarboxylic acid, 1,3-cycloheptene dicarboxylic acid, 1,4-cyclo Heptene dicarboxylic acid, 1,5-cycloheptene dicarboxylic acid, 1,2-cyclooctene dicarboxylic acid, 1,3-cyclooctene dicarboxylic acid, 1,4- 1,5-cyclooctene dicarboxylic acid, 1,5-cyclooctene dicarboxylic acid, 1,5-cyclooctene dicarboxylic acid, 1,2-cyclononenedicarboxylic acid, 1,3- Dicarboxylic acid, 1,2-cyclodecene dicarboxylic acid, 1,3-cyclodecene dicarboxylic acid, 1,4-cyclodecene dicarboxylic acid, and 1,5-cyclodecene dicarboxylic acid. .

Examples of the aromatic dicarboxylic acid include o, p-styrenedicarboxylic acid, o, p-styrenedicarboxylic acid, 4-vinyl-1,2-naphthalenedicarboxylic acid and 4-vinyl-1,3-anthraquinone Dicarboxylic acid and the like.

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

Of these ethylenically unsaturated carboxylic acids, aliphatic monocarboxylic acids and aliphatic dicarboxylic acids are preferable from the viewpoint of stability of color particles, and more preferred are (meth) acrylic acid and maleic anhydride, particularly preferably (meth) Acrylic acid.

These salts include metal salts, amine salts or ammonium salts of ethylenically unsaturated carboxylic acids and the like.

The metal salt may be a salt of an alkali metal or an alkaline earth metal.

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

Examples of the alkaline earth metals include calcium and magnesium.

As the amine salt, a salt of an aliphatic amine having 2 to 6 carbon atoms, an alicyclic amine having 3 to 6 carbon atoms, or an aromatic amine having 6 to 8 carbon atoms 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 amines include cyclopropylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine.

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

As the ammonium salt, an inorganic ammonium (NH ₄ ⁺ ) salt and a quaternary organic ammonium salt can be used.

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

In view of the stability of the color particles in these salts, alkali metal salts, amine salts and quaternary organic ammonium salts are preferable, and more preferred are lithium salts, potassium salts, sodium salts and quaternary organic ammonium salts, particularly preferably sodium salts And quaternary organic ammonium salts.

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

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

The (co) polymer (A) may contain a monomer other than the ethylenically unsaturated carboxylic acid (salt) as a constituent monomer.

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

Examples of the olefins include C2-C20? -Olefins (such as ethylene, propylene, butylene, hexylene, octylene, undecylene, tetradecylene and nonadecylene), diisobutylene, butadiene, piperylene, chloroprene, , Limonene, indene, cyclopentadiene, bicyclopentadiene, and ethylidene norbornene.

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

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

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

The weight average molecular weight (Mw) of the (co) polymer (A) is preferably from 50,000 to 1,000,000, more preferably from 100,000 to 700,000, particularly preferably from 150,000 to 500,000, Most preferably from 200,000 to 400,000. 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) are measured by gel permeation chromatography (GPC) using poly (ethylene glycol) as a standard substance (column temperature: 40 캜, eluent: Ion exchanged water: sodium acetate = 800: 1200: 15 (weight ratio), flow rate: 0.8 ml / min, sample concentration: 0.4% by weight).

(Co) polymer (A) can be obtained by using a usual polymerization method of a vinyl monomer, and suspension polymerization, bulk polymerization and solution polymerization can be applied as a polymerization method, and solution polymerization is preferable from the standpoint of productivity .

(Co) polymer (A) is prepared by polymerizing an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated carboxylic acid salt and, if necessary, another monomer (Method 1), an ethylenically unsaturated carboxylic acid and, if necessary, other monomers (Method 2); and a method (Method 3) in which these (Method 1) and (Method 2) are used in combination.

A polymerization catalyst may be used for the polymerization. As the polymerization catalyst, an ordinary polymerization catalyst or the like is used and includes azo compounds, persulfates, inorganic peroxides, redox catalysts, and organic peroxides. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (4-methoxy-2,4- Nitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azobis [2- (hydroxymethyl) propionitrile] and 1,1'-azobis (1- (2-methylpropionate) Examples of the persulfate include ammonium persulfate, potassium persulfate, and sodium persulfate, and examples of the inorganic peroxide include perborate and hydrogen peroxide. As the redox catalyst, there may be mentioned, for example, Ascorbic acid-hydrogen peroxide, etc. Examples of the organic peroxide include benzoyl peroxide, etc. These polymerization catalysts may be used singly or in combination. Straight, more preferably a persulfate and 2,2'-azobisisobutyronitrile, and particularly preferably ammonium persulfate, potassium persulfate and sodium persulfate.

When the polymerization catalyst is used, the amount (wt%) of the polymerization catalyst 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.

If necessary, a chain transfer agent for radical polymerization may be used. Examples of the chain transfer agent include thiocarboxylic acids (such as n-lauryl mercaptan, mercaptoethanol and mercaptopropanol), thiol acids (such as thioglycolic acid and thiomalic acid), secondary alcohols (such as isopropanol) Etc.), hypophosphite (sodium hypophosphite, etc.) and the like.

When a chain transfer agent is used, the amount (wt%) of the chain transfer agent 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 monomers.

In the case of solution polymerization and suspension polymerization, examples of the solvent include water (tap water, ion exchange water and industrial water etc.), alcohol solvents (methanol, ethanol, isopropyl alcohol, ethylene glycol and diethylene glycol, etc.) and / Xylene, etc.) and the like can be used. Of these, a mixed solvent of water, water and an alcohol solvent is preferable, and a mixed solvent of water and alcohol, particularly preferably a mixed solvent of ion exchanged water and isopropyl alcohol, is more preferable.

When a solvent is used, the amount of the solvent to be used 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 monomers.

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

Further, the whole amount or a part of the constituent monomers may be added dropwise while polymerization is carried out. Further, the whole or part of the polymerization catalyst may be added dropwise while polymerization is carried out. The whole or part of the solvent may be polymerized while being added dropwise together with the constituent monomers or the polymerization catalyst. On the other hand, the whole amount of the solvent may be put into a polymerization vessel and the polymerization may be carried out while removing the solvent. From the standpoint of productivity among them, a method of dropping the whole amount of the constituent monomers and the polymerization catalyst and a method of dropping a part of the solvent together with the constituent monomers or polymerization catalysts are preferable, and more preferably, the total amount of the constituent monomers and the polymerization catalyst And then dropping it together with a part of the solvent.

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

(Co) polymer (A) is in a liquid phase, it means a state in which (co) polymer (A) is dissolved or dispersed in a solvent. In this case, the (co) polymer (A) may be obtained by suspension polymerization or solution polymerization and the like without any solvent being removed, and the (co) polymer (A) obtained by bulk polymerization or the like may be dissolved or dispersed in a solvent .

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

On the other hand, when the (co) polymer (A) is in a solid phase, it may be a solid comprising the (co) polymer (A).

(Co) polymer (A) may be obtained by bulk polymerization, or a solution or dispersion containing the (co) polymer (A) may be obtained by suspension polymerization or solution polymerization, and then the solvent may be removed .

As a method of removing the solvent from the solution or dispersion containing the (co) polymer (A), known methods such as freeze drying, spray drying and drum drying may be used.

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

(Co) polymer (A) is preferably in a liquid phase, more preferably a state in which the (co) polymer (A) is dissolved in a solvent.

The granulation stabilizer for a multicolored paint of the present invention preferably contains a water-soluble polyhydric alcohol (B).

Examples of the water-soluble polyhydric alcohol (B) include water-soluble compounds having at least two hydroxyl groups in the molecule, such as diols (ethylene glycol, polyethylene glycol (number average molecular weight 88-600), propylene glycol, polypropylene glycol (number average molecular weight 116-950) Glycerin ethylene oxide adduct (addition molar number to 1 mole of glycerin), glycerin propylene oxide adduct (addition to 1 mole of glycerin) (Molar number of 1 to 10) and trimethylolpropane}, tetraol {diglycerol, sorbitan, sorbitan ethylene oxide adduct (addition mole number relative to 1 mol of sorbitan: 1 to 20) and alkyl glycoside To 10)}, hexaols {sorbitol, sorbitol propylene oxide adduct (addition molar number to 1 mole of sorbitol 1 to 10)}, and nanol {maltitol etc.}. In addition to the above, as the water-soluble polyhydric alcohol (B), a water-soluble polyoxyalkylene compound having at least two hydroxyl groups in the molecule can also be used. Of these, diols, triols and tetraols are preferred, and more preferred are diols and triols.

When the water-soluble polyhydric alcohol (B) is contained, the content (% by weight) of the water-soluble polyhydric alcohol (B) is preferably 0.1 to 10, more preferably 0.5 to 8 , And particularly preferably from 0.8 to 5. Within this range, the stability of color particles is more excellent.

The granulation stabilizer of the present invention may contain known additives (granulators, thickeners, dispersants, wetting agents, film forming aids, antifoaming agents, antifreezing agents, etc.) used in combination with the multicolor paint. These may be used alone or in combination.

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

When the granulation stabilizer for a multicolored paint of the present invention comprises a water-soluble polyhydric alcohol (B), the granulation stabilizer of the present invention may be in the form of (1) a (co) polymer (A) and a water-soluble polyhydric alcohol (A) and (B) may react with each other), or (2) a form in which the (co) polymer (A) and the water-soluble polyhydric alcohol (B) They may be either liquid or solid. And they are each mixed in a colorful paint). In the case of (2), the additive may be contained in any one of them, if necessary.

The granulation stabilizer for a multicolor paint of the present invention may be in a liquid phase or a solid phase, and in the case of a solid phase, a liquid (co) polymer (A) or a mixed liquid of the same with a water- soluble polyhydric alcohol (B) (Co) polymer (A) or a solid (optionally, an additive may be included) of a water-soluble polyvalent alcohol (B).

When the granulation stabilizing agent for liquid type multicolor paint is supported on the powder, examples of the powder include activated carbon, calcium carbonate, silica, zeolite, sirasu balloon and bentonite.

As a method of supporting on powder, a method of stirring and mixing a granulation stabilizer for powdery and liquid type multicolored paint using a known stirring mixer (such as a ribbon mixer and Henschel mixer) can be applied.

(1) When the (co) polymer (A) and the water-soluble polyhydric alcohol (B) are present together, the granulation stabilizer of the present invention contains the (co) polymer (A), the water-soluble polyhydric alcohol ), And if necessary, additives are uniformly mixed, there is no limitation in the production method.

(2) When the (co) polymer (A) and the water-soluble polyhydric alcohol (B) are separately present, when the additive is contained in (A) and / or (B) (A) or a water-soluble polyhydric alcohol (B) with an additive.

A method for producing a colorful paint of the present invention will be described.

Examples of the binder include, but not limited to, acrylic resin, polyolefin resin, silicone resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin and polycarbonate resin have. Of these, acrylic resins are preferable.

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

As the granulating agent, there is no limitation as long as it is a granulating agent for a colorful paint (that is, a protective colloid), and an organic granulating agent such as methyl cellulose, ethyl cellulose, polyvinyl alcohol, casein, transgenic rubber, carbamate rubber, cellulose acetate phthalate, (Bentonite, modified silicate metal salt, and the like), such as ethyl cellulose, polymethacrylic acid, gum arabic, karaya rubber, gelatin, sodium alginate, albumin, pectin, xanthan gum, starch and water soluble urea formaldehyde) .

The amount (mass%) used 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, the granulating agent, the colorant, the water and the (co) polymer (A).

As the colorant, any pigment or dye for a colorful paint can be used without limitation. Examples of the pigment include white pigments such as titanium dioxide and black pigments such as carbon black, acetylene black, lamp black, black black, graphite, iron black and aniline black, (Yellow iron oxide, titanium yellow, monoazo yellow, condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow and permanent yellow) Examples of the pigments include pigments (such as permanent orange), red pigments (red iron oxide, naphthol AS azo red, anthanthron, anthraquinonyl red, perylene maroon, quinacridone red pigments, diketopyrrolopyrrol, (Such as cobalt blue, phthalocyanine blue and threne blue), green pigments (such as cobalt blue, quinacridone violet and dioxazine violet), blue pigments Non-green, etc.), metallic pigments (such as aluminum powder, bronze powder, copper powder, tin powder, iron phosphate and zinc powder), pearl luster pigments (metal oxide coated mica powder and mica- Silica, barium carbonate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white and gloss white).

Examples of the dyes include azo dyes (such as monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbenazo dyes and thiazoazo dyes), anthraquinone dyes (such as anthraquinone derivatives and anthrone derivatives) (Azine dyes, oxazine dyes, oxadiazine dyes, etc.), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes and acridine dyes etc.) And thiazine dyes), methine dyes (such as polymethine (or cyanine) dyes and azomethine dyes), quinoline dyes, nitro dyes, nitrone dyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes, Dye and the like.

From the viewpoints of handleability 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 a dye with water. When a color paste is prepared from a pigment or a dye, a dispersant may be used if necessary. The content of water in the color paste is about 50 to 95% by weight.

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

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

The amount of the assembly stabilizer to be used is preferably from 0.2 to 2.3 based on the weight of the (co) polymer (A) based on the weight of the binder, the granulating agent, the colorant and the (co) polymer (A) And more preferably 0.5 to 1.5.

In the base coating step (1), the mixing method is not particularly limited and mixing can be carried out by a known method. As the mixing device, a disper, a two-axis mixer, a butterfly mixer, and a planetary mixer can be used.

In the granulation step (2), there is no limitation as long as the granular aqueous solution is composed of the above granulating agent and water, but the granulating agent concentration is preferably about 2 to 15% by weight.

The method of mixing the granule aqueous solution and the base paint is not particularly limited and may be added and mixed by a known method. As the mixing apparatus, a disper, a wire net, a twin-screw mixer, a butterfly mixer, a planetary mixer, or the like may be used, and a disper is preferable.

The amount (weight%) of the granular aqueous solution used is preferably 30 to 70, more preferably 40 to 60, based on the weight of the base paint and granular aqueous solution. The amount (weight%) of the base paint to be used is preferably 30 to 70, more preferably 40 to 60, based on the weight of the base paint and the granular aqueous solution.

The number average particle diameter of the particles contained in the slurry is the average number of at least 20 of these particles measured by visual observation.

The multicolored paint can be obtained by mixing at least two kinds of slurries of the color particles with a clear paint.

The clear paint can be obtained by mixing a binder and water.

The binder is not particularly limited as long as it can be used for a colorful paint, and may be the same as or different from the binder used for the base paint.

The content of the binder is preferably 30 to 65% by weight based on the weight of the binder and water. The content of water is preferably 35 to 70% by weight based on the weight of the binder and water.

The amount of the slurry of the color particles is preferably about 40 to 70% by weight based on the weight of the slurry of the color particles and the clear paint. The amount of the clear paint to be used is preferably about 30 to 60% by weight based on the weight of the slurry of the color particles and the clear paint.

A method of mixing the clear paint with at least two kinds of the slurries of the color particles is not particularly limited and a known method can be applied. As the mixing device, a disper, a two-axis mixer, a butterfly mixer, and a planetary mixer can be used.

A gloss removing agent, a viscosity adjusting agent, a pH adjusting agent, a dispersing agent, an antifoaming agent, an antiseptic agent, a coagulation assistant and / or a cryoprotectant may be appropriately added to the multicolored paint.

Example

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited thereto. Unless specifically stated below, " parts " means " parts by weight " and "% "

≪ Example 1 >

80 parts of ion-exchanged water and 20 parts of isopropyl alcohol were fed into a pressure-resistant reaction vessel equipped with a dropping line, a stirring device and a thermometer, 200 parts of acrylic acid and 50 parts of a 40% aqueous sodium persulfate solution were separately added The reaction was carried out under a closed condition while dropping at a constant rate over time. The reaction temperature was maintained at 80 to 100 ° C. After completion of the dropwise addition, the mixture was maintained at 95 to 100 캜 for 2 hours, 200 parts of ion-exchanged water was dropped (hereinafter, the operation of dropping ion-exchanged water was referred to as "water addition") and isopropyl alcohol was removed under reduced pressure , Cooled to 30 캜, and 231.1 parts of a 48% sodium hydroxide aqueous solution (reagent grade, Kanto Kagaku Co., Ltd.) was gradually added thereto while maintaining the temperature at 40 캜 or lower with stirring. Then, the concentration was adjusted to 30% by adding water to obtain the granulation stabilizer (1) [sodium acrylate salt polymer] for the multicolor paint of the present invention. The weight average molecular weight was 50,000 and the molecular weight distribution (Mw / Mn) was 2.5.

≪ Example 2 >

80 parts of ion exchanged water, 20 parts of isopropyl alcohol, 50 parts of 40% sodium persulfate aqueous solution and 231.1 parts of 48% sodium hydroxide aqueous solution were respectively added to 390 parts of ion-exchanged water, 10 parts of isopropyl alcohol 10 (2) of the present invention was prepared in the same manner as in Example 1, except that "40 parts aqueous solution of sodium persulfate", "25 parts aqueous solution of sodium persulfate" and "208 parts aqueous solution of 48% sodium hydroxide" Sodium salt (90 mol%) -acrylic acid (10 mol%) copolymer, concentration 30%]. The weight-average molecular weight was 100,000 and the molecular weight distribution (Mw / Mn) was 3. [

≪ Example 3 >

80 parts of ion-exchanged water, 20 parts of isopropyl alcohol, 50 parts of 40% sodium persulfate aqueous solution and 231.1 parts of 48% sodium hydroxide aqueous solution were added to 199.9 parts of ion-exchanged water, 0.1 part of isopropyl alcohol 0.1 (3) of the present invention [acrylic acid (3 parts by weight) ")," 40 parts by weight of sodium persulfate aqueous solution "and" 48 parts by weight of sodium hydroxide aqueous solution (219.5 parts by weight " Sodium salt (95 mol%) -acrylic acid (5 mol%) copolymer, concentration 30%]. The weight average molecular weight was 200,000, and the molecular weight distribution (Mw / Mn) was 3.5.

<Example 4>

80 parts of ion-exchanged water, 20 parts of isopropyl alcohol, 50 parts of a 40% sodium persulfate aqueous solution and 231.1 parts of an aqueous 48% sodium hydroxide solution were added to 720 parts of ion-exchanged water and 80 parts of isopropyl alcohol 80 Of the granular coating material (4) of the present invention [acrylic acid (4 parts by mass) "," 10 parts by mass of sodium persulfate aqueous solution "and" 184.9 parts by mass of 48% sodium hydroxide aqueous solution " Sodium salt (80 mol%) -acrylic acid (20 mol%) copolymer, concentration 30%]. The weight-average molecular weight was 400,000 and the molecular weight distribution (Mw / Mn) was 4.5.

&Lt; Example 5 &gt;

80 parts of ion-exchanged water, 20 parts of isopropyl alcohol, 50 parts of a 40% sodium persulfate aqueous solution and 231.1 parts of an aqueous 48% sodium hydroxide solution were respectively added to 999.9 parts of ion-exchanged water, 0.1 parts of isopropyl alcohol 0.1 Of the present invention was changed to "10 parts of aqueous solution of sodium persulfate", "10 parts of aqueous sodium persulfate solution" and "23.1 parts of aqueous 48% sodium hydroxide solution" Sodium salt (10 mol%) -acrylic acid (90 mol%) copolymer, concentration 30%]. The weight-average molecular weight was 500,000 and the molecular weight distribution (Mw / Mn) was 5.5.

&Lt; Example 6 &gt;

80 parts of ion-exchanged water, 20 parts of isopropyl alcohol, 50 parts of 40% sodium persulfate aqueous solution and 231.1 parts of 48% sodium hydroxide aqueous solution were added to 599.6 parts of ion-exchanged water, 0.6 parts of isopropyl alcohol 0.6 Of the present invention was changed to "10 parts of ammonium persulfate aqueous solution, 20 parts of ammonium persulfate aqueous solution, 20 parts of 10% ammonium persulfate aqueous solution and 84.2 parts of 28% ammonium aqueous solution" Ammonium salt (50 mol%) -acrylic acid (50 mol%) copolymer, concentration 30%]. The weight-average molecular weight was 300,000 and the molecular weight distribution (Mw / Mn) was 4. [

&Lt; Example 7 &gt;

1050 parts of ion-exchanged water and 100 parts of maleic anhydride were charged into a pressure-resistant reaction vessel equipped with a dropping line, a stirring device and a thermometer, and 50 parts of acrylic acid and 4.5 parts of a 10% aqueous sodium persulfate solution were separately added The reaction was carried out under a closed condition while dropping at a constant rate over time. The reaction temperature was maintained at 80 to 90 ° C. After completion of the dropwise addition, the mixture was maintained at 95 to 100 캜 for 2 hours, cooled to 30 캜, and 273.3 parts of 40% sodium hydroxide was gradually added thereto while stirring was maintained at 40 캜 or lower. And the concentration was adjusted to 30% to obtain a granulation stabilizer (7) (sodium acrylate (40 mol%)-maleic acid sodium salt (60 mol%) copolymer) for the multicolor paint of the present invention. The weight-average molecular weight was 700,000 and the molecular weight distribution (Mw / Mn) was 5.5.

&Lt; Example 8 &gt;

900 parts of ion-exchanged water was charged 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 10% aqueous sodium persulfate solution were separately added The reaction was carried out under a closed condition while dropping at a constant rate over time. The reaction temperature was maintained at 80 to 90 ° C. After completion of the dropwise addition, the mixture was maintained at 95 to 100 캜 for 2 hours, cooled to 30 캜, and 174.4 parts of 40% sodium hydroxide was slowly added thereto while stirring was maintained at 40 캜 or lower. The mixture was adjusted to a concentration of 30% to obtain a granulation stabilizer (8) (sodium acrylate (99 mol%) - acrylonitrile (1 mol%) copolymer) for the multicolor paint of the present invention. The weight average molecular weight was 1 million, and the molecular weight distribution (Mw / Mn) was 6. [

&Lt; Example 9 &gt;

900 parts of ion-exchanged water, 99.2 parts of acrylic acid, 0.8 parts 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- Acrylic acid 106 parts "," acrylamide 94 parts "," 10% sodium persulfate 20 parts "and" 40% sodium hydroxide 279.3 parts " (53% by mole) -acrylamide (47% by mole) copolymer (concentration: 30%) was obtained. Also, the weight average molecular weight was 350,000 and the molecular weight distribution (Mw / Mn) was 4.2.

&Lt; Example 10 &gt;

100 parts of the granulation stabilizer (1) (sodium acrylate salt polymer) obtained in Example 1 and 0.1 part of dipropylene glycol (B1) were heated to 40 DEG C with stirring and uniformly stirred and mixed at this temperature to prepare the multi- Stabilizer (10) was obtained.

&Lt; Example 11 &gt;

100 parts of the granulation stabilizer (3) (the sodium salt of acrylic acid (95 mol%) and acrylic acid (5 mol%)) obtained in Example 3 and 10 parts of polyethylene glycol (B2) (number average molecular weight: 400) The mixture was uniformly stirred and mixed at this temperature to obtain a granulation stabilizer (11) for a multicolor paint of the present invention.

&Lt; Example 12 &gt;

100 parts of the granulation stabilizer (5) (sodium acrylate (10 mol%) -acrylic acid (90 mol%) copolymer) and 0.8 part of glycerin (B3) obtained in Example 5 were heated to 40 DEG C with stirring, Followed by stirring and mixing to obtain a granulation stabilizer (12) for a multicolor paint of the present invention.

&Lt; Example 13 &gt;

A granulation stabilizer (13) for a multicolored paint of the present invention was obtained in the same manner as in Example 12 except that "glycerin (B3) 0.8 part" was changed to "glycerin (B3) 5 parts".

&Lt; Example 14 &gt;

100 parts of the granulation stabilizer (7) (sodium acrylate (40 mol%) - maleic acid sodium salt (60 mol%) copolymer) and 8 parts of diglycerin (B4) obtained in Example 7 were heated to 40 캜 with stirring, And uniformly stirred and mixed at this temperature to obtain a granulation stabilizer (14) for a multicolor paint of the present invention.

&Lt; Example 15 &gt;

100 parts of the granulation stabilizer (9) (sodium acrylate (53 mol%) - acrylamide (47 mol%) copolymer) obtained in Example 9 and 0.5 part of isoprene glycol (B5) were heated to 40 캜 with stirring, To obtain a granulation stabilizer (15) for a multicolor paint of the present invention.

&Lt; Comparative Example 1 &

100 parts of ion-exchanged water and 100 parts of isopropyl alcohol were charged into a pressure-resistant reaction vessel equipped with a dropping line, a stirring device and a thermometer, and 300 parts of acrylic acid and 90 parts of a 40% aqueous sodium persulfate solution were separately added The reaction was carried out under a closed condition while dropping at a constant rate over time. The reaction temperature was maintained at 80 to 100 ° C. After completion of the dropwise addition, isopropyl alcohol was removed under reduced pressure while 200 parts of ion-exchanged water was added dropwise (maintained at 95 to 100 ° C for 2 hours), and then the mixture was cooled to 30 ° C and adjusted to a concentration of 30% To thereby obtain a comparative granulation stabilizer (16) [acrylic acid polymer]. The weight average molecular weight was 2.5 thousands and the molecular weight distribution (Mw / Mn) was 1.8.

&Lt; Comparative Example 2 &

100 parts of ion-exchanged water, 100 parts of isopropyl alcohol, 300 parts of acrylic acid and 90 parts of 40% aqueous sodium persulfate were mixed with 60 parts of ion-exchanged water, 140 parts of isopropyl alcohol, Acrylic acid 300 parts &quot; and &quot; 40% aqueous sodium persulfate 90 parts &quot;, and &quot; adjusted to 30% by cooling to 30 DEG C and adjusting the concentration to 30% &quot; , And 395.3 parts of a 48% sodium hydroxide aqueous solution was gradually added thereto. Acrylic acid (5 mol%) -acrylic acid sodium salt (95 mol%) copolymer (Comparative Example 1) was prepared in the same manner as in Comparative Example 1, ]. The weight-average molecular weight was 1.5, and the molecular weight distribution (Mw / Mn) was 1.3.

&Lt; Comparative Example 3 &

500 parts of ion-exchanged water and 10 parts of isopropyl alcohol were charged 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 a 50% aqueous sodium persulfate solution were separately added The reaction was carried out under a closed condition while dropping at a constant rate over time. The reaction temperature was maintained at 80 to 100 ° C. After completion of the dropwise addition, after maintaining the temperature at 95 to 100 ° C for 1 hour, isopropyl alcohol was removed under reduced pressure while 200 parts of ion-exchanged water was added dropwise (stirred), and then cooled to 30 ° C. And 69.3 parts of a 48% sodium hydroxide aqueous solution was gradually added thereto. And the concentration was adjusted to 30% by adding water to obtain a comparative granulation stabilizer 18 (sodium acrylate salt polymer). The weight-average molecular weight was 1.3 million, and the molecular weight distribution (Mw / Mn) was 6.5.

&Lt; Comparative Example 4 &

100 parts of the comparative granulation stabilizer (16) [acrylic acid polymer] obtained in Comparative Example 1 and 15 parts of dipropylene glycol (B1) were heated to 40 占 폚 while stirring and homogeneously stirred and mixed at this temperature to prepare a comparative granulation stabilizer (19) .

Using the granulation stabilizers (1) to (19) obtained in the Examples and Comparative Examples, the color particle slurry for evaluation was prepared as follows, and the stability of color particles was evaluated. The results are shown below.

&Lt; Preparation of Base Coating (1) &gt;

The base components (C1 to 19) were obtained by mixing the components shown in Table 1 with a tablet disper.

(Note 1) Binder: Acrylic resin emulsion (water concentration 50%): Bronze CE-6400, DIC Co., Ltd. "Bronco" is a registered trademark of the company.

(Note 2) Assembling agent: Modified silicate, Laponite S482, BICKEMI Japan Co., Ltd.

(Note 3) Red paste: Concentrated colourant for water-based paints Unilant Red, Yokohama Chemical Co., Ltd., "unirant" is a registered trademark of the company. Water concentration 50%

(Note 4) Thickener: SN-Sikner 640, Sanofco Co., Ltd.

(Note 5) Dispersing agent: Nopole 5200, Sanofco Co., Ltd., "Noppe Cole" is a registered trademark of the company.

(Note 6) Antifoaming agent: Nopko NXZ, Sanofco Corporation, "NXZ" are registered trademarks of the company.

(Note 7) Temp aid: TEXANOL, Eastman Chemical Co., Ltd., "TEXANOL" is a registered trademark of YOSHIMURA OIL CHEMICAL CO., LTD.

&Lt; Preparation of base paint (2) &gt;

Yellow paste (concentrated colorant for water-based paints unilant yellow, Yokohama Kasei Co., Ltd., water concentration 50%) "and" assembly stabilizer (3) 4) and (19) ", base coatings (C20 to 22) were obtained in the same manner as in the preparation of base coating (1).

&Lt; Preparation of Base Coating (3) &gt;

(Concentration of 60% of water) "and" assembly stabilizer (3), (1) to (19) "as" black paste (concentrated colorant for aqueous paint, unilant black, Yokohama Chemical Co., 4) and (19) ", base coating materials (C23 to 25) were obtained in the same manner as in the preparation of base coating (1).

&Lt; Preparation of Base Coating (4) &gt;

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

<Preparation of color particle slurry>

200 g of each of the above base coatings (C1 to 26) and 200 g of a 10% aqueous solution of a granulating agent (Laponite S482, produced by Big Chem Japan Co., Ltd.) was dispersed in a tabletop disposer (ED-11, To obtain a color particle slurry for evaluation.

<Evaluation of Stability of Color Particles>

(1) The amount of particles contained in the color particle slurry in each of (a) immediately after the preparation, (b) in the sealed container, after being left at 50 ° C for 1 day, The shortest particle diameter was measured with the naked eye, and 20 number average values were calculated (number average particle diameter).

(2) Immediately after the preparation of the color particle slurry, it was transferred to a 500-ml measuring cylinder, and the state of separation of the color particle slurry was visually observed in the closed vessel at 50 캜 for one week, The volume percentage of the volume of the solution portion was calculated (separation degree).

- &quot; indicates that the shape of the color particles is collapsed (the shortest particle diameter is impossible to measure), and the colored layer (lower layer) and the transparent water layer (upper layer) are separated.

As described above, the granulation stabilizer for the multicolored paint of the present invention was superior to the granulation stabilizer for comparison in stability of color particles.

&Lt; Example 16 &gt;

, 900 parts of a binder (Yuko UWS-145, Sanyo Kasei Kogyo Co., Ltd., "YuKote" is a registered trademark of its own company), 20 parts of a film-forming auxiliary agent (TEXANOL, Eastman Chemical Japan Co., Ltd.) ED-11, Japan Kogyo Kogyo Co., Ltd.) to prepare a clear paint.

50 g of each of the color particle slurries (C3), (C20) and (C23) obtained in &lt; Preparation of color particle slurry &gt; and 200 g of clear paint were dispersed in a tabletop disperator ED-11 (400 rpm, ) To obtain a multicolor paint (1).

&Lt; Example 17 &gt;

Was the same as that of Example 16 except that "50 g of each of the color particle slurries (C3), (C20), and (C23)" was changed to "80 g of each of the color particle slurries (C4), (C21) To obtain a colorful paint (2).

&Lt; Comparative Example 5 &

Except that the color particle slurries (C3), (C20) and (C23) were changed to the color particle slurries C19, C22 and C25, Shaped paint.

<Evaluation of stability of colorful paint>

(1) The shortest particle size of the particles included in the multicolored paint was visually observed immediately after the preparation (a) and after leaving for one week in the sealed container (b) at 50 DEG C, (Number average particle diameter).

(2) The mixture of red, yellow and black particles was visually observed (with or without mixing) immediately after the preparation, (b) in the sealed container and after leaving for 1 week at 50 ° C.

As described above, since the granulation stabilizer for the multicolor paint of the present invention has better stability of the color granules as compared with the granulation stabilizer for comparison, the multicolor paint can be stably stored.

Claims (7)

(Co) polymer (A) having an ethylenically unsaturated carboxylic acid (salt) as an essential constituent monomer and having a weight average molecular weight of 50,000 to 1,000,000, ) Stabilizer. The method according to claim 1,
Wherein the ethylenically unsaturated carboxylic acid salt is an alkali metal salt, an amine salt or a quaternary organic ammonium salt. 3. The method according to claim 1 or 2,
Wherein the content of the ethylenically unsaturated carboxylic acid unit is from 0 to 90 mol%, the content of the ethylenically unsaturated carboxylic acid salt unit is from 10 to 100 mol%, and the content of the ethylenically unsaturated carboxylic acid unit is from 10 to 100 mol%, based on the number of moles of the ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic acid salt. In assembly stabilizer. 4. The method according to any one of claims 1 to 3,
(Co) polymer (A) has a molecular weight distribution (Mw / Mn) of 2.5 to 6.0. 5. The method according to any one of claims 1 to 4,
Further comprising a water-soluble polyvalent alcohol (B). 6. The method of claim 5,
Wherein the content of the water-soluble polyhydric alcohol (B) is 0.1 to 10% by weight based on the weight of the (co) polymer (A). (1) for obtaining a base paint by mixing a binder, a granulating agent, a colorant, water and a granulation stabilizer for a multicolored paint according to any one of claims 1 to 6, and
(2) of mixing a granular aqueous solution and a base paint to obtain a slurry containing particles having a number average particle diameter of 1 to 20 mm.