JP6901785B2 - Granulation stabilizer for multicolored paints - Google Patents

Description

The present invention relates to a granulation stabilizer for a multicolored pattern paint.

As a method for producing a multicolored pattern paint, an aqueous medium containing an aqueous liquid composition (A) containing an aqueous resin (a), a colorant (b) and a water-soluble polysaccharide (c) and a metal compound (d) ( A method for producing a granular gel (C) comprising contacting with B), characterized in that the metal compound (d) contains an organic acid metal salt (d1) as a part of its components. A method for producing a granular gel (C) to be produced is known (Patent Document 1).

Japanese Patent Application Laid-Open No. 2008-202037 (Corresponding People's Republic of China Patent Publication: CN101230141A)

In the multicolored pattern paint obtained by the conventional manufacturing method, the color particles of different colors are coalesced to cause color mixing or the colored particles are agglomerated due to insufficient stability of the colored particles. There is a problem that it may happen.
An object of the present invention is to provide a granulation stabilizer capable of stably storing a multicolored pattern paint, that is, a granulation stabilizer having excellent stability of colored particles, and to facilitate a multicolored pattern paint having excellent storage stability. Is to provide a method that can be manufactured.

The feature of the granulation stabilizer for multicolored pattern paints of the present invention is that the ethylenically unsaturated carboxylic acid (salt) is an essential constituent monomer, and the weight average molecular weight is 50,000 to 1,000,000 (co) polymer (co) Ri greens contain a),
The molecular weight distribution of a (co) polymer (A) (Mw / Mn) is summarized as points Ru der 2.5 to 6.0.

The features of the method for producing a multi-pattern paint of the present invention are the base paint-making step (1) of mixing a binder, a granulator, a colorant, water and the above-mentioned granulation stabilizer for a multi-pattern paint to obtain a base paint. ,
The gist is that it includes a granulation step (2) of mixing an aqueous solution of a granulator and a base paint to obtain a slurry containing particles having a number average particle diameter of 1 to 20 mm.

Since the granulation stabilizer for a multicolored pattern paint of the present invention is excellent in the stability of colored particles, the multicolored pattern paint can be stably stored. That is, it is excellent in storage stability of various pattern paints.

Since the method for producing a multicolored pattern paint of the present invention uses the above-mentioned granulation stabilizer for multicolored pattern paint, it is possible to easily manufacture a multicolored pattern paint having excellent storage stability.

The ethylenically unsaturated carboxylic acid (salt) includes an ethylenically unsaturated monocarboxylic acid, an ethylenically unsaturated dicarboxylic acid, and salts thereof.

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

As the aliphatic monocarboxylic acid, (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-3-butenoic acid, 2-methyl-2-butenoic acid, 2-ethyl-2-propenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-methyl- 2-Pentenoic acid, 2-Heptenoic acid, 4,4-dimethyl-2-pentenic acid, 2-octenoic acid, 3-methyl-2-heptenoic acid, 2-nonenoic acid, 3-methyl-2-octenoic acid, 2 -Decenoic acid, 2-hydroxypropenic acid and the like can be mentioned.
"(Meta) Acri ..." means methacryl ..., Acri ... (the same shall apply hereinafter).

Examples of the alicyclic monocarboxylic acid include 1-cyclopentenecarboxylic acid, 3-cyclopentenecarboxylic acid, 4-cyclopentenecarboxylic acid, 1-cyclohexenecarboxylic acid, 3-cyclohexenecarboxylic acid, 4-cyclohexenecarboxylic acid, and 1-cycloheptene. Carboxylic acid, 3-cycloheptenecarboxylic acid, 4-cycloheptenecarboxylic acid, 5-cycloheptenecarboxylic acid, 1-cyclooctenecarboxylic acid, 3-cyclooctenecarboxylic acid, 4-cyclooctenecarboxylic acid, 5- Cyclooctenecarboxylic acid, 1-cyclononencarboxylic acid, 3-cyclononencarboxylic acid, 4-cyclononencarboxylic acid, 5-cyclononencarboxylic acid, 1-cyclodecenecarboxylic acid, 3-cyclodecenecarboxylic acid, 4-cyclo Examples thereof include decenecarboxylic acid and 5-cyclodecenecarboxylic acid.

Examples of the aromatic monocarboxylic acid include o-styrene carboxylic acid, p-styrene carboxylic acid, cinnamic acid, atropic acid, 5-vinyl-1-naphthalene carboxylic acid, 4-vinyl-1-naphthalene carboxylic acid and 4-vinyl-. 1-Anthracinone carboxylic acid and the like can be mentioned.

As the unsaturated dicarboxylic acid, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid, an intramolecular acid anhydride 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-pentenylic acid, 3-pentenoic acid, 4-pentenoic acid, and 2-methyl-2-butenedi. Acids, 2-ethyl-2-propenic acid, 2-hexenedioic acid, 2-heptenedioic acid, 2-octenoic acid, 3-methyl-2-heptendioic acid, 2-nonendioic acid, 2-decenedioic acid and Examples thereof include 2-hydroxyptenrodioic acid.

Examples of the alicyclic dicarboxylic acid include 1,2-cyclopentenedicarboxylic acid, 1,3-cyclopentendicarboxylic acid, 1,4-cyclopentendicarboxylic acid, 1,2-cyclohexendicarboxylic acid, 1,3-cyclohexendicarboxylic acid, 1, 4-Cyclohexendicarboxylic 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-cyclooctendicarboxylic acid, 1,2-cyclononendicarboxylic acid, 1,3-cyclononendicarboxylic acid, 1,4-Cyclononendicarboxylic acid, 1,5-cyclononendicarboxylic acid, 1,2-cyclodecendicarboxylic acid, 1,3-cyclodecendicarboxylic acid, 1,4-cyclodecendicarboxylic acid and 1,5-cyclo Examples thereof include decendicarboxylic acid.

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

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

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

Examples of these salts include metal salts of ethylenically unsaturated carboxylic acids, amine salts, ammonium salts and the like.

As the metal salt, an alkali metal or an alkaline earth metal salt or the like can be used.
Examples of the alkali metal include lithium, potassium, sodium and the like.
Examples of the alkaline earth metal include calcium and magnesium.

As the amine salt, salts such as an aliphatic amine having 2 to 6 carbon atoms, an alicyclic amine having 3 to 6 carbon atoms, and 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, ethylenediamine and the like.

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

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

As the ammonium salt, an inorganic ammonium (NH 4 ^₊₎ salts and quaternary organic ammonium salts can be used.
As the quaternary organic ammonium salt, an organic ammonium salt having 4 to 8 carbon atoms can be used, and a tetramethylammonium salt, a tetraethylammonium salt, a trimethylethylammonium salt, an N-methylpyridinium salt, an N-methylimidazolium salt and the like can be used. Can be mentioned.

Of these salts, alkali metal salts, amine salts and quaternary organic ammonium salts are preferable, and more preferably lithium salts, potassium salts, sodium salts and quaternary organic ammonium salts, from the viewpoint of the stability of colored particles. Particularly preferred are sodium salts and quaternary organic ammonium salts.

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

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

The (co) polymer (A) may contain other monomers in addition to 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, ethylenically unsaturated amides, and the like.

Examples of olefins include α-olefins having 2 to 20 carbon atoms (ethylene, propylene, butylene, hexylene, octylene, undecylene, tetradecylene, nonadecilene, etc.), diisobutylene, butadiene, piperylene, chloroprene, pinene, limonene, indene, cyclopentadiene. , Bicyclopentadiene, etylidene norbornene and the like.

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

The ethylenically unsaturated amides include (meth) acrylamide, N-methyl (meth) acrylamide, N-2-hydroxymethyl (meth) acrylamide, N- (2-aminoethyl) (meth) acrylamide and N- (2-). Examples thereof include dimethylaminoethyl) (meth) acrylamide.

When other monomers are included as constituent monomers, the content (mol%) of the other monomer units is based on the number of moles of the ethylenically unsaturated carboxylic acid unit and the ethylenically unsaturated carboxylic acid salt unit. It is preferably 1 to 90, more 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 50,000 to 1,000,000, more preferably 100,000 to 700,000, and particularly preferably 150,000 to 50, from the viewpoint of the stability of the colored particles. 10,000, most preferably 200,000-400,000. 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 a gel permeation chromatography (GPC) method using (poly) ethylene glycol having a known molecular weight as a standard substance (column temperature 40 ° C., elution). Liquid Methanol: Ion-exchanged water: Sodium acetate = 800: 1200: 15 (weight ratio), flow velocity 0.8 ml / min, sample concentration: 0.4 wt% eluent solution).

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

The (co) polymer (A) is produced by polymerizing an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid salt, and other monomers as necessary (method 1); ethylenically unsaturated. A method (method 2) in which a carboxylic acid and other monomers are polymerized, if necessary, and then neutralized with a base (alkali metal hydroxide, ammonia, etc.); and these (method 1) and It can be obtained by a method (method 3) or the like in which (method 2) is used in combination.

A polymerization catalyst can be used for the polymerization. As the polymerization catalyst, an ordinary polymerization catalyst or the like is used, and an azo compound, a persulfate, an inorganic peroxide, a redox catalyst, an organic peroxide and the like are included. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile, 2, 2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-arbonitrile), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2' -Azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile], 1,1'-azobis (1-acetoxy1-phenylethane) and the like can be mentioned. Examples of the salt include ammonium persulfate, potassium persulfate, sodium persulfate and the like. Examples of the inorganic peroxide include perborate and hydrogen peroxide. Examples of the redox catalyst include ascorbic acid-hydrogenated acid and the like. Examples of the organic peroxide include benzoyl peroxide and the like. These polymerization catalysts may be used alone or in combination. Of these, persulfate and azo compound are preferable, and further. Persulfate and 2,2'-azobisisobutyronitrile are 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., based on the weight of the constituent monomers. It is 5 to 3.

Further, if necessary, a chain transfer agent for radical polymerization may be used. Examples of the chain transfer agent include thiocarboxylic acids (n-lauryl mercaptoethanol, mercaptoethanol, mercaptopropanol, etc.), thiolic acids (thioglycolic acid, thioapple acid, etc.), secondary alcohols (isopropanol, etc.), amines (dibutylamine, etc.). , Hypophosphate (sodium hypophosphate, etc.) and the like.

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

In the case of solution polymerization and suspension polymerization, the solvent used is water (tap water, ion-exchanged water, industrial water, etc.), alcohol solvent (methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, etc.) and / or aromatic solvent (such as aromatic solvent). (Toluene, xylene, etc.) 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 is preferable, and a mixed solvent of ion-exchanged water and isopropyl alcohol is particularly preferable.

When a solvent is used, the amount 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 monomer.

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

In addition, you may polymerize while dropping all or a part of the constituent monomer. Further, the polymerization may be carried out while dropping all or a part of the polymerization catalyst. Further, the whole amount or a part of the solvent may be polymerized while being dropped together with the constituent monomer or the polymerization catalyst. On the other hand, the whole amount of the solvent may be charged in the polymerization tank and polymerized while removing the solvent. Of these, from the viewpoint of productivity and the like, a method of dropping the entire amount 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 more preferably, the constituent unit. This is a method in which the entire amount of the monomer and the polymerization catalyst is added dropwise together with a part of the solvent.

The form of the (co) polymer (A) is not particularly limited, and may be liquid or solid.
When the (co) polymer (A) is liquid, it means a state in which 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 without removing all of the solvent, or the (co) polymer (A) obtained by bulk polymerization or the like. May be obtained by dissolving or dispersing in a solvent.

When the (co) polymer (A) obtained by bulk polymerization or the like is dissolved or dispersed in a solvent, the solvent may be a ketone having 1 to 6 carbon atoms (methyl isobutyl ketone, acetone, etc.) in addition to water and an alcohol solvent. ), Etc., which 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 composed of the (co) polymer (A).
In the case of a solid composed of the (co) polymer (A), it may be obtained by bulk polymerization, or after obtaining a solution or dispersion containing the (co) polymer (A) by suspension polymerization or solution polymerization, etc. It may be obtained by removing the solvent.
As a method for removing the solvent from the solution or dispersion containing the (co) polymer (A), known methods such as a freeze-drying method, a spray-drying method, and a drum-drying method can be used.
The size (mm; maximum length) of the solid (co) polymer (A) is preferably 0.01 to 5, more preferably 0, from the viewpoint of solubility of the granulation stabilizer of the present invention. It is 05 to 3, particularly preferably 0.08 to 1.
Of the forms of the (co) polymer (A), a liquid is preferable, and a state in which the (co) polymer (A) is dissolved in a solvent is more preferable.

The granulation stabilizer for multicolored pattern paints of the present invention preferably contains a water-soluble polyhydric alcohol (B).
The water-soluble polyhydric alcohol (B) is a water-soluble compound having at least two hydroxyl groups in the molecule, and is a diol {ethylene glycol, polyethylene glycol (number average molecular weight 88 to 600), propylene glycol, polypropylene glycol (number). Average molecular weight 116-950), isoprene glycol and 1,3-butylene glycol, etc.}, triol {glycerin, glycerin ethylene oxide adduct (1 to 20 moles added per mol of glycerin), glycerin propylene oxide adduct (per mol of glycerin 1 mol) Addition moles 1 to 10) and trimethyl propane, etc.}, tetraol {diglycerin, sorbitan, sorbitol ethylene oxide adduct (additional moles 1 to 20 per 1 mol of sorbitol) and alkyl glycosides (alkyl carbons 1 to 10) }, Hexaol {sorbitol, sorbitol propylene oxide adduct (number of moles added per 1 mol of sorbitol 1 to 10), etc.}, nonaol {martitol, etc.} and the like. 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 preferable, and diols and triols are more preferable.

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 based on the weight of the (co) polymer (A). , More preferably 0.5 to 8, particularly preferably 0.8 to 5. Within this range, the stability of the colored particles is further excellent.

The granulation stabilizer of the present invention includes known additives (granulation agents, thickeners, dispersants, wetting agents, film-forming aids, defoamers, antifreeze agents, etc.) used together with various pattern paints. Can be contained. These may be used alone or in combination.
When these known additives are contained, their content (% by weight) is preferably 1 to 25, more preferably 2 to 20, particularly preferably 2 to 20, based on the weight of the (co) polymer (A). Is 3-11.

When the granulation stabilizer for various pattern paints of the present invention contains a water-soluble polyhydric alcohol (B), the form of the granulation stabilizer of the present invention is (1) (co) polymer (A) and water-soluble. A form in which the polyhydric alcohol (B) is present together {it may be liquid or solid, and (A) and (B) may be reacting with each other. } Or (2) (co) polymer (A) and the water-soluble polyhydric alcohol (B) are present separately {they may be liquid or solid, respectively. Then, each of these is mixed in the multicolored pattern paint. } Can be any of them. In the case of (2), the additives contained as necessary may be contained in each of them or may be contained in any of them.

The granulation stabilizer for multicolored pattern paints of the present invention may be liquid or solid, and in the case of solid, a liquid (co) polymer (A) or a mixed liquid of this and a water-soluble polyhydric alcohol (B). A powder or solid (co) polymer (A) on which (an additive may be contained if necessary) is supported on a powder, or a mixed solid of this and a water-soluble polyhydric alcohol (B) (additive if necessary). May be included).
When a liquid granulation stabilizer for a multicolored pattern paint is supported on a powder, examples of the powder include activated carbon, calcium carbonate, silica, zeolite, silas balloon and bentonite.
As a method of supporting the powder, a method of stirring and mixing the powder and a liquid granulation stabilizer for various pattern paints by using a known stirring mixer (ribbon mixer, Henschel mixer, etc.) can be applied. ..

When the granulation stabilizer of the present invention is in the form in which the (1) (co) polymer (A) and the water-soluble polyhydric alcohol (B) are present together, the granulation stabilizer of the present invention is (1). Co) As long as the polymer (A), the water-soluble polyhydric alcohol (B), and, if necessary, the additives are uniformly mixed, there is no limitation on the production method.
In the case where the granulation stabilizer of the present invention is in the form in which the (2) (co) polymer (A) and the water-soluble polyhydric alcohol (B) are separately present, (A) and / or ( When the additive is contained in B), it can be obtained by a method of uniformly mixing the (co) polymer (A) or the water-soluble polyhydric alcohol (B) with the additive.

The method for producing the multicolored pattern paint of the present invention will be described.
The binder is not limited as long as it is a binder for various pattern paints, and includes acrylic resin, polyolefin resin, silicone resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin and so on. Examples include polycarbonate resin. Of these, acrylic resins are preferable.

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

The granulating agent is not limited as long as it is a granulating agent for multicolored pattern paint (that is, protective colloid), and organic granulating agents (methyl cellulose, ethyl cellulose, polyvinyl alcohol, casein, tragant rubber, carvalume rubber, cellulose acetate phthalate, hydroxy). Examples thereof include ethyl cellulose, polymethacrylic acid, arabic rubber, karaya rubber, gelatin, sodium alginate, albumin, pectin, xanthan gum, starch and water-soluble urea formaldehyde, etc.) and inorganic granulators (bentonite, modified metal silicate metal salt, etc.).

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

The colorant is not limited as long as it is a pigment or dye for multicolored pattern paints, and the pigments are white pigments (titanium dioxide, etc.) and black pigments (carbon black, acetylene black, lamp black, bone black, graphite, iron). Black and aniline black, etc.), yellow pigments (yellow iron oxide, titanium yellow, monoazo yellow, condensed azo yellow, azomethin yellow, bismus vanadate, benzimidazolone, isoindolinone, isoindrin, quinophthalone, benzidine yellow, permanent yellow, etc. ), Orange pigments (permanent orange, etc.), red pigments (red iron oxide, naphthol AS-based azo red, anthanthrone, anthracinol red, perylene maroon, quinacridone-based red pigment, diketopyrrolopyrrole, watching red, permanent red, etc.) , Purple pigments (cobalt purple, quinacridone violet, dioxazine violet, etc.), blue pigments (cobalt blue, phthalocyanine blue, slen blue, etc.), green pigments (phthalocyanine green, etc.), metallic pigments (aluminum powder, bronze powder, copper powder, etc.) Tin powder, iron phosphate and zinc powder, etc.), pearl luster pigments (metal oxide coated mica powder, mica-like iron oxide, etc.), extender pigments (varita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, etc. Clay, silica, white carbon, diatomaceous soil, talc, magnesium carbonate, alumina white, gloss white, etc.) and the like.

Examples of dyes include azo dyes (monoazo dyes, polyazo dyes, metal complex salt azo dyes, pyrazolone azo dyes, stillben azo dyes and thiazole azo dyes, etc.), anthraquinone dyes (anthraquinone derivatives and antron derivatives, etc.), indigoid dyes (indigo derivatives and thioindigo dyes). Derivatives, etc.), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (azine dyes, oxazine dyes, thiazine dyes, etc.), methine dyes (polymethine (or cyanine) dyes, and (Adimethine dye, etc.), quinoline dye, nitro dye, nitron dye, benzoquinone and naphthiquinone dye, naphthalimide dye, perinone dye and the like.

From the viewpoint of handleability and the like, as the colorant, a commercially available color paste may be used as it is, or a color paste may be prepared and used by mixing a pigment or dye with water. When preparing a color paste from pigments or dyes, dispersants can be used, if desired. The content of water in the color paste is about 50 to 95% by weight.

The usage fee (% by weight) of the colorant is preferably 29.5 to 60.2, more preferably 39 to 52, based on the weight of the binder, the granulator, the colorant and the (co) polymer (A). is there.

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

The amount of the granulation stabilizer used is the weight% of the (co) polymer (A), and the weight of the binder, the granulation agent, the colorant and the (co) polymer (A) from the viewpoint of the stability of the colored particles. Based on the above, 0.2 to 2.3 is preferable, and 0.5 to 1.5 is more preferable.

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

In the granulation step (2), the aqueous solution of the granulator is not limited as long as it is composed of the above-mentioned granulator and water, but the concentration of the granulator is preferably about 2 to 15% by weight.
The method for mixing the granulant aqueous solution and the base coating material is not particularly limited, and can be added and mixed by a known method. As the mixing device, a disper, a wire mesh, a twin-screw mixer, a butterfly mixer, a planetary mixer and the like can be used, but the disper is preferable.
The amount (% by weight) of the granulating agent aqueous solution used is preferably 30 to 70, more preferably 40 to 60, based on the weight of the base paint and the granulating agent aqueous solution. The amount (% by weight) of the base paint used is preferably 30 to 70, more preferably 40 to 60, based on the weight of the base paint and the aqueous granulating agent solution.

The number average particle size of the particles contained in the slurry is a number average value of at least 20 of these particles by visually measuring the shortest particle size of the particles.

The multicolored pattern paint can be obtained by mixing at least two types of the above-mentioned color particle slurry and a clear paint.

The clear paint can be obtained by mixing the binder and water.
The binder is not limited as long as it can be used for a multicolored pattern 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 water content is preferably 35 to 70% by weight based on the weight of the binder and water.

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

The method of mixing at least two kinds of the above-mentioned slurry of colored particles and the clear paint is not particularly limited, and a known method can be applied. As the mixing device, a disper, a twin-screw mixer, a butterfly mixer, a planetary mixer and the like can be used.

A matting agent, a viscosity regulator, a pH adjusting agent, a dispersant, a defoaming agent, a preservative, a film-forming auxiliary and / or an antifreezing agent and the like can be appropriately added to the multicolored pattern paint, if necessary. ..

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

<Example 1>
80 parts of ion-exchanged water and 20 parts of isopropyl alcohol are 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% sodium persulfate aqueous solution are separately dropped lines under stirring. The reaction was carried out in a hermetically sealed manner while dropping at a constant rate over 3 hours. The reaction temperature was maintained at 80-100 ° C. After completion of the dropping, the temperature was maintained at 95 to 100 ° C. for 2 hours, and then 200 parts of ion-exchanged water was dropped (hereinafter, the operation of dropping the ion-exchanged water is abbreviated as water) to remove isopropyl alcohol under reduced pressure. The mixture was cooled to 30 ° C., and 231.1 parts of a 48% aqueous sodium hydroxide solution (special grade reagent, Kanto Chemical Co., Ltd.) was gradually added in portions while keeping the temperature below 40 ° C. under stirring. Then, water was added to adjust the concentration to 30% to obtain the granulation stabilizer (1) [sodium acrylate polymer] for various pattern paints 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", respectively, "390 parts of ion-exchanged water", The same as in Example 1 except that it was changed to "10 parts of isopropyl alcohol", "25 parts of 40% sodium persulfate aqueous solution" and "208 parts of 48% sodium hydroxide aqueous solution". A grain stabilizer (2) [sodium acrylate (90 mol%) -acrylic acid (10 mol%) copolymer; concentration 30%] was obtained. 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", respectively, "199.9 parts of ion-exchanged water" , "0.1 part of isopropyl alcohol", "15 parts of 40% sodium persulfate aqueous solution" and "219.5 parts of 48% sodium hydroxide aqueous solution", but in the same manner as in Example 1, the present invention. (3) [Sodium acrylate (95 mol%) -acrylic acid (5 mol%) copolymer; concentration 30%] was obtained. 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 40% sodium persulfate aqueous solution" and "231.1 parts of 48% sodium hydroxide aqueous solution", respectively, "720 parts of ion-exchanged water", The colorful pattern coating material of the present invention is the same as in Example 1 except that it is changed to "80 parts of isopropyl alcohol", "10 parts of 10% sodium persulfate aqueous solution" and "184.9 parts of 48% sodium hydroxide aqueous solution". Granule stabilizer (4) [sodium acrylate (80 mol%) -acrylic acid (20 mol%) copolymer; concentration 30%] was obtained. The weight average molecular weight was 400,000, and the molecular weight distribution (Mw / Mn) was 4.5.

<Example 5>
"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", respectively, "999.9 parts of ion-exchanged water" , "0.1 part of isopropyl alcohol", "10 parts of 10% sodium persulfate aqueous solution" and "23.1 parts of 48% sodium hydroxide aqueous solution", but in the same manner as in Example 1, the present invention. (5) [Sodium acrylate (10 mol%) -acrylic acid (90 mol%) copolymer; concentration 30%] was obtained. The weight average molecular weight was 500,000, and the molecular weight distribution (Mw / Mn) was 5.5.

<Example 6>
"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", respectively, "599.6 parts of ion-exchanged water" , "0.6 parts of isopropyl alcohol", "20 parts of 10% ammonium persulfate aqueous solution" and "84.2 parts of 28% ammonium persulfate aqueous solution". A granulation stabilizer for paint (6) [ammonium acrylate salt (50 mol%) -acrylic acid (50 mol%) copolymer; concentration 30%] was obtained. The weight average molecular weight was 300,000, and the molecular weight distribution (Mw / Mn) was 4.

<Example 7>
Add 1050 parts of ion-exchanged water and 100 parts of maleic anhydride to a pressure-resistant reaction vessel equipped with a dropping line, agitator and a thermometer, and under stirring, separate 50 parts of acrylic acid and 4.5 parts of a 10% sodium persulfate aqueous solution. The reaction was carried out in a hermetically sealed manner while dropping at a constant rate over 2 hours from the dropping line of. The reaction temperature was maintained at 80-90 ° C. After completion of the dropping, the mixture was kept at 95 to 100 ° C. for 2 hours, cooled to 30 ° C., and gradually added 273.3 parts of 40% sodium hydroxide in portions while keeping the temperature below 40 ° C. under stirring. Then, water is added to adjust the concentration to 30%, and the granulation stabilizer (7) [sodium acrylic acid salt (40 mol%) -sodium maleate salt (60 mol%) copolymer for various pattern paints of the present invention is used. ] Was obtained. The weight average molecular weight was 700,000, 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 under stirring, 99.2 parts of acrylic acid, 0.8 parts of acrylonitrile and 1 part of a 10% sodium persulfate aqueous solution were separately separated. The reaction was carried out in a hermetically sealed manner while dropping at a constant rate over 2 hours from the dropping line of. The reaction temperature was maintained at 80-90 ° C. After completion of the dropping, the mixture was kept at 95 to 100 ° C. for 2 hours, cooled to 30 ° C., and gradually added 174.4 parts of 40% sodium hydroxide in portions while keeping the temperature below 40 ° C. under stirring. Then, water was added to adjust the concentration to 30% to obtain the granulation stabilizer (8) [sodium acrylate (99 mol%) -acrylonitrile (1 mol%) copolymer] for various pattern paints of the present invention. It was. The weight average molecular weight was 1 million, and the molecular weight distribution (Mw / Mn) was 6.

<Example 9>
"Ion-exchanged water 900 parts", "acrylic acid 99.2 parts", "acrylonitrile 0.8 parts", "10% sodium persulfate aqueous solution 1 part" and "40% sodium hydroxide 174.4 parts" are "ions" Example 8 except that it was changed to "600 parts of 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". In the same manner as above, a granulation stabilizer (9) [sodium acrylate (53 mol%) -acrylamide (47 mol%) copolymer; concentration 30%] for a multicolored pattern paint of the present invention was obtained. The weight average molecular weight was 350,000, and the molecular weight distribution (Mw / Mn) was 4.2.

<Example 10>
While stirring 100 parts of the granulation stabilizer (1) [sodium acrylate polymer] obtained in Example 1 and 0.1 part of dipropylene glycol (B1), the temperature was raised to 40 ° C. to reach this temperature. And uniformly stirred and mixed to obtain the granulation stabilizer (10) for various pattern paints of the present invention.

<Example 11>
100 parts of the granulation stabilizer (3) [sodium acrylate (95 mol%) -acrylic acid (5 mol%) copolymer] obtained in Example 3 and polyethylene glycol (B2) (number average molecular weight 400). The temperature was raised to 40 ° C. while stirring 10 parts, and the mixture was uniformly stirred and mixed at this temperature to obtain the granulation stabilizer (11) for a multicolored pattern coating material of the present invention.

<Example 12>
Stir 100 parts of the granulation stabilizer (5) [sodium acrylic acid salt (10 mol%) -acrylic acid (90 mol%) copolymer] obtained in Example 5 and 0.8 part of glycerin (B3). The temperature was raised to 40 ° C., and the mixture was uniformly stirred and mixed at this temperature to obtain the granulation stabilizer (12) for a multicolored pattern coating material of the present invention.

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

<Example 14>
100 parts of the granulation stabilizer (7) [sodium acrylate (40 mol%) -sodium maleate (60 mol%) copolymer] obtained in Example 7 and 8 parts of diglycerin (B4) were added. The temperature was raised to 40 ° C. with stirring, and the mixture was uniformly stirred and mixed at this temperature to obtain the granulation stabilizer (14) for a multicolored pattern coating material of the present invention.

<Example 15>
Stir 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). The temperature was raised to 40 ° C., and the mixture was uniformly stirred and mixed at this temperature to obtain the granulation stabilizer (15) for a multicolored pattern coating material of the present invention.

<Comparative example 1>
100 parts of ion-exchanged water and 100 parts of isopropyl alcohol are 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% sodium persulfate aqueous solution are separately dropped lines under stirring. The reaction was carried out in a hermetically sealed manner while dropping at a constant rate over 2 hours. The reaction temperature was maintained at 80-100 ° C. After completion of the dropping, the temperature was maintained at 95 to 100 ° C. for 2 hours, and then 200 parts of ion-exchanged water was dropped (hydrated) to remove isopropyl alcohol under reduced pressure, then cooled to 30 ° C. and watered to a concentration of 30%. After adjustment, a granulation stabilizer (16) [acrylic acid polymer] for comparison was obtained. The weight average molecular weight was 25,000, and the molecular weight distribution (Mw / Mn) was 1.8.

<Comparative example 2>
"Ion-exchanged water 100 parts", "isopropyl alcohol 100 parts", "acrylic acid 300 parts" and "40% sodium hydroxide aqueous solution 90 parts", respectively, "ion-exchanged water 60 parts", "isopropyl alcohol 140 parts", After changing to "300 parts of acrylic acid" and "90 parts of 40% aqueous sodium hydroxide solution" and "cooling to 30 ° C and adjusting the concentration to 30% by adding water", "after cooling to 30 ° C, With stirring, while keeping the temperature below 40 ° C., 395.3 parts of a 48% aqueous sodium hydroxide solution was gradually added in divided portions, and water was added to adjust the concentration to 30%. In the same manner, a granulation stabilizer (17) [acrylic acid (5 mol%) -sodium acrylate salt (95 mol%) copolymer] for comparison was obtained. The weight average molecular weight was 15,000, 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 are 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 a 50% sodium persulfate aqueous solution are separately dropped lines under stirring. The reaction was carried out in a hermetically sealed manner while dropping at a constant rate over 1 hour. The reaction temperature was maintained at 80-100 ° C. After completion of the dropping, the temperature was maintained at 95 to 100 ° C. for 1 hour, and then 200 parts of ion-exchanged water was dropped (hydrated) to remove isopropyl alcohol under reduced pressure, cooled to 30 ° C., and kept at 40 ° C. or lower under stirring. However, 69.3 parts of a 48% sodium hydroxide aqueous solution was gradually added in divided portions. The concentration was adjusted to 30% by adding water to obtain a granulation stabilizer (18) [sodium acrylate polymer] for comparison. The weight average molecular weight was 1.3 million, and the molecular weight distribution (Mw / Mn) was 6.5.

<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 ° C. at this temperature while stirring. The mixture was uniformly stirred and mixed to obtain a granulation stabilizer (19) for comparison.

Using the granulation stabilizers (1) to (19) obtained in Examples and Comparative Examples, a color particle slurry for evaluation was prepared as follows, and the color particles were stabilized. Is shown below.

<Preparation of base paint (1)>
The compounding ingredients shown in Table 1 were mixed with a tabletop disper to obtain base coating materials (C1 to 19).

(Note 1) Binter: Acrylic resin emulsion (water concentration 50%): Boncoat CE-6400, DIC Corporation, and "Boncoat" are registered trademarks of the same company.
(Note 2) Granulator: Modified silicate, Laponite S482, Big Chemie Japan Co., Ltd. (Note 3) Red paste: Concentrated colorant for water-based paint Unirant Red, Yokohama Kasei Co., Ltd., "unirant" is a registered trademark of the company. Is. Water concentration 50%
(Note 4) Thickener: SN-Sickner 640, San Nopco Ltd. (Note 5) Dispersant: Nopco Ltd. 5200, San Nopco Ltd., "Nopco Ltd." are registered trademarks of the same company.
(Note 6) Antifoaming agent: Nopco NXZ, San Nopco Ltd., and "NXZ" are registered trademarks of the same company.
(Note 7) Film-forming aid: TEXANOL, Eastman Chemical Japan Co., Ltd., and "Texanol" are registered trademarks of Yoshimura Oil Chemical Co., Ltd.

<Preparation of base paint (2)>
"Red paste" and "granulation stabilizers (1)-(19)" are replaced with "yellow paste (concentrated colorant for water-based paints, Unirant Yellow, Yokohama Kasei Co., Ltd., water concentration 50%)" and "granulation stabilizers". A base paint (C20 to 22) was obtained in the same manner as in the preparation of the base paint (1) except that the changes were made to (3), (4) and (19).

<Preparation of base paint (3)>
"Red paste" and "granulation stabilizers (1) to (19)" are replaced with "black paste (concentrated colorant for water-based paints, Unirant Black, Yokohama Kasei Co., Ltd., water concentration 60%)" and "granulation stabilizers". A base paint (C23 to 25) was obtained in the same manner as in the preparation of the base paint (1) except that the changes were made to (3), (4) and (19).

<Preparation of base paint (4)>
A base paint (blank, C26) was obtained in the same manner as in the preparation of the base paint (1) except that "granulation stabilizers (1) to (19)" were not used.

<Preparation of colored particle slurry>
200 g of each of the above base paints (C1 to 26) and 200 g of a 10% aqueous solution of a granulator (Laponite S482, Big Chemie Japan Co., Ltd.) with a desktop disper (ED-11, Nissei Tokyo Office, 400 rpm, 3 minutes). The mixture was stirred and mixed to obtain a colored particle slurry for evaluation.

<Evaluation of color particle stability>
(1) Immediately after production, (b) in a closed container, left at 50 ° C. for 1 day, (c) in a closed container, after standing at 50 ° C. for 1 week, respectively, of the particles contained in the colored particle slurry. The shortest particle size was visually measured, and the number average value of 20 particles was calculated (number average particle size).

(2) Immediately after preparing the colored particle slurry, transfer it to a 500 ml graduated cylinder, leave it in a closed container at 50 ° C. for 1 week, and then visually observe the separated state of the colored particle slurry to obtain an upper layer with respect to the total volume of the colored particle slurry. The volume% of the volume of the solution portion of was calculated (separation degree).

「−」：色粒子の形状が崩れて（最短粒子径は測定不能）、着色層（下層）と透明水層（上層）とに分離したことを表す（以下、同じである。）。

"-": Indicates that the shape of the colored particles has collapsed (the shortest particle size cannot be measured) and the colored particles (lower layer) and the transparent water layer (upper layer) are separated (the same applies hereinafter).

As shown in the above results, the granulation stabilizer for multicolored pattern paints of the present invention was superior in the stability of colored particles as compared with the granulation stabilizer for comparison.

<Example 16>
Binter (U-Court UWS-145, Sanyo Chemical Industries, Ltd., "U-Court" is a registered trademark of the company) 900 copies, film-forming aid (TEXANOL, Eastman Chemical Japan Co., Ltd.) 20 copies and 80 copies of water on the table. A clear paint was prepared by uniformly mixing with a disper (ED-11, Nippon Seiki Seisakusho Co., Ltd.).
50 g each of the colored particle slurries (C3), (C20), and (C23) obtained in <Preparation of colored particle slurry> and 200 g of clear paint are used on a desktop disper (ED-11, Nippon Seiki Seisakusho Co., Ltd., 400 rpm, 5 minutes). The mixture was stirred and mixed to obtain a multicolored pattern paint (1).

<Example 17>
Similar to Example 16 except that "color particle slurry (C3), (C20), (C23) 50 g each" was changed to "color particle slurry (C4), (C21), (C24) 80 g each". , A multicolored pattern paint (2) was obtained.

<Comparative example 5>
For comparison, as in Example 16, except that "color particle slurry (C3), (C20), (23)" was changed to "color particle slurry (C19), (C22), (C25)". Obtained a multicolored pattern paint.

<Stability evaluation of multicolored paint>
The shortest particle size of the particles contained in the multicolored pattern paint was visually measured in each of (1) (a) immediately after production, (b) in a closed container, and after standing at 50 ° C. for 1 week, and the average of 20 particles was measured. The value was calculated (number average particle size).
(2) Immediately after production, (b) in a closed container, and after standing at 50 ° C. for 1 week, the presence or absence of color mixing between the red, yellow, and black color particles was visually observed (presence or absence of color mixing). ).

As shown in the above results, the granulation stabilizer for the multicolored pattern paint of the present invention is superior in the stability of the color particles as compared with the granulation stabilizer for comparison, so that the multicolored pattern paint can be stably stored.

Claims (6)

Ethylenically unsaturated carboxylic acid (salt) becomes as an essential constituent monomer, Ri Na contain a weight average molecular weight of 50,000 to 1,000,000 (co) polymer (A),
(Co) granulating stabilizer for multicolor paint of molecular weight distribution (Mw / Mn) and wherein 2.5 to 6.0 der Rukoto of the polymer (A). The granulation stabilizer according to claim 1, wherein the ethylenically unsaturated carboxylate is an alkali metal salt, an amine salt, or a quaternary organic ammonium salt. Based on the number of moles of ethylenically unsaturated carboxylic acid and ethylenically unsaturated carboxylic acid salt, the content of ethylenically unsaturated carboxylic acid unit is 0 to 90 mol%, and the content of ethylenically unsaturated carboxylic acid salt unit is 0 to 90 mol%. The granulation stabilizer according to claim 1 or 2, which is 10 to 100 mol%. The granulation stabilizer according to any one of claims 1 to 3 , further comprising a water-soluble polyhydric alcohol (B). The granulation stabilizer according to claim 4 , 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). A base coating step (1) of mixing a binder, a granulating agent, a coloring agent, water, and a granulating stabilizer for a multicolored pattern coating according to any one of claims 1 to 5 to obtain a base coating, and
A method for producing a multicolored pattern paint, which comprises a granulation step (2) of mixing an aqueous solution of a granulator and a base paint to obtain a slurry containing particles having a number average particle size of 1 to 20 mm.