JP2015157877A - Colored resin particle and aqueous multicolor pattern coating composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide colored resin particles that enables formation of a vivid and distinct splashy pattern, and an aqueous multicolor pattern coating composition containing the colored resin particles.SOLUTION: The colored resin particles are obtained by bringing an aqueous liquid composition (I) into contact with a metal compound-containing aqueous medium (II), the aqueous liquid composition (I) comprising an aqueous resin (A) having an acid value of 35 mgKOH/g or more of a resin solid content, an aqueous resin (B) having an acid value of less than 20 mgKOH/g of a resin solid content, a colorant (C), and water-soluble polysaccharide (D). A solid content mass of the aqueous resin (A) is in a range from 0.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the aqueous resin (B); and an equivalent ratio of metal ions is in a range from 3 to 40 with respect to 1 equivalent of total acid groups included in the resin solid content of the aqueous resin (A) and the aqueous resin (B). The aqueous multicolor pattern coating composition contains the above colored resin particles.

Description

  The present invention relates to colored resin particles and an aqueous multicolor pattern coating composition containing the same, which are suitable for forming a coating film having a bright and distinct spotted pattern.

Multi-color paint is a paint in which colored paint particles of multiple colors are stably dispersed in a dispersion medium, and a multi-colored spotted pattern can be obtained with a single coating, and is mainly used for painting buildings. Has been. (For example, see JIS K 5667 (2003) multicolored paint)
In recent years, there has been a need to develop water-based multicolored paints because of environmental considerations and customer appearance needs, and the present applicant has proposed various water-based multicolored paint compositions ( Patent Documents 1 to 3).

  According to these documents, it is possible to obtain a water-based multicolored paint that forms a multicolored paint film having good coating workability and excellent design.

  On the other hand, the coloring paint particles contained in the water-based colorful pattern paint for forming a spotted pattern gradually exudes the coloring components in the particles at the storage stage, and the sharpness may be lowered.

  Regarding such a problem, Patent Document 4 discloses a granular gel excellent in storage stability by contacting an aqueous liquid composition containing an aqueous resin, a colorant and a water-soluble polysaccharide with an aqueous medium containing a specific metal compound. It is described that it is obtained.

  However, it is difficult for the aqueous multicolor pattern coating composition obtained by the method described in Patent Document 4 to satisfy both the touch feeling of the coating film and the sharpness of the spotted pattern, and there is still room for improvement.

JP 2007-321045 A JP 2008-012381 A JP 2008-038104 A JP 2008-202037 A

  An object of the present invention is to propose colored resin particles capable of forming a vivid and distinct spotted pattern and an aqueous multicolor pattern coating composition containing the same.

  As a result of intensive studies on the above-mentioned problems, the present inventors have excellent storage stability by using a plurality of aqueous resins having a specific acid value in the aqueous liquid composition to be brought into contact with the metal ion-containing aqueous medium. It was found that a colored resin particle was obtained, and a multicolored pattern coating film excellent in sharpness was obtained from the aqueous multicolored pattern paint containing this, and the present invention was achieved.

That is, the present invention
An aqueous resin (A) having an acid value of resin solid content of 35 mgKOH / g or more, an aqueous resin (B) having an acid value of resin solid content of less than 20 mgKOH / g, a colorant (C), and a water-soluble polysaccharide (D) Obtained by contacting the aqueous liquid composition (I) containing with the metal compound-containing aqueous medium (II),
The solid content mass of the aqueous resin (A) is in the range of 0.5 to 20 mass parts based on 100 mass parts solid content of the aqueous resin (B),
Colored resin particles wherein the equivalent ratio of metal ions based on 1 equivalent of total acid groups contained in the resin solids of the aqueous resin (A) and the aqueous resin (B) is in the range of 3 to 40 , A method for producing the colored resin particles, an aqueous colorful pattern coating composition containing the colored resin particles, a coating method for applying the aqueous colorful pattern paint,
About.

  The colored resin particles in the present invention are excellent in storage stability, and according to the aqueous multicolor pattern coating composition containing this, the spotted pattern is vivid and clear, and the natural feeling of roughness when touched with a hand is small. A coating film having a tactile sensation can be formed.

  The colored resin particles of the present invention include an aqueous resin (A) having an acid value of 35 mgKOH / g or more of a resin solid content, an aqueous resin (B) having an acid value of less than 20 mgKOH / g, a colorant (C), and It is obtained by bringing the aqueous liquid composition (I) containing the water-soluble polysaccharide (D) into contact with the metal ion-containing aqueous medium (II).

<Aqueous resin (A)>
The aqueous resin (A) in the present invention is a resin that can be dissolved or dispersed in water containing an acid group as an essential component, and various resins can be used as long as the solid content acid value is within the range of the present invention. Although there is no restriction | limiting as an acid group, A carboxyl group is especially suitable.

  Specific examples of the aqueous resin (A) include acrylic acid-based resins, styrene-acrylic acid-based resins, styrene-maleic acid-based resins, and styrene-acrylic-maleic acid-based resins.

  Here, the acrylic resin is a resin obtained by polymerizing other monomers as necessary with an acrylic monomer as an essential component, and the styrene-acrylic resin is a styrene monomer and an acrylic monomer. It is a resin obtained by polymerizing other monomers as necessary with other components as necessary. The styrene-maleic acid resin is a resin obtained by polymerizing other monomers with a styrene monomer and a maleic acid monomer as essential components. The styrene-acrylic acid-maleic acid resin is a styrene monomer. It is a resin obtained by polymerizing other monomers with acrylic acid monomers and maleic monomers as essential components.

  In addition, the carboxyl group of the aqueous resin (A) is selected from amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, and ammonia. It may be one partly or entirely neutralized with a hydrating agent.

  Examples of acrylic acid monomers include acrylic acid and methacrylic acid. Examples of the styrene monomer include styrene, α-methylstyrene, vinyltoluene and the like. Examples of the maleic acid monomer include maleic anhydride, maleic acid, maleic acid alkyl ester, maleic acid hydroxyalkyl ester, maleic acid alkylamide and the like.

  In the present invention, the aqueous resin (A) has a solid content acid value of 35 mgKOH / g or more. When the solid content acid value of the aqueous resin (A) is less than 35 mgKOH / g, the formed colorful pattern coating film is poor in vividness and a vivid and clear spotted pattern cannot be obtained.

  The solid content acid value of the aqueous resin (A) is preferably 35 to 600 mgKOH / g, preferably 40 to 300 mgKOH / g, and the weight average molecular weight is 3000 to 300,000, preferably 5000 to 250,000. It is suitable from the viewpoint of production stability and water resistance of the colored resin particles.

  In addition, the number average molecular weight or the weight average molecular weight in this specification is the number average molecular weight or the weight average of polystyrene measured by a gel permeation chromatograph (manufactured by Tosoh Corporation, “HLC8120GPC”). It is a value converted based on the molecular weight. In this measurement, the columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (all trade names, Tosoh Corporation) The measurement conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, detector RI were used.

<Water-based resin (B)>
The aqueous resin (B) is a resin other than the aqueous resin (A), and a resin that can be dissolved or dispersed in water is used, and various resins can be used. Specific examples include acrylic resins, silicon resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, alkyd resins, polycarbonate resins, and the like. It can be used in combination of more than one species. These resins may be modified like, for example, urethane-modified acrylic resin, or may be graft-polymerized.

  An acid group is not essential for the aqueous resin (B), but a carboxyl group is preferred when it has an acid group.

  The aqueous resin (B) is suitably in the form of dispersed particles, and may be a single layer or a multilayer such as a core / shell type. When the aqueous resin (B) has a carboxyl group, amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, and ammonia A part or all of them may be neutralized with a neutralizing agent such as

  The aqueous resin (B) is preferably an acrylic resin from the viewpoint of durability and weather resistance of the colored resin particles, and as the acrylic resin, a copolymer containing a (meth) acryloyl group-containing compound is used. Can be mentioned.

  Examples of the monomer used for copolymerization of the compound include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth). Linear or branched alkyl (meth) acrylates such as acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) Alicyclic alkyl (meth) acrylate such as acrylate; Aralkyl (meth) acrylate such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, etc. Alkoxyalkyl (meth) acrylate; perfluoroalkyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylate such as N, N-diethylaminoethyl (meth) acrylate; (meth) acrylamide; (meth) acrylonitrile; Vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene Glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopen Tyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-tris Hydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinyl Polyvinyl compounds having at least two polymerizable unsaturated groups in one molecule such as benzene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) a Relate, hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, allyl alcohol, ε-caprolactone modified products of the above hydroxyalkyl (meth) acrylates, polyoxyethylene chain-containing (meth) acrylates whose molecular ends are hydroxyl groups, etc. Hydroxyl group-containing polymerizable unsaturated monomers; (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and other carboxyl group-containing polymerizable unsaturated monomers; (meth) acrolein, formylstyrene, 4 to 7 carbon atoms Vinyl alkyl ketones (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), acetoacetoxyethyl (meth) acrylate, acetoacetoxyallyl ester, diacetone (meth) acrylamide, etc. Rubonyl group-containing polymerizable unsaturated monomer: glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3, Epoxy group-containing polymerizable unsaturated monomers such as 4-epoxycyclohexylpropyl (meth) acrylate and allyl glycidyl ether; isocyanato group-containing polymerization such as isocyanatoethyl (meth) acrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate Unsaturated monomers; alkoxysilyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane Polymerized unsaturated monomer; reaction product of epoxy group-containing polymerizable unsaturated monomer or hydroxyl group-containing polymerizable unsaturated monomer and unsaturated fatty acid, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meta ) Oxidizing curable group-containing polymerizable unsaturated monomers such as acrylate and dicyclopentenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  The method for polymerizing the monomer is not particularly limited, and can be produced, for example, by (co) polymerizing the monomer in the presence of an emulsifier according to a general emulsion polymerization method.

  As the emulsifier to be used, an emulsifier known per se can be used, and applicable emulsifiers include, for example, anionic emulsifier, nonionic emulsifier, amphoteric emulsifier, and polymerizable unsaturated A reactive emulsifier containing both a group and an anionic group or a nonionic group in the molecule can also be used, and the amount used is usually 0.5 to 4, based on the total mass of the polymerizable unsaturated monomer. It can be in the range of 6% by weight, preferably 1-4% by weight.

  In the present invention, the aqueous resin (B) has a solid content acid value of less than 20 mgKOH / g.

  When the solid content acid value of the aqueous resin (B) is 20 mgKOH / g or more, the water resistance of the formed coating film becomes insufficient, which is not preferable.

  The solid content acid value of the aqueous resin (B) is 0.5 or more and less than 20 mgKOH / g, preferably 1 to 15 mgKOH / g, more preferably 1 to 10 mgKOH / g, and the weight average molecular weight. Is in the range of 10,000 to 500,000, preferably 15,000 to 350,000.

  Further, when the aqueous resin (B) is dispersed particles, the average particle size is preferably in the range of 0.1 to 0.5 μm, preferably 0.1 to 0.3 μm.

  The average particle diameter in this specification is a value measured at 20 ° C. after diluting with deionized water by a conventional method using a submicron particle size distribution analyzer. As the submicron particle size distribution measuring device, for example, “COULTER N4 type” (trade name, manufactured by Beckman Coulter, Inc.) can be used.

  In the present invention, the solid content mass of the aqueous resin (A) is in the range of 0.5 to 20 parts by mass based on 100 parts by mass of the aqueous resin (B) solids, preferably Is suitably in the range of 1 to 15 parts by weight.

  When the amount of the aqueous resin (A) is less than 0.5 parts by mass, the color stability of the colored resin particles is deteriorated. On the other hand, if it exceeds 20 parts by mass, the colored resin particles may be crushed, which is not preferable.

<Colorant (C)>
Examples of the colorant (C) that can be contained in the colored resin particles of the present invention include a color pigment, a bright pigment, and a fluorescent material. Examples of the color pigment include white pigments such as titanium dioxide; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and aniline black; yellow iron oxide, titanium yellow, monoazo yellow, and condensed azo. Yellow pigments such as yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow; orange pigments such as permanent orange; red iron oxide, naphthol AS azo red, ansanthrone , Anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyrrolopyrrole, watching red, permanent red and other red pigments; cobalt purple, quinacridone violet, dioxa Purple pigments such as cobalt violet, blue pigments such as cobalt blue, phthalocyanine blue, and selenium blue; green pigments such as phthalocyanine green, and the like. The bright pigments include aluminum powder, bronze powder, copper powder, and tin powder. Metal pigments such as iron phosphide and zinc powder; pearlescent pigments such as metal oxide-coated mica powder and mica-like iron oxide, and these may be used alone or in combination of two or more. Can do. The titanium dioxide as the white pigment includes functional titanium dioxide such as micro titanium having an average particle diameter of 10 to 80 nm and anatase type titanium dioxide having photocatalytic activity.

  Examples of fluorescent materials include fluorescent or phosphorescent pigments and dyes, such as diphenylethylene, oxazole, thiazole, imidazole, triazole, pyrazole, furan, thiophene, and peridicarboxylic amide. And inorganic compounds such as copper, silver, manganese and europium added to metal compounds such as zinc sulfide, strontium aluminate and calcium aluminate.

  These colorants (C) can be used alone or in combination of two or more depending on the color of the target colored resin particles.

  In the colored resin particles, an extender can be used together with the colorant (C). Specific examples include barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, quartz sand, quartz powder and the like. Or in combination of two or more.

  Although the compounding quantity of the said coloring agent (C) can be suitably adjusted according to the kind, generally 0.01-400 mass normally on the basis of the total solid content mass of aqueous resin (A) and aqueous resin (B). %, In particular within the range of 0.1 to 300% by weight.

<Water-soluble polysaccharide (D)>
The colored resin particles of the present invention are those in which an aqueous coloring composition containing an aqueous resin (A), an aqueous resin (B), and a colorant (C) is stabilized by a water-soluble polysaccharide metal salt. Obtained by contacting an aqueous liquid composition (I) containing an aqueous resin (A), an aqueous resin (B), a colorant (C) and a water-soluble polysaccharide (D) with a metal compound-containing aqueous medium (II). Can do.

  The water-soluble polysaccharide (D) itself is a compound that can be gelled by contact with a metal compound-containing aqueous medium (II) described later, specifically, alginic acid, gellan gum, carrageenan, galacto Compounds such as mannan, cellulose, gelatin, casein, albumin; metal salts of these compounds; compounds modified by oxidation, methylation, carboxymethylation, hydroxyalkylation, sulfation, phosphorylation, etc. Can be used alone or in combination of two or more.

  The water-soluble polysaccharide (D) is 0 on the basis of the solid content mass of the aqueous liquid composition from the viewpoint of suppressing the outflow of the inclusions of the colored resin particles and forming a coating film with less roughness. 0.5 to 10% by mass, preferably 0.7 to 9.0% by mass.

  The aqueous liquid composition for producing the colored resin particles as described above may further comprise a thickener, a specific gravity adjusting material such as balloon particles, an antifoaming agent, a curing catalyst, a pigment dispersant, a fragrance, if necessary. Deodorant, antibacterial agent, neutralizer, surfactant, aqueous water repellent, antiseptic, antifungal agent, antifreeze agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, formaldehyde adsorbent In addition, flame retardants such as antimony trioxide, antimony pentoxide, and aluminum hydroxide can be contained.

<Colored resin particles>
In the present invention, the metal compound contained in the metal compound-containing aqueous medium (II), which is a raw material for producing colored resin particles, can form a water-insoluble or hardly soluble salt with the water-soluble polysaccharide (D) in the aqueous medium. It is a compound capable of generating monovalent or polyvalent metal ions.

  The metal species in such a metal compound is preferably a polyvalent metal from the viewpoint of the strength of the colored resin particles to be formed, for example, a periodic table group 2 element such as magnesium, calcium, strontium, barium; titanium, zirconium Periodic table Group 4 elements such as chromium and molybdenum; Periodic table Group 7 elements such as manganese; Periodic table Group 8 elements such as iron and ruthenium; Group 9 elements such as cobalt and rhodium Periodic table group 10 elements such as nickel and palladium; periodic table group 11 elements such as copper and silver; periodic table group 12 elements such as zinc and cadmium; periodic table group 13 elements such as aluminum; periodic table group 16 such as cerium; An element etc. can be mentioned, These can be used individually or in combination of 2 or more types.

  Moreover, in addition to the polyvalent metal, a metal compound of a Group 1 element of the periodic table such as sodium or potassium may be used in combination.

  The metal compound is preferably a Group 2 element of the periodic table, particularly calcium.

  Compounds that can be counter ions of the above metal species include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, oxalic acid, fumaric acid, succinic acid, phosphoric acid, citric acid, and gluconic acid; hydroxide; Sulfates; nitrates; silicates, and the like. These may be used alone or in combination of two or more.

  An aqueous medium containing metal ions can be prepared by dissolving at least a part of the metal compound in an aqueous medium such as water. At that time, the metal compound does not need to be completely dissolved in the aqueous medium, and may be partially dissolved.

  The concentration of the metal compound in the aqueous medium is not strictly limited, but can be usually 0.05 to 20% by mass, preferably 0.05 to 15% by mass.

  In the aqueous medium (II), the pH is adjusted to 4.0 to 13.7, preferably 7.0 to 13.5, from the viewpoint of storage stability and production stability of the colored resin particles. Is preferred.

  The contact between the aqueous liquid composition (I) and the metal compound-containing aqueous medium (II) is, for example, a method in which the composition is dropped into the aqueous medium from the tip of a syringe; A method in which the composition is atomized from the tip of a spray nozzle and dropped into the aqueous medium; a method in which the composition is added into the aqueous medium and agitated and mixed with a disperser It can be performed by such a method.

  In the present invention, the equivalent ratio of metal ions based on 1 equivalent of total acid groups contained in the aqueous resin (A) and the aqueous resin (B) is in the range of 3 to 40. 3 to 25 is more preferable.

  If the equivalent ratio of metal ions is small relative to the total amount of acid groups, the stability of the colored resin particles is poor. On the other hand, if the equivalent ratio of metal ions is too large, the surface of the coating film may become rough and water resistance Since it is inferior, it is not preferable.

  The colored resin particles described above can have an average particle diameter in the range of 0.05 to 20 mm, preferably 0.1 to 10 mm.

  In this specification, the average particle diameter of the colored resin particles is an average value obtained by measuring the particle diameters of 10 colored resin particles randomly extracted with a ruler.

<Water-based colorful pattern paint composition>
The water-based colorful pattern coating composition of the present invention can contain a single color or a plurality of colors of colored resin particles, and a combination in the case of a plurality of colors can be appropriately selected according to the intended design.

  The aqueous multicolor pattern coating composition preferably contains a coating film forming component in addition to the colored resin particles from the viewpoint of coating film properties such as weather resistance of the coating film to be formed.

  As the water-based resin contained in the coating film-forming component, those generally used as a resin binder in the water-based paint field can be used. For example, as appropriate from those described above as the water-based resin (B) in the colored resin particles You can choose and use it.

  In the aqueous multicolor pattern coating composition of the present invention, it is suitable that the colored resin particles and the coating film-forming component are capable of reacting with each other from the viewpoint of long-term weather resistance and water resistance of the coating film. Specifically, it is suitable that the water-based multicolor pattern coating composition contains a compound having two or more functional groups per molecule capable of reacting with the functional groups contained in the colored resin particles and / or coating film forming components. ing.

  The combination of the functional groups is not particularly limited as long as they can react with each other. Specifically, for example, a hydroxyl group and an isocyanate group, a hydroxyl group and an alkyl ether group, a hydroxyl group and an imino group, an amino group And epoxy group, amide group and epoxy group, acid group and epoxy group, acid group and hydroxyalkylamide group, carbonyl group and hydrazine group, carbonyl group and hydrazide group, carbonyl group and semicarbazide group, and carbonyl group and bisacetyldihydrazone A combination of a group and the like can be mentioned, and in particular, a combination of a carbonyl group and a hydrazide group is preferable because it can be cross-linked at one room temperature.

  In the aqueous colorful pattern coating composition of the present invention, it is suitable that both the colored resin particles and the aqueous resin contained in the coating film-forming component contain a carboxyl group and a carbonyl group. Specifically, it is desirable that the colored paint particle component (A) and / or the coating film forming component contain a hydrazine derivative as a crosslinking agent.

  Examples of the hydrazine derivative for reacting with the carbonyl group that can be contained in the colored resin particles or the coating film forming component include hydrazine, hydrazine hydrate, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid Dihydrazides of saturated aliphatic carboxylic acids having 2 to 18 carbon atoms such as dihydrazide and sebacic acid dihydrazide; dihydrazides of monoolefinically unsaturated dicarboxylic acids such as maleic acid dihydrazide, fumaric acid dihydrazide and itaconic acid dihydrazide; phthalic acid, terephthalic acid or Isophthalic acid dihydrazide; pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotriacetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide; ethylene Amine tetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide; polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride), etc .; carbonic acid Dihydrazide, bissemicarbazide; obtained by excessively reacting a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate and a polyisocyanate compound derived therefrom with an N, N-substituted hydrazine such as N, N-dimethylhydrazine or the above-mentioned hydrazide. Polyfunctional semicarbazide; an isocyanate group in a reaction product of the polyisocyanate compound and an active hydrogen compound containing a hydrophilic group such as polyether polyols or polyethylene glycol monoalkyl ethers. Examples thereof include an aqueous polyfunctional semicarbazide obtained by excessively reacting the exemplified dihydrazide; a mixture of the polyfunctional semicarbazide and an aqueous polyfunctional semicarbazide; bisacetyldihydrazone, and the like. These may be used alone or in combination of two or more. Can be used.

  The coating film-forming component can contain the metal compound, the colorant (C), extender pigments and paint additives as necessary. The paint additives include thickeners, Resin beads, neutralizers, antistatic agents, softeners, antibacterial agents, fragrances, curing catalysts, pH adjusters, humidity control agents, powdered or particulate activated carbon, photocatalytic titanium oxide, aqueous water repellents, dispersants, Antifoaming agent, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, curing accelerator, aldehyde adsorbent, wax, antimony trioxide, antimony pentoxide, Examples include flame retardants such as aluminum hydroxide.

  The blending ratio of the colored resin particles and the coating film forming component is determined by the solid content of the colored resin particles / coating film forming component from the viewpoint of the dispersion of the spotted pattern due to the colored resin particles of the multicolored pattern coating film and the weather resistance. By mass ratio, it can be in the range of 1/99 to 60/40, preferably 10/90 to 50/50.

  When mixing the colored resin particles and the coating film-forming component, an additive usually used in the paint field, water, and the like can be blended as necessary.

<Paint>
The surface to be coated with the water-based multicolor pattern paint composition of the present invention is not limited, and examples thereof include gypsum board, concrete wall, concrete block, siding board, mortar wall, slate board, PC board, and ALC. Surface of base materials such as boards, cement calcium silicate boards, wood, stones, plastic moldings, ceramics, porcelain tiles, metal workpieces, acrylic resin system, acrylic urethane resin system, polyurethane resin system provided on these base materials , Fluororesin, silicone resin, silicone acrylic resin, vinyl acetate resin, epoxy resin and other old coatings and wallpaper surfaces made of materials such as polyvinyl chloride, polyolefin, paper, cloth, etc. There may be. Although it does not restrict | limit especially as a to-be-coated object, a building outer wall or an inner wall etc. are suitable.

  The surface to be coated or the object to be coated may be one that has been treated with a sealer in advance, and a known top coat coloring paint may be applied as necessary.

  The water-based multicolor pattern coating composition of the present invention can be applied by using a coating means known per se. Applications of base materials such as rollers, air sprays, airless sprays, lysing guns, universal guns, brushes, roll coaters, etc. It can be appropriately selected according to the like. Moreover, you may apply repeatedly several times in the range which does not impair the coating-film external appearance.

  The formed multicolor pattern coating film can be dried by any one of heat drying, forced drying, and room temperature drying depending on the type of the aqueous multicolor pattern coating composition used.

  Furthermore, after applying the water-based colorful pattern paint of the present invention, a step of applying a clear paint on the colorful pattern coating film may be provided as necessary.

  Examples of such clear paints include acrylic resins, acrylic silicon resins, polyolefin resins, silicone resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, alkyd resins, biodegradable resins, and the like. Examples thereof include water-based or solvent-based paints comprising a water-based or solvent-based resin comprising the above resin species as a resin binder, and water-based paints comprising a water-based resin are preferably used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to only these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Production of aqueous resin Production Example 1 (Emulsion for resin particles)
285 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added to a 4-liter flask having a volume of 2 liters, and maintained at 85 ° C. after purging with nitrogen. 41 parts of an initiator aqueous solution obtained by dissolving 3 parts of a pre-emulsion obtained by emulsifying the components of the following composition therein and 3 parts of ammonium persulfate in 120 parts of deionized water are added and added. 20 minutes after completion, the remaining pre-emulsion and ammonium persulfate aqueous solution were dropped into the flask over 4 hours.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 400 parts n-Butyl acrylate 200 parts 2-Ethylhexyl acrylate 200 parts Diacetone acrylamide 20 parts 2-Hydroxyethyl acrylate 24 parts Acrylic acid 6 parts "New Coal 707SF" (Note 1) 66 After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Subsequently, pH was adjusted with ammonia water to obtain an aqueous resin (a1) having a solid content of 55%. The obtained aqueous resin (a1) was milky white, had an average particle diameter of 175 nm, pH of 8.3, a solid content acid value of 5 mgKOH / g, and a weight average molecular weight of 200,000.

  (Note 1) “New Coal 707SF”: trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, nonvolatile content 30%.

Production Example 2
By stirring and mixing 15 parts of DSS-11 (trade name, manufactured by Gifu Shellac Co., Ltd., styrene maleic acid half ester), 3.5 parts of triethanolamine and 81.5 parts of deionized water, a solid content of 15 parts was obtained. % Aqueous resin (a2) was obtained. The obtained aqueous resin (a2) was milky white, had an average particle diameter of 50 nm, a pH of 7.2, a solid content acid value of 180 mg KOH / g, and a weight average molecular weight of 18,000.

Production Example 3
To a 4 liter four-necked flask equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, 1000 parts of ethylene glycol monobutyl ether was added and heated to 120 ° C. A mixture having the following composition was gradually dropped therein over 3 hours, and then aged for 1 hour. Thereafter, while gradually adding 1400 parts of deionized water, the mixture was cooled to 30 ° C. and adjusted with dimethylethanolamine to obtain an aqueous resin (a3) having a solid content of 20% and a pH of 8.0. The obtained aqueous resin (a3) was milky white, the solid content acid value was 30 mgKOH / g, and the weight average molecular weight was 14000.
Styrene 97 parts Methyl methacrylate 270 parts n-Butyl acrylate 120 parts 2-Hydroxyethyl methacrylate 90 parts Acrylic acid 23 parts Benzoyl peroxide 3 parts Production Example 4
To a 4 liter four-necked flask equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, 500 parts of ethylene glycol monobutyl ether was added and heated to 120 ° C. A mixture having the following composition was gradually dropped therein over 3 hours, and then aged for 1 hour. Thereafter, while gradually adding 1000 parts of deionized water, the mixture was cooled to 30 ° C. and adjusted with dimethylethanolamine to obtain an aqueous resin (a4) having a solid content of 40% and a pH of 7.8. The obtained aqueous resin (a4) was transparent, the solid content acid value was 39 mgKOH / g, and the weight average molecular weight was 15000.
Styrene 150 parts Methyl methacrylate 450 parts n-Butyl acrylate 200 parts 2-Hydroxyethyl methacrylate 150 parts Acrylic acid 50 parts Benzoyl peroxide 5 parts Production Example 5 (Emulsion for coating film forming component)
285 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added to a 4-liter flask having a volume of 2 liters, and maintained at 85 ° C. after purging with nitrogen. 41 parts of an initiator aqueous solution obtained by dissolving 3 parts of a pre-emulsion obtained by emulsifying the components of the following composition therein and 3 parts of ammonium persulfate in 120 parts of deionized water are added and added. 20 minutes after completion, the remaining pre-emulsion and ammonium persulfate aqueous solution were dropped into the flask over 4 hours.
Deionized water 368 parts Methyl methacrylate 550 parts n-butyl acrylate 200 parts 2-ethylhexyl acrylate 200 parts diacetone acrylamide 10 parts 2-hydroxyethyl acrylate 37 parts acrylic acid 3 parts "New Coal 707SF" (Note 1) 66 parts Thereafter, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Next, the pH was adjusted with aqueous ammonia to obtain an aqueous resin (a5) having a solid content of 55%. The aqueous resin (a5) was milky white and had an average particle size of 180 nm and a pH of 8.0.

Production of white pigment paste Production Example 6
The following components were charged into a 1 liter stainless steel container, stirred and mixed with a stirrer for 30 minutes, filtered and discharged with a 100 mesh nylon cloth to obtain a white pigment paste (b1).
Water 240 parts Hydroxyethyl cellulose 1 part Aqueous resin (a2) 100 parts “BYK-028” (Note 2) 10 parts “TITANIX JR-605” (Note 3) 400 parts (Note 2) “BYK-028”: Trade name, BYK Chemie, antifoam (Note 3) “TITANIX JR-605”: trade name, manufactured by Teika, titanium white.

Production of black pigment paste Production Example 7
The following components were charged in a 1 liter stainless steel container, stirred and mixed with a stirrer for 30 minutes, filtered and discharged with a 100 mesh nylon cloth to obtain a black pigment paste (b2).
Water 240 parts Hydroxyethyl cellulose 1 part Aqueous resin (a2) 100 parts “BYK-028” (Note 2) 10 parts Carbon black 20 parts.

Production of red rust pigment paste Production example 8
The following components were charged in a 1 liter stainless steel container, stirred and mixed with a stirrer for 30 minutes, filtered and discharged with a 100 mesh nylon cloth to obtain a red rust pigment paste (b3).
Water 240 parts Hydroxyethyl cellulose 1 part Aqueous resin (a2) 100 parts “BYK-028” (Note 2) 10 parts Iron oxide 250 parts.

Production Example 9
A white pigment paste (b4) was obtained in the same manner as in Production Example 6 except that in Example 6 above, the aqueous resin (a2) was replaced with the aqueous resin (a3).

Production Example 10
A black pigment paste (b5) was obtained in the same manner as in Production Example 7 except that the aqueous resin (a2) was replaced with the aqueous resin (a3) in Production Example 7.

Production Example 11
In the above production example, a red rust pigment paste (b6) was obtained in the same manner as in Production Example 8 except that the aqueous resin (a2) was replaced with the aqueous resin (a3).

Production of composition for colored resin particles Production Example 12
The following components were sequentially charged into a stainless steel container, and stirred and mixed with a stirrer to obtain a uniform composition for colored resin particles (A-1).
55% emulsion (a1) 100 parts white pigment paste (b1) 100 parts 10% adipic acid dihydrazide aqueous solution 1 part “TEXANOL” (Note 4) 6 parts “BYK-028” (Note 2) 2 parts “Adecanol UH-420” (Note 5) 1 part 2% sodium alginate aqueous solution 200 parts (Note 4) “TEXANOL”: trade name, manufactured by Eastman Chemical Co., Ltd., 2,2,4-trimethylpentanediol monoisobutyrate, film-forming aid,
(Note 5) “Adecanol UH-420”: trade name, manufactured by Adeka, urethane-modified thickener.

Production Examples 13 to 23
In Production Example 12, colored resin particle compositions (A-2) to (A-12) were produced in the same manner as in Production Example 12 except that the composition was changed to the composition shown in Table 1 below.

Production of metal compound-containing aqueous medium Production Example 24
After adding 1995 parts of deionized water to a 4 liter stainless steel container, 2 parts of calcium acetate monohydrate and 3 parts of calcium hydroxide were added and stirred until uniform to obtain an aqueous medium (B-1). It was.

Production Examples 25 to 28
Aqueous media (B-2) to (B-5) were obtained in the same manner as in Production Example 24 except that the formulation composition was changed to the following Table 2 in Production Example 24.

Manufacture example 29 of water-based clear paint for coating film forming component
The following components were sequentially charged into a 2 liter stainless steel container and stirred and mixed with a stirrer until uniform for 30 minutes to obtain an aqueous clear paint (D-1).
55% emulsion (a5) 925 parts “TEXANOL” (Note 4) 60 parts “BYK-028” (Note 2) 10 parts 10% adipic acid dihydrazide aqueous solution 2 parts “Primal ASE 60” (Note 6) 3 parts (Note 6) “Primal ASE60”: trade name, manufactured by Rohm and Haas, polyacrylic acid viscosity modifier.

Production Example 1 of Colored Resin Particles
In a 4-liter stainless steel container, 2000 parts of the aqueous medium (B-1) for producing colored resin particles obtained in Production Example 24 and 3 parts of BYK-028 (trade name, manufactured by BYK Chemie, defoaming agent) are added. 820 parts of the colored resin particle composition (A-1) obtained in Production Example 8 was gradually dropped into the container while stirring and stirring at a rotation speed of 2,000 rpm using a stirring blade having a diameter of 75 mm. Colored resin particles were generated. Next, the liquid in the container was further stirred for 10 minutes at the same rotation speed, and then filtered using a 100-mesh wire mesh to obtain colored resin particles (C-1). The obtained colored paint particles (C-1) had an average particle diameter of 4 mm and a solid content of 20%.

Examples 2 to 16 and Comparative Examples 1 to 6
In Example 1, the colored resin particles (C-2) to (C-24) were prepared in the same manner as in Example 1 except that the composition of the aqueous resin and the composition for colored resin particles to be dropped was as shown in Table 3. Manufactured.

Production of water-based colorful pattern paint Examples 19-23 and Comparative Examples 7-9
The components shown in Table 4 below were charged into a stainless steel container while sequentially stirring, and then stirred until uniform, thereby obtaining water-based multicolored paints (E-1) to (E-7).
The performance evaluation of the obtained paint is also shown in Table 4.

Preparation of test coated plate "Eco-cation sealer" (trade name, manufactured by Kansai Paint Co., Ltd., water-based cationic emulsion-based sealer) is applied to a flexible plate (150 x 70 x 4 mm) at a coating amount of 100 g / m ² . After coating with a roller and drying in standard conditions (temperature 23 ° C., relative humidity 50%) for 24 hours, “Ares Aqua Gloss White” (manufactured by Kansai Paint Co., Ltd., acrylic resin water-based paint) is applied. A plate to be coated was obtained by roller coating so as to be 100 g / m ² and similarly dried in a standard state for 24 hours. Each water-based colorful pattern paint was applied on this with a universal gun so that the coating amount was 250 g / m ² , dried in a standard state for 7 days, and then subjected to each performance evaluation test.

(* 1) Vividness The coating film surface of each test coated plate was visually observed and evaluated according to the following criteria.
A: The granular particles can be clearly confirmed and the boundary between the particles is clear. O: The granular particles can be clearly confirmed, but the interface between the particles is somewhat unclear. Δ: The granular particles cannot be clearly confirmed. Particles are completely crushed and there is no variety. (* 2) Concavity and convexity Tactile sensation on the coating surface of each test coating plate was confirmed by hand and evaluated according to the following criteria.
◎: There is no unevenness and is smooth ○: There is a slight unevenness but there is no feeling of catching △: There is a feeling of unevenness and there is a feeling of slightly catching ×: The unevenness feeling is remarkable and there is a feeling of catching (* 3) Water resistance Each test coated plate was immersed in clean water at 23 ° C. for 4 days, then taken out, washed with water, dried for 2 hours, visually observed for the coating state, and evaluated according to the following criteria.
◎: No swelling, cracking, peeling, etc. on coating film soaked in water ○: Swelling, cracking, peeling, etc. less than 3% of coating film immersed in water Δ: Coating area of 3% or more immersed in water Swells less than 30%, cracks, peels off, etc. x: Swells, cracks, peels off, etc. over 30% of the coating area immersed in water

Claims (5)

An aqueous resin (A) having an acid value of resin solid content of 35 mgKOH / g or more, an aqueous resin (B) having an acid value of resin solid content of less than 20 mgKOH / g, a colorant (C), and a water-soluble polysaccharide (D) Obtained by contacting the aqueous liquid composition (I) containing with the metal compound-containing aqueous medium (II),
The solid content mass of the aqueous resin (A) is in the range of 0.5 to 20 mass parts based on 100 mass parts solid content of the aqueous resin (B),
Colored resin particles wherein the equivalent ratio of metal ions based on 1 equivalent of total acid groups contained in the resin solids of the aqueous resin (A) and the aqueous resin (B) is in the range of 3 to 40 . An aqueous resin (A) having an acid value of resin solid content of 35 mgKOH / g or more, an aqueous resin (B) having an acid value of resin solid content of less than 20 mgKOH / g, a colorant (C), and a water-soluble polysaccharide (D) Obtained by contacting the aqueous liquid composition (I) containing with the metal compound-containing aqueous medium (II),
The solid content mass of the aqueous resin (A) is in the range of 0.5 to 20 mass parts based on 100 mass parts solid content of the aqueous resin (B),
Colored resin particles wherein the equivalent ratio of metal ions based on 1 equivalent of total acid groups contained in the resin solids of the aqueous resin (A) and the aqueous resin (B) is in the range of 3 to 40 Manufacturing method. An aqueous multicolor pattern coating composition comprising the colored resin particles according to claim 1. Furthermore, the water-based colorful pattern coating composition of Claim 3 containing a coating-film formation component. The coating method which coats the to-be-coated surface with the water-based multicolored pattern paint composition according to claim 3 or 4.