JP5873432B2 - Water-based colorful pattern paint composition - Google Patents

Description

  The present invention relates to a water-based multicolor pattern coating composition which is excellent in durability such as weather resistance and can form a multicolored paint film excellent in sharpness not only in spray coating but also in roller coating.

Multi-color paint is a paint containing multi-colored colored paint particles that are stably dispersed in a dispersion medium. A multi-color paint can be obtained with a single application, mainly for building construction. Is used.
In recent years, there are various needs for environmental considerations and customer appearances, so the development of water-based multicolored paints is required.

  For example, in JP-A-2005-15645, an aqueous resin having a reactive functional group, a colored pigment, water, and a colored gel particle prepared from a reactive compound capable of reacting in the presence of water are designated as an aqueous resin and a specific one. A water-in-water multicolor pattern coating composition dispersed in a transparent matte coating containing an extender having a refractive index of 5 is disclosed.

  In general, water-based paints tend to be inferior in coating workability such as being easy to sag compared to solvent-based paints, and can impart a variety of design properties to the formed coating film and have good paint workability. In particular, it is desired to develop a water-based multicolored pattern paint having a good roller coating workability with less scattering to the surrounding environment.

  Under such circumstances, Japanese Unexamined Patent Application Publication No. 2007-262350 and Japanese Unexamined Patent Application Publication No. 2009-173770 propose an aqueous colorful pattern paint containing a specific combination thickener and an aqueous colorful pattern paint containing a specific amount of resin beads, respectively. Has been.

  According to these documents, the water-based colorful pattern paint is less likely to sag after coating, and can form a coating film with a variety of design properties with little roughness, but a large load is applied to the paint during roller coating work. In such a case, the colored paint particles may be crushed and the inclusions may ooze out from the inside, resulting in a problem that the pattern becomes unclear.

JP 2008-202037 A discloses a coating composition containing a granular gel obtained by utilizing a reaction between a water-soluble polysaccharide and a specific metal compound and a coating film-forming component. It is described that the inclusion of the metal compound can suppress the exudation of the inclusion of the granular gel during the production stage or storage of the coating composition.
However, the multi-pattern coating film formed from the above coating composition has insufficient outdoor long-term weather resistance, leaving room for improvement.

JP 2005-15645 A JP 2007-262350 A JP 2009-173770 A JP 2008-202037 A

  The main object of the present invention is to provide a water-based multicolored paint composition which is excellent in durability such as weather resistance and can form a multicolored paint film excellent in sharpness not only in spray painting but also in roller painting. That is.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors now include a specific amount of a polyvalent metal in an aqueous colorful pattern paint containing a specific coating film forming component and a specific colored paint particle component. The water-based multicolored pattern that can form a multicolored paint film that is resistant to crushing during roller coating, is colorful and has excellent image clarity, and has excellent adhesion to the base and long-term weather resistance. The present inventors have found that a coating composition can be obtained and have completed the present invention.

Thus, the present invention
(A) Colored paint particle component containing an aqueous resin (a1) having a carboxyl group and other crosslinkable functional groups and a colorant (a2), and (B) a carboxyl group and a hydrolyzable silyl group and the same An aqueous multicolored paint composition comprising a coating film-forming component comprising an aqueous resin (b1) having a crosslinkable functional group other than the above and a polyvalent metal compound (b2),
At least one of the colored paint particle component (A) and the coating film forming component (B) has a functional group capable of reacting with the crosslinkable functional group in the aqueous resin (a1) and the crosslinkable functional group in the aqueous resin (b1). Containing at least two compounds (c) in one molecule;
The coating film-forming component (B) contains the polyvalent metal compound (b2) in a ratio of 0.1 to 0.9 equivalent in terms of metal to 1 equivalent of the carboxyl group in the aqueous resin (b1). An aqueous multicolor pattern coating composition characterized by the above is provided.

  According to the aqueous colorful pattern coating composition of the present invention, the colored coating particle component (A) and the coating film-forming component (B) react with each other through the crosslinking agent compound (c) and are strongly bonded to each other. The hydrolyzable silyl group in the resin (b1) is self-condensed by hydrolysis, and further, a metal bridge is formed by the polyvalent metal compound (b2) between the carboxyl groups in the aqueous resin (a1) and the aqueous resin (b1). In addition, it is extremely excellent in durability such as weather resistance, and even when a coating that places a heavy load on the paint such as roller coating is applied, the colored paint particles are not crushed, and there is little occurrence of pattern unevenness. It is possible to form a multi-pattern coating film with excellent film quality.

  In addition, according to the water-based multicolor pattern paint composition of the present invention further comprising a paint particle component (C) formed by granulating a paint film forming component having transparency, the depth of the formed multicolor pattern paint film is improved. It can be further improved, and an excellent effect is obtained that a texture of a stone texture can be expressed depending on the color of the colored paint particle component (A).

  Hereinafter, the aqueous colorful pattern coating composition of the present invention and the coating method of the coating composition will be described in more detail.

<Colored paint particle component (A)>
The colored paint particle component (A) in the aqueous colorful pattern paint composition of the present invention contains an aqueous resin (a1) and a colorant (a2).

Aqueous resin (a1)
The aqueous resin (a1) is a resin that can be dissolved or dispersed in water, and the type of resin is not particularly limited, and examples thereof include acrylic resins, silicon resins, polyurethane resins, epoxy resins, A phenol resin, a polyester resin, an alkyd resin, a polycarbonate resin, etc. can be mentioned, These can be used individually or in combination of 2 or more types, respectively. These resins may be modified, for example, as a urethane-modified acrylic resin, may be graft-polymerized, or may be in the form of dispersed particles.

  When the aqueous resin (a1) is in the form of dispersed particles, the aqueous resin (a1) can have a single layer structure (homogeneous granular shape) or a multilayer structure such as a core / shell structure. Alternatively, the shell may be cross-linked. The carboxyl group of the aqueous resin (a1) is an amine such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol; It may be partially or substantially completely neutralized with a base.

  The aqueous resin (a1) is preferably an acrylic resin from the viewpoint of durability, weather resistance, etc. of the colored paint particle component (A). As the acrylic resin, at least one (meth) acryloyl group is used. A resin obtained by (co) polymerizing the containing compound with other polymerizable unsaturated monomer copolymerizable as necessary can be mentioned.

  Examples of the (meth) acryloyl group-containing compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. An alicyclic alkyl (meth) acrylate; an aralkyl (meth) acrylate such as benzyl (meth) acrylate; an alfa such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate Xylalkyl (meth) acrylate; perfluoroalkyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylate such as N, N-diethylaminoethyl (meth) acrylate; (meth) acrylamide; 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, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentae Thritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1 , 1-trishydroxymethylpropane tri (meth) acrylate and the like (meth) acryloyl monomer having at least two polymerizable unsaturated groups in one molecule; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylates, hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc., ε-caprolactone modified products of the above hydroxyalkyl (meth) acrylates, polyoxyethylenes whose molecular ends are hydroxyl groups Hydroxyl group-containing (meth) acryloyl monomers such as len chain-containing (meth) acrylates; (meth) acrylic acid; carbonyl group-containing (meth) acryloyl monomers such as acetoacetoxyethyl (meth) acrylate and diacetone (meth) acrylamide; glycidyl ( Such as (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, etc. Epoxy group-containing (meth) acryloyl monomer; Isocyanato group-containing (meth) acryloyl monomer such as isocyanatoethyl (meth) acrylate; γ-methacryloyloxypropyltrimethoxysilane, γ-me Alkoxysilyl group-containing (meth) acryloyl monomers such as acryloyloxypropyltriethoxysilane; oxidative curing of dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc. Include a functional group-containing (meth) acryloyl monomer, and these can be used alone or in combination of two or more.

  Other copolymerizable unsaturated monomers that can be copolymerized include, for example, (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; triallyl Polyvinyl compounds having at least two polymerizable unsaturated groups in one molecule such as isocyanurate, diallyl terephthalate and divinylbenzene; allyl alcohol; carboxyl group-containing polymerizable such as maleic acid, crotonic acid and β-carboxyethyl acrylate Unsaturated monomers: (meth) acrolein, formylstyrene, carbonyl group-containing polymerizable monomers such as vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxy allyl ester, etc. Saturated monomer An epoxy group-containing polymerizable unsaturated monomer such as allyl glycidyl ether; an isocyanato group-containing polymerizable unsaturated monomer such as m-isopropenyl-α, α-dimethylbenzyl isocyanate; an alkoxy such as vinyltrimethoxysilane and vinyltriethoxysilane; Examples include silyl group-containing polymerizable unsaturated monomers; epoxy group-containing polymerizable unsaturated monomers or hydroxyl-containing polymerizable unsaturated monomers and reaction products of unsaturated fatty acids with oxidatively curable group-containing polymerizable unsaturated monomers. These can be used alone or in combination of two or more.

  The aqueous resin (a1) in the present invention has a carboxyl group, thereby making the resin (a1) aqueous and improving the production stability.

  In addition, examples of the crosslinkable functional group other than the carboxyl group that the aqueous resin (a1) has include a hydroxyl group, an isocyanato group, an amino group, an amide group, a carbonyl group, and the like, such as weather resistance and storage stability. From the viewpoint, a carbonyl group is particularly desirable.

  Examples of the aqueous resin (a1) having a carboxyl group and a carbonyl group include, as at least a part of the monomer component, (meth) acrylic acid and / or other carboxyl group-containing polymerizable unsaturated monomers as described above and the like. By using carbonyl group-containing (meth) acryloyl monomer and / or other carbonyl group-containing polymerizable unsaturated monomer and copolymerizing with other (meth) acryloyl group-containing compound and / or other polymerizable unsaturated monomer Can be manufactured. The amount of such (meth) acrylic acid and other carboxyl group-containing polymerizable unsaturated monomers and carbonyl group-containing (meth) acryloyl monomers and other carbonyl group-containing polymerizable unsaturated monomers is used for the total polymerization (Meth) acrylic acid and other carboxyl group-containing polymerizable unsaturated monomers are usually in the range of 0.05 to 10% by mass, preferably in the range of 0.1 to 3% by mass, based on the total mass of the polymerizable unsaturated monomers. The carbonyl group-containing (meth) acryloyl monomer and the carbonyl group-containing polymerizable unsaturated monomer are usually in the range of 0.2 to 30% by mass, preferably 0.3 to 15% by mass.

  The method for polymerizing the monomer is not particularly limited, and can be performed, for example, by (co) polymerizing the monomer in the presence of an emulsifier according to a general emulsion polymerization method. As the emulsifier, known emulsifiers can be used. Specific examples include anionic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers, and polymerizable unsaturated groups and anionic emulsifiers. A reactive emulsifier containing both a group and a nonionic group in the molecule can also be used. The amount used can be in the range of usually 0.5 to 6% by mass, preferably 1 to 4% by mass, based on the total mass of all polymerizable unsaturated monomers. The resulting emulsion particles can have an average particle size in the range of usually 50 to 500 nm, preferably 100 to 400 nm, more preferably 100 to 300 nm. In this specification, the “average particle size” is a submicron particle analyzer N4 (trade name, manufactured by Beckman Coulter, Inc., particle size distribution measuring device), and the sample is diluted to a concentration suitable for measurement with deionized water. And it is a value measured at normal temperature (about 20 degreeC).

  The aqueous resin (a1) generally has an acid value in the range of 0.1-50 mg KOH / g, preferably 0.1-25 mg KOH / g, more preferably 0.1-20 mg KOH / g, and generally 0-250 mg KOH / g. , Preferably 0 to 225 mgKOH / g, more preferably 0 to 200 mgKOH / g. In addition, the aqueous resin (a1) can generally have a weight average molecular weight in the range of 2,000 to 5,000,000, preferably 10,000 to 3,000,000, and more preferably 50,000 to 1,000,000.

  In this specification, "weight average molecular weight" uses "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) as a gel permeation chromatograph apparatus, and "TSKgel GMHHR-L" (trade name, 1) manufactured by Tosoh Corporation, using a differential refractometer as a detector, mobile phase: dimethylformamide (containing 10 mM each of lithium bromide and phosphoric acid), measurement temperature: 25 ° C., flow rate: 1 mL / It can be measured under min conditions.

Colorant (a2)
The colorant (a2) contained in the colored paint particle component (A) includes a color pigment, a bright pigment, a fluorescent material, and the like.

  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, dioxadi Purple pigments such as violet; Blue pigments such as cobalt blue, phthalocyanine blue, and selenium blue; Green pigments such as phthalocyanine green, and the like. Examples of bright pigments include aluminum powder, bronze powder, and copper powder. Metallic pigments such as tin powder, iron phosphide, zinc powder; pearlescent pigments such as metal oxide-coated mica powder and mica-like iron oxide, and these pigments may be used alone or in combination of two or more. Can be used in combination. 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 acid. Examples include amide-based and coumarin-based organic compounds; inorganic compounds obtained by adding metals such as copper, silver, manganese, and europium to metal compounds such as zinc sulfide, strontium aluminate, and calcium aluminate. These colorants (a2) can be used alone or in combination of two or more depending on the intended color.

  Although the compounding quantity of a coloring agent (a2) can be changed over a wide range according to the kind, it is 1-400 mass% normally on the basis of the mass of aqueous resin (a1), Especially 2-300 mass%, Furthermore, it is particularly preferable that the content be in the range of 2 to 250% by mass.

  In the colored paint particle component (A), an extender pigment can be used together with the colorant (a2). Specific examples thereof 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, etc. It can be used alone or in combination of two or more. The amount of the extender pigment can be varied over a wide range depending on the type, but is usually 0 to 1000% by mass, particularly 0 to 800% by mass, more particularly, based on the mass of the aqueous resin (a1). It can be in the range of 1.0 to 750% by mass.

  The colored paint particle component (A) in the present invention has a particle structure in which an aqueous colored paint containing an aqueous resin (a1) and a colorant (a2) is encapsulated in a shell formed of a metal salt of a water-soluble polysaccharide. Preferably it is a component. For example, the colored paint particle component (A) having such a structure is obtained by converting a composition containing an aqueous colored paint containing an aqueous resin (a1) and a colorant (a2) and a water-soluble polysaccharide (a3) to a metal compound (a4). ) Can be obtained by contacting with an aqueous medium.

  The water-soluble polysaccharide (a3) includes a polysaccharide having an ability to change (gel) into a water-insoluble or hardly soluble gel when contacted with a monovalent or polyvalent metal ion in an aqueous medium. Specifically, for example, alginic acid or an alkali metal salt thereof, gellan gum, carrageenan, bio gum, galactomannan derivative, alginic acid or derivative thereof, cellulose derivative, gelatin, casein, albumin, etc., or these are oxidized, methylated, carboxy Examples thereof include those chemically modified by methylation, hydroxyethylation, hydroxypropylation, sulfation, phosphorylation, cationization and the like, and these can be used alone or in combination of two or more.

  The water-soluble polysaccharide (a3) suppresses the outflow of the inclusion of the colored paint particle component (A) into the aqueous medium, forms a coating film with less roughness, and is also clearly visible in roller coating. In general, from the viewpoint that a coating film excellent in weather resistance can be formed, based on the total mass of the aqueous resin (a1) and the colorant (a2), generally 0.5 to 10% by mass, preferably It can be used in the range of 0.7 to 9.0% by mass, more preferably 1.0 to 8.0% by mass, and thereby the storage stability of the colored paint particle component (A) and the The rough feeling of the coating film formed using the water-based colorful pattern coating composition can be reduced.

  When the composition containing the water-based colored paint and the water-soluble polysaccharide (a3) comes into contact with an aqueous medium containing the metal compound (a4), the water-soluble polysaccharide (a3) in the composition is a metal in the aqueous medium. A metal ion derived from the compound (a4) and a water-insoluble or sparingly soluble salt are formed, and the aqueous colored paint is granulated to form a colored paint particle component (A).

  The metal compound (a4) is a compound capable of forming a monovalent or polyvalent metal ion capable of forming a water-insoluble or hardly soluble salt with the water-soluble polysaccharide (a3) in an aqueous medium. It is desirable to include an organic acid metal salt as at least a part of the above.

  By using an organic acid metal salt as at least a part of the metal compound (a4), the colored paint particle component (A) that is excellent in storage stability and that is not easily crushed by roller coating can be easily obtained. It can be formed, and the coating film properties such as weather resistance of the multicolored coating film can be improved.

  The metal species in the organic acid metal salt is preferably a polyvalent metal from the viewpoint of the strength of the colored coating particle component (A) to be formed, for example, an element periodic table such as magnesium, calcium, strontium, barium, etc. Group 2 element; Periodic table group 4 element such as titanium and zirconium; Periodic table group 6 element such as chromium and molybdenum; Group 7 element element such as manganese; Group 8 element periodic table such as iron and ruthenium; Periodic Table 9 elements such as cobalt and rhodium; Group 10 elements of the periodic table such as nickel and palladium; Group 11 elements of the periodic table such as copper and silver; Group 12 elements of the periodic table such as zinc and cadmium; Aluminum etc. Periodic table group 13 element of the element; Periodic table group 16 element such as cerium can be listed, and these can be used alone or in combination of two or more. It can be. In addition to the polyvalent metal, metals of Group 1 elements of the Periodic Table of Elements such as sodium and potassium can be used in combination. As the metal species in the metal compound (a4), an element of the periodic table group 2 element, particularly calcium, is particularly preferable.

  The organic acid in the organic acid metal salt is not particularly limited as long as it is a compound capable of forming a salt with the metal as exemplified above. For example, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, oxalic acid, fumaric acid, Succinic acid, phosphoric acid, citric acid, gluconic acid and the like can be mentioned. Of these, organic acids having a molecular weight in the range of 50 to 1000, particularly 50 to 400, more particularly 170 to 400 are suitable from the viewpoint of storage stability of the colored paint particle component (A).

  As the organic acid metal salt, calcium acetate, calcium propionate and calcium lactate are particularly preferable from the viewpoints of production stability and storage stability of the colored paint particle component (A).

  The metal compound (a4) desirably contains a metal hydroxide in addition to the organic acid metal salt. As a result, in addition to the storage stability and production stability of the colored paint particle component (A), the texture of the multicolored paint film formed from the aqueous multicolored paint composition of the present invention is reduced. The sharpness of the obtained multicolor pattern coating film can be further improved.

  Specific examples of the metal species of the metal hydroxide used for such purposes include alkali metals belonging to Group 1 elements of the Periodic Table of Elements in addition to those described above.

  In the metal compound (a4), when the organic acid metal salt and the metal hydroxide are used in combination, the use ratio thereof is the storage stability of the colored paint particle component (A), the suppression of the rough feeling of the formed multi-pattern coating film, From the viewpoint of the visibility of the formed multi-pattern coating film, the molar ratio of organic acid metal salt / metal hydroxide is generally 99/1 to 10/90, particularly 90/10 to 15/85, more particularly 85 / It is suitable to be within the range of 15-20 / 80.

  An aqueous medium containing metal ions can be prepared by dissolving at least a part of the metal compound (a4) in an aqueous medium such as water. At that time, the metal compound (a4) does not need to be completely dissolved in the aqueous medium, but may be in a state where only a part thereof is dissolved.

  The concentration of the metal compound (a4) in the aqueous medium is not strictly limited, but is usually 0.05 to 20% by mass, preferably 0.05 to 15% by mass.

  The aqueous medium adjusts the pH within the range of usually 4.0 to 13.7, preferably 7.0 to 13.5, from the viewpoint of storage stability and production stability of the colored paint particle component (A). It is preferable.

  The contact between the composition containing the water-based colored paint and the water-soluble polysaccharide (a3) and the aqueous medium containing a metal ion derived from the metal compound (a4) is performed by, for example, bringing the composition into the aqueous medium from the tip of a syringe. A method in which the composition is dispersed using centrifugal force and dropped into an aqueous medium; a method in which the composition is atomized from the tip of a spray nozzle and dropped into the aqueous medium; Can be added to an aqueous medium, followed by stirring and mixing with a disperser.

  In the production of the colored paint particle component (A), the composition and the aqueous medium comprise the storage stability of the colored paint particle component (A) and the multicolored paint film formed from the aqueous multicolored paint composition of the present invention. Metals contained in an aqueous medium with respect to 1 equivalent of carboxyl groups in the water-soluble polysaccharide (a3) contained in the composition from the viewpoints of suppression of roughness, sharpness of the multi-pattern coating film, weather resistance, etc. The compound (a4) is contained in an amount in terms of metal of 1.5 equivalents or less, particularly 0.2 or more and less than 1.0 equivalent, more particularly 0.2 to 0.9 equivalents. Is preferred.

  If necessary, the above-mentioned water-based colored paint further comprises a thickener, a specific gravity adjusting material such as balloon particles, an antifoaming agent, a curing catalyst, a pigment dispersant, a fragrance, a deodorant, an antibacterial agent, a neutralizing agent, an interface. Activator, aqueous water repellent, dispersant, preservative, antifungal agent, antifreeze agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, formaldehyde adsorbent, antimony trioxide, antimony pentoxide Further, a flame retardant such as aluminum hydroxide can be contained.

  Thus, a colored paint particle component (A) having a particle structure in which an aqueous colored paint containing an aqueous resin (a1) and a colorant (a2) is encapsulated in a shell formed of a metal salt of a water-soluble polysaccharide is obtained. Can do.

<Coating film forming component (B)>
The water-based multicolor pattern coating composition of the present invention has a coating film forming component (B) in addition to the colored paint particle component (A) in order to ensure the coating properties such as the weather resistance of the multicolor pattern coating film to be formed. Containing. The coating film-forming component (B) itself has film-forming properties. From the viewpoint of the weather resistance of the multi-pattern coating film and the vividness of the multi-pattern coating film obtained by roller coating, the carboxyl group and water It contains an aqueous resin (b1) having a degradable silyl group and other crosslinkable functional groups and a polyvalent metal compound (b2).

Aqueous resin (b1)
The aqueous resin (b1) contained in the coating film forming component (B) has a carboxyl group, a hydrolyzable silyl group, and other crosslinkable functional groups. By having a carboxyl group, the aqueous resin (b1) is made aqueous and contributes to improving the weather resistance of the multicolored paint film. Further, since the water-based resin (b1) has a hydrolyzable silyl group, it is provided under the weather resistance of the multicolor pattern coating film formed from the aqueous multicolor pattern paint composition of the present invention and the base, for example, under the multicolor pattern coating film. Adhesion with the resulting undercoat film is further improved.

  In this specification, the “hydrolyzable silyl group” is a group capable of forming a silanol group by hydrolysis and dehydrating and condensing the silanol group to form a siloxane bond, which is directly bonded to a silicon atom. Monovalent hydrolyzable atoms (atoms that form silanol groups by reacting with water), for example, monovalent hydrolyzable groups (silanol groups that react with water directly bonded to halogen atoms and silicon atoms) For example, silyl groups having both or one of the alkoxy groups.

  Specific examples of the hydrolyzable silyl group include halogenated silyl groups such as a trichlorosilyl group and a tribromosilyl group; a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a tributoxysilyl group, and the like. Trialkoxysilyl group; halodialkoxy groups such as chlorodimethoxy group and chlorodiethoxy group, and the like. Among them, trialkoxysilyl group is preferable.

  Examples of the other crosslinkable functional group that the aqueous resin (b1) has include a hydroxyl group, an isocyanato group, an amino group, an amide group, and a carbonyl group. From the viewpoint of weather resistance, storage stability, etc. A carbonyl group is preferred.

  Resins containing a carboxyl group, a hydrolyzable silyl group and a carbonyl group include, for example, (meth) acrylic acid and / or other carboxyl group-containing polymerizable unsaturated monomer as described above as at least part of the monomer component; A decomposable silyl group-containing polymerizable unsaturated monomer; and a carbonyl group-containing (meth) acryloyl monomer and / or another carbonyl group-containing polymerizable unsaturated monomer as described above, and other (meth) acryloyl groups as described above. It can be produced by copolymerization with the containing compound and / or other polymerizable unsaturated monomer. The amount of such a monomer component used is the total polymerizable unsaturation used in the copolymerization from the viewpoint of the weather resistance of the multicolored coating film to be formed, adhesion to the undercoat film, storage stability of the coating composition, etc. Based on the total weight of the monomers, (meth) acrylic acid and other carboxyl group-containing polymerizable unsaturated monomers are usually 0.05 to 10% by weight, particularly 0.03 to 6% by weight, more particularly 0.1 to 0.1%. Within the range of 3% by mass; the hydrolyzable silyl group-containing polymerizable unsaturated monomer is usually 0.01 to 10% by mass, particularly 0.03 to 7% by mass, more particularly 0.05 to 5% by mass; The carbonyl group-containing (meth) acryloyl monomer and other carbonyl group-containing polymerizable unsaturated monomers are usually in the range of 0.2 to 30% by mass, particularly 0.25 to 20% by mass, more particularly 0.3 to 15% by mass. Preferred to be within There.

  Examples of the hydrolyzable silyl group-containing polymerizable unsaturated monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, β- (meth) acryloxyethyltrimethoxysilane, γ -(Meth) acryloxybutylphenyldimethoxysilane, vinyl monohydroxydimethoxysilane, vinyltrihydroxysilane and the like.

  The method for polymerizing the monomer is not particularly limited, and can be performed, for example, by (co) polymerizing the monomer component in the presence of an emulsifier according to a general emulsion polymerization method. As the emulsifier, known emulsifiers can be used. Specific examples include anionic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers, and polymerizable unsaturated groups and anionic emulsifiers. A reactive emulsifier containing both a group and a nonionic group in the molecule can also be used. The amount used can be in the range of usually 0.5 to 6% by mass, preferably 1 to 4% by mass, based on the total mass of all polymerizable unsaturated monomers. The resulting emulsion particles can have an average particle size in the range of usually 50 to 500 nm, preferably 100 to 400 nm, more preferably 100 to 300 nm.

  In the copolymerization, different monomer components are polymerized in multiple stages, and the water-based resin (b1) is formed into a multi-layered structure such as a core / shell type, thereby improving the weather resistance and structure of the multi-pattern coating film. The film property can be improved.

  The aqueous resin (b1) is generally from 0.5 to 100 mg KOH / g, preferably from 1 to 75 mg KOH / g, more preferably from 1 to 50 mg KOH / g, and generally from 0 to 250 mg KOH / g, preferably 0. It can have a hydroxyl value in the range of ˜225 mg KOH / g, more preferably 1 to 200 mg KOH / g. In addition, the aqueous resin (a1) can generally have a weight average molecular weight in the range of 2,000 to 5,000,000, preferably 10,000 to 3,000,000, and more preferably 50,000 to 1,000,000.

Multivalent metal compound (b2)
The coating film-forming component (B) contains a polyvalent metal compound (b2), whereby the storage stability of the aqueous multicolor pattern coating composition of the present invention, and the sharpness of the pattern when the coating composition is roller-coated. And the weather resistance of the formed multi-color coating film can be improved.

As the polyvalent metal compound (b2), a compound capable of releasing a polyvalent metal ion capable of forming a metal bridge with a carboxyl group of the aqueous resin (b1) in an aqueous medium can be used. Elemental periodic table group 2 elements such as magnesium, calcium, strontium, barium; periodic table group 4 elements such as titanium and zirconium; periodic table group 6 elements such as chromium and molybdenum; periodic table group 7 elements such as manganese; Periodic table group 8 elements such as iron and ruthenium; periodic table group 9 elements such as cobalt and rhodium; periodic table group 10 elements such as nickel and palladium; periodic table 11 elements such as copper and silver; zinc; Elemental periodic table group 12 element such as cadmium, elemental periodic table group 13 element such as aluminum; compound containing metal element such as elemental periodic table group 16 element such as cerium Can be cited, among others, periodic table group 2 element, particularly compounds containing calcium are preferred.
Examples of the polyvalent metal compound (b2) include organic acid salts, hydroxides, oxides and carbonates of the above metals.

  In the present invention, from the viewpoints of improving the weather resistance of the multicolored coating film, having good paint storage stability, and being excellent in the sharpness of the multicolored coating film during roller coating, etc. The compound (b2) preferably contains an organic acid metal salt as a part of its components. As an organic acid in the said organic acid metal salt, it can select from the compound illustrated in description of the metal compound (a4) in a coloring coating particle component (A) suitably, and can be used.

  The content of the polyvalent metal compound (b2) is generally 0.1 to 0.9 equivalent in terms of metal with respect to 1 equivalent of the carboxyl group in the aqueous resin (b1) contained in the coating film forming component (B). In particular, it is preferable to be within the range of 0.15 to 0.8 equivalent, more particularly 0.15 to 0.5 equivalent. If the amount of the polyvalent metal compound (b2) used is less than 0.1 equivalent, the roller coating workability and the sharpness of the formed multi-pattern coating film are insufficient. Workability, paint storage stability, weather resistance of the coating film, etc. are insufficient.

  If necessary, the coating film forming component (B) may further contain a coloring pigment, a bright pigment, a fluorescent material, an extender pigment, other paint additives, and the like. Examples of the color pigment, the luster pigment and the fluorescent material include those exemplified for the colorant (a2) described above. Examples of the other paint additives include thickeners, resin beads, neutralizers, antistatic agents, softeners, antibacterial agents, fragrances, curing catalysts, pH adjusters, humidity control agents, and powders. Or fine particle activated carbon, photocatalytic titanium oxide, aqueous water repellent, dispersant, antifoaming agent, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, Examples thereof include flame retardants such as curing accelerators, aldehyde adsorbents, waxes, antimony trioxide, antimony pentoxide, and aluminum hydroxide.

  Among these, as the thickener, those known per se can be used without limitation, and specific examples thereof include, for example, inorganic compounds such as water-soluble alkali silicate, montmorillonite, colloidal alumina; Fibrin derivative compounds such as hydroxyethyl cellulose, carboxymethyl cellulose; polyether compounds such as pluronic polyether, polyether dialkyl ester, polyether dialkyl ether, polyether urethane modified product, polyether epoxy modified product; polyacrylic acid soda , Polyacrylic acid compounds such as polyacrylic acid (meth) acrylic acid ester copolymers; polyvinyl compounds such as polyvinyl alcohol, polyvinyl pyrrolidone and polyvinyl benzyl alcohol copolymers; sodium caseinate And protein derivatives such as ammonium caseinate; partial esters of vinyl methyl ether-maleic anhydride copolymer, drying oil fatty acid allyl alcohol ester-maleic anhydride copolymer, and the like. Can be used in combination. Among them, it is preferable to use a polyacrylic acid-based compound as a thickener, thereby improving the weather resistance of the multicolored paint film, roller coating workability, and the vividness of the multicolored pattern formed by roller painting. Can do.

  The amount of the thickener used is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass, and more preferably 0, based on the solid content mass of the aqueous colorful pattern coating composition of the present invention. 0.03 to 7.5% by mass.

  Moreover, it is preferable that a coating-film formation component (B) contains a resin bead from viewpoints of the moderate matte feeling of a multicolored pattern coating film formed, sharpness, long-term weather resistance, etc. Examples of such resin beads include acrylic resin beads, polystyrene resin beads, polyethylene resin beads, polypropylene resin beads, urethane resin beads, silicon resin beads, fluororesin beads, polyester resin beads, polyamide resin beads, and nylon resin beads. It is done. The blending amount of the resin beads is usually 1 to 100% by mass, preferably 3 to 75% by mass, more preferably 5 to 50% by mass, based on the solid content of the coating film forming component (B). Is preferred.

Crosslinker compound (c)
In the present invention, at least one of the colored paint particle component (A) and the coating film forming component (B) reacts with the crosslinkable functional group in the aqueous resin (a1) and the crosslinkable functional group in the aqueous resin (b1). The compound (c) having at least two functional groups per molecule is obtained, and as a result, the colored coating particle component (A) and the coating film forming component (B) are cross-linking agents in the multi-pattern coating film forming stage. It reacts with each other via the compound (c) and is firmly crosslinked to form a multi-pattern coating film excellent in long-term weather resistance, water resistance and the like.

  Examples of the functional group that the crosslinking agent compound (c) can have include a hydroxyl group, an isocyanato group, an alkyl ether group, an imino group, an amino group, an amide group, a carbonyl group, an epoxy group, a hydrazine group, a semicarbazide group, and a bis. Examples of the compound having at least two such functional groups in one molecule include, for example, a polyol compound, a polyisocyanate compound, a melamine compound, a polyamine compound, as well as a hydrazine derivative described later. Polyamide compounds, carbonyl group-containing resins, epoxy group-containing resins and the like can be mentioned.

  The combination of the crosslinkable functional group possessed by each of the aqueous resin (a1) and the aqueous resin (b1) and the functional group contained in the crosslinker compound (c) is a combination that can react with each other under the drying conditions of the coating film. Are not particularly limited, and specific examples include, for example, hydroxyl group and isocyanate group, hydroxyl group and alkyl ether group, hydroxyl group and imino group, amino group and epoxy group, amide group and epoxy group, carbonyl group and hydrazine. Groups, carbonyl groups and hydrazide groups, carbonyl groups and semicarbazide groups, carbonyl groups and bisacetyldihydrazone groups, and the like. A combination is preferred.

  The water-based multicolored paint composition of the present invention satisfies all of the weather resistance of the multicolored paint film, adhesion to the undercoat paint, paint storage stability, and the clarity of the paint film formed by roller painting. In order to obtain a coating composition, the aqueous resin (a1) contains a carboxyl group and a carbonyl group, and the aqueous resin (b1) contains a carboxyl group, a trialkoxysilyl group and a carbonyl group. It is desirable that the colored coating particle component (A) and / or the coating film forming component (B) contain a hydrazine derivative that reacts with a carbonyl group as the crosslinking agent compound (c).

  Examples of the hydrazine derivatives include saturated aliphatic carboxylic acids having 2 to 18 carbon atoms such as hydrazine, hydrazine hydrate, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and the like. Dihydrazides of monoolefinic unsaturated dicarboxylic acids such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid, terephthalic acid or isophthalic acid dihydrazide; pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotrizide Acetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide; ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetra Hydrazide; polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride), etc .; dihydrazide carbonate, bissemicarbazide; diisocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, and the like Polyfunctional semicarbazide obtained by excessively reacting the derived polyisocyanate compound with N, N-substituted hydrazine such as N, N-dimethylhydrazine or the hydrazide exemplified above; the polyisocyanate compound and polyether polyols or polyethylene glycol An aqueous polyfunctional semicarba obtained by excessively reacting the above-exemplified dihydrazide with an isocyanate group in a reaction product with an active hydrogen compound containing a hydrophilic group such as monoalkyl ethers De; mixture of polyfunctional semicarbazide and aqueous polyfunctional semicarbazide; include bis-acetyl-di hydrazone etc., which can be used either alone or in combination of two or more.

<Water-based colorful pattern paint composition and its coating>
The aqueous colorful pattern coating composition of the present invention can be easily prepared by mixing the colored coating particle component (A) and the coating film forming component (B) obtained as described above, and the two are mixed. In this case, additives usually used in the paint field, water, and the like can be blended as necessary. The blending ratio of the colored paint particle component (A) and the coating film forming component (B) is determined from the viewpoint of the design properties, weather resistance, etc. of the resulting multicolored paint film, and the colored paint particle component (A) / coating film forming component ( The mass ratio of B) is generally within the range of 1/99 to 60/40, preferably 5/95 to 55/45, and more preferably 10/90 to 50/50.

<Paint particle component (C)>
In addition to the colored paint particle component (A) and the coating film forming component (B), the water-based colorful pattern paint composition of the present invention further contains a paint particle component (C) having transparency as necessary. be able to. The coating particle component (C) preferably has a carboxyl group and other crosslinkable functional groups.
The paint particle component (C) is formed by granulating a paint composition that forms a transparent coating film.

  The aqueous colorful pattern coating composition of the present invention can further improve the depth of the formed coating film by further including the coating particle component (C).

In the composition of the present invention, even if it does not contain the paint particle component (C), by appropriately selecting the type and combination of the colorant (a2) based on the color paint particle component (A), However, by using the paint particle component (C) in combination with the colored paint particle component (A), the texture of the grain texture and the texture are remarkably improved, and the design has an appearance close to that of a real stone. can do.
Here, the term “having transparency” includes not only the case of being completely transparent but also the state of translucency, which may be colorless or colored.

  The paint particle component (C) having transparency is, for example, the transparency of the coating film formed even if the colorant (a2) is not used or used in the production of the color paint particle component (A) described above. Is used in an amount of less than 1.0% by mass, preferably 0.5% by mass or less, based on the solid content of the aqueous resin (a1), for example, as in the case of the colored paint particle component (A). Can be manufactured.

  The paint particle component (C) may contain extender pigments as long as the coating film formed from the composition before granulation has transparency. When the paint particle component (C) having transparency contains extender pigment, its content is 100% by mass or less, preferably based on the solid content of the aqueous resin (b1) contained in the paint particle component (C). May be 80% by weight or less.

  In the water-based multicolor pattern coating composition of the present invention, when the paint particle component (C) having transparency is used in combination with the color paint particle component (A) as the particle component, the combination ratio is obtained as a multicolor pattern coating obtained. From the viewpoint of the design properties of the film, the solid content mass ratio of the colored paint particle component (A) / transparent paint particle component (C) is generally 20/80 to 99/1, preferably 25/75 to 97/3, More preferably, it can be in the range of 30/70 to 95/5.

  The water-based colorful pattern coating composition of the present invention can form a colorful pattern coating film having various design properties and excellent performance such as water resistance by coating on the surface of the substrate.

  The substrate surface to which the aqueous colorful pattern coating composition of the present invention can be applied is not particularly limited, but examples thereof include gypsum board, concrete wall, concrete block, siding board, mortar wall, slate board, PC board, ALC board, cement calcium silicate board, wood, stone, plastic molding, ceramics, porcelain tile, surface of base material such as metal processing material, acrylic resin system, acrylic urethane resin system provided on these base materials , Polyurethane resin-based, fluororesin-based, silicone resin, silicone-acrylic resin-based, vinyl acetate resin-based, epoxy resin-based coating surfaces, wallpaper surfaces made of materials such as polyvinyl chloride, polyolefin, paper, cloth, etc. be able to.

  The water-based colorful pattern coating composition of the present invention can be applied by using a coating means known per se, for example, roller, air spray, airless spray, lysing gun, universal gun, brush, roll coater and the like and a coating method. Can be appropriately selected and used according to the type of the substrate, the application and the like. Moreover, the water-based colorful pattern coating composition of the present invention can be applied a plurality of times as long as the appearance of the coating film is not impaired.

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

  In some cases, the water-based colorful pattern coating composition of the present invention can be applied on the surface of the base coating formed after the base coating has been previously applied to the surface of the substrate.

  The undercoat paint can be appropriately selected according to the type and state of the substrate surface, and for example, an undercoat paint such as a sealer or a base conditioner can be used. It is also possible to apply a normal top coat as a base forming paint of the aqueous multicolor pattern paint composition of the present invention.

  Examples of the top coat used for forming the base include acrylic resins, acrylic silicon resins, polyolefin resins, silicon resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, alkyd resins. Examples of the coating material include a water-based or solvent-based resin composed of a resin species such as a biodegradable resin as a resin binder. It is preferable to use a water-based coating material including a water-based resin.

  The coating for forming the undercoat can be performed using a coating method known per se. For example, a coating method such as roller, air spray, airless spray, lysine gun, universal gun, brush, roll coater or the like can be used. It can be appropriately selected and used according to the application. The undercoat coating film to be formed can be dried by any of heat drying, forced drying or room temperature drying depending on the type of the undercoating paint used.

  In addition, a clear paint can be applied on the coated surface on which the aqueous colorful pattern paint composition of the present invention is applied. 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. Such a clear paint may contain a colorant as exemplified with respect to the colored paint particle component (A), as required, to an extent that does not impair the transparency of the coating film.

  The clear coating can be applied using a coating means known per se, for example, roller, air spray, airless spray, ricin gun, universal gun, brush, roll coater, etc. It can be appropriately selected and used. The clear coating film to be formed can be dried by any of heat drying, forced drying or room temperature drying depending on the type of clear coating 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.

<Manufacture of emulsion>
Production Example 1: Production of carboxyl group- and carbonyl group-containing emulsion (a1) for the production of red and white colored paint particle components

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. Among them, 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 and 3 parts of ammonium persulfate in 120 parts of deionized water were added, respectively. 20 minutes after the completion of the addition, the remaining pre-emulsion and aqueous ammonium persulfate were dropped into the flask over 4 hours.
<Pre-emulsion composition>
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 410 parts n-Butyl acrylate 240 parts 2-ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 2-hydroxyethyl acrylate 25 parts Acrylic acid 5 parts Newcol 707SF (Note 1) 66 Part

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 emulsion (a1) having a solid content of 55%. The average particle size of the emulsion (a1) was 175 nm, and the pH was 8.3.
(Note 1) “New Coal 707SF”: trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%.

Production Example 2: Production of a core / shell emulsion (a2) containing a carboxyl group, an alkoxysilyl group and a carbonyl group for the production of a coating film forming component contained in a water-based colorful pattern paint

To a three-liter four-necked flask, 400 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added, and the temperature was kept at 85 ° C. after purging with nitrogen. Among them, 3% of the pre-emulsion (for core) formed by emulsifying the components of the following composition, and 25% of the initiator aqueous solution 105 parts of 5 parts of ammonium persulfate dissolved in 100 parts of deionized water, respectively. After 20 minutes from the end of addition, the remaining pre-emulsion (for core) and 50% of the ammonium persulfate aqueous solution were added dropwise to the flask over 3 hours.
<Pre-emulsion composition (for core)>
Deionized water 300 parts Styrene 100 parts Methyl methacrylate 250 parts n-Butyl acrylate 230 parts 2-ethylhexyl acrylate 100 parts 2-hydroxyethyl acrylate 13 parts Vinyltriethoxysilane 6 parts Acrylic acid 1 part "New Coal 707SF" (Note 1) 46 copies

After completion of the dropwise addition, this was further aged for 2 hours at 85 ° C., and then a pre-emulsion (for shell) formed by emulsifying the components of the following composition and 25% of the aqueous ammonium persulfate solution were added dropwise over 2 hours.
<Pre-emulsion composition (for shell)>
Deionized water 200 parts Styrene 41 parts Methyl methacrylate 176 parts n-Butyl acrylate 41 parts 2-Ethylhexyl acrylate 15 parts Diacetone acrylamide 15 parts Hydroxyethyl acrylate 6 parts Vinyltriethoxysilane 2 parts Acrylic acid 4 parts "Newcol 707SF" ( Note 1) 20 parts

  After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Subsequently, the pH was adjusted with aqueous ammonia to obtain a core / shell emulsion (a2) having a solid content of 50%. The average particle size of the emulsion (a2) was 190 nm and the pH was 8.6.

Production Example 3: Production of emulsion containing carboxyl group and carbonyl group (a3) for production of paint particle component having transparency

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. Among them, 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 and 3 parts of ammonium persulfate in 120 parts of deionized water were added, respectively. 20 minutes after the completion of the addition, the remaining pre-emulsion and aqueous ammonium persulfate were dropped into the flask over 4 hours.
<Pre-emulsion composition>
Deionized water 368 parts Styrene 200 parts Methyl methacrylate 400 parts n-Butyl acrylate 300 parts 2-Ethylhexyl acrylate 69 parts Diacetone acrylamide 20 parts 2-Hydroxyethyl acrylate 10 parts Acrylic acid 1 part "New Coal 707SF" (Note 1) 66 Part

  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 aqueous ammonia to obtain an emulsion (a3) having a solid content of 55%. The average particle size of the emulsion (a3) was 190 nm and the pH was 8.1.

Production Example 4: Production of hydrolyzable silyl group-free emulsion (a4) for Comparative Example

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. Among them, 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 and 3 parts of ammonium persulfate in 120 parts of deionized water were added, respectively. 20 minutes after the completion of the addition, the remaining pre-emulsion and aqueous ammonium persulfate were dropped into the flask over 4 hours.
<Pre-emulsion composition>
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 400 parts n-Butyl acrylate 360 parts 2-ethylhexyl acrylate 67 parts Diacetone acrylamide 10 parts 2-hydroxyethyl acrylate 10 parts Acrylic acid 3 parts Newcol 707SF (Note 1) 66 Part

  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 emulsion (a4) having a solid content of 55%. The average particle size of the emulsion (a4) was 180 nm, and the pH was 8.0.

<Manufacture of white pigment paste>
Production Example 5
A white pigment paste (b1) was obtained by charging the following components in a 1 liter stainless steel container and stirring and mixing with a stirrer for 30 minutes.
Water 225 parts "Slulloff 72N" (Note 2) 15 parts "DISPER BYK-190" (Note 3) 30 parts "SN Deformer 380" (Note 4) 15 parts "TITANIX JR-605" (Note 5) 500 parts (Note) 2) “Sura-off 72N”: trade name, manufactured by Takeda Pharmaceutical Co., Ltd., antiseptic,
(Note 3) “DISPER BYK-190”: trade name, manufactured by BYK Chemie, pigment dispersant,
(Note 4) “SN deformer 380”: trade name, manufactured by San Nopco, antifoaming agent,
(Note 5) “TITANIX JR-605”: trade name, manufactured by Teika, titanium white.

<Manufacture of red rust color pigment paste>
Production Example 6
The following components were charged in a 1 liter stainless steel container, and were stirred and mixed with a stirrer for 60 minutes to obtain a red rust color pigment paste (b2).
Water 400 parts “Slull Off 72N” (Note 2) 15 parts “DISPER BYK-190” (Note 3) 48 parts “SN Deformer 380” (Note 4) 15 parts Iron oxide 240 parts.

<Production of water-based paint composition for colored paint particles (white)>
Production Example 7
The following components were sequentially blended in a container and mixed with stirring so as to be uniform to obtain an aqueous coating composition for colored coating particles (A-1).
55% emulsion (a1) 250 parts White pigment paste (b1) 154 parts "TEXANOL" (Note 6) 20 parts "SN deformer 380" (Note 4) 2 parts "SN thickener 612" (Note 7) 2 parts 2% alginic acid 280 parts of sodium aqueous solution (Note 6) “TEXANOL”: trade name, manufactured by Eastman Chemical Co., 2,2,4-trimethylpentanediol monoisobutyrate, film-forming aid,
(Note 7) “SN thickener 612”: trade name, manufactured by San Nopco, polyurethane polyether viscosity modifier.

<Manufacture of aqueous paint composition for colored paint particles (red rust color)>
Production Example 8
The following components were sequentially blended in a container and stirred and mixed so as to be uniform to obtain an aqueous coating composition (A-2) for colored coating particles.
55% emulsion (a1) 250 parts Red rust pigment paste (b2) 276 parts "TEXANOL" (Note 6) 20 parts "SN deformer 380" (Note 4) 2 parts "SN thickener 612" (Note 7) 2 parts 2% alginic acid 280 parts of aqueous sodium solution

<Manufacture of aqueous coating composition for transparent coating particles>
Production Example 9
The following components were sequentially blended in a container and mixed with stirring so as to be uniform to obtain an aqueous coating composition for transparent coating particles (A-3).
55% emulsion (a3) 250 parts "TEXANOL" (Note 6) 20 parts "SN deformer 380" (Note 4) 2 parts "SN thickener 612" (Note 7) 2 parts 2% sodium alginate aqueous solution 280 parts

<Production of aqueous medium for producing colored paint particles>
Production Example 10
In a stainless steel container having a capacity of 4 liters, 7.0 parts of calcium acetate monohydrate and 2,000 parts of deionized water were charged and stirred until uniform to obtain an aqueous medium containing calcium acetate (B-1 ) Was manufactured.

Production Examples 11-12
Aqueous media (B-2) to (B-3) were produced in the same manner as in Production Example 10 except that the formulation shown in Production Example 10 was as shown in Table 1 below.

<Manufacture of colored paint particle components>
Production Example 13
Into a stainless steel container having a capacity of 4 liters, 1,300 parts of the aqueous medium (B-1) obtained in Production Example 10 was charged, while stirring at a rotational speed of 2,000 rpm using a stirring blade having a diameter of 75 mm, 650 parts of the aqueous coating composition (A-1) obtained in Production Example 7 was gradually dropped into the container to produce colored coating particles. Next, the liquid in the container was further stirred for 15 minutes at the same rotation speed, and then filtered using a 200-mesh wire mesh to obtain colored paint particles (C-1). The obtained colored paint particles (C-1) had a solid content of 20%.

Production Examples 14-20
In the above Production Example 13, the colored paint particles (C-2) to (C-) were prepared in the same manner as in Production Example 13 except that the formulation of the aqueous medium and the aqueous coating composition to be dropped was changed to those shown in Table 2. 8) was produced. Table 2 shows the equivalent ratio of the metal compound contained in the aqueous medium to one equivalent of the carboxyl group derived from sodium alginate (the equivalent ratio of the total amount when a plurality of compounds are used in combination as the metal compound). Here, the molecular weight of sodium alginate is 90,000.

<Manufacture of transparent paint particles>
Production Example 21
Into a stainless steel container having a capacity of 4 liters, 1,300 parts of the aqueous medium (B-1) obtained in Production Example 10 was charged, while stirring at a rotational speed of 2,000 rpm using a stirring blade having a diameter of 75 mm, 510 parts of the aqueous coating composition (A-3) obtained in Production Example 9 was gradually dropped into the container to produce transparent coating particles. Next, the liquid in the container was further stirred for 15 minutes at the same rotation speed, and then filtered using a 200-mesh wire mesh to obtain transparent paint particles (C-9). The obtained transparent paint particles (C-9) had a solid content of 22%.

<Manufacture of aqueous clear paint for coating film forming component>
Production Example 22
The following components were sequentially charged into a 2 liter Stellens container, and stirred and mixed with a stirrer until uniform for 30 minutes to obtain an aqueous clear paint (D-1).
50% emulsion (a2) 750 parts "TEXANOL" (Note 6) 55 parts "BYK-028" (Note 8) 10 parts "Primal ASE 60" (Note 9) 3 parts Calcium acetate 0.7 parts (Note 8) "BYK -028 ": trade name, manufactured by Big Chemie, antifoaming agent,
(Note 9) “Primal ASE60”: trade name, manufactured by Rohm and Haas, polyacrylic acid viscosity modifier.

（注１０）「ＭＢＸ−１５」：商品名、積水化成品工業社製、メタクリル酸メチル樹脂ビーズ、平均粒子径１５μｍ。Production Examples 23-30
In the said manufacture example 22, water-based clear coating material (D-2)-(D-9) was obtained like the manufacture example 22 except having set a compounding composition as following Table 3.

(Note 10) “MBX-15”: trade name, manufactured by Sekisui Plastics Co., Ltd., methyl methacrylate resin beads, average particle size 15 μm.

<Manufacture of water-based colorful paint>
Examples 1-10 and Comparative Examples 1-4
The components shown in the following Table 4 were charged into a stainless steel container having a capacity of 500 ml while sequentially stirring, and then stirred until uniform, thereby producing water-based colorful pattern paints (E-1) to (E-14). .

<Performance evaluation>
Examples 11-20 and Comparative Examples 5-8
On a slate plate (600 × 900 × 3 mm), “EP sealer transparent” (manufactured by Kansai Paint Co., Ltd., trade name, water-based acrylic emulsion sealer) was roller-coated to a coating amount of 100 g / m ² and dried. After that, “Ares Aqua Gloss White” (Kansai Paint Co., Ltd., trade name, acrylic emulsion paint) was applied with a roller so that the coating amount was 100 g / m ² , and the temperature was 20 ° C. and the relative humidity was 60%. What was dried for 1 day was used as a coated plate, and each water-based colorful pattern paint obtained in the above Examples and Comparative Examples was subjected to the following test. The results are shown in Table 5 below.

Example 21
The aqueous colorful pattern paint obtained in Example 1 was applied with a roller so that the coating amount was 250 g / m ² , dried for 1 day under the conditions of an air temperature of 23 ° C. and a relative humidity of 60%, and then on the coated surface. The test coating plate obtained by applying the clear coating obtained in Production Example 22 with a roller so that the coating amount is 100 g / m ² and drying for 7 days under conditions of an air temperature of 23 ° C. and a relative humidity of 60%. The following (* 2) designability test and (* 6) weather resistance evaluation test were used. The results are also shown in Table 5 below.
In Example 21, the results of (* 1) roller workability, (* 4) smoothness, and (* 5) storability test are the same as in Example 11.

(* 1) Roller workability The workability when each water-based multicolored paint was applied to the above-mentioned coated plate by roller coating so that the coating amount was 250 g / m ² was evaluated according to the following criteria.
◎: Colored paint particles are not crushed during roller coating, and workability is very good.
○: Colored paint particles are not easily crushed during roller coating, and workability is good.
Δ: Colored paint particles may be crushed during roller coating, and workability is slightly poor.
X: The colored paint particles are often crushed during roller coating, resulting in poor workability.

(* 2) Designability Each aqueous colorful pattern paint is applied to the above-mentioned coated plate with a roller so that the coating amount is 250 g / m ^2, and dried for 7 days under conditions of an air temperature of 23 ° C. and a relative humidity of 60%. The coated surface was visually observed and the design properties were evaluated according to the following criteria.
◎: The pattern sharpness by each colored paint particle is very good.
○: The pattern sharpness of each colored paint particle is good.
Δ: Slightly poor pattern vividness due to each colored paint particle,
X: The pattern by each coloring paint particle is unclear.

(* 3) Texture The water-based colorful pattern paint is applied to the above-mentioned coated plate with a spray so that the coating amount is 250 g / m ² , dried for 7 days at a temperature of 23 ° C. and a relative humidity of 60%. The surface was visually observed and the texture was evaluated according to the following criteria.
◎: Excellent texture, versatility and depth,
○: There is a sense of texture and a variety of feelings.
Δ: The texture is inferior and the variety is blurred.
X: There is no texture and a variety of feelings cannot be felt.

(* 4) Smoothness Feeling when each test coating plate used in the above (* 2) designability test was touched by hand was evaluated according to the following criteria.
A: Good smoothness of the coating film,
○: The smoothness of the coating film is slightly good.
Δ: The coating film has a slight roughness.
X: The coating film has a noticeable rough feeling.

(* 5) Storability Each aqueous colorful pattern paint obtained in Examples and Comparative Examples was placed in a 250 ml mayonnaise bottle, and the state after 40 months at 1 month was visually observed and evaluated according to the following criteria.
A: No change before and after storage
○: Some change in viscosity is observed before and after storage, but there is no outflow of colored paint particle inclusions,
Δ: Slight outflow of colored paint particle inclusions is observed,
X: Outflow of colored paint particle inclusions is remarkable.

(* 6) Weather resistance A part of each test coated plate used in the above (* 2) designability test was cut into a size of 70 × 150 × 3 mm, and a 4000 hour weather resistance test was performed using a xenon weatherometer. After performing, the coated surface state was visually observed and evaluated according to the following criteria.
A: Equivalent to the test plate before the test, no change
○: Compared to the test coating plate before the test, there is a slight glossiness, but there is a variety of feelings and no problems.
△: Some whitening and yellowing are observed, and the feeling of versatility is slightly inferior to the test coating plate before the test.
X: Whitening and yellowing are observed on the entire surface, and the change to the test coated plate before the test is remarkable.

(* 7) Adhesiveness (* 2) Using a cutter knife in the center of the test coating plate used in the above design, a cut that reaches the substrate intersecting at an angle of 30 degrees is made, and then the two intersecting cuts Adhesive tape was affixed from above so that there were no air bubbles, the tape was completely adhered to the coating film, peeled off instantaneously, and evaluated according to the following criteria.
○: No peeling.
Δ: Slight peeling between the undercoat / multicolored coating film around the cut.
×: Remarkably peeled in the undercoat / multicolored coating film.

The water-based colorful pattern coating composition provided by the present invention provides various design properties on the surface of the base material by, for example, coating the surface of the base material such as a wall of a building, various building materials, and iron parts such as doors. It is possible to provide a multi-pattern coating film having excellent performance such as water resistance.

Claims (13)

(A) A colored paint particle component comprising an aqueous colored paint containing an aqueous resin (a1) having a carboxyl group and other crosslinkable functional groups and a colorant (a2), wherein the aqueous colored paint is carboxyl Colored paint particle component having a particle structure encapsulated in a shell formed of a metal salt of a group-containing water-soluble polysaccharide and a calcium-containing compound, and (B) a carboxyl group, a hydrolyzable silyl group and others An aqueous multicolor pattern coating composition for roller coating comprising a water-based resin (b1) having a crosslinkable functional group and a coating film-forming component containing a calcium-containing compound (b2), wherein the colored coating particle component (A ) And the coating film-forming component (B) have few functional groups capable of reacting with the crosslinkable functional group in the aqueous resin (a1) and the crosslinkable functional group in the aqueous resin (b1) in one molecule. The compound (c) which has both two, and a coating-film formation component (B) is 0.1 for 0.1 equivalent with respect to 1 equivalent of carboxyl groups in water-based resin (b1) in conversion of a calcium containing compound (b2). A water-based multicolor pattern coating composition for roller coating , characterized by containing at a ratio of -0.9 equivalents. The aqueous multi-color paint composition according to claim 1, wherein the aqueous resin (a1) and the aqueous resin (b1) each have a carbonyl group as a reactive functional group. The aqueous multicolored paint composition according to claim 1 or 2, wherein the calcium-containing compound in the colored paint particle component (A) contains an organic acid calcium salt as a part of the component. The water-based multicolored paint according to claim 3, wherein the colored paint particle component (A) contains a calcium-containing compound in a metal equivalent in an amount of 1.5 equivalents or less with respect to 1 equivalent of a carboxyl group in the water-soluble polysaccharide. Composition. The water-based colorful pattern coating composition according to any one of claims 1 to 4, wherein the hydrolyzable silyl group is a trialkoxysilyl group. The aqueous multicolored paint composition according to any one of claims 1 to 5, wherein the coating film-forming component (B) further contains a thickener. The water-based colorful pattern coating composition according to any one of claims 1 to 6, wherein the coating film-forming component (B) further contains resin beads. The water-based multicolored paint composition according to any one of claims 1 to 7, wherein the compound (c) has a hydrazide group. The aqueous resin (a1) contains a carboxyl group and a carbonyl group, the aqueous resin (b1) contains a carboxyl group, a trialkoxysilyl group and a carbonyl group, and the colored paint particle component (A) and The water-based multicolored paint composition according to claim 1, wherein at least one of the coating film-forming components (B) contains, as the compound (c), a hydrazine derivative that reacts with a carbonyl group. The aqueous colorful pattern paint according to any one of claims 1 to 9, further comprising a paint particle component (C) having transparency in addition to the colored paint particle component (A) and the coating film forming component (B). Composition. A coating method comprising applying the water-based multicolor pattern coating composition according to any one of claims 1 to 10 to a surface to be coated with or without an undercoat coating film. After applying the water-based multicolored pattern paint composition according to any one of claims 1 to 10 on the surface to be coated with or without an undercoat film, the clear paint is applied on the surface to be coated. A painting method characterized by An aqueous medium containing a calcium-containing compound, a composition containing an aqueous coloring paint containing a water-soluble resin (a1) having a carboxyl group and other crosslinkable functional groups and a colorant (a2) and a water-soluble polysaccharide, A step of providing a colored paint particle component (A) comprising a calcium calcium salt formed by contact and having a particle structure in which the aqueous colored paint is encapsulated in a shell formed of the polysaccharide calcium salt ,
A step of providing a coating film forming component (B) containing an aqueous resin (b1) having a carboxyl group and a hydrolyzable silyl group and other crosslinkable functional groups and a calcium-containing compound (b2); Comprising the step of mixing the colored paint particle component (A) and the coating film forming component (B) obtained in
At least one of the colored paint particle component (A) and the coating film forming component (B) has a functional group capable of reacting with the crosslinkable functional group in the aqueous resin (a1) and the crosslinkable functional group in the aqueous resin (b1). It contains at least two compounds (c) in one molecule, and the coating film forming component (B) converts the calcium-containing compound (b2) to 1 equivalent of carboxyl group in the aqueous resin (b1) in terms of metal. A method for producing a water-based multicolor pattern coating composition for roller coating , characterized by comprising 0.1 to 0.9 equivalents.