JP2009067870A - Aqueous multi-colored pattern coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous multi-colored pattern coating suitable for forming a multi-color-patterned coated film excellent in following property to an undercoat and soil resistance, and without damaging designing property, texture and clarity as the multi-colored pattern coating. <P>SOLUTION: This aqueous multi-colored pattern coating is provided by containing (A) a carbonyl group-containing copolymer, (B) colored coating particles and (C) a coated film-forming component, wherein, the copolymer (A) is obtained by copolymerizing a monomer mixture containing (a) a carbonyl group-containing polymerizable unsaturated monomer, (b) a carboxy group-containing polymerizable unsaturated monomer and (c) a hydrophilic polymerizable unsaturated monomer other than the monomers (a) and (b) in the presence of a hydrophilic organic solvent, and having ≥30 mass% copolymerization ratio of the total of the (b) and (c) based on the total of the unsaturated monomers used for producing the carbonyl group-containing copolymer (A), and also 0.1 to 70 mass% range copolymerization ratio of the (b). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a water-based multicolored paint that is suitable for forming a multicolored paint film that exhibits a variety of design properties and is excellent in stain resistance and base following ability.

  A multi-pattern paint is well known as a paint in which granular gel is stably dispersed in a dispersion medium. The multicolored paint is a paint that can produce a variety of patterns of two or more colors with a single coating, and is mainly used for interior and exterior surfaces of buildings and the like.

  As a multicolored paint, Patent Document 1 discloses a copolymer having a weight average molecular weight of 20,000 to 200,000 and an acid value of 2 or less, which is obtained by copolymerizing a monomer mixture containing at least 20% by weight of an acrylic monomer. A multi-pattern coating composition containing at least one enamel-dispersed particle obtained by mixing and dispersing a composition mainly composed of a colorant and an organic solvent into enamel and dispersing it in an aqueous dispersion medium is disclosed. This multi-color paint composition has good stability of enamel-dispersed particles, and the multi-color paint film formed therefrom has a variety of design feelings and excellent weather resistance and water resistance. Since the film is formed by fusing the enamel-dispersed particles, the coating film tends to become dirty, and the enamel-dispersed particles contain a large amount of organic solvent.

  For example, Patent Document 2 discloses a water-based resin having a reactive functional group, a color pigment, water, and a gel derived from a reactive compound capable of reacting in the presence of water as a multicolor pattern coating composition having a low organic solvent content. A water-in-water multicolor paint composition is disclosed in which colored gel particles, which are chemicals, are dispersed in a transparent matte paint containing an aqueous resin and an extender having a specific refractive index. The coating composition can form a multi-pattern coating film excellent in sharpness without using a large amount of an organic solvent. However, since the coating film has insufficient flexibility, In some cases, followability is insufficient, and it is difficult to maintain the initial appearance due to the adhesion of dirt due to long-term exposure.

Japanese Patent Application Laid-Open No. 09-1000042 JP 2005-15645 A

  An object of the present invention is to provide a water-based multicolored pattern paint suitable for forming a multicolored paint film excellent in followability to the ground and stain resistance without impairing the design, texture, and sharpness of the multicolored paint. It is to provide.

As a result of intensive studies on the above-described problems, the present inventors have found that an aqueous variegated pattern paint containing colored paint particles and a coating film-forming component contains a carbonyl group-containing copolymer having a specific composition. The present inventors have found that a multi-pattern coating film having flexibility and excellent stain resistance can be formed. That is, the present invention
1. A water-based multicolored paint comprising a carbonyl group-containing copolymer (A), colored paint particles (B) and a film-forming component (C), wherein the copolymer (A) is a carbonyl group-containing polymerizable unsaturated. Monomer mixture containing monomer (a), carboxyl group-containing polymerizable unsaturated monomer (b) and hydrophilic polymerizable unsaturated monomer (c) other than monomer (a) and monomer (b) in the presence of a hydrophilic organic solvent A copolymer obtained by copolymerization with a carbonyl group-containing copolymer in which the total copolymerization ratio of the carboxyl group-containing polymerizable unsaturated monomer (b) and the hydrophilic polymerizable unsaturated monomer (c) is 30% by mass or more of all polymerizable unsaturated monomers used for the production of (A), and the copolymerization ratio of the carboxyl group-containing polymerizable unsaturated monomer (b) is in the range of 0.1 to 70% by mass. There is Aqueous multicolor paint characterized by,
2. The aqueous variegated polythene according to item 1, wherein the carbonyl group-containing copolymer (A) is obtained by further copolymerizing other polymerizable unsaturated monomers (d) in addition to the monomers (a), (b) and (c). Pattern paint,
3. The water-based multicolored paint according to item 2, wherein the other polymerizable unsaturated monomer (d) contains a fluorine-containing polymerizable unsaturated monomer as a part of its components,
4). The colored coating particle (B) contains a carbonyl group-containing aqueous resin, the coating film forming component (C) contains a carbonyl group-containing aqueous resin, and the colored coating particle (B) and / or the coating film forming component (C 4) The water-based multicolored paint according to any one of items 1 to 3, which contains a hydrazine derivative,
5). 5. The method for producing an aqueous colorful pattern paint according to any one of items 1 to 4, wherein the colored paint particles (B) comprise an aqueous paint composition containing an aqueous resin, a colorant and a water-soluble polysaccharide as a metal. A method for producing an aqueous multicolored pattern paint, which is produced by contacting with an aqueous medium containing the compound (D), wherein the metal compound (D) contains an organic acid metal salt (e) as a part of its components,
6). 6. The aqueous variegated product according to 5, wherein the metal compound (D) is a combination of a metal compound (f) selected from a metal hydroxide, a metal oxide and a metal carbonate in addition to the organic acid metal salt (e). Pattern paint manufacturing method,
7). A coating method for applying the water-based multicolored pattern paint according to any one of items 1 to 4 to the surface to be coated with or without an undercoat coating film,
About.

  According to the present invention, by including a specific carbonyl group-containing copolymer in the water-based colorful pattern paint, the stain resistance can be exhibited without impairing the texture and design of the colorful pattern paint. . Moreover, since the coating film formed with the water-based colorful pattern paint of this invention has moderate softness | flexibility, it is excellent also in base followability.

  The aqueous colorful pattern paint of the present invention comprises a carbonyl group-containing copolymer (A), colored paint particles (B) and a coating film forming component (C).

Carbonyl group-containing copolymer (A):
In the present invention, the carbonyl group-containing copolymer (A) is a hydrophilic group other than the carbonyl group-containing polymerizable unsaturated monomer (a), the carboxyl group-containing polymerizable unsaturated monomer (b), the monomer (a), and the monomer (b). It is a copolymer obtained by copolymerizing a monomer mixture containing a polymerizable polymerizable unsaturated monomer (c) in the presence of a hydrophilic organic solvent.

  In the present invention, the carbonyl group-containing polymerizable unsaturated monomer (a) exerts the stain resistance of the formed coating film for a long time, and when the coating film forming component (C) described later has a carbonyl group, the coating film A monomer that is copolymerized in order to improve compatibility with the forming component (C) and improve film properties such as finish and weather resistance of the finally formed film, such as (meth) acrolein, Formyl styrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyethyl (meth) acrylate, acetoacetoxyallyl ester, diacetone (meth) acrylamide These can be used alone or in combination of two or more, particularly diacetone (meth) Acrylamide is preferred.

  The carboxyl group-containing polymerizable unsaturated monomer (b) gives hydrophilicity to the coating film formed from the water-based multicolored paint of the present invention and improves the finishing performance. For example, (meth) acrylic An acid, itaconic acid, a maleic acid, a crotonic acid, (beta) -carboxyethyl acrylate etc. can be mentioned, It can use individually or in combination of 2 or more types.

  In the present specification, the hydrophilic polymerizable unsaturated monomer (c) is a polymerizable unsaturated monomer other than the above-mentioned monomers (a) and (b), and a coating film formed from the aqueous multicolored paint of the present invention. It is a generic term for monomers introduced into the carbonyl group-containing copolymer (A) in order to improve the hydrophilicity and to exhibit stain resistance. Such hydrophilic polymerizable unsaturated monomer has a temperature of 25 ° C. Examples thereof include polymerizable unsaturated monomers having a solubility in water of 0.5 or more, particularly 1.0 or more.

  Specific examples of the hydrophilic polymerizable unsaturated monomer (c) include alkyl (meth) acrylates having 1 to 2 carbon atoms, alkoxyalkyl (meth) acrylates, hydroxyl group-containing polymerizable unsaturated monomers, and alkoxypolyoxyalkylene groups. Examples thereof include at least one selected from the group consisting of a containing polymerizable unsaturated monomer, an amide group-containing polymerizable unsaturated monomer, a morpholino group-containing polymerizable unsaturated monomer, and a sulfonyl group-containing polymerizable unsaturated monomer.

  Examples of the alkyl (meth) acrylate having 1 to 2 carbon atoms in the ester part include methyl (meth) acrylate and ethyl (meth) acrylate.

  Examples of the alkoxyalkyl (meth) acrylate include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and the like.

  Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as: (meth) acrylates having a hydroxyl group such as modified ε-caprolactone of the above hydroxyalkyl (meth) acrylates; (meth) acrylates having a polyoxyethylene chain whose molecular terminal is a hydroxyl group; allyl Alcohol, trimethylolpropane monoallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether Propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol mono And hydroxyl group-containing allyl compounds such as allyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, and pentaerythritol triallyl ether.

  As said alkoxy polyoxyalkylene group containing polymerizable unsaturated monomer, the compound which can be represented, for example by a following formula can be mentioned.

(In the formula, R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 1 to 24 carbon atoms, p represents an integer of 2 or 3, and q represents an integer of 2 to 200).

  Examples of the amide group-containing polymerizable unsaturated monomer include (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylacrylimide, dimethylaminopropylacrylamide, and the like. These can be used in combination.

  Examples of the morpholino group-containing polymerizable unsaturated monomer include (meth) acryloylmorpholine.

  Examples of the sulfonyl group-containing polymerizable unsaturated monomer include 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, sodium styrene sulfonate, sulfoethyl methacrylate, and sodium and ammonium salts thereof. .

  In the present invention, the total copolymerization ratio of the carboxyl group-containing polymerizable unsaturated monomer (b) and the hydrophilic polymerizable unsaturated monomer (c) used in the production of the carbonyl group-containing copolymer (A) is It is 30 mass% or more in all the polymerizable unsaturated monomers used for manufacture of a carbonyl group-containing copolymer (A), Comprising: The copolymerization ratio of a carboxyl group-containing polymerizable unsaturated monomer (b) is 0.1-0.1. It exists in the range of 70 mass%.

  If the total copolymerization ratio of the carboxyl group-containing polymerizable unsaturated monomer (b) and the hydrophilic polymerizable unsaturated monomer (c) is less than 30% by mass, the stain resistance and finish of the formed coating film are insufficient. It is not preferable.

  When the copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer (b) is less than 0.1% by mass, the weather resistance and stain resistance of the formed coating film are deteriorated, while when it exceeds 70% by mass, the formed coating film is formed. This is not preferable because the stain resistance and weather resistance of the resin deteriorate and the water resistance deteriorates.

  In the present invention, the carbonyl group-containing copolymer (A) may be copolymerized with other polymerizable unsaturated monomers (d) other than the monomers (a), (b) and (c) as necessary. Good. Specific examples of such other polymerizable unsaturated monomers include n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert- Butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, etc. Alkyl or cycloalkyl (meth) acrylate; isobornyl (meth) acrylate, adamantyl (meth) acrylate or other condensed polycyclic alkyl group-containing (meth) acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene; vinyl acetate Vinyl ester compounds such as: Mono (acryloyloxyethyl) acid phosphate, mono (methacryloyloxyethyl) acid phosphate, and other phosphate group-containing polymerizable unsaturated monomers: fumaric acid ester compounds; butyl vinyl ether, cyclohexyl vinyl ether, triethylene glycol di Vinyl ether, cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, propenyl ether propylene carbonate, hydroxybutyl vinyl Vinyl ether compounds of the vinyl ether terminated urethane oligomer obtained by reacting a ether and an isocyanate; or the like can be cited, and may be used alone or in combination.

  In order to make the carbonyl group-containing copolymer (A) easily orientated on the surface of the coating film in the coating film forming stage of the aqueous coating composition of the present invention, the other polymerizable unsaturated monomer (d) is Further, a fluorine-containing polymerizable unsaturated monomer may be included as a part of the component.

  Examples of such fluorine-containing polymerizable unsaturated monomers include fluorine such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, and hexafluoropropylene. Containing -α-olefins; perfluoroalkyl perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether and (per) fluoroalkyl vinyl ethers; containing perfluoroalkyl groups ( (Meth) acrylates can be mentioned, and perfluoroalkyl group-containing (meth) acrylates are suitable.

Specific examples of such a perfluoroalkyl group-containing (meth) acrylate include, for example:
_{CH 2 = CHCO 2 CH 2 C} 2 F 5, CH 2 = CHCO 2 CH 2 C 3 F 7, CH 2 = CHCO 2 CH 2 C 4 F 9, CH 2 = CHCO 2 CH 2 C 5 F 11, CH 2 _{= CHCO 2 CH 2 C 6 F} 13, CH 2 = CHCO 2 CH 2 C 7 F 15, CH 2 = CHCO 2 CH 2 C 8 F 17, CH 2 = CHCO 2 CH 2 C 9 F 19, CH 2 = CHCO _{2 CH 2 C 10 F 21,} CH 2 = CHCO 2 CH 2 C 11 F 23, CH 2 = CHCO 2 CH 2 C 12 F 25, CH 2 = C (CH 3) CO 2 CH 2 C 2 F 5, CH _{2 = C (CH 3) CO} 2 CH 2 C 3 F 7, CH 2 = C (CH 3) CO 2 CH 2 C 4 F 9, CH 2 = C (CH 3) CO 2 CH 2 C 5 F 1 ₁ , CH ₂ = C (CH ₃ ) CO ₂ CH ₂ C ₆ F ₁₃ , CH ₂ = C (CH ₃ ) CO ₂ CH ₂ C ₇ F ₁₅ , CH ₂ = C (CH ₃ ) CO ₂ CH ₂ C _{8 F 17, CH 2 = C (} CH 3) CO 2 CH 2 C 9 F 19, CH 2 = C (CH 3) CO 2 CH 2 C 10 F 21, CH 2 = C (CH 3) CO 2 CH 2 C _{11 F 23, CH 2 = C} (CH 3) CO 2 CH 2 C 12 F 25, CH 2 = CHCO 2 C 2 H 4 C 2 F 5, CH 2 = CHCO 2 C 2 H 4 C 3 F 7, CH _{2 = CHCO 2 C 2 H 4} C 4 F 9, CH 2 = CHCO 2 C 2 H 4 C 5 F 11, CH 2 = CHCO 2 C 2 H 4 C 6 F 13, CH 2 = CHCO 2 C 2 H 4 _{C 7 F 15, CH 2 =} CHCO 2 _{2 H 4 C 8 F 17,} CH 2 = CHCO 2 C 2 H 4 C 9 F 19, CH 2 = CHCO 2 C 2 H 4 C 10 F 21, CH 2 = CHCO 2 C 2 H 4 C 11 F 23, _{CH 2 = CHCO 2 C 2 H} 4 C 12 F 25, CH 2 = C (CH 3) CO 2 C 2 H 4 C 2 F 5, CH 2 = C (CH 3) CO 2 C 2 H 4 C 3 F _{7, CH 2 = C (CH} 3) CO 2 C 2 H 4 C 4 F 9, CH 2 = C (CH 3) CO 2 C 2 H 4 C 5 F 11, CH 2 = C (CH 3) CO 2 _{C 2 H 4 C 6 F 13} , CH 2 = C (CH 3) CO 2 C 2 H 4 C 7 F 15, CH 2 = C (CH 3) CO 2 C 2 H 4 C 8 F 17, CH 2 = _{C (CH 3) CO 2 C} 2 H 4 C 9 F 19, CH 2 = C (C _{3) CO 2 C 2 H 4} C 10 F 21, CH 2 = C (CH 3) CO 2 C 2 H 4 C 11 F 23, CH 2 = C (CH 3) CO 2 C 2 H 4 C 12 F 25 , CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ CF ₂ CHF ₂ , CH ₂ ═C (CH ₃ ) CO ₂ C ₂ H ₄ CF (CF ₃ ) _2, etc., alone or in combination of two or more Can be used.

In the production of the carbonyl group-containing copolymer (A), suitable copolymerization ratios of the monomers (a), (b), (c) and (d) are as follows:
The monomer (a) is 0.1 to 70% by mass, preferably 1 to 40% by mass,
The monomer (b) is 0.1 to 70% by mass, preferably 1 to 40% by mass,
The monomer (c) is 29.9 to 99.8% by weight, preferably 59 to 98% by weight,
When the monomer (d) is 0 to 69.9% by mass, preferably 0 to 39% by mass, the finish of the finally formed coating film is good, and the stain resistance, water resistance and weather resistance are good. It is suitable because it can exhibit the physical properties of the coating film in a well-balanced manner.

  As a polymerization initiator used for copolymerization of the above monomers, tert-butylperoxy 2-ethylhexanoate, benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert- Organic peroxides such as butyl hydroperoxide, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobisisobutyronitrile, azobis (2 , 4-dimethylvaleronitrile), azobis (2-methylpropiononitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethyl Luazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide } And persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate.

  As a suitable usage-amount of the said polymerization initiator, 0.001-15 mass% with respect to all the polymerizable unsaturated monomers used for manufacture of a carbonyl group containing copolymer (A), Preferably 0.2- It is desirable to be within the range of 8% by mass.

  In applying the solution polymerization method, usable hydrophilic organic solvents include alcohol organic solvents such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ether organic solvents such as dioxane and tetrahydrofuran; ethylene glycol monomethyl Ethylene glycol ether organic solvents such as ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono tert-butyl ether; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propi Diethylene glycol ether organic solvents such as ether, diethylene glycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono tert-butyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, Propylene glycol ether organic solvents such as propylene glycol monoisopropyl ether; dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol monoisopropyl ether Machine solvent; 3- ester organic solvents such as methoxybutyl acetate and the like, which alone or may be used in combination of two or more. In particular, when a propylene glycol ether-based organic solvent is used, the water-soluble or water-dispersible property of the carbonyl group-containing copolymer (A) is good. It is suitable from the point of property and weather resistance.

  As a weight average molecular weight of the carbonyl group-containing copolymer (A) obtained as described above, the surface layer of the coating film formed from the aqueous colorful pattern paint of the present invention is in the range of 1000 to 50000, particularly 1000 to 30000. Since the carbonyl group-containing copolymer (A) can be oriented and the surface of the coating film is made hydrophilic, it is possible to efficiently exhibit stain resistance and impart appropriate flexibility to the multi-pattern coating film. Background followability can be improved.

  In this specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: RI.

  The amount of the copolymer (A) used is 0.1 to 20% by weight, preferably 0.5 to 15% by weight in the solid content of the aqueous colorful pattern paint of the present invention. It is suitable from the viewpoint of the stain resistance of the coating film, the background following property, and the water resistance.

Colored paint particles (B):
In the present invention, the coloring paint particles (B) are not particularly limited in terms of materials and production methods, and conventionally known ones can be used. For example, there are many aqueous coating compositions containing an aqueous resin and a colorant. What is contained in saccharide metal salt gel can be mentioned.

  The aqueous resin contained in the aqueous coating composition for producing the colored paint particles (B) contributes to the durability of the colored paint particles (B), and a resin that can be dissolved or dispersed in water is used. The The resin type is not particularly limited. Specifically, for example, acrylic resin, polyolefin resin, silicon resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin, polycarbonate These resins can be used, and these can be used alone or in combination of two or more. These resins may be modified like, for example, urethane-modified acrylic resins, or may be graft-polymerized.

  When the aqueous resin is in the form of dispersed particles, it can be a single layer or a core / shell type multilayer. In addition, the aqueous resin can be a resin having an anionic group, for example, a carboxyl group as a hydrophilic group from the viewpoint of the production stability of the colored paint particles (B). In this case, the resin is neutralized. Examples of the neutralizing agent that can be used in this case include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, and the like. Examples thereof include amines and ammonia, and these can be used alone or in combination of two or more.

  The aqueous resin is preferably an acrylic resin from the viewpoints of durability and weather resistance of the colored paint particles (B).

  Examples of such acrylic resins include resins that copolymerize polymerizable unsaturated monomers. Examples of the polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n -Linear or branched such as butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Alkyl (meth) acrylates; alicyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-methoxyethyl ( T) acrylate, alkoxyalkyl (meth) acrylate such as 2-ethoxyethyl (meth) acrylate; perfluoroalkyl (meth) acrylate; N, N-dialkylaminoalkyl such as N, N-diethylaminoethyl (meth) acrylate ( (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, neopentyl 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-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1,1-trishydroxymethyl Polyvinyl compounds having at least two polymerizable unsaturated groups in one molecule such as propane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene; 2-hydroxyethyl (meth) acrylate, 2 -Hydroxyp Pyr (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate, allyl alcohol, ε-caprolactone modified form of the above hydroxyalkyl (meth) acrylate, molecular end is Hydroxyl group-containing polymerizable unsaturated monomers such as polyoxyethylene chain-containing (meth) acrylate which is a hydroxyl group; carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate; (Meth) acrolein, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), acetoacetoxyethyl (meth) acrylate, acetoacetate Carbonyl group-containing polymerizable unsaturated monomers such as xylyl ester and diacetone (meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3, Epoxy group-containing polymerizable unsaturated monomers such as 4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; isocyanate ethyl (meth) acrylate, m-isopropenyl-α , Α-dimethylbenzyl isocyanate and other isocyanate group-containing polymerizable unsaturated monomers; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-meta An alkoxysilyl group-containing polymerizable unsaturated monomer such as liloyloxypropyltriethoxysilane; an epoxy group-containing polymerizable unsaturated monomer or a reaction product of a hydroxyl group-containing polymerizable unsaturated monomer and an unsaturated fatty acid, dicyclopentenyloxyethyl Examples thereof include oxidatively curable group-containing polymerizable unsaturated monomers such as (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. These may be used alone or in combination of two or more. Can be used.

  The polymerization method of the monomer is not particularly limited. For example, according to a general emulsion polymerization method, an acrylic resin can be easily produced by (co) polymerizing the monomer in the presence of an emulsifier. Can do.

  As the emulsifier used in the production of the acrylic resin, known emulsifiers can be used. Examples of applicable emulsifiers include anionic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers. Can do.

  Examples of anionic emulsifiers include alkyl diphenyl ether disulfonates such as diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, sodium alkyl diphenyl ether disulfonate; sodium dodecyl benzene sulfonate, dodecyl benzene sulfonic acid Alkyl benzene sulfonates such as ammonium; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; aliphatic carboxylates such as fatty acid sodium and potassium oleate; sulfate salts containing polyoxyalkylene units (for example, polyoxyethylene alkyl) Sodium ether sulfate, polyoxyethylene alkyl ether sulfate Polyoxyethylene alkyl ether sulfates such as ammonium; polyoxyethylene alkylphenyl ether sulfate sodium, polyoxyethylene alkylphenyl ether sulfates such as ammonium polyoxyethylene alkylphenyl ether sulfate; polyoxyethylene polycyclic sodium phenyl ether sulfate; Polyoxyethylene polycyclic phenyl ether sulfates such as polyoxyethylene polycyclic phenyl ether ammonium sulfate); Naphthalene sulfonic acid formalin condensate such as sodium naphthalene sulfonic acid formalin condensate salt; Sodium dialkyl sulfosuccinate, monoalkyl succinate Alkyl succinate sulfonates such as disodium sulfonate, and the like. It can be used in combination of two or more.

  Examples of nonionic emulsifiers include polyoxyalkylene unit-containing ether compounds (for example, polyoxyalkylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene oleyl ether). Polyoxyalkylene alkyl phenyl ether compounds such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyalkylene polycyclic phenyl ether compounds such as polyoxyethylene polycyclic phenyl ether); polyoxyethylene monolaurate Polyoxyalkylene alkyl ester compounds such as polyoxyethylene monostearate and polyoxyethylene monooleate; Polyoxyalkylene alkylamine compounds such as reoxyethylene alkylamine; sorbitan compounds such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, etc. These can be used alone or in combination of two or more.

  Examples of amphoteric emulsifiers include dimethylalkyl betaines, dimethylalkyl lauryl betaines, and alkyl glycines.

  As the emulsifier, a reactive emulsifier containing both a polymerizable unsaturated group and an anionic group or nonionic group in the molecule can also be used.

  The amount of the emulsifier used is usually in the range of 0.5 to 6% by mass, preferably 1 to 4% by mass, based on the total mass of polymerizable unsaturated monomers used for the production of the acrylic resin. Can do.

  As the colorant that can be contained in the colored paint particles (B), pigments and dyes can be used. Examples of coloring pigments 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 condensation. Yellow pigments such as azo 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, ansan Red pigments such as throne, anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyrrolopyrrole, watching red, permanent red; 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. Examples of glittering 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.

  On the other hand, examples of the dye include azo dyes such as monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes and thiazole azo dyes; anthraquino dyes such as anthraquinone derivatives and anthrone derivatives; indigo derivatives and thioindigo derivatives Indigoid dyes such as: phthalocyanine dyes; diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, carbonium dyes such as acridine dyes; quinoneimine dyes such as azine dyes, oxazine dyes, thiazine dyes; polymethine (or cyanine) dyes, adimethine dyes, etc. Methine dyes; quinoline dyes; nitro dyes; nitrone dyes; benzoquinone and naphthyquinone dyes; naphthalimide dyes; perinone dyes, and the like. Not to be able to use. These colorants can be used alone or in combination of two or more according to the target color.

  In the colored paint particles (B), an extender can be used together with the colorant. 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.

  The blending amount of the colorant is usually 0.01 to 500% by mass, preferably from 0.01 to 500% by mass based on the mass of the aqueous resin, from the viewpoints of colorability, specific gravity, durability, water resistance and the like by the colored paint particles (B). It is suitable to be in the range of 0.05 to 400% by mass.

  The colored paint particles (B) can be produced, for example, by bringing an aqueous paint composition containing an aqueous resin, a colorant and a water-soluble polysaccharide into contact with an aqueous medium containing a metal compound (D). Thus, colored paint particles comprising the aqueous paint composition in a polysaccharide metal salt gel can be formed.

  The water-soluble polysaccharide is a polysaccharide capable of changing to a water-insoluble or sparingly soluble gel when contacted with a monovalent or polyvalent metal ion in an aqueous medium, generally about 3,000 to about 3,000. Those having a number average molecular weight in the range of 2,000,000 and exhibiting a water solubility of about 10 g / l (25 ° C.) or more are preferred. Specifically, for example, alginic acid or an alkali metal salt thereof, Gellan gum, carrageenan and the like can be mentioned, and these can be used alone or in combination of two or more.

  The water-soluble polysaccharide is the stability of the colored paint particles (B) in water, the handleability when producing the colored paint particles (B), and the water resistance of the coating film formed from the paint containing the colored paint particles (B). From the point of view of properties, it is preferable to use 0.1 to 7% by mass, preferably 0.1 to 5% by mass, based on the total mass of the aqueous resin and the water-soluble polysaccharide.

  The above-mentioned aqueous coating composition further comprises a specific gravity adjusting material such as balloon particles, an antifoaming agent, a curing catalyst, a pigment dispersant, a fragrance, a deodorizing agent, an antibacterial agent, a neutralizing agent, a surfactant, if necessary. Aqueous water repellent, dispersant, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, formaldehyde adsorbent, antimony trioxide, antimony pentoxide, hydroxylation A flame retardant such as aluminum can be contained.

  In the present invention, the aqueous coating composition for producing the colored coating particles (B) is prepared by, for example, mixing an aqueous resin, a colorant paste, and an aqueous solution of a water-soluble polysaccharide together with the above-described other components as appropriate. Can be prepared.

  When the aqueous coating composition is brought into contact with an aqueous medium containing the metal compound (D), the water-soluble polysaccharide in the aqueous coating composition contains metal ions and water derived from the metal compound (D) in the aqueous medium. Insoluble or sparingly soluble salt is formed, and the aqueous coating composition is granulated to form colored coating particles.

  The metal compound (D) is a compound capable of forming a monovalent or polyvalent metal ion capable of forming a water-insoluble or hardly soluble salt with a water-soluble polysaccharide in an aqueous medium. It is desirable to include e).

  The metal compound (D) contains an organic acid metal salt (e) as a part of its components, whereby colored paint particles having excellent storage stability can be easily formed, and a coating film formed from an aqueous multicolored paint It is possible to improve the physical properties of the coating film such as water resistance, and to reduce the burden on the production apparatus and environment by the waste liquid and granular gel suspension produced in the production of the granular gel.

  The metal species in the organic acid metal salt (e) is preferably a polyvalent metal, particularly a divalent metal, from the viewpoint of the strength of the colored coating particle (B) to be formed. Periodic Table Group 2 elements such as magnesium, calcium, strontium and barium; Periodic Table Group 6 elements such as chromium and molybdenum; Periodic Table 7 elements such as manganese; Periodic Table 8 elements such as iron and ruthenium; Cobalt and Rhodium Periodic Table Group 9 elements such as nickel and palladium; Periodic Table Group 11 elements such as copper and silver; Periodic Table 12 elements such as zinc and cadmium; Periodic Group 13 elements such as aluminum; There may be mentioned group 16 elements of the periodic table such as cerium, among which group 2 elements of the periodic table, especially calcium are preferred.

  As the organic acid in the organic acid metal salt (e), any conventionally known compounds can be used without limitation as long as they are compounds capable of forming a salt with the metal as exemplified above. For example, formic acid, acetic acid, propionic acid, butyric acid, Examples thereof include lactic acid, oxalic acid, fumaric acid, succinic acid, phosphoric acid, citric acid, and gluconic acid.

  In the present invention, among the above-mentioned organic acid metal salts (e), calcium acetate is suitable from the viewpoint of the production stability of the colored paint particles (B).

  Further, as the metal compound (D) in the present invention, when the metal compound (f) selected from metal hydroxide, metal oxide and metal carbonate is used in addition to the organic acid metal salt (e), colored paint particles In addition to the storage stability and production stability of (B), the unevenness of the coating film formed from the water-based multicolored paint of the present invention can be reduced to make it difficult to stain, and the sharpness can be improved. ,Is suitable.

  Specific examples of the metal of the metal compound (f) used for such purposes include alkali metals belonging to Group 1 elements of the periodic table in addition to those described above.

  In the present invention, it is preferable to use a hydroxide as the metal compound (f) from the viewpoint of the production stability of the colored paint particles (B).

  In the metal compound (D), when the organic acid metal salt (e) and the metal compound (f) are used in combination, the usage ratio is 99 / mole ratio of the organic acid metal salt (e) / metal compound (f). 1 to 10/90, especially 90/10 to 15/85, the storage stability of the colored paint particles (B) and the unevenness of the coating film formed from the aqueous multicolored paint of the present invention. It is possible to reduce the burden on the production apparatus and the environment by reducing waste and making it difficult to stain and having good visibility, and further, the waste liquid and granular gel suspension generated in the production of the colored paint particles (B), Is suitable.

  The metal compound (D) can prepare an aqueous medium containing metal ions by dissolving at least a part thereof in an aqueous medium such as water. At that time, the metal compound (D) does not have to be completely dissolved in the aqueous medium, and may be partially dissolved.

  The contact between the aqueous coating composition and the aqueous medium containing metal ions derived from the metal compound (D) is, for example, a method of dropping the aqueous coating composition into the aqueous medium from the tip of a syringe; Method of scattering using centrifugal force and dropping into aqueous medium; Method of atomizing aqueous coating composition from tip of spray nozzle and dropping into aqueous medium; Adding aqueous coating composition into aqueous medium; It can be performed by a method such as stirring and mixing with a disperser.

  In the production of the colored paint particles (B), the aqueous paint composition and the aqueous medium are contained in the aqueous medium with respect to 1 mol of the group derived from the carboxyl group of the water-soluble polysaccharide contained in the aqueous paint composition. Use of the metal compound (D) in a proportion such that the amount of the metal compound (D) is in the range of 0.2 to 3 mol, particularly 0.4 to 2 mol, and the storage stability of the formed colored paint particles (B) and the present invention. The coating film formed from this water-based multicolored paint can reduce the unevenness and make it difficult to become dirty, and also has good definition and water resistance.

Examples of the group derived from the carboxyl group include a carboxyl group, a carboxylate metal base, and a carboxylate ion group (—COO ⁻ ).

  By the method described above, colored paint particles (B) formed by encapsulating an aqueous paint composition containing an aqueous resin and a colorant in a polysaccharide metal salt gel can be obtained.

Coating film forming component (C):
The water-based multicolored paint of the present invention comprises a film-forming component (in addition to the carbonyl group-containing copolymer (A) and the colored paint particles (B) in order to ensure the film properties such as water resistance of the multicolored paint film. C). The coating film forming component (C) itself has film-forming properties, and may be either non-crosslinked type or crosslinked type.

  In the present invention, the coating film-forming component (C) is an aqueous resin from the viewpoint of affinity with the carbonyl group-containing copolymer (A) and the colored paint particles (B) and storage stability as an aqueous multicolor paint. It is desirable that it is an aqueous composition comprising

  As the aqueous resin contained in the coating film forming component (C), those generally used as a resin binder in the aqueous paint field can be used. For example, those described above as the aqueous resin in the colored paint particles (B) It can be used by appropriately selecting from among them.

  Further, from the viewpoint of the water resistance of the coating film formed from the water-based colorful pattern of the present invention, the colored coating particle (B) and the coating film forming component (C) are each functional group (x) and It is desirable to contain (y), the colored coating particle (B) contains the reactive functional group (x), and the coating film forming component (C) reacts with the reactive functional group (x). It is desirable to have a reactive functional group (y) that can be used.

  The combination of the reactive functional group (x) contained in the colored paint particles (B) and the reactive functional group (y) contained in the coating film forming component (B) It is not particularly limited as long as it can be reacted, and specifically, for example, hydroxyl group and isocyanate group, hydroxyl group and alkyl ether group, hydroxyl group and imino group, carboxyl group and epoxy group, amino group and epoxy group, Examples include amide groups and epoxy groups, carbonyl groups and hydrazine groups, carbonyl groups and hydrazide groups, carbonyl groups and semicarbazide groups, and carbonyl groups and bisacetyldihydrazone groups. When it exists, it is possible to carry out one-component crosslinking at room temperature, which is preferable.

  In order to achieve both the water resistance, weather resistance, storage stability and the like of the coating film formed using the water-based colorful pattern paint of the present invention, the colored paint particles (B) include a carbonyl group-containing water-based resin, It is desirable that the film-forming component (C) comprises a carbonyl group-containing aqueous resin, and the colored paint particles (B) and / or the coating film-forming component (C) contain a hydrazine derivative. By including the hydrazine derivative, the stain resistance of the formed coating film can be exhibited for a long period by crosslinking reaction with the carbonyl group-containing copolymer (A).

  Examples of the hydrazine derivative for reacting with the carbonyl group that can be contained in the colored paint particles (B) or the coating film forming component (C) include hydrazine, hydrazine hydrate, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, Dihydrazides of saturated aliphatic carboxylic acids having 2 to 18 carbon atoms such as glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide; monohydric unsaturated dicarboxylic acid dihydrazides such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; Dihydrazide of phthalic acid, terephthalic acid or isophthalic acid; dihydrazide, trihydrazide or tetrahydrazide of pyromellitic acid; nitrilotriacetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide Ethylenediaminetetraacetic 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; diisocyanate such as hexamethylene diisocyanate and isophorone diisocyanate and polyisocyanate compounds derived therefrom are reacted with N, N-substituted hydrazine such as N, N-dimethylhydrazine and the above-mentioned hydrazide in excess. The resulting polyfunctional semicarbazide; an isocyanate in the reaction product of the polyisocyanate compound and an active hydrogen compound containing a hydrophilic group such as polyether polyols and polyethylene glycol monoalkyl ethers. An aqueous polyfunctional semicarbazide obtained by excessively reacting the above-exemplified dihydrazide with an nate group; a mixture of the polyfunctional semicarbazide and an aqueous polyfunctional semicarbazide; bisacetyldihydrazone, and the like. These can be used in combination.

  In the present invention, the coating film forming component (C) may form a colored coating film or may form a clear coating film. Coloring agents can be included.

  The colorant that can be contained in the coating film forming component (C) can be appropriately selected from those exemplified above as the colorant in the colored paint particles. Further, from the viewpoints of improving the drying property of the multicolored coating film, improving the appropriate gloss, and improving the tactile sensation, it is desirable to incorporate the above-mentioned extender pigment into the coating film forming component (C).

  When the colorant and / or extender pigment is blended in the coating film forming component (C), the total blending amount is usually 5 to 300% by mass with respect to the resin solid content contained in the coating film forming component (C). , Preferably 10 to 200% by mass, more preferably 15 to 150% by mass.

  The blending ratio of the colored paint particles (B) to the coating film forming component (C) is determined from the viewpoint of the design properties, water resistance, and stain resistance of the multicolored paint film obtained. The solid content mass ratio of the component (C) can be in the range of 1/99 to 60/40, preferably 10/90 to 50/50, and more preferably 20/80 to 45/55.

  The water-based colorful pattern paint may contain paint additives as necessary in addition to the carbonyl group-containing copolymer (A), the colored paint particles (B) and the coating film forming component (C) described above. it can.

  Examples of the paint additive include a neutralizer, balloon particles, a viscosity modifier, an anti-settling agent, an antistatic agent, a softener, an antibacterial agent, a fragrance, a curing catalyst, a pH adjuster, a humidity control agent, powder or fine particles. Activated carbon, photocatalytic titanium oxide, hydrolyzable silyl group-containing organosilane compound, colloidal silica, aqueous water repellent, dispersant, antifoaming agent, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stability Examples thereof include flame retardants such as an agent, a film-forming aid, zinc whisker, a curing accelerator, an aldehyde adsorbent, wax, antimony trioxide, antimony pentoxide, and aluminum hydroxide.

Painting method:
The water-based colorful pattern paint of the present invention can form a protective coating film having various design properties and excellent performance such as water resistance, stain resistance, and background followability by coating on the substrate surface. it can.

  Examples of the substrate surface to which the aqueous colorful pattern paint of the present invention can be applied include gypsum board, concrete wall, mortar wall, slate board, PC board, ALC board, cemented calcium silicate board, wood, stone, and plastic molding. Surface of base materials such as materials and metal processed materials, acrylic resin system, acrylic urethane resin system, polyurethane resin system, fluororesin system, silicon acrylic resin system, vinyl acetate resin system, epoxy resin system provided on these base materials And a wallpaper surface made of a material such as polyvinyl chloride, polyolefin, paper, and cloth.

The application amount of the aqueous colorful pattern paint of the present invention can be changed according to the composition of the coating composition to be used, the kind of the substrate to be applied, etc., but is usually 100 to 1,000 g / m ² per time, preferably be in the range of 150~700g / ^{m 2.} Moreover, you may apply repeatedly several times in the range which does not impair the coating-film external appearance.

  The water-based colorful pattern paint of the present invention can be applied using a coating means known per se, for example, using a coating device such as a roller, an air spray, an airless spray, a lysine gun, a universal gun or a brush. it can. Moreover, when using a roller, a wool roller, a sand-bone roller, etc. can be used.

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

  The water-based colorful pattern paint of the present invention may be applied, for example, to a base coat surface in advance for a protective coating, and then the water-based colorful pattern paint of the present invention is applied to the formed undercoat surface. it can.

  The undercoat paint can be appropriately selected according to the type and state of the surface of the base material. 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 coating composition of the present invention.

  Examples of the top coat for forming the base include, for example, an aqueous resin composed of a resin type such as an acrylic resin, a polyolefin resin, a silicon resin, a polyurethane resin, an epoxy resin, a phenol resin, a polyester resin, and an alkyd resin. Or the coating material which contains solvent-type resin as a resin binder can be mentioned, It is preferable to use the coating material which contains water-system resin.

  When applying the undercoat paint, two or more kinds of undercoat paints can be repeated as necessary.

  The undercoating can be applied using a coating means known per se, for example, using a coating device such as a roller, an air spray, an airless spray, a lysine gun, a universal gun, or a brush.

The undercoat coating amount of the coating can be varied according to the types of base material to be coated, usually once per 50~2,000g / ^{m 2,} preferably in the range of 70~1,000g / ^{m 2} It can be.

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

  By using the water-based colorful pattern paint of the present invention, it is possible to form a protective coating film having various design properties and excellent in coating surface smoothness, finish, water resistance, stain resistance, etc. If necessary, an overcoating paint known per se may be further applied on the coating film of the water-based colorful pattern paint.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited only to these Examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Manufacture example 1 of acrylic resin solution
A four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was charged with 70 parts of propylene glycol monomethyl ether, heated to 110 ° C. with stirring, and then the temperature of the liquid in the four-necked flask The composition of the monomer, solvent and polymerization initiator shown in Table 1 below was added dropwise at a constant rate over 3 hours using a dropping pump. An initiator solution in which 0.5 part of an additional polymerization initiator (tert-butylperoxy 2-ethylhexanoate) was dissolved in 10 parts of propylene glycol monomethyl ether was maintained at 110 ° C. for 1.5 hours after completion of the dropping. Was added dropwise at a constant rate over 1.5 hours, and further kept at 110 ° C. for 3 hours, and stirring was continued to obtain an acrylic resin solution (A-1). The weight average molecular weight of the obtained resin was about 4,500. The solid content was 43%, and the acid value was 78 mgKOH / g.

Production Examples 2-5
Except having shown the compounding composition in Table 1, it carried out similarly to manufacture example 1, and obtained each acrylic resin solution (A-2)-(A-5). The property values of the obtained resin solution are also shown in Table 1.

Production and production example 6 of emulsion for water-based colorful pattern paint
285 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added to a 4-liter flask having a capacity of 2 liters, and maintained at 85 ° C. after purging with nitrogen. 3% of the pre-emulsion obtained by emulsifying the components of the following composition therein, and 41 parts of 123 parts of an aqueous initiator solution obtained by dissolving 3 parts of ammonium persulfate in 120 parts of deionized water, 20 minutes after the addition, 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 413 parts n-Butyl acrylate 240 parts 2-ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 1,6-hexanediol diacrylate 5 parts 2-hydroxyethyl acrylate 20 parts Acrylic acid 2 parts “New Coal 707SF” (Note 1) After dropping 66 parts, 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 170 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 of white pigment paste Production Example 7
The following components were charged in a 1 liter stainless steel container and stirred and mixed with a stirrer for 30 minutes to obtain a white pigment paste (b1).
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, defoaming agent (Note 5) “TITANIX JR-605”: trade name, manufactured by Teika, titanium white.

Production of red rust pigment paste Production example 8
The following components were charged into a 1 liter stainless steel container and stirred and mixed with a stirrer for 60 minutes to obtain a red rust 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 black pigment paste Production Example 9
A black pigment paste (b3) was obtained by charging the following components in a 1 liter stainless steel container and stirring and mixing with a stirrer for 60 minutes.
Water 520 parts Monoethylene glycol 40 parts “Slulloff 72N” (Note 2) 8 parts “DISPER BYK-190” (Note 3) 48 parts “SN Deformer 380” (Note 4) 16 parts Carbon black 200 parts.

Production of aqueous liquid composition for colored paint particles Production Example 10
The following components were sequentially blended in a container and mixed with stirring so as to be uniform to obtain an aqueous liquid composition for colored paint particles (B-1).
55% emulsion (a1) 250 parts white pigment paste (b1) 154 parts 10% adipic acid dihydrazide aqueous solution 4 parts “TEXANOL” (Note 6) 20 parts “SN deformer 380” (Note 4) 2 parts “Adecanol UH-438” (Note 7) 2 parts 2% sodium alginate aqueous solution 280 parts (Note 6) “TEXANOL”: trade name, manufactured by Eastman Chemical Co., Ltd., 2,2,4-trimethylpentanediol monoisobutyrate, film-forming aid,
(Note 7) “ADEKA NOL UH-438”: trade name, manufactured by ADEKA, modified polyether urethane, viscosity modifier.

Production Examples 11 and 12
In the production example 10 described above, the aqueous liquid compositions for colored paint particles (B-2) and (B-3) were produced in the same manner as in the production example 10 except that the composition was changed to the composition shown in Table 2 below. .

Production of aqueous medium for colored paint particles Production Example 13
In a 4 liter stainless steel container, 7.0 parts of calcium acetate monohydrate and 2,000 parts of deionized water are charged, and stirred until uniform to obtain an aqueous medium (C-1) containing calcium acetate. Manufactured.
Production Example 14
In a 4 liter stainless steel container, 3.0 parts of calcium acetate monohydrate, 3.0 parts of calcium hydroxide and 2,000 parts of deionized water were charged, and an aqueous medium (C- 2) was produced.

Production of colored paint particles Production Example 15
Into a 4 liter stainless steel container, 1,300 parts of the aqueous medium (C-1) obtained in Production Example 13 was charged, and the above production was performed 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 liquid composition (B-1) obtained in Example 10 was gradually dropped into the container to produce colored paint 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 (D-1). The obtained colored paint particles (D-1) had a white color visually and a solid content of 20%.
Production Examples 16-18
In the above Production Example 15, colored paint particles (D-2) to (D-4) are produced in the same manner as in Production Example 15 except that the composition of the aqueous liquid composition to be added dropwise is as shown in Table 3. did.

Production of water-based clear paint for coating film forming component Production Example 19
The following components were charged in a 2 liter stainless steel container, and stirred and mixed with a stirrer for 30 minutes to obtain an aqueous clear paint (c1).
55% emulsion (a1) 750 parts “TEXANOL” (Note 5) 50 parts Water 279 parts “Talc SS” (Note 8) 250 parts “SN Deformer 380” (Note 4) 10 parts “Adecanol UH-438” (Note 7) ) 6 parts (Note 8) “Talc SS”: trade name, manufactured by Nippon Talc Co., Ltd.

Production of water-based colorful pattern paint Examples 1-5 and Comparative Examples 1-2
The various pattern paints (E-1) to (E-7) were produced by sequentially charging the components shown in Table 4 below into a 500 ml stainless steel container while stirring the mixture, and then stirring until uniform. Table 4 also shows the coating film performance evaluation of the obtained paint.

Preparation of test coated plate On a slate plate (300 x 100 x 4 mm), "EP sealer transparent" (manufactured by Kansai Paint Co., Ltd., water-based acrylic emulsion sealer) is roller-coated to a coating amount of 100 g / m ² and dried. After that, “Vini Deluxe 300 White” (manufactured by Kansai Paint Co., Ltd., JIS K5663 1 type compliant 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 under the conditions was used as a plate to be coated, and each of the various pattern paints was applied thereon with a spray so that the coating amount was 300 g / m ² . Then, it dried for 7 days under the conditions of air temperature 23 degreeC and relative humidity 60%, and obtained each test coating board, and used for the performance test of (* 1)-(* 4).

(* 1) Appearance of coating film The appearance of each test coating plate was visually observed and evaluated according to the following criteria.
○: Various design feelings, textures are sufficient, good,
△: Variety of design feelings, slightly poor texture,
X: Coating film defects such as cracks and chijimi are observed.
(* 2) Contamination resistance After fixing each of the above test coating plates to the south side of the building roof in Ota-ku, Tokyo at an angle of 30 ° and leaving it in that state for 3 months, the degree of contamination of the coating film is visually checked as follows. Evaluation based on the criteria.
◎: I do not know the dirt compared to before leaving,
○: Slightly dirty compared to before leaving, but the stains are not noticeable by washing.
Δ: Dirt is conspicuous compared to before leaving, and some dirt is recognized even after washing with water.
X: Dirt is conspicuous as compared to before leaving, and it is recognized even after washing with water.
(* 3) Water resistance After each test coating plate was immersed in clean water at 20 ° C. for 7 days, the coated surface state was observed and evaluated according to the following criteria.
○: Good,
Δ: Gloss, whitening, blisters are observed,
X: Remarkably blistering is observed, or the coating film is softened.
(* 4) Substrate following After coating “Ares Holder GII” (manufactured by Kansai Paint Co., Ltd., water-based substrate preparation) on a slate plate (70 × 150 × 5 mm), “Aqua Gloss White” (manufactured by Kansai Paint Co., Ltd., acrylic) Emulsion paint) is coated with a roller so that the application amount is 100 g / m ^2, and dried for 1 day under the conditions of an air temperature of 20 ° C. and a relative humidity of 60%. Was applied by spraying so that the coating amount was 300 g / m ² . Then, it dried for 7 days on the conditions of air temperature 23 degreeC and relative humidity 60%, and obtained each test coating plate. By observing the state of the coating film after 10 cycles of the test, [immersion in water (20 ° C.) for 18 hours to 3 hours in a -20 ° C. incubator to 3 hours in a 50 ° C. incubator] evaluated.
○: No cracking, peeling or swelling is observed, good
△: Some cracks, peels and blisters are recognized.
X: Cracks, peels and blisters are observed on the entire surface.

Claims (7)

A water-based multicolored paint comprising a carbonyl group-containing copolymer (A), colored paint particles (B) and a film-forming component (C), wherein the copolymer (A) is a carbonyl group-containing polymerizable unsaturated. Monomer mixture containing monomer (a), carboxyl group-containing polymerizable unsaturated monomer (b) and hydrophilic polymerizable unsaturated monomer (c) other than monomer (a) and monomer (b) in the presence of a hydrophilic organic solvent A copolymer obtained by copolymerization with a carbonyl group-containing copolymer in which the total copolymerization ratio of the carboxyl group-containing polymerizable unsaturated monomer (b) and the hydrophilic polymerizable unsaturated monomer (c) is It is 30 mass% or more in all the polymerizable unsaturated monomers used for manufacture of (A), Comprising: The copolymerization ratio of a carboxyl group-containing polymerizable unsaturated monomer (b) is in the range of 0.1-70 mass%. There is Aqueous multicolor paint according to claim. The aqueous solution according to claim 1, wherein the carbonyl group-containing copolymer (A) is obtained by further copolymerizing other polymerizable unsaturated monomers (d) in addition to the monomers (a), (b) and (c). Multicolored paint. The water-based multicolored paint according to claim 2, wherein the other polymerizable unsaturated monomer (d) contains a fluorine-containing polymerizable unsaturated monomer as a part of its components. The colored coating particle (B) contains a carbonyl group-containing aqueous resin, the coating film forming component (C) contains a carbonyl group-containing aqueous resin, and the colored coating particle (B) and / or the coating film forming component (C 4) The water-based colorful pattern paint according to any one of claims 1 to 3, which comprises a hydrazine derivative. 5. The method for producing a water-based multicolored paint according to claim 1, wherein the colored paint particles (B) comprise an aqueous paint composition containing a water-based resin, a colorant and a water-soluble polysaccharide as a metal. A method for producing an aqueous colorful pattern paint, which is produced by contacting with an aqueous medium containing a compound (D), wherein the metal compound (D) contains an organic acid metal salt (e) as a part of its components. 6. The aqueous solution according to claim 5, wherein the metal compound (D) is a combination of a metal compound (f) selected from a metal hydroxide, a metal oxide and a metal carbonate in addition to the organic acid metal salt (e). A method for producing multicolored paints. The coating method which coats the to-be-coated surface with the water-based multicolored pattern paint according to any one of claims 1 to 4 with or without an undercoating film.