Coating material

Abstract

To provide a coating material capable of forming a coating film exhibiting colorful beautiful appearance and excellent in weather resistance, crack resistance, substrate followability or the like.SOLUTION: The coating material of the present invention is a coating material in which liquid or gel-like colored particles are dispersed in a water-based clear coating material, wherein the water-based clear coating material contains an acrylic silicone resin emulsion (A1) having a silica residual amount ratio of 0.01 to 3% by mass and a glass-transition temperature of 30 °C or lower, and the liquid or gel-like colored particles are granules of a coloring material containing an acrylic silicone resin emulsion (A2) having a silica residual amount ratio of 0.1 to 40% by mass and coloring pigments.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel coating material. [Background technology]

[0002] Conventionally, wall surfaces of buildings, civil engineering structures, etc. have been coated with various coating materials for the purposes of surface protection, improving aesthetics, etc. Among these, coating materials comprising liquid or gel-like color particles dispersed in an aqueous medium are used in applications where high aesthetics are required, because they can form colorful coatings.

[0003] Regarding such coating materials, for example, Patent Document 1 (JP 2018-193526 A) describes a paint in which gel-like color particles are dispersed in a dispersion liquid whose main component is a silicone acrylic synthetic resin emulsion (paragraphs 0047 to 0052, etc.). Such coating materials can form coatings with a colorful finish and are expected to also have improved weather resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-193526 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the above-mentioned Patent Document 1 does not take into consideration the crack resistance of the coating, its ability to conform to the substrate, etc. Therefore, when the coating is exposed to sunlight, rain, etc., cracks may occur over time, which may impair the finished appearance.

[0006] The present invention has been made in consideration of the above points, and aims to provide a coating material that can form a coating film that exhibits a colorful and beautiful appearance and is excellent in weather resistance, crack resistance, and conformability to the substrate. [Means for solving the problem]

[0007] In order to solve these problems, the inventors conducted extensive research and came up with the idea of ​​a coating material in which liquid or gel-like color particles are dispersed in an aqueous clear coating material, in which the color particles and the aqueous clear coating material each contain a specific acrylic silicone resin emulsion, and thus completed the present invention.

[0008] That is, the present invention has the following features. 1. A coating material in which liquid or gel-like color particles are dispersed in a water-based clear coating material, The water-based clear coating material contains an acrylic silicone resin emulsion (A1) having a silica residual ratio of 0.01 to 3 mass% in the resin solid content and a glass transition temperature of 30 ° C or less, The liquid or gel-like color particles are colorant particles containing an acrylic silicone resin emulsion (A2) having a silica residual ratio of 0.1 to 40 mass% in the resin solid content, and a coloring pigment. [Effects of the Invention]

[0009] According to the present invention, it is possible to form a coating that exhibits a colorful and beautiful appearance and is excellent in weather resistance, crack resistance, conformability to the substrate, and the like. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an embodiment of the present invention will be described.

[0011] The coating material of the present invention is a coating material in which liquid or gel-like color particles are dispersed in an aqueous clear coating material. The liquid or gel-like color particles (hereinafter simply referred to as "color particles") in the coating material of the present invention contribute to the formation of a colorful coating film. On the other hand, the aqueous clear coating material serves as a medium for the color particles and also plays a role in fixing the color particles in the formed coating.

[0012] The coating material of the present invention can be used as a material specified in JIS K5667:2003 "Multicolored Pattern Paint." Such materials are classified into oil-in-water (O / W) and water-in-water (W / W) types depending on the combination of color particles and medium (color particles / medium). The coating material of the present invention can be in the form of a water-in-water (W / W) type.

[0013] In the present invention, the aqueous clear coating material is capable of forming a clear coating film, and contains, as a constituent, an acrylic silicone resin emulsion (A1) having a silica residual ratio of 0.01 to 3 mass% in the resin solid content and a glass transition temperature of 30°C or less. Such component (A1) contributes to improving weather resistance, crack resistance, and substrate conformability. The aqueous clear coating material may be any material capable of forming a transparent coating film in which color particles are visually recognizable.

[0014] The acrylic silicone resin emulsion (A1) (hereinafter also referred to as "component (A1)"), which has a silica residual ratio of 0.01 to 3 mass% in the resin solid content and a glass transition temperature of 30°C or lower, acts as a binder for the coating and is capable of forming a clear coating.

[0015] The component (A1) may contain, as a monomer component (resin component) constituting the resin, an alkyl (meth)acrylate ester and an alkoxysilane compound. In the present invention, alkyl acrylate esters and alkyl methacrylate esters are collectively referred to as alkyl (meth)acrylate esters. In the present invention, "α to β" is synonymous with "α or more and β or less."

[0016] Examples of (meth)acrylic acid alkyl esters include rigid (meth)acrylic acid alkyl esters whose homopolymers have a Tg of 50°C or higher, such as methyl methacrylate (Tg: 105°C), ethyl methacrylate (Tg: 65°C), tert-butyl methacrylate (Tg: 107°C), iso-butyl methacrylate (Tg: 53°C), iso-propyl methacrylate (Tg: 81°C), cyclohexyl methacrylate (Tg: 83°C), isobornyl acrylate (Tg: 94°C), isobornyl methacrylate (Tg: 155°C), dicyclopentanyl acrylate (Tg: 120°C), dicyclopentanyl methacrylate (Tg: 175°C), and dicyclopentenyl acrylate (Tg: 120°C); Methyl acrylate (Tg: 8°C), ethyl acrylate (Tg: -20°C), propyl acrylate (Tg: 3°C), propyl methacrylate (Tg: 35°C), isopropyl acrylate (Tg: -3°C), n-butyl acrylate (Tg: -54°C), n-butyl methacrylate (Tg: 20°C), isobutyl acrylate (Tg: -26°C), tert-butyl acrylate (Tg: 43°C), isobutyl methacrylate (Tg: 48°C), isoamyl acrylate (Tg: -45°C), 2-ethylhexyl acrylate (Tg: -70°C), 2-ethylhexyl methacrylate (Tg: -10°C), n-octyl acrylate (Tg: -65°C), 2-octyl acrylate soft (meth)acrylic acid alkyl esters having a homopolymer Tg of less than 50°C, such as hexadecyl acrylate (Tg: -44°C), iso-octyl methacrylate (Tg: -45°C), iso-octyl acrylate (Tg: -70°C), cyclohexyl acrylate (Tg: 15°C), lauryl acrylate (Tg: 10°C), lauryl methacrylate (Tg: -65°C), stearyl acrylate (Tg: 35°C), hexadecyl acrylate (Tg: 35°C), hexadecyl methacrylate (Tg: 15°C), hexyl acrylate (Tg: -57°C), hexyl methacrylate (Tg: -5°C), tetradecyl acrylate (Tg: 24°C), and tetradecyl methacrylate (Tg: -72°C); These can be used alone or in combination of two or more.

[0017] Examples of alkoxysilane compounds include silane coupling agents (i), alkoxysilanes (ii), and cyclic siloxanes (iii). Among these, examples of the silane coupling agents (i) include polymerizable unsaturated double bond-containing silane coupling agents, epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, ureido group-containing silane coupling agents, chloroalkyl group-containing silane coupling agents, sulfide group-containing silane coupling agents, and isocyanate group-containing silane coupling agents. Specific examples of polymerizable unsaturated double bond-containing silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane; Examples of epoxy group-containing silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Examples of amino group-containing silane coupling agents include N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; Examples of mercapto group-containing silane coupling agents include γ-mercaptopropyltrimethoxysilane; examples of ureido group-containing silane coupling agents include 3-ureidopropyltriethoxysilane; examples of chloroalkyl group-containing silane coupling agents include 3-chloropropyltrimethoxysilane; examples of sulfide group-containing silane coupling agents include bis(triethoxysilylpropyl)tetrasulfide; and examples of isocyanate group-containing silane coupling agents include 3-isocyanatepropyltriethoxysilane. Examples include:

[0018] Examples of the alkoxysilanes (ii) include tetrafunctional alkoxysilanes, alkylalkoxysilanes, modified alkoxysilanes, etc. Specific examples of the tetrafunctional alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetraacetoxysilane, etc. Examples of alkylalkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrippropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrippropoxysilane, butyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, methyltriacetoxysilane, and phenyl Triacetoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane, methylphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane, etc.; Examples of the alkoxysilane-modified products include alkoxysilane-modified products obtained by modifying at least a portion of the alkoxyl groups of tetrafunctional alkoxysilanes or alkylalkoxysilanes with a polyoxyalkylene group-containing compound, a fluorine-containing compound, or the like; etc.

[0019] Examples of cyclic siloxanes (iii) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc. These alkoxysilane compounds can be used alone or in combination of two or more.

[0020] The component (A1) may contain other monomers (other monomers) as resin constituents. Examples of such other monomers include: Carboxyl group-containing monomers such as acrylic acid (Tg: 106°C), methacrylic acid (Tg: 185°C), itaconic acid (Tg: 100°C), and maleic acid (Tg: 130°C); Aromatic monomers such as styrene (Tg: 100°C) and α-methylstyrene (Tg: 168°C); Carbonyl group-containing monomers such as acrolein (Tg: 60°C) and diacetone acrylamide (Tg: 65°C); hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate (Tg: -15°C), 2-hydroxyethyl methacrylate (Tg: 55°C), 2-hydroxybutyl acrylate (Tg: -7°C), 2-hydroxybutyl methacrylate (Tg: 26°C), and 4-hydroxybutyl acrylate (Tg: -80°C); Amino group-containing monomers such as N,N-dimethylaminoethyl acrylate (Tg: 18°C), N,N-dimethylaminoethyl methacrylate (Tg: 18°C), and N,N-diethylaminoethyl methacrylate (Tg: 20°C); Amide group-containing monomers such as acrylamide (Tg: 179°C) and N,N-dimethylaminopropylacrylamide (Tg: 134°C); Nitrile group-containing monomers such as acrylonitrile (Tg: 125°C); Epoxy group-containing monomers such as glycidyl methacrylate (Tg: 46°C); 2-Isopropenyl-2-oxazoline (Tg: 100°C) oxazoline group-containing monomer; UV absorbers containing an ethylenically unsaturated double bond, such as 2-[2'-hydroxy-5'-methacryloyloxyethylphenyl]-2H-benzotriazole (Tg: 100°C); ethylenically unsaturated double bond-containing light stabilizers such as 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (Tg: 130°C); Other examples include sulfonic acid-containing vinyl monomers, acid anhydrides, chlorine-containing monomers, fluorine-containing monomers, alkylene glycol monoallyl ethers, vinyl acetate, vinyl propionate, vinyl ethers, ethylene, propylene, isobutylene, etc. These can be used alone or in combination of two or more.

[0021] Component (A1) can be produced by polymerizing a group of monomers containing the resin constituents described above. Any known polymerization method can be used, including conventional emulsion polymerization, soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, and multistage emulsion polymerization. Multistage emulsion polymerization can be carried out using a two-stage or three-stage or more emulsion polymerization method. During polymerization of component (A1), for example, emulsifiers, initiators, dispersants, polymerization inhibitors, polymerization retarders, buffers, chain transfer agents, pH adjusters, and the like can be used.

[0022] Among these, various surfactants that can be used in emulsion polymerization can be used as the emulsifier, and these may be reactive types (reactive surfactants) having polymerizable unsaturated double bonds. Examples of emulsifiers that can be used include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Polymer emulsifiers such as polyurethane resins, polyacrylic acid resins, polyvinyl alcohol, and polyvinylpyrrolidone can also be used. These emulsifiers can be used alone or in combination.

[0023] The silica content of component (A1) in the resin solid content is 0.01 to 3 mass%, preferably 0.02 to 1 mass%, more preferably 0.03 to 0.5 mass%, and even more preferably 0.04 to 0.4 mass%. By ensuring that the silica content of component (A1) is within the above range, excellent weather resistance can be achieved while maintaining physical properties such as crack resistance and substrate conformability. If the silica content is below the lower limit, it becomes difficult to achieve sufficient physical properties such as weather resistance, and performance such as crack resistance and substrate conformability may be reduced. If the silica content is above the upper limit, crack resistance, substrate conformability, and other properties are likely to be insufficient. In the present invention, it is desirable that the silica content of component (A1) in the resin solid content is smaller than the silica content of component (A2).

[0024] The residual silica ratio is the mass ratio of silica (SiO2) that remains when a component with Si-O bonds is baked at 900°C. Generally, alkoxysilanes react with water to undergo a hydrolysis reaction, becoming silanols, which then undergo a condensation reaction between silanols or between silanols and alkoxy. When this reaction is carried to the extreme, silica (SiO2) is formed. These reactions are expressed by the general formula: RO(Si(OR)2O) n R+(n+1)H2O→nSiO2+(2n+2)ROH The residual silica ratio is calculated based on this reaction formula and is the amount of remaining silica component.

[0025] In component (A1), the type and ratio of the alkoxysilane compound in the resin constituents can be set so as to satisfy the above-mentioned residual silica ratio. Examples of the alkoxysilane compound in component (A1) include (1) an embodiment containing a silane coupling agent (i), (2) an embodiment containing an alkoxysilane (ii) and / or a cyclic siloxane (iii), and (3) an embodiment containing a silane coupling agent (i) and an alkoxysilane (ii) and / or a cyclic siloxane (iii).

[0026] The glass transition temperature (Tg) of component (A1) is 30°C or lower, preferably -10°C to 30°C, and more preferably -5°C to 25°C. When component (A1) has such a glass transition temperature, it becomes possible to form a coating film that has excellent crack resistance, substrate conformability, etc. When the glass transition temperature of component (A1) is at or above the lower limit, it is possible to improve stain resistance, etc., and the aesthetic appearance of the coating film can be maintained for a long period of time. The glass transition temperature can be calculated using the Fox formula. However, alkoxysilane compounds are excluded from the calculation of the glass transition temperature in the present invention.

[0027] In the component (A1), the type and ratio of monomers such as (meth)acrylic acid alkyl esters in the resin constituents can be set so as to satisfy the above-mentioned glass transition temperature. As the (meth)acrylic acid alkyl ester, it is desirable to use the above-mentioned hard (meth)acrylic acid alkyl esters and soft (meth)acrylic acid alkyl esters. This embodiment makes it easy to set the Tg of the resin within the above-mentioned range, which is also advantageous in terms of the weather resistance and strength of the coating.

[0028] The average particle size of the component (A1) is preferably 300 nm or less, more preferably 20 to 250 nm, and even more preferably 50 to 200 nm. The average particle size referred to here is a value measured by dynamic light scattering.

[0029] The solid content of component (A1) in the aqueous clear coating material is preferably 5 to 50 mass %, and more preferably 15 to 45 mass %.

[0030] The water-based clear coating material can contain an extender pigment in addition to the component (A1). The inclusion of an extender pigment in the water-based clear coating material allows the coating to have a matte appearance. In this case, the 60-degree gloss of the water-based clear coating material coating is preferably 30 or less, more preferably 15 or less, and even more preferably 8 or less. The 60-degree gloss is a value obtained by applying a sample to one side of a black acrylic plate using a film applicator with a gap of 150 μm, placing the coated surface horizontally, and then drying it under standard conditions (temperature 23°C, relative humidity 50%) for 48 hours, and then measuring the specular gloss (measurement angle 60 degrees).

[0031] Examples of extender pigments include heavy calcium carbonate, kansui stone, light calcium carbonate, white carbon, talc, kaolin, clay, china clay, diatomaceous earth, barite powder, barium sulfate, precipitated barium sulfate, silica sand, silica powder, quartz powder, gravel, glass beads, resin beads, and crushed rocks, glass, shells, sintered bodies, plastics, rubber, etc. These may be surface-treated. These may be used alone or in combination of two or more. From the viewpoint of the clarity of the coating, it is desirable that such extender pigments have a refractive index of 1.4 to 1.7. The refractive index can be measured using an Abbe refractometer.

[0032] In the water-based clear coating material, the extender pigments that can be used are an extender pigment (B) (hereinafter also referred to as "component (B)") with an average particle size of more than 15 μm and an extender pigment (C) (hereinafter also referred to as "component (C)") with an average particle size of 15 μm or less. In the present invention, by using a combination of components (B) and (C) with different average particle sizes as extender pigments, it is possible to give the coating a matte appearance while also exhibiting excellent performance in terms of crack resistance, substrate conformability, etc.

[0033] The average particle size of component (B) is greater than 15 μm, preferably 16 μm or more but less than 75 μm, more preferably 18 to 60 μm. The average particle size of component (C) is 15 μm or less, preferably 0.1 to 14 μm, more preferably 0.5 to 12 μm. The average particle sizes of components (B) and (C) are D50 values, i.e., 50% cumulative particle size values ​​on a volume basis (cumulative from the finest particles), and can be measured using a laser diffraction particle size distribution analyzer.

[0034] The mixing ratio of component (B) is preferably 3 to 100 parts by mass, more preferably 5 to 90 parts by mass, and even more preferably 10 to 80 parts by mass per 100 parts by mass of the solid content of component (A1). The mixing ratio of component (C) is preferably 0.5 to 80 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 2 to 30 parts by mass per 100 parts by mass of the solid content of component (A1). The mass ratio of component (B) to component (C) (component (B):component (C)) is preferably 99:1 to 20:80, more preferably 98:2 to 50:50, and even more preferably 97:3 to 60:40. Such a mixing ratio of components (B) and (C) allows the formation of a clear coating exhibiting a sufficiently matte appearance and is also advantageous in terms of improving physical properties such as crack resistance and substrate conformability.

[0035] The water-based clear coating material can contain powder particles having an average particle diameter of 75 μm or more. In the present invention, the water-based clear coating material contains powder particles having an average particle diameter of 75 μm or more, thereby enhancing the natural feel of the coating. It is presumed that this effect is due to one or more of the following factors: the ease of forming fine irregularities on the coating surface; the ease of forming non-linear outer edges of color particles in the coating; the ease of imparting accent design to the coating.

[0036] Examples of powders and granules (hereinafter referred to as "component (D)") having an average particle diameter of 75 μm or more in aqueous clear coating materials include marble, granite, serpentine, granite, fluorite, sapphire, feldspar, limestone, silica, silica sand, crushed stone, mica, siliceous shale, and their crushed products, crushed ceramics, crushed ceramics, crushed glass, glass beads, crushed resin, resin beads, rubber particles, metal particles, shirasu balloons, glass balloons, perlite, pumice, hollow balloons, etc. Crushed materials such as shells, coral, wood, charcoal, activated carbon, and waste glass can also be used. Furthermore, colored coatings obtained by surface treatment with pigments, dyes, glazes, etc. can also be used.

[0037] Component (D) may include particles having a scaly particle shape (hereinafter also referred to as "scaly powders"). Examples of such scaly powders include inorganic pieces such as mica, sericite, clay, talc, platy kaolin, barium sulfate flakes, glass flakes, alumina flakes, shell fragments, and metal fragments, as well as rubber fragments, plastic fragments, and wood fragments. Also included are surface-treated base particles (for example, surface-treated by coating (or adsorbing) a colorant, such as a pigment or dye, on the base particles, or by subjecting the base particles to a calcination treatment). These may be used alone or in combination of two or more.

[0038] The scaly powder particles are not particularly limited as long as they are scaly (thin), but the aspect ratio (ratio of "minor diameter / thickness") is preferably 1.5 to 2000, more preferably 2 to 500, and even more preferably 3 to 100. The ratio of the minor diameter to the major diameter (minor diameter / major diameter) is preferably 0.3 to 1, more preferably 0.4 to 1, and even more preferably 0.5 to 1. The "minor diameter," "major diameter," and "thickness" referred to here are calculated by placing the scaly particles stably on a horizontal surface and observing them from above using a microscope, with the length of the shortest part being the "minor diameter," the length of the longest part being the "major diameter," and the maximum height from the bottom being the "thickness."

[0039] The average particle size of component (D) is 75 μm or more, preferably 75 to 4000 μm. The average particle size of component (D) is the D50 value, which is determined by sieving using a metal mesh sieve as specified in JIS Z8801-1:2019. This average particle size D50 is the 50% cumulative particle size, and refers to the particle size that, when sieved, cumulatively accounts for 50% by mass (average value of mass distribution) from the finest particles.

[0040] The mixing ratio of component (D) is preferably 0.1 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 2 to 30 parts by mass per 100 parts by mass of the solid content of component (A1).

[0041] In addition to the above-mentioned components, known additives can be suitably mixed in the aqueous clear coating material.Such additives include, for example, dispersion stabilizer, water-soluble resin, pigment dispersant, emulsifier, thickener, film-forming aid, leveling agent, coupling agent, wetting agent, plasticizer, antifreeze agent, pH adjuster, dryness adjuster, preservative, antifungal agent, anti-algae agent, antibacterial agent, antifoaming agent, adsorbent, deodorizer, ultraviolet absorber, light stabilizer, antioxidant, catalyst, crosslinking agent, solvent, water, etc.As long as it does not significantly impair the effect of the present invention, it is also possible to mix resin emulsions other than component (A1).

[0042] The proportion of water (including water as a medium for component (A1) etc.) in the aqueous clear coating material is preferably 80 to 800 parts by mass, more preferably 100 to 600 parts by mass, and even more preferably 120 to 500 parts by mass per 100 parts by mass of the solid content of component (A1).

[0043] The aqueous clear coating material may contain a dispersion stabilizer to stably disperse the color particles described below. The dispersion stabilizer is a component that stabilizes the colorant in a granular form and can be selected depending on the type of resin and colorant that make up the colorant. Specific examples of dispersion stabilizers include magnesium salts, calcium salts, barium salts, aluminum salts, sodium salts, potassium salts, borates, silicates, and phosphates. Other dispersion stabilizers that can be used include water-soluble polymers and clays. Such dispersion stabilizers can also be used as gelling agents. The mixing ratio of the dispersion stabilizer is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the solid content of component (A1).

[0044] The color particles in the coating material of the present invention are dispersed in the above-mentioned water-based clear coating material. The coating material of the present invention can contain one or more types of color particles. When the coating material contains color particles of two or more different colors, a color pattern can be formed using color particles of two or more colors.

[0045] These color particles are prepared by dispersing a coloring material containing an aqueous resin, a color pigment, and, if necessary, various additives, in a liquid or gel state in an aqueous clear coating material. By including an aqueous resin in the coloring material (hereinafter simply referred to as "coloring material") that constitutes the color particles, the coating material can be made into a water-in-water (W / W) type. The aqueous resin can be a resin emulsion and / or a water-soluble resin.

[0046] In the present invention, the aqueous resin in the coloring material is an acrylic silicone resin emulsion (A2) (hereinafter also referred to as "component (A2)") in which the silica residual ratio in the resin solid content is 0.1 to 40 mass%. In the present invention, by using component (A1) in the aqueous clear coating material and component (A2) in the color granules, it is possible to achieve excellent effects in weather resistance, crack resistance, and substrate conformability.

[0047] As such component (A2), a compound containing an alkyl (meth)acrylate and an alkoxysilane compound as a monomer component (resin component) that constitutes the resin can be used.

[0048] The (meth)acrylic acid alkyl ester, alkoxysilane compound, and other monomers in component (A2) can be the same as those in component (A1), and these can be used alone or in combination of two or more.

[0049] Component (A2) can be produced by polymerizing a group of monomers containing these resin-constituting components. Any known polymerization method can be used, including conventional emulsion polymerization, soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, and multistage emulsion polymerization. Multistage emulsion polymerization can be carried out using a two-stage or three-stage or more emulsion polymerization method. During polymerization of component (A2), for example, emulsifiers, initiators, dispersants, polymerization inhibitors, polymerization retarders, buffers, chain transfer agents, pH adjusters, and the like can be used. Among these, various surfactants that can be used in emulsion polymerization can be used as emulsifiers, including those similar to those used for component (A1).

[0050] The silica content of component (A2) in the resin solid content is preferably 0.1 to 40% by mass, more preferably 0.3 to 20% by mass, and even more preferably 0.5 to 10% by mass. Furthermore, the silica content of component (A2) in the resin solid content is desirably greater than the silica content of component (A1). When the silica content of component (A2) satisfies the above conditions, excellent weather resistance can be achieved. While the mechanism of action is not limited to the following, it is believed that a silica content of component (A2) within the above range enhances the weather resistance of the resin itself and contributes to the suppression of radical generation by covering the color pigment with the silicon component. If the silica content is below the above lower limit, it is difficult to achieve sufficient physical properties such as weather resistance, coating degradation is likely to occur, and performance such as crack resistance and substrate conformability is likely to be impaired. If the silica content exceeds the above upper limit, cracks and other problems may occur within the color particles.

[0051] In component (A2), the type and ratio of the alkoxysilane compound in the resin constituents can be set so as to satisfy the above-mentioned residual silica ratio. Examples of the alkoxysilane compound in component (A2) include (1) an embodiment containing a silane coupling agent (i), (2) an embodiment containing an alkoxysilane (ii) and / or a cyclic siloxane (iii), and (3) an embodiment containing a silane coupling agent (i) and an alkoxysilane (ii) and / or a cyclic siloxane (iii). Of these, the above embodiments (2) and (3) (particularly embodiment (3)) are preferred in terms of increasing the proportion of the silicon component.

[0052] The glass transition temperature (Tg) of the component (A2) is preferably from −10 to 80° C., more preferably from 10 to 60° C., and even more preferably from 25 to 50° C., and can be set to a temperature equal to or higher than the glass transition temperature of the component (A1).

[0053] In the component (A2), the type and ratio of monomers such as (meth)acrylic acid alkyl esters in the resin constituents can be set so as to satisfy the above-mentioned glass transition temperature. As the (meth)acrylic acid alkyl ester, it is desirable to use the above-mentioned hard (meth)acrylic acid alkyl esters and soft (meth)acrylic acid alkyl esters. This embodiment makes it easy to set the Tg of the resin within the above-mentioned range, which is also advantageous in terms of the weather resistance and strength of the coating.

[0054] The average particle size of component (A2) is preferably 300 nm or less, more preferably 20 to 250 nm, and even more preferably 50 to 200 nm. The average particle size referred to here is a value measured by dynamic light scattering.

[0055] The solid content of the component (A2) in the colorant is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.

[0056] The coloring material constituting the color particles preferably contains the component (A2) as an aqueous resin and a water-soluble resin.

[0057] Examples of water-soluble resins include polyvinyl alcohol, poly(meth)acrylic acid, polyethylene oxide, water-soluble urethane, biogum, galactomannan derivatives, alginic acid or its derivatives, cellulose derivatives, gelatin, casein, albumin, etc., as well as chemically modified versions of these resins by oxidation, methylation, carboxymethylation, hydroxyethylation, hydroxypropylation, sulfation, phosphate, cationization, etc. These can be used alone or in combination. Such water-soluble resins contribute to stabilizing the formation of color particles and can also be used as gel-forming agents. In the present invention, the colorant contains both of these, which allows for stable formation of color particles and also improves the weather resistance, water resistance, etc. of the coating.

[0058] The ratio of component (A2) to the water-soluble resin in the colorant is preferably 99.5:0.5 to 70:30, more preferably 99:1 to 80:20, in terms of solid content mass ratio (solid content of component (A2):solid content of water-soluble resin).

[0059] The color pigment in the colorant is a component that imparts color to the color particles. Examples of color pigments include inorganic chromatic pigments such as ferric oxide (red iron oxide), yellow iron oxide, ultramarine, cobalt blue, and cobalt green; organic chromatic pigments such as azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, and quinophthalone; black pigments such as carbon black, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper-manganese-chromium composite oxide, black iron oxide, iron-chromium composite oxide, manganese-bismuth composite oxide, and manganese-yttrium composite oxide; white pigments such as titanium oxide, zinc oxide, and alumina; and pearl pigments, aluminum pigments, photoluminescent pigments, phosphorescent pigments, and fluorescent pigments. These pigments can be used alone or in combination of two or more. The average particle size of the color pigment is preferably less than 1 μm, more preferably 0.01 to 0.9 μm. The average particle size of the color pigment is the D50 value, i.e., the 50% cumulative particle size value on a volume basis (cumulative from the finest particles), and can be measured using a laser diffraction particle size distribution analyzer.

[0060] In the present invention, when titanium oxide is contained as a coloring pigment in the colorant, particularly advantageous effects can be achieved in terms of weather resistance, crack resistance, and substrate conformability. While the mechanism of action is not limited to the following, it is believed that while titanium oxide is generally a substance that is prone to generating radicals that cause film deterioration, in the present invention, the silicon component of component (A2) covers the titanium oxide particles, thereby suppressing radical generation. Surface-treated titanium oxide is preferred, and titanium oxide surface-treated with at least silica is more preferred. Examples of titanium oxide surface-treated with at least silica include titanium oxide surface-treated with silica, titanium oxide surface-treated with silica and alumina, titanium oxide surface-treated with silica and zirconia, and titanium oxide surface-treated with silica, alumina, and zirconia, and the like. These can be used alone or in combination of two or more.

[0061] The mixing ratio of the color pigment in the coloring material is preferably 1 to 100 parts by mass, and more preferably 5 to 80 parts by mass, per 100 parts by mass of the solid content of the component (A2).

[0062] The colorant constituting the color particles can contain an extender pigment. In particular, when an aqueous clear coating material contains an extender pigment, the inclusion of the extender pigment in the colorant can improve the prevention of uneven gloss in the formed coating. Examples of extender pigments in the colorant include heavy calcium carbonate, kansui stone, light calcium carbonate, white carbon, talc, kaolin, clay, china clay, diatomaceous earth, barite powder, barium sulfate, precipitated barium sulfate, silica sand, silica powder, quartz powder, and resin beads. These can be used alone or in combination of two or more. The refractive index of the extender pigment is preferably 1.4 to 1.7. The average particle size of the extender pigment is preferably less than 75 μm, more preferably 50 μm or less, even more preferably 35 μm or less, particularly preferably 0.1 to 25 μm, and most preferably 0.5 to 15 μm. The blending ratio of the extender pigment in the colorant is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 30 to 150 parts by mass, per 100 parts by mass of the solid content of the resin.

[0063] The coloring material constituting the color particles can contain powder particles with an average particle diameter of 75 μm or more. In the present invention, the coloring material containing powder particles with an average particle diameter of 75 μm or more can enhance the natural feel of the coating. This effect is presumably due to one or more of the following factors: the surface of the color particles is more likely to have fine irregularities; the outer edges of the color particles are more likely to be nonlinear; etc. When the above-mentioned aqueous clear coating material contains component (D) and the coloring material constituting the color particles contains powder particles with an average particle diameter of 75 μm or more, the natural feel of the coating can be further enhanced.

[0064] Examples of powders and granules with an average particle size of 75 μm or more in colorants include marble, granite, serpentine, granite, fluorite, galspar, feldspar, limestone, silica, silica sand, crushed stone, mica, siliceous shale, and crushed products thereof, crushed ceramics, crushed ceramics, crushed glass, glass beads, crushed resin, resin beads, rubber particles, metal particles, shirasu balloons, glass balloons, perlite, pumice, hollow balloons, etc. Crushed materials such as shells, coral, wood, charcoal, activated carbon, and waste glass can also be used. Furthermore, these materials can also be colored and coated by surface treatment with pigments, dyes, glazes, etc.

[0065] The powder or granule may include those having a scaly particle shape (hereinafter also referred to as "scaly powder or granule"). Examples of such scaly powder or granule include inorganic pieces such as mica, sericite, clay, talc, plate-like kaolin, barium sulfate flakes, glass flakes, alumina flakes, shell fragments, and metal fragments, as well as rubber fragments, plastic fragments, and wood fragments. Also included are those surface-treated base particles (for example, those surface-treated by coating (or adsorbing) a colorant containing a pigment or dye onto the base particle, or by subjecting the base particle to a calcination treatment). These can be used alone or in combination of two or more.

[0066] The scaly powder particles are not particularly limited as long as they are scaly (thin), but the aspect ratio (ratio of "minor diameter / thickness") is preferably 1.5 to 2000, more preferably 2 to 500, and even more preferably 3 to 100. The ratio of the minor diameter to the major diameter (minor diameter / major diameter) is preferably 0.3 to 1, more preferably 0.4 to 1, and even more preferably 0.5 to 1. The "minor diameter," "major diameter," and "thickness" referred to here are calculated by placing the scaly particles stably on a horizontal surface and observing them from above using a microscope, with the length of the shortest part being the "minor diameter," the length of the longest part being the "major diameter," and the maximum height from the bottom being the "thickness."

[0067] The powder or granule has an average particle size of 75 μm or more, preferably 75 to 1000 μm. The average particle size of the powder or granule is the D50 value, which is determined by sieving using a metal mesh sieve as specified in JIS Z8801-1:2019. This average particle size D50 is the 50% cumulative particle size, which refers to the particle size that, when sieved, cumulatively accounts for 50% by mass (average value of mass distribution) from the finest particles.

[0068] The mixing ratio of the powder or granule is preferably 5 to 300 parts by mass, more preferably 8 to 200 parts by mass, and even more preferably 10 to 150 parts by mass per 100 parts by mass of the solid content of component (A2).

[0069] In addition to the above-mentioned components, the colorant may contain various additives. Examples of such additives include pigment dispersants, emulsifiers, thickeners, film-forming aids, leveling agents, coupling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, dryness adjusters, preservatives, antifungal agents, antialgae agents, antibacterial agents, antifoaming agents, fibers, gel-forming agents, adsorbents, deodorizers, UV absorbers, light stabilizers, antioxidants, catalysts, crosslinking agents, solvents, and water. Resin emulsions other than component (A2) may also be mixed in as long as they do not significantly impair the effects of the present invention.

[0070] The proportion of water in the colorant (including water as a medium for aqueous resins, etc.) is preferably 80 to 800 parts by mass, and more preferably 100 to 600 parts by mass, per 100 parts by mass of the solid content of component (A2).

[0071] The method for granulating the colorant is not particularly limited, and known methods can be used. For example, a method based on the material manufacturing method specified in JIS K5667:2003 "Multicolored Paint" can be used. Specifically, for example, a method can be used in which the colorant is dispersed in a medium (some or all of the constituent components of the water-based clear coating material) containing a dispersion stabilizer, etc. The dispersion stabilizer is a component that stabilizes the colorant in a granular form, and acts, for example, as a gelling agent for the colorant.

[0072] The particle size and shape of the color particles can be set as appropriate. Specifically, for example, the shape of the stirring blade during production, the size and position of the stirring blade relative to the stirring tank, the rotation speed of the stirring blade, the stirring time, the viscosity of the colorant, the method and concentration of the dispersion stabilizer added, the viscosity of the medium, etc. may be appropriately selected and adjusted. The average particle size of the color particles is preferably 0.05 to 20 mm (more preferably 0.1 to 18 mm). In the present invention, the average particle size of the color particles is a value obtained by drying the color particles on a standard white paper for 48 hours under standard conditions (temperature 23°C, relative humidity 50%; the same applies below) and calculating the average major axis (average value of 50 color particles).

[0073] To obtain a coating material containing two or more types (two or more colors) of color particles, for example, A method of preparing a color particle dispersion liquid (a color particle dispersion liquid containing one type of color particle) in which one type of coloring material is dispersed in a medium, and then mixing these, or A method of simultaneously or sequentially adding and dispersing two or more colorants with different color tones into a medium to obtain a color particle dispersion (a color particle dispersion containing two or more types of color particles); In such a method, part or all of the aqueous clear coating material can be used as the medium. When a color particle dispersion liquid is produced using part of the components of the aqueous clear coating material as the medium, the remaining components of the aqueous clear coating material can be mixed with the color particle dispersion liquid.

[0074] In the coating material of the present invention, the mass ratio of color particles to water-based clear coating material (color particles:water-based clear coating material) is preferably 1:99 to 80:20 (more preferably 10:90 to 75:25, and even more preferably 30:70 to 70:30).

[0075] The coating material of the present invention can be applied to various substrates. Examples of substrates include interior and exterior wall surfaces, floors, ceilings, and roofs of buildings and civil engineering structures. Substrates constituting such substrates include concrete, mortar, and various plate-like substrates such as cement boards, extruded boards, slate boards, PC boards, ALC boards, fiber-reinforced cement boards, metal siding boards, ceramic siding boards, ceramic boards, calcium silicate boards, gypsum boards, plastic boards, hardwood cement boards, PVC extruded siding boards, and plywood. These substrates may have undergone some surface treatment (filler treatment, putty treatment, surfacer treatment, sealer treatment, etc.), may already have a coating film formed on them, or may have wallpaper attached. Furthermore, when the substrate surface is composed of multiple plate-like substrates, the joints between the plate-like substrates are preferably filled with a joint material (sealant, dry joint material, etc.).

[0076] Before applying the coating material of the present invention, the surface to be coated can be subjected to a surface treatment as needed. Examples of surface treatments include cleaning, scraping, filler treatment, putty treatment, surfacer treatment, sealer treatment, etc. Such surface treatments can be carried out appropriately, taking into account, for example, the type and condition of the surface to be coated.

[0077] Before applying the coating material of the present invention, a step of applying one or more colored primers can be carried out. As the colored primer, for example, a material containing a resin and a colored pigment, which can form a uniform monochromatic coating by its color development, can be used. The color tone of the colored primer can be set in consideration of the color tone of the coating material, for example, it can be set to an approximate color of the coating material. As the colored primer, for example, a material that forms a flat coating, a material that forms various uneven patterns, etc. can be used.

[0078] The colored primer can be applied by, for example, spray coating, roller coating, trowel coating, brush coating, etc. The amount of the colored primer applied is preferably 0.05 to 1 kg / m 2 , more preferably 0.1 to 0.8 kg / m 2 It is desirable that the colored primer be applied evenly over the entire surface to be painted. The application and drying of the colored primer are preferably carried out at room temperature (0 to 40°C).

[0079] In the present invention, the coating material of the present invention can be applied after the above-mentioned surface treatment, application of a colored primer, etc., as necessary. When a colored primer is applied, it is desirable to apply the coating material after the coating of the colored primer has dried.

[0080] The coating material of the present invention can be applied by, for example, spray coating, roller coating, brush coating, etc. The coating material can be applied in an amount of, for example, 1.5 kg / m 2 The concentration can be set to 0.1 to 1.2 kg / m or less, preferably 0.1 to 1.2 kg / m 2 , more preferably 0.2 to 1 kg / m 2 The coating and drying of the coating material may be preferably carried out at room temperature.

[0081] When applying the coating material of the present invention, the viscosity can be adjusted appropriately by adding a diluent such as water. The dilution ratio is preferably 0 to 10% by mass. The viscosity of the coating material to be applied is preferably 1 to 30 Pa s (more preferably 2 to 20 Pa s), and the thixotropy index is preferably 2 to 9 (even more preferably 3 to 8).

[0082] In the present invention, such coating can form a coating that is colorful and aesthetically pleasing. The coating material of the present invention can be used as a material for forming the outermost coating on the surface to be coated. [Example]

[0083] The following examples and comparative examples will be given to clarify the features of the present invention, but the present invention should not be construed as being limited to these examples. Note that the water-based clear coating material is abbreviated to water-based clear.

[0084] The following raw materials were used in the production of the coating material: Resin 1: Acrylic silicone resin emulsion (glass transition temperature 16°C, solid content 40% by mass, residual silica ratio 0.1% by mass) Resin 2: Acrylic silicone resin emulsion (glass transition temperature 20°C, solid content 40% by mass, residual silica ratio 0.2% by mass) Resin 3: Acrylic silicone resin emulsion (glass transition temperature 12°C, solid content 40% by mass, residual silica ratio 0.3% by mass) Resin 4: Acrylic silicone resin emulsion (glass transition temperature 35°C, solid content 40% by mass, residual silica ratio 0.6% by mass) Resin 5: Acrylic silicone resin emulsion (glass transition temperature 32°C, solid content 40% by mass, residual silica ratio 1.4% by mass) Resin 6: Acrylic silicone resin emulsion (glass transition temperature 38°C, solid content 40% by mass, residual silica ratio 3% by mass) Resin 7: Acrylic resin emulsion (glass transition temperature 20°C, solid content 40% by mass) Resin 8: Water-soluble resin (galactomannan derivative aqueous solution, solid content 3% by mass) Dispersant: Anionic dispersant Extender pigment 1: Resin beads (average particle size 38 μm, refractive index 1.5) Extender pigment 2: Diatomaceous earth (average particle size 6 μm, refractive index 1.5) Extender pigment 3: Heavy calcium carbonate (average particle size 4 μm, refractive index 1.6) Extender pigment 4: Talc (average particle size 5 μm, refractive index 1.6) Color pigment 1: White pigment dispersion {water dispersion of titanium dioxide (average particle size 0.3 μm, silica-alumina treated), solid content 60% by mass} Color pigment 2: Black pigment dispersion {aqueous dispersion of black iron oxide (average particle size 0.8 μm), solid content 60% by mass} Color pigment 3: Yellow pigment dispersion {water dispersion of yellow iron oxide (average particle size 0.5 μm), solid content 50% by mass} Color pigment 4: Red pigment dispersion {red iron oxide (average particle size 0.2 μm) water dispersion, solid content 60% by mass} Color pigment 5: Blue pigment dispersion {cobalt blue (average particle size 0.4 μm) aqueous dispersion, solid content 50% by mass} Powder 1: Perlite (average particle size 125-150 μm) Powder 2: Mica (average particle size 1000-1180 μm) Coalescence agents: ester-based coalescence agents, ether-based coalescence agents Dispersion stabilizer: Gelling agent 5% by weight aqueous solution Thickener: urethane-based thickener Additives: preservatives, anti-mold agents, anti-algae agents, light stabilizers Antifoaming agent: Silicone antifoaming agent

[0085] [Table 1]

[0086] [Table 2]

[0087] (Production of coating material 1) (1) In the coloring material 1 having the composition shown in Table 2, as the coloring pigment, Color pigment 1: Color pigment 2: Color pigment 3: Color pigment 4 A colorant 1-1 was prepared using a ratio of 7.632:0.224:0.133:0.011 (8 parts by mass in total), and this colorant 1-1 (100 parts by mass) was added to the a mixture of aqueous clear 1 having the formulation shown in Table 1 and stirred and dispersed. Then, the b mixture of aqueous clear 1 was added to obtain a color particle dispersion 1-1 in which gel-like color particles (high-brightness color particles) with an average particle size of approximately 3 mm were dispersed. (2) In the coloring material 1 having the composition shown in Table 2, as the coloring pigment, Color pigment 1: Color pigment 2: Color pigment 3: Color pigment 4 A colorant 1-2 was prepared using a ratio of 5.548:1.135:1.043:0.274 (8 parts by mass in total), and this colorant 1-2 (100 parts by mass) was added to the mixture a of aqueous clear 1 having the formulation shown in Table 1 and stirred and dispersed. Then, the mixture b of aqueous clear 1 was added to obtain a color particle dispersion 1-2 in which gel-like color particles (low-brightness color particles) with an average particle size of approximately 3 mm were dispersed. (3) In the coloring material 1 having the composition shown in Table 2, as the coloring pigment, Color pigment 1: Color pigment 2: Color pigment 3: Color pigment 4 Colorant 1-3 was prepared using a ratio of 6.927:0.593:0.407:0.073 (8 parts by mass in total), and this colorant 1-3 (100 parts by mass) was added to mixture a of aqueous clear 1 with the formulation shown in Table 1 and stirred and dispersed. Then mixture b of aqueous clear 1 was added to obtain color particle dispersion 1-3 in which gel-like color particles (medium-brightness color particles) with an average particle size of approximately 3 mm were dispersed. (4) The color particle dispersion liquid 1-1, the color particle dispersion liquid 1-2, and the color particle dispersion liquid 1-3 were mixed in a mass ratio of 40:20:40 to produce a coating material 1.

[0088] (Production of coating material 2) In the production steps (1) to (4) of the coating material 1, water-based clear 2 was used instead of water-based clear 1, to obtain color particle dispersion 2-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 2-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 2-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersion 2-1, color particle dispersion 2-2, and color particle dispersion 2-3 were mixed in a mass ratio of 40:20:40 to produce coating material 2.

[0089] (Production of coating material 3) In the production steps (1) to (4) of the coating material 1, colorant 2 was used instead of colorant 1 and aqueous clear 2 was used instead of aqueous clear 1, to obtain color particle dispersion 3-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 3-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 3-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm).The color particle dispersion 3-1, color particle dispersion 3-2, and color particle dispersion 3-3 were mixed in a mass ratio of 40:20:40 to produce coating material 3.

[0090] (Production of coating material 4) In the production steps (1) to (4) of the coating material 1, colorant 3 was used instead of colorant 1, and aqueous clear 2 was used instead of aqueous clear 1, to obtain color particle dispersion 4-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 4-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 4-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). Coating material 4 was produced by mixing color particle dispersion 4-1, color particle dispersion 4-2, and color particle dispersion 4-3 in a mass ratio of 40:20:40.

[0091] (Production of coating material 5) In the production steps (1) to (4) of the coating material 1, colorant 3 was used instead of colorant 1, and aqueous clear 3 was used instead of aqueous clear 1, to obtain color particle dispersion 5-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 5-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 5-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersion 5-1, color particle dispersion 5-2, and color particle dispersion 5-3 were mixed in a mass ratio of 40:20:40 to produce coating material 5.

[0092] (Production of coating material 6) In the production steps (1) to (4) of the coating material 1, colorant 3 was used instead of colorant 1, and aqueous clear 4 was used instead of aqueous clear 1, to obtain color particle dispersion 6-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 6-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 6-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). Coating material 6 was produced by mixing color particle dispersion 6-1, color particle dispersion 6-2, and color particle dispersion 6-3 in a mass ratio of 40:20:40.

[0093] (Production of coating material 7) In the production steps (1) to (4) of the coating material 1, colorant 3 was used instead of colorant 1, and aqueous clear 5 was used instead of aqueous clear 1, to obtain color particle dispersion 7-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 7-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 7-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersions 7-1, 7-2, and 7-3 were mixed in a mass ratio of 40:20:40 to produce coating material 7.

[0094] (Production of coating material 8) In the production steps (1) to (4) of the coating material 1, colorant 4 was used instead of colorant 1, and aqueous clear 5 was used instead of aqueous clear 1, to obtain color particle dispersion 8-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 8-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 8-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). Coating material 8 was produced by mixing color particle dispersion 8-1, color particle dispersion 8-2, and color particle dispersion 8-3 in a mass ratio of 40:20:40.

[0095] (Production of coating material 9) In the production steps (1) to (4) of the coating material 1, colorant 5 was used instead of colorant 1, and aqueous clear 2 was used instead of aqueous clear 1, to obtain color particle dispersion 9-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 9-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 9-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersion 9-1, color particle dispersion 9-2, and color particle dispersion 9-3 were mixed in a mass ratio of 40:20:40 to produce coating material 9.

[0096] (Manufacturing of the covering material 10) In the production steps (1) to (4) of the coating material 1, colorant 3 was used instead of colorant 1, and aqueous clear 6 was used instead of aqueous clear 1, to obtain color particle dispersion 10-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 10-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 10-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersions 10-1, 10-2, and 10-3 were mixed in a mass ratio of 40:20:40 to produce coating material 10.

[0097] (Production of coating material 11) In the production steps (1) to (4) of the coating material 1, colorant 5 was used instead of colorant 1, and aqueous clear 7 was used instead of aqueous clear 1, to obtain color particle dispersion 11-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 11-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 11-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersions 11-1, 11-2, and 11-3 were mixed in a mass ratio of 40:20:40 to produce coating material 11.

[0098] (Production of coating material 12) In the production steps (1) to (4) of the coating material 1, colorant 2 was used instead of colorant 1, and aqueous clear 8 was used instead of aqueous clear 1, to obtain color particle dispersion 12-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 12-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 12-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersions 12-1, 12-2, and 12-3 were mixed in a mass ratio of 40:20:40 to produce coating material 12.

[0099] (Production of Coating Material 13) In the production steps (1) to (4) of the coating material 1, colorant 7 was used instead of colorant 1, and aqueous clear 8 was used instead of aqueous clear 1, to obtain color particle dispersion 13-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 13-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 13-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersions 13-1, 13-2, and 13-3 were mixed in a mass ratio of 40:20:40 to produce coating material 13.

[0100] (Production of coating material 14) In the production steps (1) to (4) of the coating material 1, colorant 6 was used instead of colorant 1, and aqueous clear 9 was used instead of aqueous clear 1, to obtain color particle dispersion 14-1 in which high-brightness gel-like color particles were dispersed, color particle dispersion 14-2 in which low-brightness gel-like color particles were dispersed, and color particle dispersion 14-3 in which medium-brightness gel-like color particles were dispersed (all with an average particle size of approximately 3 mm). The color particle dispersions 14-1, 14-2, and 14-3 were mixed in a mass ratio of 40:20:40 to produce coating material 14.

[0101] (Production of coating material 15) After producing the coating material 1, the coating material 1 was mixed with powder 2 (8 parts by mass of powder 2 was mixed with 100 parts by mass of resin solids in the water-based clear 1) to produce the coating material 15.

[0102] (Production of Coating Material 16) In the production steps (1) to (4) of the coating material 1, color particle dispersion 16-1 containing high-brightness gel-like color particles, color particle dispersion 16-2 containing low-brightness gel-like color particles, color particle dispersion 16-3 containing medium-brightness gel-like color particles, and color particle dispersion 16-4 containing medium-brightness gel-like color particles (all with an average particle size of approximately 3 mm) were obtained by substituting colorant 8 for colorant 1 in place of colorant 1. The coating material 16 was produced by mixing color particle dispersion 16-1, color particle dispersion 16-2, color particle dispersion 16-3, and color particle dispersion 16-4 in a mass ratio of 70:10:10:10.

[0103] (Production of Coating Material 17) After producing the coating material 16, the coating material 16 was mixed with the powder 2 (8 parts by mass of the powder 2 was mixed with 100 parts by mass of the resin solid content in the water-based clear 1) to produce the coating material 17.

[0104] (Test Method) Coating materials 1 to 17 were tested in the following manner and evaluated as 1 to 3. All coating and drying were carried out under standard conditions (temperature 23°C, relative humidity 50%).

[0105] (Rating 1) A slate board (900mm x 900mm x 3mm) that had been previously treated with a sealer was coated with 0.2kg / m of acrylic resin-based colored primer. 2 After drying for 24 hours, the coating material was applied at a coating rate of 0.6 kg / m 2 The test panels were spray-painted with a paint finish and then dried and cured for seven days. The test panels obtained in this manner were irradiated with light from the right side, and their appearance was visually inspected from the left front of the test panel. Evaluation was made on a three-point scale (excellent: A > B > C: poor), with "A" indicating that gloss unevenness was suppressed and "C" indicating that gloss unevenness was observed.

[0106] (Rating 2) The test substrate was made by placing two 100mm x 300mm x 6mm slate boards side by side and filling the joints (10mm wide) between the boards with a modified silicone sealant. An acrylic resin colored primer was applied to the entire surface of the test substrate at a rate of 0.2kg / m. 2 After drying for 24 hours, the coating material was applied at a coating rate of 0.6 kg / m 2 The test specimens obtained using this method were subjected to a total of 10 cycles of repeated heating and cooling, with one cycle consisting of 18 hours of water immersion, 3 hours of rest at -20°C, and 3 hours of rest at 50°C, after which the appearance of the coating was checked and its conformability to the substrate was evaluated. The evaluation was conducted on a three-point scale (excellent: A>B>C: poor), with "A" indicating no abnormalities in the coating appearance and excellent conformability to the substrate, and "C" indicating obvious abnormalities such as cracks.

[0107] (Rating 3) The test panels obtained in Evaluation 1 above were cut into 60 x 40 mm pieces and subjected to weathering tests. The weathering tests were carried out using an accelerated weathering tester "Metal Weather" (manufactured by Daipla Wintes Co., Ltd.), with 100 cycles consisting of 4 hours of light exposure and 4 hours of condensation (a total of 8 hours). The appearance of the coating was observed after 100 cycles and rated on a three-point scale (A>B>C: excellent), with "A" indicating no abnormalities and "C" indicating abnormalities (color change, swelling, peeling, etc.).

[0108] (Test results) The test results are shown in Table 3. Coating materials 1 to 11 and 15 to 17 (especially coating materials 1 to 8 and 15 to 17) gave good results in each test. Coating materials 15 to 17 (especially coating material 17) also had an excellent natural feel to the coating.

[0109] [Table 3]

[0110] [Table 4]

Claims

[Claim 1] A coating material in which liquid or gel-like color particles are dispersed in an aqueous clear coating material, The aqueous clear coating material contains an acrylic silicone resin emulsion (A1) having a silica residual ratio of 0.01 to 3 mass% in the resin solid content and a glass transition temperature of 30 ° C. or less, The liquid or gel-like color particles are granular coloring materials containing an acrylic silicone resin emulsion (A2) having a silica residual ratio of 0.1 to 40 mass% in the resin solid content, and a coloring pigment.

Images