Coating Formation Method

Abstract

The present invention provides a method for forming a paint film that can create a richly colored and aesthetically pleasing film, suppress the occurrence of defects such as blistering, peeling, and cracking in the paint film, and maintain its initial aesthetic appearance over a long period of time. [Solution] The present invention relates to a method for forming a coating film by sequentially applying a main material and a topcoat to a surface to be coated, wherein the main material comprises a resin emulsion and powder particles and forms a main material coating film having an uneven pattern, and the topcoat comprises a resin emulsion and forms a patterned coating film with color particles, and the resin emulsion of the main material and the resin emulsion of the topcoat each contain, as monomers constituting the resin, 10% by mass or more of an alkyl (meth)acrylate (p) having a cyclic alkyl group in the resin components, and 10% by mass or more of an alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms in the resin components.

Description

[Technical Field]

[0001] This invention relates to a novel method for forming a coating film. [Background technology]

[0002] Traditionally, the walls of buildings and civil engineering structures have been coated with various topcoats for purposes such as surface protection and aesthetic improvement. Among these, topcoats that form patterned coatings using colored particles (for example, topcoats in which liquid or gel-like colored particles are dispersed in an aqueous medium) are used in applications where high aesthetic appeal is required, as they can form richly colored coatings.

[0003] As a method for forming such a coating film, for example, Patent Document 1 (Japanese Patent Application Publication No. 2013-99725) describes a method for forming a coating film in which two types of intermediate coating paints are applied to form a blurred pattern coating film, and then a coating paint containing colored paint particles is applied. According to such a coating film forming method, it is possible to form original multi-colored patterns that are three-dimensional and have a sense of depth. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2013-99725 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the above-mentioned patent documents do not take into consideration blistering, peeling, cracking, etc., of the coating film. With coating films formed by the methods described above, repeated exposure to sunlight and rainfall may cause defects such as blistering, peeling, and cracking, potentially impairing the initial aesthetic appearance.

[0006] The present invention has been made in view of these points, and aims to provide a method for forming a coating film that can form a colorful and aesthetically pleasing coating film, suppress the occurrence of defects such as blistering, peeling, and cracking in the coating film, and maintain its initial aesthetic appearance for a long period of time. [Means for solving the problem]

[0007] To solve these problems, the inventors, after diligent research, conceived a method for forming a coating film using specific main materials and topcoat materials, and thus completed the present invention.

[0008] In other words, the present invention has the following features. 1. A method for forming a coating film by sequentially applying a main material and a topcoat material to a surface to be coated, The above main material includes a resin emulsion and powders and granules, and forms a main material coating film having an uneven pattern. The above topcoat material contains a resin emulsion and forms a patterned coating film with colored particles. The resin emulsion of the main material and the resin emulsion of the topcoat material are, respectively, composed of the monomers that make up the resin. A cyclic alkyl group (m) alkyl ester (p) is added to the resin components in an amount of 10% by mass or more. The resin component contains 10% by mass or more of an alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms. A method for forming a coating film, characterized by the features described above. 2. A method for forming a coating film by sequentially applying a main material and a topcoat material to a surface to be coated, The above main material includes a first resin emulsion and powder / granular material, and forms a main material coating film having an uneven pattern. The above topcoat material consists of liquid or gel-like color particles dispersed in a water-based clear coating material containing a second resin emulsion. The first resin emulsion and the second resin emulsion each contain the following monomers as constituents of the resin: An alkyl (meth)acrylate (p) having a cyclic alkyl group is contained in the resin constituent at 10% by mass or more. An alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms is contained in the resin constituent at 10% by mass or more. A coating film forming method characterized by this. 3. A coating film forming method in which a main material and a topcoat material are sequentially applied to a coated surface, The main material includes a first resin emulsion and powder particles, and forms a main material coating film having an uneven pattern. The topcoat material is formed by dispersing liquid or gel-like color particles in an aqueous clear coating material. The color particles are particulate materials of a coloring material containing a third resin emulsion and a coloring pigment. The first resin emulsion and the third resin emulsion each contain, as a monomer constituting the resin, An alkyl (meth)acrylate (p) having a cyclic alkyl group is contained in the resin constituent at 10% by mass or more. An alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms is contained in the resin constituent at 10% by mass or more. A coating film forming method characterized by this. 4. A coating film forming method in which a main material and a topcoat material are sequentially applied to a coated surface, The main material includes a first resin emulsion and powder particles, and forms a main material coating film having an uneven pattern. The topcoat material is a colored topcoat material containing a fourth resin emulsion and a coloring pigment, and the colored topcoat material is applied in a granular form to form a pattern coating film with color particles. The first resin emulsion and the fourth resin emulsion each contain, as a monomer constituting the resin, An alkyl (meth)acrylate (p) having a cyclic alkyl group is contained in the resin constituent at 10% by mass or more. An alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms is contained in the resin constituent at 10% by mass or more. A coating film forming method characterized by the following. 5. The coating film forming method according to any one of 1. to 4., characterized in that after applying the topcoat material, the color particles are stretched using a pressing tool while the coating film of the topcoat material is still undried.

Effects of the Invention

[0009] According to the present invention, a coating film with rich and colorful aesthetics can be formed. In this coating film, the occurrence of defects such as swelling, peeling, and cracking is suppressed, and the initial aesthetics can be maintained over a long period.

Modes for Carrying Out the Invention

[0010] Hereinafter, modes for carrying out the present invention will be described.

[0011] The coating film forming method of the present invention is a coating film forming method in which a main material and a topcoat material are sequentially applied to a coated surface. The main material includes a resin emulsion and powder particles, and forms a main material coating film having an uneven pattern. The topcoat material includes a resin emulsion and forms a pattern coating film with color particles. The resin emulsion of the main material and the resin emulsion of the topcoat material each contain, as a monomer constituting the resin, an alkyl (meth)acrylate (p) having a cyclic alkyl group (hereinafter also referred to as the "(p) component") in an amount of 10% by mass or more in the resin constituent components, and an alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms (hereinafter also referred to as the "(q) component") in an amount of 10% by mass or more in the resin constituent components. It is characterized by this.

[0012] This coating film formation method allows for the creation of a colorful and aesthetically pleasing coating film. Furthermore, the occurrence of defects such as blistering, peeling, and cracking in the coating film is suppressed, and the initial aesthetic appearance can be maintained for a long period of time. In the present invention, the reasons for these effects are not limited to the following, but it is thought that the (p) component improves hydrophobicity and light resistance, and the (q) component improves hydrophobicity and flexibility, thereby increasing the resistance to water and light in both the main coating film and the topcoat coating film. In addition, the fact that the main material and the topcoat contain a resin emulsion having these common components strengthens their mutual adhesion, allowing the effects of both components to be fully exerted.

[0013] <Resin Emulsion> First, we will explain the common characteristics of the resin emulsion used in the main material and topcoat material.

[0014] The above-described resin emulsion contains, as monomers constituting the resin, 10% by mass or more of an alkyl (meth)acrylate (p) having a cyclic alkyl group, and 10% by mass or more of an alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms. In such a resin emulsion, component (p) acts to improve hydrophobicity and light resistance, while component (q) acts to improve hydrophobicity and flexibility. As a result, the formed coating film can be made more resistant to water and light, and is suitable in terms of improving weather resistance.

[0015] Examples of alkyl (meth)acrylates (p) having a cyclic alkyl group include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. These can be used individually or in combination of two or more. Among these, cyclohexyl methacrylate is particularly preferred. In this invention, alkyl acrylates and alkyl methacrylates are collectively referred to as alkyl (meth)acrylates.

[0016] The ratio of component (p) is 10% by mass or more in the resin components, preferably 15 to 60% by mass, and more preferably 18 to 55% by mass. When the ratio of component (p) is above the lower limit, the effects of hydrophobicity, light resistance, etc. are fully exhibited, and resistance to water and light can be increased. When the ratio of component (p) is below the upper limit, it is preferable in terms of the exhibiting of the flexibility effect of component (q) described later, and performance such as crack resistance can be increased. In this invention, "α to β" is synonymous with "α or more and β or less".

[0017] Alkyl (meth)acrylate (q) having an alkyl main chain with 3 or more carbon atoms has an alkyl main chain with 3 or more carbon atoms in the alkyl portion. The alkyl portion of component (q) may have various side chains (for example, alkyl groups with fewer carbon atoms than the alkyl main chain) as long as it has such an alkyl main chain. Examples of component (q) include n-propyl (meth)acrylate, isobutyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, t-pentyl (meth)acrylate, neopentyl (meth)acrylate, n-butyl (meth)acrylate, 2-methylbutyl (meth)acrylate, isopentyl (meth)acrylate, 3-methylbutyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-pentyl (meth)acrylate Examples include methylpentyl(meth)acrylate, 2-methylpentyl(meth)acrylate, 4-methylpentyl(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-heptyl(meth)acrylate, isooctyl(meth)acrylate, n-octyl(meth)acrylate, n-nonyl(meth)acrylate, n-decyl(meth)acrylate, n-undecyl(meth)acrylate, and n-lauryl(meth)acrylate. These can be used individually or in combination of two or more. Among these, the (q) component is preferably one having an alkyl main chain with 4 or more carbon atoms (more preferably 4 to 10).

[0018] The ratio of component (q) is 10% by mass or more in the resin components, preferably 20 to 60% by mass, and more preferably 25 to 55% by mass. When the ratio of component (q) is above the lower limit, the effects of hydrophobicity, flexibility, etc. are fully exhibited, and resistance to water can be increased. When the ratio of component (q) is below the upper limit, it is preferable in terms of exhibiting the light resistance effect of component (p) as described above.

[0019] Such resin emulsions may contain other monomers besides component (p) and component (q) (hereinafter also referred to as "component (r)") as resin components. Examples of component (r) include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, or carboxyl group-containing monomers, amino group-containing monomers, pyridine monomers, hydroxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, aromatic monomers, fluorine-containing monomers, ultraviolet-absorbing group-containing monomers, and photostable group-containing monomers. These can be used individually or in combination of two or more. The proportion of these (r) components in the resin components is preferably 0 to 80% by mass, more preferably 10 to 65% by mass, and even more preferably 15 to 60% by mass.

[0020] Such resin emulsions can be produced, for example, by polymerizing a group of monomers containing component (p), component (q), and optionally component (r). Known polymerization methods can be used, including not only conventional emulsion polymerization, but also soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, multi-stage emulsion polymerization, etc. Multi-stage emulsion polymerization can be produced by emulsion polymerization methods of two or three or more stages. During polymerization, emulsifiers, initiators, dispersants, polymerization inhibitors, polymerization inhibitors, buffers, chain transfer agents, pH adjusters, etc., can be used. The glass transition temperature (Tg) of the resin constituting the resin emulsion is preferably -20 to 80°C, more preferably -10 to 60°C.

[0021] In the present invention, an acrylic silicone resin emulsion can be used as the resin emulsion. The use of an acrylic silicone resin emulsion is preferable in terms of the strength and weather resistance of the coating film, thereby improving the effects of the present invention.

[0022] As an acrylic silicone resin emulsion, one can be used that contains component (p), component (q), and an alkoxysilane compound (s) as monomer components (resin components) constituting the resin.

[0023] Examples of alkoxysilane compounds (s) (hereinafter also referred to as "s" component) include silane coupling agents (i), alkoxysilanes (ii), cyclic siloxanes (iii), etc., and one or more of these can be used.

[0024] Specifically, examples include polymerizable unsaturated double-bond-containing silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane; Epoxy group-containing silane coupling agents such as γ-glycidoxymethacryloxypropyltrimethoxysilane, γ-glycidoxymethacryloxypropylmethyldimethoxysilane, γ-glycidoxymethacryloxypropyltriethoxysilane, γ-glycidoxymethacryloxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Amino group-containing silane coupling agents such as 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; Silane coupling agents containing mercapto groups such as γ-mercaptopropyltrimethoxysilane; silane coupling agents containing ureido groups such as 3-ureidopropyltriateoxysilane; silane coupling agents containing chloroalkyl groups such as 3-chloropropyltrimethoxysilane; silane coupling agents containing sulfide groups such as bis(triateoxysilylpropyl)tetrasulfide; silane coupling agents containing isocyanate groups such as 3-isocyanethopropyltriateoxysilane; Silane coupling agents such as (i),

[0025] Tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and tetraacetoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrippropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrippropoxysilane, butyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, Alkylalkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane, methylphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, dimethyldiacetoxysilane, and diphenyldiacetoxysilane; Alternatively, alkoxysilane modified products obtained by modifying at least some of the alkoxyl groups of these tetrafunctional alkoxysilanes or alkylalkoxysilanes with a polyoxyalkylene group-containing compound, a fluorine-containing compound, and the like; Alkoxysilanes such as (ii),

[0026] Examples include cyclic siloxanes (iii) such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These can be used individually or in combination of two or more.

[0027] The acrylic silicone resin emulsion has a silica content ratio in the resin solids of 0.01 to 40% by mass, preferably 0.02 to 30% by mass, and more preferably 0.03 to 20% by mass.

[0028] The silica residue ratio refers to the proportion of the mass that remains as silica (SiO2) when components with Si-O bonds are calcined at 900°C. Generally, alkoxysilanes react with water to undergo hydrolysis, becoming silanols, and then undergo condensation reactions with other silanols or with alkoxy compounds. This reaction, when carried to its ultimate conclusion, results in silica (SiO2). These reactions are represented by the general formula: RO(Si(OR)2O) n R + (n+1)H2O → nSiO2 + (2n+2)ROH This is represented by the following reaction equation. The silica residue ratio is calculated based on this reaction equation, determining the amount of remaining silica component.

[0029] Such acrylic silicone resin emulsions can be produced, for example, by polymerizing a group of monomers containing component (p), component (q), component (s), and optionally component (r). Any known polymerization method can be used, including conventional emulsion polymerization, soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, and multi-stage emulsion polymerization. In multi-stage emulsion polymerization, the emulsion can be produced by two-stage or three-stage or more emulsion polymerization methods. During polymerization, emulsifiers, initiators, dispersants, polymerization inhibitors, polymerization inhibitors, buffers, chain transfer agents, pH adjusters, etc., can be used.

[0030] <Surface to be coated> Examples of surfaces to be painted in this invention include interior and exterior surfaces of buildings, civil engineering structures, etc. (e.g., exterior walls, interior walls, ceilings, roofs, etc.). Examples of substrates constituting such surfaces to be painted include concrete, mortar, and plate-shaped substrates. Among these, examples of plate-shaped substrates include 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, plastic boards, hard wood chip cement boards, PVC extruded siding boards, and plywood. When the surface to be painted is composed of multiple plate-shaped substrates, the joints between the plate-shaped substrates may be filled with jointing materials such as sealants and dry jointing materials.

[0031] The surface to be coated may have an existing coating film. Such an existing coating film is formed, for example, by one or more types of coating agents. Various types of coating agents can be used, such as colored or uncolored, or opaque or transparent. Examples include those containing one or more resins selected from vinyl acetate resin, alkyd resin, epoxy resin, acrylic resin, urethane resin, acrylic silicone resin, silicone resin, fluororesin, etc. The existing coating film is one or more layers and may be, for example, an elastic type or a rigid type.

[0032] <Main material> The main material of the present invention can be applied directly to the surface to be coated as described above, or it can be applied after treating the surface to be coated with an undercoat or surface preparation coating material (for example, a sealer, primer, surfacer, filler, putty, etc.).

[0033] The main material in this invention comprises a resin emulsion and powder / granules, forming a main material coating film having an uneven pattern. The resin emulsion in the main material is referred to as the first resin emulsion. In this invention, the uneven pattern of such a main material coating film can impart a sense of three-dimensionality, shading, etc., thereby enhancing the design. Such an uneven pattern is a surface pattern with a height difference of approximately 0.2 to 5 mm. The main material is not particularly limited and can be used as long as it is capable of forming an uneven pattern.

[0034] As the first resin emulsion in the main material, the aforementioned resin emulsion can be used.

[0035] As the main material, granular materials such as aggregates and pigments can be used. Of these, aggregates with an average particle size of 50 μm or more, and more preferably 53 μm to 5 mm, can be used. Examples of such aggregates include marble, granite, serpentinite, fluorite, feldspar, limestone, silica, silica sand, crushed stone, mica, siliceous shale, and their crushed products, crushed ceramics, crushed glass, glass beads, crushed resin, resin beads, rubber granules, metal granules, etc. In addition, crushed seashells, coral, wood, charcoal, activated carbon, waste glass, etc. can also be used. Furthermore, aggregates whose surfaces have been colored by surface treatment with pigments, dyes, glazes, etc. (colored aggregates) can also be used. The average particle size of the aggregate is the D50 value, which is determined by sieving using a metal mesh sieve as specified in JIS Z8801-1:2019. This average particle diameter D50 is the 50% cumulative particle diameter, which refers to the particle diameter that, after sieving, accumulates to 50% by mass (average value of mass distribution) from the finer particles.

[0036] Examples of pigments that can be used include coloring pigments and extender pigments. Specifically, examples of coloring pigments include titanium dioxide, zinc oxide, alumina, carbon black, graphite, black iron oxide, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper-manganese-chromium composite oxide, copper-magnesium composite oxide, bismuth-manganese composite oxide, ferric oxide (red iron oxide), molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzoimidazolone yellow, chromium green, cobalt green, phthalocyanine green, ultramarine, Prussian blue, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, aluminum pigments, and pearl pigments. These can be used individually or in combination of two or more. The average particle size of the coloring pigment is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 0.01 to 0.9 μm.

[0037] Examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, pottery clay, china clay, diatomaceous earth, hydrated fine silica, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate, silica powder, aluminum hydroxide, resin beads, and resin powder. These can be used individually or in combination of two or more. The average particle size of the extender pigment is preferably less than 50 μm, more preferably 0.5 to 48 μm, and even more preferably 1 to 45 μm. In this invention, the average particle size of the pigment is the D50 value, i.e., the value of the 50% cumulative particle size based on volume (cumulative from the fine particle side), and can be measured using a laser diffraction particle size distribution analyzer.

[0038] Specific examples of main materials include, for instance, stone-like finishing coatings, and coatings such as thin-layer and thick-layer finishing coatings specified in JIS A6909.

[0039] Stone-like finish coatings are coatings capable of forming a coating film that exhibits color due to the color development of aggregates, and are coatings that have resin components and colored aggregates as essential components. With stone-like finish coatings, various colors can be imparted to the main coating film by using one or more types of colored aggregates in appropriate combinations, and fine irregularities can also be given to the coating film surface. The finish can also be improved by using transparent aggregates. The mixing ratio of aggregates is preferably 100 to 4000 parts by mass, more preferably 150 to 3000 parts by mass, and even more preferably 200 to 2000 parts by mass, per 100 parts by mass of solid content of the resin component.

[0040] Stone-like finish coatings may contain other components besides those listed above. Examples of such components include coloring pigments, extender pigments, fibers, film-forming aids, plasticizers, antifreeze agents, preservatives, fungicides, antibacterial agents, defoaming agents, pigment dispersants, thickeners, leveling agents, coupling agents, wetting agents, pH adjusters, matting agents, UV absorbers, antioxidants, catalysts, and crosslinking agents.

[0041] Thin-coat and thick-coat finish coatings specified in JIS A6909 can be obtained by uniformly mixing resin components, coloring pigments, extender pigments, aggregates, and other admixtures (dispersants, thickeners, defoamers, preservatives, etc.). With such coatings, the desired color can be imparted to the coating film by using one or more coloring pigments in combination. The mixing ratio of the coloring pigments is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, per 100 parts by mass of the solid content of the resin component.

[0042] Extender pigments primarily act as bulking agents and are components that effectively contribute to the formation of thick coating films. The mixing ratio of extender pigments is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of solid content of the resin component.

[0043] The aggregate plays a role in creating fine irregularities on the surface of the coating film. The mixing ratio of the aggregate is preferably 10 to 2000 parts by mass, more preferably 30 to 1500 parts by mass, per 100 parts by mass of the solid content of the resin component.

[0044] When applying such coatings, various textured patterns can be formed by appropriately selecting the type of coating tool and its usage method. These patterns include sand-like, orange peel-like, fibrous-like, ripple-like, stucco-like, uneven, moon-like, comb-like, and insect-eaten patterns. Suitable coating tools include sprays, rollers, trowels, and brushes. Furthermore, various textured patterns can be formed by treating the surface with a design roller, trowel, brush, comb, or spatula before the coating dries. It is also possible to create multi-colored patterns by combining two or more coatings of different colors.

[0045] The amount of coating material applied depends on the type of pattern to be formed, but is preferably 0.5 to 10 kg / m². 2 More preferably 1-8 kg / m 2 More preferably 1.5 to 6 kg / m 2The viscosity of the coating material can be adjusted as needed by mixing in a diluent such as water during painting. The dilution ratio is preferably 0 to 10% by mass. Drying can be carried out at room temperature (preferably 0 to 50°C, more preferably 5 to 45°C).

[0046] <Top coat material> The topcoat material of the present invention contains a resin emulsion and forms a patterned coating film with colored particles. For example, the following method can be used to form the patterned coating film with colored particles. (a) A method of applying a topcoat material in which liquid or gel-like color particles are dispersed in a water-based clear coating material. (b) A method of applying a colored topcoat material containing a resin emulsion and a colored pigment in granular form.

[0047] First, let's explain the topcoat material mentioned in (a) above.

[0048] The topcoat material described in (a) above consists of liquid or gel-like color particles dispersed in a water-based clear coating material. In the topcoat material described in (a) above, a water-based clear coating material containing a resin emulsion can be used as the water-based clear coating material (hereinafter, the resin emulsion contained in the water-based clear coating material will be referred to as the "second resin emulsion"). In addition, in the topcoat material described in (a) above, granular material containing a resin emulsion and a coloring agent containing a coloring pigment can be used as the color particles (hereinafter, the resin emulsion contained in the coloring agent constituting the color particles will be referred to as the "third resin emulsion"). In the topcoat material described in (a) above, a water-based clear coating material containing the second resin emulsion can be used as the water-based clear coating material, and granular material containing a third resin emulsion and a coloring agent containing a coloring pigment can be used as the color particles.

[0049] Such topcoat materials can be used as materials specified in JIS K5667:2003 "Multicolor Pattern Paints". Such materials are classified into oil-in-water (O / W) type, water-in-water (W / W) type, etc., depending on the combination of color particles and medium (color particles / medium). Such topcoat materials can preferably be of the water-in-water (W / W) type.

[0050] In the topcoat material described in (a) above, a water-based clear coating material containing a second resin emulsion can be used as the water-based medium. Such a water-based clear coating material serves as a medium for color particles and can form a clear coating film, playing a role in fixing the color particles in the formed coating film. The water-based clear coating material only needs to be capable of forming a transparent coating film in which the color particles are visible to the naked eye. As the second resin emulsion in the water-based clear coating material, the aforementioned resin emulsion can be used. The glass transition temperature of the resin constituting the second resin emulsion is preferably -10°C to 30°C.

[0051] As the second resin emulsion, an acrylic silicone resin emulsion having a silica residue ratio of 0.01 to 3% by mass in the resin solids is particularly preferred. Such an acrylic silicone resin emulsion can contribute to improvements in weather resistance, crack resistance, substrate conformability, etc. In such an acrylic silicone resin emulsion, the silica residue ratio in the resin solids is 0.01 to 3% by mass, preferably 0.02 to 1.0% by mass, and more preferably 0.03 to 0.8% by mass. By having the silica residue ratio within the above range, excellent weather resistance can be achieved while ensuring physical properties such as crack resistance and substrate conformability.

[0052] The second resin emulsion preferably has a solid content of 5 to 50% by mass in the water-based clear coating material, and more preferably 15 to 45% by mass.

[0053] The water-based clear coating material may contain, in addition to the second resin emulsion, granular particles (g) with an average particle size of 1 μm or larger. By including granular particles (g) with an average particle size of 1 μm or larger in the water-based clear coating material, the workability and finish quality during the formation of the topcoat film can be improved.

[0054] Examples of powders and granules (g) with an average particle size of 1 μm or more in a water-based clear coating material (hereinafter also referred to as "(g) component") include heavy calcium carbonate, crushed stone, light calcium carbonate, white carbon, talc, kaolin, clay, earthenware clay, china clay, diatomaceous earth, barite powder, barium sulfate, precipitated barium sulfate, silica sand, silica powder, quartz powder, gravel, glass beads, resin beads, mica, sericite, plate-like kaolin, barium sulfate flakes, glass flakes, alumina flakes, shell fragments, metal fragments and other inorganic fragments, or rubber fragments, plastic fragments, wood fragments, etc., or crushed materials such as rocks, glass, shells, sintered bodies, plastics, rubber, waste glass, etc. These may be surface-treated. These can be used individually or in combination of two or more types. The mixing ratio of powders (g) with an average particle size of 1 μm or more is preferably 3 to 200 parts by mass, more preferably 5 to 150 parts by mass, and even more preferably 10 to 120 parts by mass, per 100 parts by mass of solid content of the second resin emulsion.

[0055] In water-based clear coatings, powders with an average particle size of 1 μm or more and less than 50 μm (g1) (hereinafter also referred to as "(g1) component") can be used as the (g) component (g) with an average particle size of 1 μm or more. By using the (g1) component as the (g) component in water-based clear coatings, in addition to the above effects, the gloss of the topcoat film can be reduced and the finish can be improved. From the viewpoint of the clarity of the coating film, it is desirable that the refractive index of the (g1) component be 1.4 to 1.7. The refractive index can be measured using an Abbe refractometer. The average particle size of the (g1) component is the D50 value measured using a laser diffraction particle size distribution analyzer, as described above.

[0056] Furthermore, in water-based clear coatings, the (g1) component can be either a powder or granular material with an average particle size of 1 μm or more and less than 15 μm (g11) (hereinafter also referred to as "(g11) component") or a powder or granular material with an average particle size of 15 μm or more and less than 50 μm (g12) (hereinafter also referred to as "(g12) component"). By using a combination of (g11) component and (g12) component with different average particle sizes as the (g) component in a water-based clear coating, in addition to the effects mentioned above, it is possible to enhance performance such as matte finish, crack resistance, and substrate conformability.

[0057] The average particle size of component (g11) is 1 μm or more and less than 15 μm, preferably 1 to 14 μm, more preferably 2 to 12 μm. The average particle size of component (g12) is 15 μm or more and less than 50 μm, preferably 16 to 48 μm, more preferably 18 to 45 μm.

[0058] The mixing ratio of component (g11) 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 the second resin emulsion. The mixing ratio of component (g12) 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 the second resin emulsion. Furthermore, the mass ratio of component (g11) to component (g12) {(g11):(g12)} is preferably 1:99 to 80:20, more preferably 2:98 to 50:50, and even more preferably 3:97 to 40:60. With such mixing ratios of component (g11) and component (g12), in addition to the above effects, performance such as matte finish, crack resistance, and substrate conformability can be sufficiently enhanced.

[0059] In water-based clear coatings, powders with an average particle size of 50 μm or more (g2) (hereinafter also referred to as "(g2) component") can be used as the powder (g) component (g) with an average particle size of 1 μm or more. Using powders (g2) with an average particle size of 50 μm or more as the (g) component in water-based clear coatings is preferable because it can further improve workability and finish when forming the topcoat film.

[0060] The average particle size of component (g2) is 50 μm or more, preferably 150 to 4000 μm, more preferably 300 to 2800 μm, and particularly preferably 500 to 2000 μm. The average particle size of component (g2) 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 is the particle size that, when sieved, accumulates to 50% by mass (average value of mass distribution) from the finer particles.

[0061] The mixing ratio of component (g2) 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 solid content of the second resin emulsion. With such a mixing ratio of component (g2), the workability and finish when forming the topcoat film can be further improved.

[0062] The (g) component in the water-based clear coating material may include particles with a flaky shape (hereinafter referred to as "flaky powder"). The inclusion of flaky powder in the water-based clear coating material is preferable because it can further improve workability and finish when forming the topcoat film. This is particularly effective when the color particles include the (h2) component described later.

[0063] Examples of such flake-like powders include mica, sericite, clay, talc, plate-like kaolin, barium sulfate flakes, glass flakes, alumina flakes, shell fragments, metal fragments, and other inorganic materials, as well as rubber fragments, plastic fragments, and wood fragments. Other examples include substrate particles that have been surface-treated (for example, by coating (or adsorbing) colorants containing pigments or dyes onto the substrate particles, or by applying calcination treatments to the substrate particles). These can be used individually or in combination of two or more types.

[0064] The flake-like granular material is not particularly limited as long as its shape is flake-like (thin flake-like), but its aspect ratio (ratio of "short diameter / thickness") is preferably 1.5 to 2000, more preferably 2 to 500, and even more preferably 3 to 100. The ratio of the short diameter to the long diameter (short diameter / long diameter) is preferably 0.3 to 1, more preferably 0.4 to 1, and even more preferably 0.5 to 1. The "short diameter," "long diameter," and "thickness" referred to here are calculated by observing the flake-like particles stably on a horizontal surface using a microscope from above, with the shortest part being the "short diameter," the longest part being the "long diameter," and the maximum height from the bottom surface being the "thickness."

[0065] The average particle size of such flake-like granules can be 50 μm or more, preferably 150 to 4000 μm, more preferably 300 to 2800 μm, and even more preferably 500 to 2000 μm. In the present invention, flake-like granules can be used as component (g2).

[0066] The mixing ratio of the flake-like powder 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 solid content of the second resin emulsion. Such a mixing ratio of flake-like powder further improves workability and finish during the formation of the topcoat film.

[0067] When using flake-shaped granules as component (g2), component (g1) can be used in combination. This configuration is advantageous for improving workability and finish when forming a topcoat film. In this case, the above effect can be further enhanced by using a material with a perfectly spherical particle shape (hereinafter referred to as "perfectly spherical granules") as component (g1). As for the perfectly spherical granules, those with a ratio of major axis to minor axis (major axis / minor axis) of 0.8 to 1.2 (preferably 0.9 to 1.1, more preferably 0.95 to 1.05) are preferred. Various materials can be used for the perfectly spherical granules, regardless of whether they are organic or inorganic. Examples include glass beads, resin beads, hollow glass beads, hollow resin beads, etc. These can be used one or more types. The mass ratio of flaky granules to spherical granules (flaky granules:spherical granules) is preferably 5:95 to 80:20, and more preferably 10:90 to 50:50.

[0068] In the water-based clear coating material, known additives can be appropriately mixed in addition to the components described above. Examples of such additives include dispersion stabilizers, water-soluble resins, pigment dispersants, emulsifiers, thickeners, film-forming aids, leveling agents, coupling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, drying adjusters, preservatives, antifungal agents, antialgal agents, antibacterial agents, defoaming agents, adsorbents, deodorizers, ultraviolet absorbers, light stabilizers, antioxidants, catalysts, crosslinking agents, solvents, and water. It is also possible to mix in resin emulsions other than the second resin emulsion, as long as they do not significantly impair the effects of the present invention.

[0069] The ratio of water (including water used as a medium such as the second resin emulsion) 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 solid content of the second resin emulsion.

[0070] In water-based clear coatings, a dispersion stabilizer may be included to stably disperse the color particles. The dispersion stabilizer can be selected according to the type of resin and coloring agent that constitute the color particles. Specific examples of dispersion stabilizers include magnesium salts, calcium salts, barium salts, aluminum salts, sodium salts, potassium salts, borates, silicates, phosphates, etc. In addition, water-soluble polymers, clays, etc. can also be used as dispersion stabilizers. 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 the second resin emulsion.

[0071] Liquid or gel-like color particles in topcoat materials contribute to the formation of highly decorative coating films. Color particles in topcoat materials can be obtained, for example, by dispersing a coloring material containing an aqueous resin, a coloring pigment, and various additives as needed, in an aqueous medium in a liquid or gel-like state. The inclusion of an aqueous resin in the coloring material constituting the color particles allows the topcoat material to be in a water-in-water (W / W) configuration. As the aqueous resin, resin emulsions and / or water-soluble resins can be used.

[0072] In the present invention, a third resin emulsion can be used as the aqueous resin in the coloring agent. The resin emulsion described above can be used as the third resin emulsion. The glass transition temperature of the resin constituting the third resin emulsion is preferably -10 to 80°C, more preferably 10 to 60°C, and can also be set to be higher than the glass transition temperature of the resin constituting the second resin emulsion.

[0073] In the present invention, it is particularly desirable to use an acrylic silicone resin emulsion as the third resin emulsion, having a silica residue ratio of 0.5 to 40% by mass in the resin solids. Furthermore, in the present invention, it is even more desirable to use an acrylic silicone resin emulsion in both the water-based clear coating material and the color particles, thereby exhibiting even better effects in terms of weather resistance, crack resistance, substrate conformability, etc. In this case, it is desirable that the silica residue ratio in the resin solids of the third resin emulsion be greater than the silica residue ratio in the resin solids of the second resin emulsion.

[0074] When the third resin emulsion is an acrylic silicone resin emulsion, the silica content ratio in the resin solids is preferably 0.5 to 40% by mass, more preferably 1.0 to 20% by mass, and even more preferably 1.2 to 10% by mass. By having the silica content ratio within the above range, even better weather resistance can be achieved. The mechanism of action is not limited to the following, but it is thought that having the silica content ratio of the third resin emulsion within the above range enhances the weather resistance of the resin itself, and that the coloring pigment is covered by the silicone component, suppressing radical generation, etc. This improvement in weather resistance makes film degradation less likely, and it is thought that performance such as crack resistance and substrate conformability is also improved.

[0075] The third resin emulsion preferably has a solid content of 5 to 50% by mass in the coloring agent, and more preferably 10 to 40% by mass.

[0076] The coloring agent constituting the color particles preferably comprises a third resin emulsion and a water-soluble resin as an aqueous resin. 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., or chemically modified versions thereof obtained by oxidation, methylation, carboxymethylation, hydroxyethylation, hydroxypropylation, sulfation, phosphorylation, cationization, etc. These can be used individually or in combination of two or more. Such water-soluble resins can contribute to the stabilization of color particle formation and can also be used as gel-forming agents. In the present invention, by including both of these in the coloring agent, color particles can be stably formed, and the weather resistance, water resistance, etc. of the coating film can be improved.

[0077] The ratio of the third resin emulsion to the water-soluble resin in the coloring agent is preferably 99.8:0.2 to 70:30, and more preferably 99.5:0.5 to 90:10, in terms of solid content mass ratio (solid content of the third resin emulsion: solid content of the water-soluble resin).

[0078] In colorants, coloring pigments are components that impart color to color particles. Examples of coloring 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 dioxide, zinc oxide, and alumina; and other pigments such as pearl pigments, aluminum pigments, luminescent pigments, phosphorescent pigments, and fluorescent pigments. These can be used individually or in combination of two or more. The average particle size of the coloring pigment is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 0.01 to 0.9 μm. The average particle size of the coloring pigment is the D50 value measured using a laser diffraction particle size distribution analyzer, as described above.

[0079] The mixing ratio of the coloring pigment in the coloring material is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, per 100 parts by mass of the solid content of the third resin emulsion.

[0080] The coloring material constituting the color particles may include, in addition to the above-mentioned third resin emulsion and coloring pigment, powder particles (h) with an average particle size of 1 μm or more. This results in color particles containing powder particles (h) with an average particle size of 1 μm or more. In the present invention, by including powder particles (h) with an average particle size of 1 μm or more in the color particles of the topcoat material, the pattern created by the color particles blends more easily with the main coating film, thereby improving the texture of the finished appearance. In particular, when the above color particles are stretched using a pressing tool, the edges of the stretched color particles become blurred, which blends even more easily with the main coating film, enhancing the natural appearance.

[0081] As the powdery material (h) (hereinafter also referred to as "(h) component") with an average particle diameter of 1 μm or more in the colored particles, for example, extender pigments, aggregates, etc., can be used. Among these, examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, pottery clay, china clay, diatomaceous earth, hydrated fine silica, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate, silica powder, aluminum hydroxide, resin beads, resin powder, etc. These can be used individually or in combination of two or more. The average particle diameter of the extender pigment contained in the colored particles is preferably 1 μm or more and less than 50 μm, more preferably 2 to 48 μm. The average particle diameter of the extender pigment is the D50 value measured using a laser diffraction particle size distribution analyzer, as described above.

[0082] Preferably, aggregates with an average particle size of 50 μm or more, more preferably 53 to 1000 μm, even more preferably 63 to 600 μm, and particularly preferably 75 to 300 μm can be used. Examples of such aggregates include marble, granite, serpentinite, fluorite, feldspar, limestone, silica, silica sand, crushed stone, mica, siliceous shale, and their crushed products, crushed ceramics, crushed glass, glass beads, crushed resin, resin beads, rubber granules, metal granules, shirasu balloons, glass balloons, perlite, pumice, hollow balloons, etc. Crushed seashells, coral, wood, charcoal, activated carbon, waste glass, etc., can also be used. Furthermore, aggregates whose surfaces have been colored by surface treatment with pigments, dyes, glazes, etc., can also be used. The average particle size of the aggregate 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, after sieving, accumulates to 50% by mass (average value of mass distribution) from the finer particles.

[0083] The color particles preferably contain powders with an average particle diameter of 1 μm or more and less than 50 μm (h1), and / or powders with an average particle diameter of 50 μm or more (h2). In the present invention, it is preferable that the color particles contain either one of these powders, and more preferably both. In this configuration, the ability to prevent uneven gloss of the formed coating film can be improved, which is advantageous in terms of improving aesthetics. In particular, when the color particles are stretched using a pressing tool, the ends of the stretched color particles become more naturally faded, which is even more advantageous in terms of improving aesthetics. For example, the above-mentioned extender pigment can be used as the powders with an average particle diameter of 1 μm or more and less than 50 μm (h1), and the above-mentioned aggregate can be used as the powders with an average particle diameter of 50 μm or more (h2).

[0084] It is desirable that powder particles (h) with an average particle diameter of 1 μm or more be included in the colored particles in a ratio of preferably 2 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 8 to 30% by mass. Furthermore, the mass ratio {(h1 component):(h2 component)} of powder particles with an average particle diameter of 1 μm or more and less than 50 μm (h1) to powder particles with an average particle diameter of 50 μm or more (h2) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80. When powder particles are included in such a ratio, the above effects can be enhanced and it is more preferable.

[0085] The mixing ratio of powders (h) with an average particle size of 1 μm or more in the coloring agent is preferably 10 to 500 parts by mass, more preferably 30 to 400 parts by mass, and even more preferably 50 to 300 parts by mass, per 100 parts by mass of solid content of the third resin emulsion. Furthermore, the mass ratio {(h1) component:(h2) component} of powders (h1) with an average particle size of 1 μm or more and less than 50 μm and powders (h2) with an average particle size of 50 μm or more is preferably 90:10 to 10:90, and more preferably 80:20 to 20:80. When the powders are included in such a ratio, the above effects can be enhanced and it is more preferable.

[0086] In addition to the components mentioned above, the coloring agent 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, drying adjusters, preservatives, antifungal agents, antialgal agents, antibacterial agents, defoaming agents, fibers, gel-forming agents, adsorbents, deodorizers, UV absorbers, light stabilizers, antioxidants, catalysts, crosslinking agents, solvents, and water. It is also possible to mix in resin emulsions other than the third resin emulsion, as long as they do not significantly impair the effects of the present invention.

[0087] The ratio of water (including water used as a medium such as aqueous resin) in the coloring agent is preferably 80 to 800 parts by mass, more preferably 100 to 600 parts by mass, per 100 parts by mass of solid content of the third resin emulsion.

[0088] The method for granulating the coloring agent is not particularly limited, and known methods can be used. For example, a method similar to the manufacturing method of materials specified in JIS K5667:2003 "Multicolor Pattern Paints" can be used. Specifically, for example, a method can be used in which the coloring agent is dispersed in a medium containing a dispersion stabilizer (some or all of the components of the aqueous clear coating material). The dispersion stabilizer is a component that stabilizes the coloring agent into granules, and acts as a gelling agent for the coloring agent, for example.

[0089] The particle size and shape of the color particles can be set as appropriate. Specifically, for example, the shape of the stirring blades during manufacturing, the size and position of the stirring blades relative to the stirring tank, the rotation speed of the stirring blades, the stirring time, the viscosity of the coloring agent, the method and concentration of adding the dispersion stabilizer, the viscosity of the medium, etc., can be appropriately selected and adjusted. The average particle size of the color particles is preferably 0.5 to 20 mm (more preferably 1 to 18 mm, and even more preferably 1.2 to 15 mm). In this invention, the average particle size of the color particles is 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 hereinafter) and calculating the average value of their major axis (average value of 50 color particles).

[0090] In order to obtain a topcoat material containing two or more (two or more colors) color particles, for example, After separately manufacturing color particle dispersion liquids (color particle dispersion liquids containing one kind of color particle) in which one kind of coloring material is dispersed in a medium, these are mixed, or A method of adding and dispersing two or more kinds of coloring materials having different color tones, etc. into a medium simultaneously or in sequence to obtain a color particle dispersion liquid (a color particle dispersion liquid containing two or more kinds of color particles), Methods such as these can be employed. In such a method, as the medium, a part or all of an aqueous clear coating material can be used. When manufacturing a color particle dispersion liquid using a part of the components of an aqueous clear coating material as the medium, the remaining components of the aqueous clear coating material may be mixed with the said color particle dispersion liquid.

[0091] In the topcoat material, the mass ratio of the color particles to the aqueous clear coating material (color particles : aqueous clear coating material) is preferably 1:99 to 80:20 (more preferably 10:90 to 75:25, even more preferably 30:70 to 70:30).

[0092] The topcoat material may contain the above-mentioned color particles and may also contain transparent gel particles, etc., as long as the effects of the present invention are not significantly impaired.

[0093] As a coating method of the topcoat material, for example, spray coating, roller coating, brush coating, etc. can be employed. The coating amount of the topcoat material is preferably 0.6 kg / m 2 or less, more preferably 0.1 to 0.5 kg / m 2 and even more preferably 0.2 to 0.4 kg / m 2 . The coating amount (in terms of solid content) of the topcoat material is preferably 0.3 kg / m 2 or less, more preferably 0.05 to 0.2 kg / m 2 and even more preferably 0.08 to 0.18 kg / m 2 . By coating the topcoat material under such conditions, while making use of the uneven pattern of the main material coating film, a highly designed pattern in which the pattern by the color particles is combined can be sufficiently imparted. The coating or drying of the topcoat material is preferably carried out at room temperature.

[0094] When applying the topcoat, the viscosity can be adjusted as needed by mixing in a diluent such as water. The dilution ratio is preferably 0 to 10% by mass. The viscosity of the topcoat 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).

[0095] Next, we will explain the topcoat material mentioned in (b) above.

[0096] The topcoat material described in (b) above is a colored topcoat material containing a resin emulsion (hereinafter referred to as "fourth resin emulsion") and a coloring pigment. In the present invention, a patterned coating film can be formed by applying such a colored topcoat material in a granular form.

[0097] As the fourth resin emulsion in the colored topcoat material, the aforementioned resin emulsion can be used. The glass transition temperature of the resin constituting the fourth resin emulsion is preferably -10°C to 50°C.

[0098] When the fourth resin emulsion is an acrylic silicone resin emulsion, the silica content ratio in the resin solids is preferably 0.01 to 40% by mass, more preferably 0.02 to 30% by mass, and even more preferably 0.03 to 20% by mass. By having the silica content ratio within the above range, even better weather resistance can be achieved. The mechanism of action is not limited to the following, but it is thought that having the silica content ratio of the fourth resin emulsion within the above range enhances the weather resistance of the resin itself, and that the coloring pigment is covered by the silicone component, suppressing radical generation, etc., which contributes to this. With such improved weather resistance, film degradation becomes less likely, and it is thought that performance such as crack resistance and substrate conformability also improves.

[0099] The fourth resin emulsion preferably has a solid content of 5 to 50% by mass in the colored topcoat material, and more preferably 10 to 40% by mass.

[0100] In colored topcoats, the coloring pigments are components that impart color to the color particles. The same coloring pigments as those described above for colorants can be used.

[0101] The mixing ratio of the colored pigment in the colored topcoat is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, per 100 parts by mass of the solid content of the fourth resin emulsion.

[0102] The colored topcoat may contain, in addition to the above-mentioned fourth resin emulsion and coloring pigment, granular particles (h) with an average particle size of 1 μm or more. By including granular particles (h) with an average particle size of 1 μm or more in the colored topcoat, the pattern created by the color particles blends more easily with the main coating film, thereby improving the texture of the finished appearance. In particular, when the above-mentioned color particles are stretched using a pressing tool, the edges of the stretched color particles become blurred, which blends even more easily with the main coating film, enhancing the natural appearance.

[0103] For the (h) component in the colored topcoat, which has an average particle size of 1 μm or more, examples include extender pigments and aggregates. The same components as those described above for the coloring materials can be used for the (h) component (e.g., extender pigments and aggregates).

[0104] The colored topcoat preferably contains granular particles with an average particle diameter of 1 μm or more and less than 50 μm (h1), and / or granular particles with an average particle diameter of 50 μm or more (h2). In the present invention, it is desirable for the colored topcoat to contain either one of these granular particles, and more preferably both. In this configuration, the ability to prevent uneven gloss of the formed coating film can be improved, which is advantageous in terms of improving aesthetics. In particular, when the color particles are stretched using a pressing tool, the ends of the stretched color particles become more naturally faded, which is even more advantageous in terms of improving aesthetics. For example, the above-mentioned extender pigment can be used as the granular particles with an average particle diameter of 1 μm or more and less than 50 μm (h1), and the above-mentioned aggregate can be used as the granular particles with an average particle diameter of 50 μm or more (h2).

[0105] It is desirable that the granular material (h) with an average particle size of 1 μm or more be included in the colored topcoat in a ratio of preferably 2 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 8 to 30% by mass. Furthermore, the mass ratio {(h1 component):(h2 component)} of granular material (h1) with an average particle size of 1 μm or more and less than 50 μm and granular material (h2) with an average particle size of 50 μm or more is preferably 90:10 to 10:90, more preferably 80:20 to 20:80. When the granular material is included in such a ratio, the above effects can be enhanced and it is more preferable.

[0106] The mixing ratio of granular particles (h) with an average particle size of 1 μm or more in the colored topcoat material is preferably 10 to 500 parts by mass, more preferably 30 to 400 parts by mass, and even more preferably 50 to 300 parts by mass, per 100 parts by mass of solid content of the fourth resin emulsion. Furthermore, the mass ratio {(h1) component:(h2) component} of granular particles with an average particle size of 1 μm or more and less than 50 μm (h1) to granular particles with an average particle size of 50 μm or more (h2) is preferably 90:10 to 10:90, and more preferably 80:20 to 20:80. When granular particles are included in such a ratio, the above effects can be enhanced, and this is more preferable.

[0107] In addition to the components described above, the colored topcoat material 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, drying adjusters, preservatives, antifungal agents, antialgal agents, antibacterial agents, defoaming agents, fibers, adsorbents, deodorizers, UV absorbers, light stabilizers, antioxidants, catalysts, crosslinking agents, solvents, and water. It is also possible to mix in resin emulsions other than the fourth resin emulsion, as long as they do not significantly impair the effects of the present invention.

[0108] As for the application method of the colored topcoat, various application methods can be used as long as the colored topcoat is applied in granular form to form a patterned coating film with color particles. For example, spray application and roller application can be used. The average particle size of the color particles is preferably 0.5 to 20 mm (more preferably 1 to 18 mm, and even more preferably 1.2 to 15 mm).

[0109] In method (b) above, one or more types of colored topcoats can be used. In method (b) above, it is desirable to use two or more types of colored topcoats with different color tones. When using two or more types of colored topcoats, these topcoats may be applied simultaneously or sequentially. When applying multiple types of colored topcoats simultaneously, a multi-head spray painter or the like can be used as the painting equipment.

[0110] The amount of colored topcoat applied is preferably 0.5 kg / m². 2 More preferably, 0.02 to 0.4 kg / m 2 More preferably 0.04 to 0.3 kg / m 2 The amount of colored topcoat material applied (in terms of solid content) is preferably 0.25 kg / m². 2 More preferably, 0.01 to 0.2 kg / m 2 More preferably 0.02 to 0.15 kg / m 2 Therefore, by applying a colored topcoat under these conditions, it is possible to fully impart a highly decorative pattern that combines the uneven texture of the main coating film with patterns created by color particles. The application and drying of the topcoat may preferably be carried out at room temperature.

[0111] When applying the colored topcoat, the viscosity can be adjusted as appropriate by mixing in a diluent such as water. The dilution ratio is preferably 0 to 30% by mass. The viscosity of the topcoat to be applied is preferably 0.1 to 30 Pa·s (more preferably 0.2 to 20 Pa·s), and the thixotropy index is preferably 1 to 9 (more preferably 2 to 8).

[0112] <Stretching process> In this invention, after applying the topcoat material, the color particles can be stretched using a pressing tool (stretching process) while the topcoat film is still wet. In this invention, by performing this stretching process, a flow pattern is formed on the main material film, and a highly aesthetic finish can be obtained through the composite of the main material film and the topcoat film, creating a new, highly decorative coating film unlike any other. In this invention, since the color particles are stretched on the main material film which has an uneven pattern, the degree of stretching differs depending on the position of the color particles, etc., and a natural-looking pattern is formed with a mixture of flow patterns of various shapes. If the color particles of the topcoat material contain the above-mentioned granular material, the flow pattern created by the color particles will blend more easily with the main material film, and a finish with excellent texture can be obtained.

[0113] In topcoat coatings that form flow patterns through such a stretching process, areas of the coating become thicker and areas of thinner due to the degree of crushing of color particles. Generally, when such differences in film thickness occur, areas with thinner film thickness are more prone to discoloration, peeling, and other defects. As a result, it becomes difficult to maintain the color and appearance of the pattern, and the original pattern may change over time. In contrast, the present invention employs a specific resin emulsion for both the main material and the topcoat material, making it less likely for discoloration, peeling, and other defects to occur in any area, and allowing the original pattern to be maintained for a long period of time.

[0114] In the stretching process, a pressing tool is brought into contact with the color particles, and the shape of the color particles is deformed and stretched by dragging while pressing, thereby forming a flowing pattern. Examples of pressing tools that can be used in the stretching process include trowels, spatulas, brushes, brooms, etc. The stretching of the color particles can be performed while the topcoat material is still wet, preferably within 20 minutes after application of the topcoat material (more preferably within 10 minutes, and even more preferably within 5 minutes).

[0115] The degree of load on the pressing tool can be appropriately set within the range in which the color particles are crushed and can be stretched. By adjusting the load on the pressing tool, the length, width, thickness, etc. of the formed pattern can also be changed. The direction in which the color particles are stretched by the pressing tool can be set according to the desired pattern. For example, to form a linear pattern, the particles should be stretched straight in a certain direction. To form an arc-shaped pattern, the particles should be stretched in a semicircle. Random stretching is also possible. When the surface to be coated is a vertical surface such as a wall, it is desirable to stretch the particles horizontally. This method is preferable because it can suppress the falling of color particles, improve work efficiency, and enhance the finished design.

[0116] After spreading the color particles, the topcoat film is dried. Drying is preferably carried out at room temperature. In addition, in this invention, the application of the topcoat and the spreading process may be repeated as necessary.

[0117] In this invention, since the laminated coating film of the main material and the topcoat material exhibits excellent weather resistance, there is no need to apply a clear coating after applying the topcoat material. [Examples]

[0118] Examples and comparative examples are shown below to further clarify the features of the present invention, but the present invention is not limited to these examples.

[0119] (Manufacturing of main material 1) To 200 parts by mass of resin 1 (see below), 700 parts by mass of aggregate (a mixture of white colored silica sand, light gray colored silica sand, light yellow colored silica sand, and transparent glass pulverized material, particle size 0.08-0.2 mm), 16 parts by mass of film-forming aid, 1 part by mass of thickener, and 2 parts by mass of defoamer were mixed and uniformly stirred by conventional methods to produce a light gray main material 1.

[0120] (Manufacturing of main material 2) To 200 parts by mass of resin 1 (see below), 120 parts by mass of extender pigment (heavy calcium carbonate, average particle size 20 μm), 18 parts by mass of film-forming aid, 1 part by mass of thickener, 2 parts by mass of defoaming agent, 30 parts by mass of coloring pigment (mixed dispersion of titanium dioxide, yellow iron oxide, and carbon black), and 500 parts by mass of aggregate (colonite, particle size 0.1-0.4 mm) were mixed and uniformly stirred by conventional methods to produce a light gray main material 2.

[0121] (Manufacturing of main material 3) In main material 2, resin 1 was replaced with resin 2 (see below) to produce a light gray main material 3.

[0122] (Manufacturing of main material 4) In main material 2, resin 1 was replaced with resin 3 (see below) to produce a light gray main material 4.

[0123] (Manufacturing of main material 5) In main material 2, resin 1 was replaced with resin 4 (see below) to produce a light gray main material 5.

[0124] The resins used in the manufacture of the main material are as follows:

[0125] • Resin 1: Acrylic silicone resin emulsion (Emulsion polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-methacrylic acid-silane coupling agent, (p) component ratio 28% by mass, (q) component ratio 33% by mass, glass transition temperature 18°C, silica residue ratio in resin solids 0.3% by mass, solids content 50% by mass) • Resin 2: Acrylic resin emulsion (emulsified polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-methacrylic acid, (p) component ratio 30% by mass, (q) component ratio 33% by mass, glass transition temperature 20°C, solids content 50% by mass)

[0126] • Resin 3: Acrylic resin emulsion (emulsified polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-methacrylic acid, (p) component ratio 12% by mass, (q) component ratio 35% by mass, glass transition temperature 20°C, solids content 50% by mass) • Resin 4: Acrylic resin emulsion (emulsified polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-methacrylic acid, (p) component ratio 3% by mass, (q) component ratio 38% by mass, glass transition temperature 20°C, solids content 50% by mass)

[0127] (Manufacturing of topcoat material 1) (1) In the colorant 1 with the formulation shown in Table 3, the coloring pigment is: Coloring pigment 1: Coloring pigment 3: Coloring pigment 4: Coloring pigment 5 A white coloring agent was prepared using a ratio of 1.960:0.004:0.004:0.032 (total 2 parts by mass). This white coloring agent (100 parts by mass) was added to mixture a of aqueous clear coating material 1 with the formulation shown in Table 1 and stirred to disperse. Then, mixture b of aqueous clear coating material 1 was added to obtain a white color particle dispersion liquid containing gel-like color particles (white) with an average particle size of approximately 3 mm. (2) In the colorant 1 with the formulation shown in Table 3, the coloring pigment is: Coloring pigment 1: Coloring pigment 2: Coloring pigment 3: Coloring pigment 4 A gray coloring agent was prepared using a ratio of 1.508:0.400:0.084:0.008 (total 2 parts by mass). This gray coloring agent (100 parts by mass) was added to mixture a of aqueous clear coating material 1 with the formulation shown in Table 1 and stirred to disperse. Then, mixture b of aqueous clear coating material 1 was added to obtain a gray color particle dispersion liquid containing gel-like color particles (gray) with an average particle size of approximately 3 mm. (3) In the colorant 1 with the formulation shown in Table 3, the coloring pigment is: Coloring pigment 1: Coloring pigment 2: Coloring pigment 3: Coloring pigment 4 A purple coloring agent was prepared using the ratio =1.000:0.764:0.016:0.220 (total 2 parts by mass). This purple coloring agent (100 parts by mass) was added to mixture a of aqueous clear coating material 1 with the formulation shown in Table 1 and stirred to disperse. Then, mixture b of aqueous clear coating material 1 was added to obtain a purple color particle dispersion liquid containing gel-like color particles (purple) with an average particle size of approximately 3 mm. (4) Topcoat material 1 was manufactured by mixing the white granular dispersion, gray granular dispersion, and purple granular dispersion in a mass ratio of 55:40:5.

[0128] (Manufacturing of topcoat materials 2-15) Instead of colorant 1 and water-based clear coating material 1, white granular dispersion, gray granular dispersion, and purple granular dispersion were prepared using the combinations of colorant and water-based clear coating materials shown in Tables 4 to 7, respectively. These were then mixed in a mass ratio of 55:40:5 to produce topcoat materials 2 to 15.

[0129] (Manufacturing of topcoat material 16) In the colorant 4 formulation shown in Table 3, the coloring pigment is: Coloring pigment 1: Coloring pigment 3: Coloring pigment 4: Coloring pigment 5 A white coloring agent using the ratio =1.960:0.004:0.004:0.032 (total 2 parts by mass) was used as the topcoat material 16.

[0130] (Manufacturing of topcoat material 17) In the colorant 5 formulation shown in Table 3, the coloring pigment is: Coloring pigment 1: Coloring pigment 3: Coloring pigment 4: Coloring pigment 5 A white coloring agent using the ratio =1.960:0.004:0.004:0.032 (total 2 parts by mass) was used as the topcoat material 17.

[0131] (Manufacturing of topcoat material 18) In the colorant 6 formulation shown in Table 3, the coloring pigment is: Coloring pigment 1: Coloring pigment 3: Coloring pigment 4: Coloring pigment 5 A white coloring agent using the ratio =1.960:0.004:0.004:0.032 (total 2 parts by mass) was used as the topcoat material 18.

[0132] The following raw materials were used in the manufacture of the topcoat material.

[0133] • Resin 5: Acrylic silicone resin emulsion (Emulsion polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-2-hydroxyethyl methacrylate-silane coupling agent-alkoxysilanes, (p) component ratio 50% by mass, (q) component ratio 25% by mass, glass transition temperature 38°C, silica residue ratio in resin solids 2% by mass, solids content 40% by mass) • Resin 6: Acrylic silicone resin emulsion (Emulsion polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-2-hydroxyethyl methacrylate-silane coupling agent, (p) component ratio 28% by mass, (q) component ratio 33% by mass, glass transition temperature 25°C, silica residue ratio in resin solids 0.3% by mass, solids content 40% by mass)

[0134] • Resin 7: Acrylic resin emulsion (emulsified polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-2-hydroxyethyl methacrylate, (p) component ratio 25% by mass, (q) component ratio 33% by mass, glass transition temperature 25°C, solids content 40% by mass) • Resin 8: Acrylic resin emulsion (emulsified polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-2-hydroxyethyl methacrylate, (p) component ratio 20% by mass, (q) component ratio 37% by mass, glass transition temperature 20°C, solids content 40% by mass)

[0135] • Resin 9: Acrylic resin emulsion (emulsified polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-2-hydroxyethyl methacrylate, (p) component ratio 11% by mass, (q) component ratio 37% by mass, glass transition temperature 21°C, solids content 40% by mass) • Resin 10: Acrylic resin emulsion (emulsified polymer mainly composed of cyclohexyl methacrylate-methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-2-hydroxyethyl methacrylate, (p) component ratio 2% by mass, (q) component ratio 38% by mass, glass transition temperature 21°C, solids content 40% by mass)

[0136] • Resin 11: Water-soluble resin (galactomannan derivative aqueous solution, solid content 3% by mass) • Dispersant: Anionic dispersant • Powder / Granule 1: Diatomaceous earth (average particle size 6 μm, refractive index 1.5) • Powder / Granule 2: Heavy calcium carbonate (average particle size 4 μm, refractive index 1.6) • Powder / Granule 3: Talc (average particle size 5 μm, refractive index 1.6) • Powder / granular material 4: Resin beads (average particle size 38 μm, refractive index 1.5) • Powder / Granule 5: Perlite (average particle size 125-150 μm) ·Powder 6: Silica sand (average particle size 150~180μm) • Powder / Granule 7: Mica (average particle size 1000-1180 μm) • Coloring pigment 1: White pigment dispersion {Aqueous dispersion of titanium dioxide (average particle size 0.3 μm), solid content 60% by mass} • Coloring Pigment 2: Black Pigment Dispersion {Aqueous dispersion of black iron oxide (average particle size 0.8 μm), solid content 60% by mass} • Coloring Pigment 3: Yellow Pigment Dispersion {Aqueous dispersion of yellow iron oxide (average particle size 0.5 μm), solid content 50% by mass} • Coloring pigment 4: Red pigment dispersion {Aqueous dispersion of reddish-brown pigment (average particle size 0.2 μm), solid content 60% by mass} • Coloring Pigment 5: Blue Pigment Dispersion {Aqueous dispersion of cobalt blue (average particle size 0.4 μm), solid content 50% by mass} • Film-forming aids: Ester-based film-forming aids, ether-based film-forming aids • Dispersion stabilizer: 5% by mass aqueous solution of gelling agent • Thickener: Urethane-based thickener • Additives: Preservatives, fungicides, algaecides, light stabilizers • Defoaming agent: Silicone-based defoaming agent

[0137] [Table 1]

[0138] [Table 2]

[0139] [Table 3]

[0140] (Exam I) The tests were conducted using the following method, and evaluations 1-6 were performed. Painting and drying were all carried out under standard conditions (temperature 23°C, relative humidity 50%).

[0141] Slate boards (900mm x 900mm x 3mm) that had been pre-treated with a sealer were installed vertically. The main material was then applied to these slate boards using a spray gun at a rate of 3kg / m². 2 After painting, a trowel was immediately used to create a pattern, and it was allowed to dry for 24 hours to form a main coating film with an uneven surface (insect-eaten uneven coating film, with a height difference of 1.5 mm). Next, the topcoat was spray-painted onto the main coating film (topcoat materials 1-15 had an application rate of 0.13 kg / m based on solid content). 2 Apply evenly to the entire surface. For topcoat materials 16-18, the application rate is calculated based on solid content: 0.06 kg / m². 2The material was coated in granular form (average particle size approximately 3 mm) to form a patterned coating film with colored particles. Immediately afterward (within 5 minutes after application of the topcoat), a pressing tool (brush) was brought into contact with the colored particles, and the material was stretched horizontally while applying constant pressure. The material was then allowed to dry and cure for 7 days. Test panels were obtained using the above method. The main material and topcoat used in the test are shown in Tables 4 to 7.

[0142] (Rating 1) Evaluation 1 assessed the workability when stretching the color particles. Of the methods described above, those where the color particles were stretched a relatively long distance were rated "AA", and those where the stretched distance was relatively short were rated "C", on a four-point scale (Excellent: AA > A > B > C: Poor).

[0143] (Rating 2) In Evaluation 2, the aesthetic appeal of the flow pattern formed by the stretching process was evaluated. The appearance of the test panels obtained by the above method was visually observed, and those with a blurred edge to the flow pattern and a texture that blended well with the main coating were rated "AA," while those with a straight edge to the flow pattern and a large difference in texture from the main coating were rated "C." This was evaluated on a four-point scale (Excellent: AA > A > B > C: Poor).

[0144] (Rating 3) In Evaluation 3, the state of gloss unevenness was evaluated. With light shining from the right side of the test plate obtained using the method described above, the appearance of the test plate was visually observed from the left front. At this time, a three-level evaluation (Excellent: A > B > C: Poor) was used, with "A" indicating suppressed gloss unevenness and "C" indicating gloss unevenness.

[0145] (Rating 4) The test boards obtained using the above method were cut to 100mm x 300mm and immersed in water for 96 hours. After immersion, the appearance of the coating was visually inspected. The evaluation was performed on a three-tiered scale (Excellent: AA > A > B > C: Poor), with "AA" indicating no abnormalities and "C" indicating obvious abnormalities (blistering, peeling, whitening, etc.).

[0146] (Rating 5) The test boards obtained by the above method were cut to 60 x 40 mm and subjected to weather resistance testing. The weather resistance testing was performed using the accelerated weathering tester "Metal Weather" (manufactured by Daipla Wintes Co., Ltd.), with one cycle consisting of 4 hours of light irradiation and 4 hours of condensation (total 8 hours), for up to 80 cycles. The evaluation was performed on a four-level scale (Excellent: AA > A > B > C: Poor) by observing the appearance of the coating film after 80 cycles. Those that showed no abnormalities and retained their initial design were rated "AA", and those that showed abnormalities (color change, blistering, peeling, cracking, etc.) and whose initial design was impaired were rated "C".

[0147] (Rating 6) In evaluation 5 above, weather resistance tests were conducted for up to 120 cycles. The evaluation was performed on a four-level scale (Excellent: AA > A > B > C: Poor) by observing the appearance of the coating after 120 cycles. Those that showed no abnormalities and retained their initial aesthetic appearance were rated "AA", while those that showed abnormalities (color change, blistering, peeling, cracking, etc.) and whose initial aesthetic appearance was impaired were rated "C".

[0148] (Exam II) The tests were conducted using the following method, and evaluations 7-9 were performed. Painting and drying were all carried out under standard conditions (temperature 23°C, relative humidity 50%).

[0149] Slate boards (900mm x 900mm x 3mm) that had been pre-treated with a sealer were installed vertically. The main material was then applied to these slate boards using a spray gun at a rate of 3kg / m². 2 After painting, a trowel was immediately used to create a pattern, and it was allowed to dry for 24 hours to form a main coating film with an uneven surface (insect-eaten uneven coating film, with a height difference of 1.5 mm). Next, the topcoat was spray-painted onto the main coating film (topcoat materials 1-15 had an application rate of 0.13 kg / m based on solid content). 2 Apply evenly to the entire surface. For topcoat materials 16-18, the application rate is calculated based on solid content: 0.06 kg / m². 2 The material was coated in granular form (average particle size approximately 3 mm), and a patterned coating film was formed using colored particles. After this, it was dried and cured for 7 days. Test boards were obtained using the above method. The main material and topcoat material used in the test are shown in Tables 4 to 7.

[0150] (Rating 7) The test boards obtained using the above method were cut to 100mm x 300mm and immersed in water for 96 hours. After immersion, the appearance of the coating was visually inspected. The evaluation was performed on a three-tiered scale (Excellent: AA > A > B > C: Poor), with "AA" indicating no abnormalities and "C" indicating obvious abnormalities (blistering, peeling, whitening, etc.).

[0151] (Rating 8) The test boards obtained by the above method were cut to 60 x 40 mm and subjected to weather resistance testing. The weather resistance testing was performed using the accelerated weathering tester "Metal Weather" (manufactured by Daipla Wintes Co., Ltd.), with one cycle consisting of 4 hours of light irradiation and 4 hours of condensation (total 8 hours), for up to 80 cycles. The evaluation was performed on a four-level scale (Excellent: AA > A > B > C: Poor) by observing the appearance of the coating film after 80 cycles. Those that showed no abnormalities and retained their initial design were rated "AA", and those that showed abnormalities (color change, blistering, peeling, cracking, etc.) and whose initial design was impaired were rated "C".

[0152] (Rating 9) In evaluation 8 above, weather resistance tests were conducted for up to 120 cycles. The evaluation was performed on a four-level scale (Excellent: AA > A > B > C: Poor) by observing the appearance of the coating after 120 cycles. Those that showed no abnormalities and retained their initial aesthetic appearance were rated "AA," while those that showed abnormalities (color change, blistering, peeling, cracking, etc.) and whose initial aesthetic appearance was impaired were rated "C."

[0153] (Test results) The test results are shown in Tables 4-7. In Examples 1-19, favorable results were obtained in each evaluation.

[0154] [Table 4]

[0155] [Table 5]

[0156] Table 6

[0157] Table 7

Claims

1. A method for forming a coating film by sequentially applying a main material and a topcoat material to a surface to be coated, The above main material includes a resin emulsion and powders and granules, and forms a main material coating film having an uneven pattern. The above topcoat material contains a resin emulsion and forms a patterned coating film with colored particles. The resin emulsion of the main material and the resin emulsion of the topcoat material are, respectively, composed of the monomers that make up the resin. A cyclic alkyl group-containing alkyl (meth)acrylate (p) is added to the resin components in an amount of 10% by mass or more. The resin component contains 10% by mass or more of an alkyl ester (q) (meth)acrylate having an alkyl main chain with 3 or more carbon atoms. A method for forming a coating film, characterized by the features described above.

2. A method for forming a coating film by sequentially applying a main material and a topcoat material to a surface to be coated, The above main material comprises a first resin emulsion and powders and granules, and forms a main material coating film having an uneven pattern. The above topcoat material consists of liquid or gel-like color particles dispersed in a water-based clear coating material containing a second resin emulsion. The first resin emulsion and the second resin emulsion each contain the following monomers as constituents of the resin: A cyclic alkyl group-containing alkyl (meth)acrylate (p) is added to the resin components in an amount of 10% by mass or more. The resin component contains 10% by mass or more of an alkyl ester (q) (meth)acrylate having an alkyl main chain with 3 or more carbon atoms. A method for forming a coating film, characterized by the features described above.

3. A method for forming a coating film by sequentially applying a main material and a topcoat material to a surface to be coated, The above main material comprises a first resin emulsion and powders and granules, and forms a main material coating film having an uneven pattern. The above topcoat material consists of liquid or gel-like color particles dispersed in a water-based clear coating material. The above-mentioned color particles are granular material containing a third resin emulsion and a coloring agent containing a coloring pigment. The first resin emulsion and the third resin emulsion described above each contain the following monomers as constituents of the resin: A cyclic alkyl group-containing alkyl (meth)acrylate (p) is added to the resin components in an amount of 10% by mass or more. The resin component contains 10% by mass or more of an alkyl ester (q) (meth)acrylate having an alkyl main chain with 3 or more carbon atoms. A method for forming a coating film, characterized by the features described above.

4. A method for forming a coating film by sequentially applying a main material and a topcoat material to a surface to be coated, The above main material comprises a first resin emulsion and powders and granules, and forms a main material coating film having an uneven pattern. The above-mentioned topcoat material is a colored topcoat material containing a fourth resin emulsion and a colored pigment, and the colored topcoat material is applied in a granular form to form a patterned coating film with colored particles. The first resin emulsion and the fourth resin emulsion each contain the following monomers as constituents of the resin: A cyclic alkyl group-containing alkyl (meth)acrylate (p) is added to the resin components in an amount of 10% by mass or more. The resin component contains 10% by mass or more of an alkyl ester (q) (meth)acrylate having an alkyl main chain with 3 or more carbon atoms. A method for forming a coating film, characterized by the features described above.

5. A method for forming a coating film according to any one of claims 1 to 4, characterized in that, after applying the topcoat material, the color particles are stretched using a pressing tool while the coating film of the topcoat material is still wet.

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