Coating material set, coating film forming method, and laminate

Abstract

To provide a coating material that enables formation of a coated film, which prevents deviation in a pattern of scaly particles, shows uniform hue and is excellent in aesthetic appearance, with a simple method.SOLUTION: There is provided a coating material set for forming a laminate coated film. The coating material set is composed of at least a first coating material and a second coating material. The first coating material is a coating material for forming a base layer. The second coating material is a coating material containing a resin component and coloring particles, and forming a design layer. The coloring particles contain base color scaly particles and accent particles. A color difference (▵E) between the base layer and the base color scaly particles is 0.5-15.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel dressing set and the like. [Background technology]

[0002] Conventionally, decorative finishing methods have been known that impart the aesthetic appearance of natural stone to buildings and civil engineering structures. In recent years, there has been an increasing demand for decorative finishing that incorporates the diverse colors and other design features unique to natural stone. For example, Patent Document 1 describes such a method in which a resin containing a mixture of colored mica (scale-like particles) of multiple colors is applied to a base material. The use of scale-like particles in this way is advantageous in terms of thinning the formed coating and reducing its weight. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 6-262134 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when a coating material containing a combination of scale-like particles of multiple colors is applied as in Patent Document 1, there is a risk of unevenness in the pattern and color formed due to partial overlap, dense areas, or sparse areas between the scale-like particles.

[0005] The present invention has been made in consideration of the above points, and aims to provide a coating material that can form, by a simple method, a coating film that is less likely to have uneven patterns in the scale-like particles and that presents a unified design with little unevenness in the pattern or color, and that is excellent in aesthetics. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors came up with the idea of ​​a coating material set comprising at least two specific coating materials, and completed the present invention.

[0007] That is, the present invention has the following features. 1. A coating material set for forming a laminated coating, the coating material set including at least a first coating material and a second coating material, the first coating material being a coating material that forms a base layer, and the second coating material being a coating material that includes a resin component and colored particles and that forms a design layer, the colored particles are scaly particles, The scale-like particles include large particles (L) having a short diameter of more than 2 mm, medium particles (M) having a short diameter of more than 0.7 mm and 2 mm or less, and small particles (S) having a short diameter of 0.7 mm or less, the colored particles include base color scale-like particles and accent color scale-like particles, The base color scaly particles are the color that is contained most abundantly in the colored particles, and the content of the base color scaly particles is 40 to 95% by weight in the colored particles; the accent color scale-like particles are of one or more colors different from the base color scale-like particles, and the content thereof in the colored particles is 5 to 60 wt %; the color difference (△E) between the base layer and the base-colored scaly particles is 1.0 to 10; A coating material set, wherein the color difference (ΔE) between the base color scale-like particles and the accent color scale-like particles is 2.5 or more. 2. A method characterized in that the weight ratio [(M) + (S)] / (L) of the medium particles (M) and small particles (S) to the large particles (L) is 1 or more and 50 or less. 1. A coating material set according to claim 1. 3. A coating forming method for applying a first coating material and a second coating material to a substrate in this order, wherein the first coating material is a coating material that forms a base layer, and the second coating material contains a resin component and colored particles and is a coating material that forms a design layer, the colored particles are scaly particles, The scale-like particles include large particles (L) having a short diameter of more than 2 mm, medium particles (M) having a short diameter of more than 0.7 mm and 2 mm or less, and small particles (S) having a short diameter of 0.7 mm or less, the colored particles include base color scale-like particles and accent color scale-like particles, The base color scaly particles are the color that is contained most abundantly in the colored particles, and the content of the base color scaly particles is 40 to 95% by weight in the colored particles; the accent color scale-like particles are of one or more colors different from the base color scale-like particles, and the content thereof in the colored particles is 5 to 60 wt %; the color difference (△E) between the base layer and the base-colored scaly particles is 1.0 to 10; The coating forming method is characterized in that the color difference (ΔE) between the base color scale-like particles and the accent color scale-like particles is 2.5 or more. 4. The coating forming method according to 3, wherein the weight ratio [(M) + (S)] / (L) of the medium particles (M) and small particles (S) to the large particles (L) is 1 or more and 50 or less. 5. A laminate comprising a base layer and a design layer laminated in this order on a substrate, wherein the base layer is formed from a first coating material, and the design layer is formed from a second coating material containing a resin component and colored particles, the colored particles are scaly particles, The scale-like particles include large particles (L) having a short diameter of more than 2 mm, medium particles (M) having a short diameter of more than 0.7 mm and 2 mm or less, and small particles (S) having a short diameter of 0.7 mm or less, the colored particles include base color scale-like particles and accent color scale-like particles, The base color scaly particles are the color that is contained most abundantly in the colored particles, and the content of the base color scaly particles is 40 to 95% by weight in the colored particles; the accent color scale-like particles are of one or more colors different from the base color scale-like particles, and the content thereof in the colored particles is 5 to 60 wt %; the color difference (△E) between the base layer and the base-colored scaly particles is 1.0 to 10; A laminate characterized in that the color difference (ΔE) between the base color scale-like particles and the accent color scale-like particles is 2.5 or more. 6. A method characterized in that the weight ratio of the medium particles (M) and small particles (S) to the large particles (L), [(M) + (S)] / (L), is 1 or more and 50 or less. 5. The laminate according to claim 1. [Effects of the Invention]

[0008] According to the present invention, it is possible to form a coating that is less likely to have uneven distribution of scale-like particles, has a good balance (arrangement) of the pattern, has a colorful feel due to the accent pattern, and has an aesthetically excellent design with a uniform feel with little unevenness in color. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described.

[0010] The present invention relates to a coating material set for forming a laminate coating, characterized by comprising at least a first coating material and a second coating material.

[0011] <First covering material> The first coating material of the present invention is a coating material that forms a base layer. The first coating material preferably contains at least a resin component (A) and a color pigment (B). The resin component (A) (hereinafter also referred to as "component (A)") is not particularly limited, but is preferably one or more selected from water-soluble resins and water-dispersible resins (resin emulsions). Examples of resins include vinyl acetate resins, polyester resins, alkyd resins, vinyl chloride resins, epoxy resins, acrylic resins, urethane resins, acrylic silicone resins, fluororesins, etc., as well as composites thereof. These resins can be used alone or in combination of two or more. In the present invention, acrylic resins and acrylic silicone resins are preferred. Furthermore, these component (A) may be crosslinkable. Using a component (A) that is crosslinkable can improve the water resistance, weather resistance, chemical resistance, etc. of the coating.

[0012] In the present invention, acrylic resins are particularly suitable as component (A). Acrylic resins have a (meth)acrylic acid alkyl ester as the main component of the resin skeleton, and are copolymerized with other monomers as necessary. In the present invention, acrylic acid alkyl esters and methacrylic acid alkyl esters are collectively referred to as (meth)acrylic acid alkyl esters. Furthermore, "monomer" is a general term for compounds having a polymerizable unsaturated double bond.

[0013] Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and cyclohexyl (meth)acrylate, and one or more of these can be used.

[0014] Specific examples of other monomers include: Aromatic monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene, phenyl (meth)acrylate, and benzyl (meth)acrylate; nitrile group-containing monomers such as (meth)acrylonitrile, vinylidene cyanide, and α-cyanoethyl (meth)acrylate; Amide group-containing monomers such as maleic acid amide, (meth)acrylamide, N-monoalkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, 2-(dimethylamino)ethyl(methacrylate), N-[3-(dimethylamino)propyl](meth)acrylamide, and vinylamide; Carbonyl group-containing monomers such as acrolein, diacetone (meth)acrylamide, vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone;

[0015] Carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, and salicylic acid; amino group-containing monomers such as aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth)acrylate, amino-n-butyl (meth)acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, N-methylaminoethyl (meth)acrylate, and Nt-butylaminoethyl (meth)acrylate; Epoxy group-containing monomers such as glycidyl (meth)acrylate, diglycidyl fumarate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, ε-caprolactone-modified glycidyl (meth)acrylate, and β-methylglycidyl (meth)acrylate; hydroxyl group-containing monomers such as hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, and glycerol mono(meth)acrylate; vinylidene halide monomers such as vinylidene fluoride; Alkoxysilyl group-containing monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, and γ-(meth)acryloyloxypropylmethyldimethoxysilane; Examples include ethylene, propylene, isoprene, butadiene, vinyl ether, vinyl ketone, etc. These can be used alone or in combination of two or more.

[0016] When the above-mentioned alkoxysilyl group-containing monomer is used as the other monomer, an acrylic silicone resin can be obtained.

[0017] Component (A) can be produced by emulsion polymerization of a group of monomers obtained by appropriately mixing the above-mentioned monomers. Any known polymerization method can be used, including conventional emulsion polymerization, soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, and the like. During polymerization, emulsifiers, initiators, dispersants, polymerization inhibitors, polymerization retarders, buffers, chain transfer agents, and the like can be used.

[0018] As the emulsifier, various surfactants that can be used in emulsion polymerization can be used, and these may be reactive types (reactive surfactants) having polymerizable unsaturated double bonds. As the emulsifier, anionic surfactants and nonionic surfactants can be preferably used alone or in combination.

[0019] The glass transition temperature (hereinafter simply referred to as "Tg") of the component (A) is preferably set to -50°C to 50°C. If Tg is within this range, the effects of the present invention can be stably obtained. In the present invention, Tg is a value calculated using Fox's formula. In addition, the average particle size of the component (A) is preferably 300 nm or less (more preferably 20 to 200 nm). If the average particle size is within this range, the water resistance, weather resistance, chemical resistance, etc. of the coating can be improved. In addition, the average particle size referred to here is a value measured by dynamic light scattering.

[0020] The color pigment (B) (hereinafter also referred to as "component (B)") is a component that imparts color, hiding power, and the like to the first coating material. Examples of component (B) include inorganic chromatic pigments such as ferric oxide (red iron oxide), yellow iron oxide, ultramarine, 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, and black iron oxide; white pigments such as titanium oxide, zinc oxide, and alumina; and other luster pigments (pearl pigments, aluminum pigments, metallic pigments, etc.), phosphorescent pigments, and fluorescent pigments. These can be used alone or in combination of two or more. The average particle size of component (B) is preferably 1 μm or less, more preferably 0.01 to 0.9 μm. The average particle size of the color pigment is measured using a laser diffraction particle size distribution analyzer. In the present invention, "α to β" is synonymous with "α or more and β or less."

[0021] The component (B) is preferably contained in an amount of 3 to 300 parts by weight (more preferably 5 to 250 parts by weight) per 100 parts by weight of the solid content of the component (A). With the component (B) in this ratio, the first covering material (base layer) can be colored in a desired color, thereby improving the aesthetic appearance, etc.

[0022] Furthermore, the first coating material preferably contains a powder component other than the color pigment (hereinafter also referred to as "component (C)"). Examples of such component (C) include extender pigments such as heavy calcium carbonate, light calcium carbonate, kaolin, clay, china clay, diatomaceous earth, hydrous fine silica, talc, mica, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate, silica powder, and aluminum hydroxide; and powders and granules such as silica particles, kansui stone, diatomaceous earth, silica stone, silica sand, gravel, glass beads, resin beads, metal particles, and crushed rocks, glass, ceramics, shells, sintered bodies, concrete, mortar, plastics, and rubber. These may be colored. These may be used alone or in combination of two or more.

[0023] Component (C) preferably has a particle size of 1 to 1,000 μm (more preferably 5 to 850 μm, and even more preferably 10 to 600 μm). For example, when component (C) contains granular material (C1) having a particle size of 53 to 300 μm in an amount of preferably 40 wt % or more (more preferably 45 wt % or more, and even more preferably 50 wt % or more) based on the total amount of component (C), a coating with even more excellent aesthetics can be formed. The upper limit is preferably 100 wt % or less (more preferably 95 wt % or less, and even more preferably 90 wt % or less). This embodiment is even more preferable in terms of improving the effects of the present invention. When the particle size of component (C) exceeds 20 μm, it can be measured by sieving using a metal mesh sieve as specified in JIS Z8801-1:2000. When the particle size is 20 μm or less, it can be measured using a laser diffraction particle size distribution analyzer.

[0024] The component (C) is preferably contained in an amount of 10 to 600 parts by weight (more preferably 30 to 500 parts by weight, and even more preferably 50 to 400 parts by weight) per 100 parts by weight of the solid content of the component (A). By including the component (C) in such a ratio, a base layer with even more excellent aesthetics can be formed. Furthermore, by including the powdery particulate material (C1) having a particle diameter of 53 to 300 μm, it is possible to form fine irregularities on the surface of the base layer due to the component (C1). This makes it easier to visually recognize the color as a uniform color, further enhancing the effects of the present invention. Furthermore, it is possible to suppress the roughness caused by the flaking of the edges of the scale-like particles in the design layer.

[0025] The first coating material can be produced by uniformly mixing the above components by a known method, but if necessary, other components that are typically used in coating materials can also be mixed in. Examples of such components include pigment dispersants, emulsifiers, thickeners, film-forming aids, leveling agents, coupling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, dryness adjusters, preservatives, antifungal agents, antialgae agents, antibacterial agents, antifoaming agents, adsorbents, deodorizers, fibers, UV absorbers, light stabilizers, antioxidants, catalysts, and crosslinking agents.

[0026] <Second covering material> The second coating material of the present invention is a coating material that forms a design layer, and is characterized by containing a resin component (A) and colored particles (D).

[0027] The resin component (A) in the second coating material is not particularly limited, and can be selected from the same resins as component (A) in the first coating material. These can be used alone or in combination of two or more.

[0028] The colored particles (D) (hereinafter referred to as "component (D)") impart a design. The present invention is characterized in that component (D) contains base color scale-like particles (d1) and accent particles (d3). This results in an accent pattern in which accent particles (d3) are scattered within a base pattern formed by the base color scale-like particles (d1), and a design layer with a uniform appearance and little unevenness in the pattern and color derived from the scale-like particles can be obtained.

[0029] In the present invention, the base color scaly particles (d1) (hereinafter referred to as "component (d1)") are scaly particles of one color (one type) that represent the base color of the design layer and are the main component (highest content) in component (D). Component (d1) can be, for example, a colored scaly base particle. Specific examples of the base particle include inorganic particles such as mica, sericite, clay, talc, platy kaolin, barium sulfate flakes, glass flakes, alumina flakes, shell fragments, and metal fragments, as well as rubber fragments, plastic fragments, and wood fragments. The coloring treatment can be, but is not limited to, a method of coating (or adsorbing) a colorant, such as a pigment or dye, on the base particle, or a method of subjecting the base particle to a calcination treatment. In the present invention, it is preferable to use mica (colored mica) coated with a colorant. By including such a component (d1) as the main component, it is advantageous not only for the design but also for making the design layer thinner and lighter.

[0030] The "scaly particles" of the present invention are not particularly limited as long as they are scaly (thin) in shape, but preferably have an aspect ratio (ratio of "minor diameter / thickness") of 1.5 to 2000 (more preferably 2 to 500, and even more preferably 3 to 100). Furthermore, the ratio of the minor diameter to the major diameter (minor diameter / major diameter) is preferably 0.3 to 1 (more preferably 0.4 to 1, and even more preferably 0.5 to 1). When the size of the scaly particles satisfies the above range, their shape is easily visible and suitable for design. Furthermore, it is possible to form a design layer that is excellent in terms of thinness and weight reduction. The "minor diameter," "major diameter," and "thickness" referred to here are calculated by placing the scaly particles stably on a horizontal surface and observing them from above with a microscope, where the length of the shortest part is the "minor diameter," the length of the longest part is the "major diameter," and the maximum height from the bottom is the "thickness," and these values ​​are measured with a micrometer.

[0031] The present invention is characterized in that the color difference (ΔE) between the base layer formed from the first coating material and the component (d1) is 0.5 to 15 (preferably 1.0 to 10, more preferably 1.5 to 8). In such cases, the hues of the base layer and the component (d1) are harmonized, making it easy to visually recognize a uniform hue as the base color, resulting in a laminated coating with minimal color unevenness and a unified, aesthetically pleasing appearance. In particular, when the color difference (ΔE) satisfies the above range, a laminated coating with minimal color unevenness and excellent aesthetics can be obtained even if the thickness (coating amount) of the design layer is partially uneven. On the other hand, when the color difference (ΔE) is less than 0.5, color unevenness is likely to occur. Furthermore, when the color difference (ΔE) exceeds 15, the hues of the base layer and the design layer are unlikely to harmonize, potentially resulting in poor design. Note that in the present invention, it is preferable to set the color difference between the base layer and the component (d1) within the above range, using the color of the component (d1) as the standard.

[0032] On the other hand, if the color difference (ΔE) is less than 0.5, color unevenness is likely to occur. Although this mechanism of action is not limited, the design layer formed by the second coating material exhibits a design using base-color scale-like particles (d1), and subtle changes may occur depending on the degree of overlap, the viewing direction, and the environment (light exposure conditions). Furthermore, in the design layer of the present invention, accent particles (d3) are scattered within a base pattern formed by the base-color scale-like particles (d1). In such a coating, the contrast between the base color and the accent color (color contrast) makes the base color easily perceived as a different hue from the original color (e.g., perceived as lower in saturation). When a base layer and a design layer with a color difference (ΔE) of less than 0.5 are laminated, color unevenness is likely to be visible due to the characteristics of the scale-like particles. Furthermore, if the color difference (ΔE) exceeds 15, the hues of the base layer and the design layer will be difficult to harmonize, and the design may be inferior. In the present invention, it is preferable to use the color of component (d1) as a reference and set the color difference between the base layer and component (d1) within the above range.

[0033] The color difference (ΔE) is a value measured using a color difference meter, and can be calculated from the respective L*, a*, and b* values ​​using the following formula: <Formula>△E={(L *1 -L *2 ) 2 +(a *1 -a *2 ) 2 +(b *1 -b *2 ) 2} 0.5 During the ceremony, L *1 , a *1 , b *1 are the base layer L * , a * , b * . L *2 , a *2 , b *2 are the (d1) component L * , a * , b * . The L*, a*, and b* values ​​of the base layer can be calculated from the L*, a*, and b* values ​​(average values ​​of three or more measurement points) of the coating when the first coating material is applied to a standard white paper using a film applicator with a gap of 2 mm, the coated surface is placed horizontally, and the coating is dried for 48 hours under standard conditions (temperature 23°C, relative humidity 50%; the same applies below). Furthermore, the L*, a*, and b* of the (d1) component can be calculated by placing the (d1) component on a glass plate until the glass surface is hidden, and then measuring the surface that is covered with a PE film (colorless and transparent).

[0034] In the present invention, the component (D) can contain, in addition to the component (d1), scale-like particles of a similar color (approximate color) to the component (d1) (hereinafter, component (d2)). The component (d2) constitutes the base color of the design layer together with the component (d1). The component (d2) is a color other than that exhibited by the component (d1), and preferably has a color difference (ΔE) from the component (d1) of less than 2.5 (preferably more than 0 and not more than 2.4). The component (d2) can be the same as the component (d1) described above. The component (d2) can also contain two or more colors.

[0035] The color difference (ΔE) of the above-mentioned (d1) component and the above-mentioned (d2) component is a value measured using a color difference meter, and can be calculated from the respective L* value, a* value, and b* value using the following formula. <Formula>△E={(L *3 -L *2 ) 2 +(a *3 -a *2 ) 2 +(b *3 -b *2 ) 2} 0.5 During the ceremony, L *2 , a *2 , b *2 are the (d1) component L * , a * , b * . L *3 , a *3 , b*3 are the (d2) component L * , a * , b * . The L*, a*, and b* values ​​of the components (d1) and (d2) can be calculated by placing the component (D) on a glass plate until the glass surface is covered, and then measuring the surface after covering it with a PE film (colorless and transparent).

[0036] The present invention is characterized in that component (D) contains accent particles (d3) (hereinafter also referred to as component (d3)). Accent particles are components that are scattered throughout the base color pattern obtained from component (d1) (and component (d2)) to impart an accent pattern. The present invention is characterized in that component (d3) contains at least one particle of a different type and / or color from component (d1). This makes it possible to impart an aesthetically pleasing design with an accent pattern. Examples of such component (d3) include aggregates, luster pigments, etc., which are particles of a different type from component (d1), or scale-like particles (accent color scale-like particles) having a hue different from component (d1). These can be used alone or in combination of two or more types.

[0037] When an aggregate is included as component (d3), a granular accent pattern can be imparted to the flat pattern formed by component (d1). The aggregate can be, for example, either an organic aggregate or an inorganic aggregate, and can also be either a transparent (semi-transparent) aggregate or a colored aggregate. Examples of such aggregates include crushed natural stone, porcelain powder, ceramic powder, metal particles, silica sand, feldspar, silica stone, kansui stone, glass beads, rubber particles, and resin beads, which may be colored. Aggregates with the same hue as component (d1) can also be used. The particle diameter of the colored aggregate is 0.01 mm to 5 mm (more preferably 0.03 mm to 4.5 mm). Furthermore, when a luster pigment is contained as component (d3), a sense of brilliance can be imparted to the pattern formed by component (d1). Examples of luster pigments include pearl pigments, aluminum pigments, and metallic pigments. The particle size of the luster pigment is preferably 0.5 to 100 μm (more preferably 1 to 80 μm). The particle size of the aggregate can be measured by sieving using a metal mesh sieve specified in JIS Z8801-1:2000. The particle size of the luster pigment can also be measured using a laser diffraction particle size distribution analyzer.

[0038] In the present invention, the component (d3) preferably contains accent-colored scale-like particles (d31) (hereinafter also referred to as "component (d31)"). Component (d31) provides an accent color for the design layer and can be scattered throughout the base color pattern obtained by the component (d1) (and component (d2)) to create an accent pattern. The component (d31) can be the same as the component (d1) but in a color other than that provided by the component (d1) (and component (d2)). The component (d31) can also be uncolored; for example, the scale-like base particles of the component (d1) can be used untreated. The component (d31) can also contain two or more colors (preferably 2 to 6 colors). This allows for the laminate (laminated coating) formed by laminating the base layer and the design layer to have a wider variety of design features, such as a variety of colors. In the present invention, a "different color" may be a color that is different enough to be distinguishable by the naked eye, and it is preferable that the color difference ΔE from the (d1) component is 2.5 or more (more preferably 3 or more).

[0039] The color differences (ΔE) of the (d1) and (d31) components are values ​​measured using a color difference meter, and can be calculated using the following formula from the respective L*, a*, and b* values. <Formula>△E={(L *4 -L *2 ) 2 +(a *4 -a *2 ) 2 +(b*4 -b *2 ) 2} 0.5 During the ceremony, L *2 , a *2 , b *2 are the (d1) component L * , a * , b * . L *4 , a *4 , b *4 are the L of the (d31) component, respectively. * , a * , b * . The L*, a*, and b* values ​​of the (d1) and (d31) components can be calculated by placing the (D) component on a glass plate until the glass surface is covered, and then measuring the surface after covering it with a PE film (colorless and transparent).

[0040] Component (D) of the present invention is preferably scaly particles (D') (hereinafter also referred to as "component (D')"). Component (D') preferably comprises base color scaly particles (d1), and, as necessary, similar color scaly particles (d2) and / or accent color scaly particles (d31). Furthermore, component (D') preferably comprises large particles (L) with a short diameter of more than 2 mm (hereinafter referred to as "large particles (L)"), medium particles (M) with a short diameter of more than 0.7 mm and 2 mm or less (hereinafter referred to as "medium particles (M)"), and small particles (S) with a short diameter of 0.7 mm or less (hereinafter referred to as "small particles (S)"). Using scaly particles of different sizes in this manner reduces the occurrence of uneven distribution of the scaly particles, resulting in the formation of a coating with a well-balanced pattern (arrangement) and excellent aesthetics with minimal roughness, and can impart natural stone-like colors and other designs such as large patterns.

[0041] Specifically, the large particles (L) are primarily suitable for effectively imparting a large design to the formed coating, and the present invention preferably includes large particles (L) as component (d31). The medium particles (M) are primarily suitable for forming the base pattern (base color) of the formed coating, and the present invention preferably includes medium particles (M) as component (d1) (and optionally component (d2)). The small particles (S) are primarily suitable for imparting a small design to the formed coating and for imparting hiding properties to the formed coating, and the present invention preferably includes small particles (S) as one or more selected from component (d1), component (d2), and component (d31) (preferably one or more selected from component (d1) and component (d2)).

[0042] In the present invention, it is preferable to use the large particles (L), medium particles (M), and small particles (S) in combination at a specific weight ratio, and it is preferable that the weight ratio of the medium particles (M) and small particles (S) to the large particles (L), [(M) + (S)] / (L), is 1 or more and 50 or less (more preferably 3 or more and 40 or less, and even more preferably 5 or more and 30 or less). When this range is satisfied, the large particles (L) are less likely to be biased, and a coating with excellent aesthetics can be formed in which the large pattern formed by the large particles (L) is well balanced (placed) within the base pattern formed by the medium particles (M) and small particles (S). Furthermore, the medium particles (M) and small particles (S) can suppress the edge lift of the large particles (L), allowing the formation of a flat coating with little roughness. Furthermore, the weight ratio (M) / (S) of the medium particles (M) to the small particles (S) is preferably 1 or more and 30 or less (more preferably 1.5 or more and 20 or less, and even more preferably 2 or more and 10 or less).

[0043] When this range is satisfied, the above-mentioned effects can be further enhanced. The mechanism by which this effect is achieved is not limited, but for example, the medium particles (M) and small particles (S), which are smaller than the large particles (L), act as spacers for the large particles (L), contributing to the dispersibility of the large particles (L). Furthermore, the small particles (S), which are smaller than the medium particles (M), act as spacers for the medium particles (M), contributing to the dispersibility of the medium particles (M). This is thought to enable the large particles (L), medium particles (M), and small particles (S) of the (D') component dispersed in the coating material to maintain good dispersibility. In particular, it is thought that in a coating material containing a relatively large amount of medium particles (M), the large particles (L) and small particles (S) are dispersed in a balanced manner within the medium particles (M). It is thought that applying such a coating material results in a coating with a well-balanced pattern, with little particle imbalance, and sufficient suppression of particle edge bounce.

[0044] As mentioned above, the minor axis of component (D') in the present invention refers to the length of the shortest part when the scale-like particles are placed stably and stationary on a horizontal surface. The large particles (L), medium particles (M), and small particles (S) can be classified by sieving using a metal mesh sieve (standard sieve) specified in JIS Z8801-1:2000. In this case, if the mesh size of the standard sieve is "a," the length of its diagonal line (L = √2a) can be considered to correspond to the minor axis. Specifically, 100 g of component (D') is weighed and sieved for 10 minutes using a test method (manual sieving) in accordance with JIS K 0069. · Large particles (L) are those that do not pass through a 12 mesh (a=1.4 mm, L=2.0 mm) sieve. Those that pass through a 12 mesh (a=1.4mm, L=2.0mm) sieve but do not pass through a 30 mesh (a=0.5mm, L=0.7mm) sieve are called medium particles (M), Those that pass through a 30 mesh (a=0.5 mm, L=0.7 mm) sieve are small particles (S), Let's say. The upper limit of the large particles (L) is preferably those that pass through a 6.5 mesh (a=2.8 mm, L=4.0 mm) sieve (particles with a minor axis of 4 mm or less), while the lower limit of the small particles (S) is preferably those that do not pass through a 70 mesh (a=0.21 mm, L=0.3 mm) sieve (particles with a minor axis of more than 0.3 mm).

[0045] In the present invention, the component (D) is preferably contained in an amount of 5 to 200 parts by weight (more preferably 10 to 100 parts by weight, and even more preferably 15 to 80 parts by weight) per 100 parts by weight of the solid content of the component (A). The content of the component (d1) contained as the main component in the component (D) is preferably 40 to 100% by weight (more preferably 45 to 98% by weight, and even more preferably 50 to 97% by weight) of the total amount of the component (D). In such a case, the component (d1) can be sufficiently visually recognized as the base color of the second coating material (design layer), and a coating with excellent aesthetics and a uniform color can be formed. The content of components other than the component (d1) is preferably 0 to 60% by weight (more preferably 2 to 55% by weight, and even more preferably 3 to 50% by weight) of the total amount of the component (D). The content of the component (d2) (total content in the case of multiple colors) is preferably 0 to 50% by weight (more preferably 0 to 40% by weight) of the total amount of the component (D). The content of component (d3) (total content in the case of multiple colors) is preferably 1 to 60% by weight (more preferably 1.5 to 50% by weight) of the total amount of component (D). However, in components (d2) and (d3), the content of one color (one type) of scaly particles (or aggregate, etc.) is less than the content of component (d1). In such a case, the accent pattern of component (d3) is well-balanced within the base color formed by components (d1) and (d2), and a coating with a design such as a natural stone look can be obtained.

[0046] The second coating material of the present invention can be produced by uniformly mixing the above-mentioned components by known methods, but if necessary, other components that can be used in conventional coating materials can also be mixed in. Such components include, for example, color pigments, extender pigments, fibers, film-forming aids, thickeners, leveling agents, coupling agents, plasticizers, antifreeze agents, pH adjusters, preservatives, antifungal agents, anti-algae agents, antibacterial agents, dispersants, antifoaming agents, UV absorbers, light stabilizers, antioxidants, and water.

[0047] The coating material of the present invention is preferably an aqueous coating material. The pH of the coating material is preferably 7 to 12 (more preferably 7.5 to 11). Within this range, the effects of the present invention can be sufficiently enhanced. Furthermore, the non-volatile content of the coating material is preferably 10 to 80% by weight (more preferably 15 to 70% by weight). Within this range, designs such as the diverse colors unique to natural stone can be easily formed, and a coating film with less roughness and superior aesthetics can be obtained. The non-volatile content can be adjusted by adjusting the blending ratio of each component, etc.

[0048] <Film formation method> The coating film forming method of the present invention is characterized in that a first coating material and a second coating material are applied to a substrate in this order. For example, (1) applying a first coating material to a substrate to form a base layer; (2) applying a second coating material onto the base layer to form a design layer; and the like.

[0049] Substrates constitute the surfaces of buildings, civil engineering structures, etc. Examples of such substrates include concrete, mortar, siding boards, extruded boards, gypsum boards, slate boards, perlite boards, plywood, bricks, plastic boards, metal boards, glass, porcelain tiles, etc. These substrates may have a coating already formed on their surface, or may have wallpaper attached thereto, etc.

[0050] In the above step (1), before applying the first coating material, the substrate may be subjected to a surface treatment, if necessary. Examples of surface treatments include filler treatment, putty treatment, surfacer treatment, and sealer treatment.

[0051] The first coating material (1) is the first coating material described above. The first coating material can be applied by, for example, spray coating, roller coating, trowel coating, brush coating, or a combination of these methods.

[0052] The first coating material can be applied once or multiple times. The number of times the first coating material is applied is preferably 1 to 2 times (more preferably 2 times). The amount of the first coating material applied per application is preferably 0.05 to 1 kg / m 2 (More preferably 0.1 to 0.8 kg / m 2 By applying the first coating material under these conditions, a base layer suitable for application of the second coating material can be formed, making it easier to achieve the effects of the present invention.

[0053] When applying the first coating material, the viscosity can be adjusted appropriately by mixing a diluent such as water. The dilution ratio is preferably 0 to 20% by weight. The viscosity of the first coating material to be applied is preferably 3 to 30 Pa·s (more preferably 4 to 20 Pa·s), and the thixotropy index is preferably 2 to 9 (more preferably 3 to 8). The viscosity and thixotropy index referred to here are values ​​obtained using a BH-type viscometer as the measuring instrument (measurement temperature: 23°C). The viscosity is a measurement value at a rotation speed of 20 rpm. The thixotropy index is a value obtained by dividing the measurement value at a rotation speed of 2 rpm by the measurement value at a rotation speed of 20 rpm.

[0054] The first coating material may be dried preferably at room temperature (0 to 40° C.). When the first coating material is applied multiple times, it is desirable to apply the subsequent first coating material after the coating of the previous first coating material has dried.

[0055] In step (2), a second coating material is applied to the base layer formed in step (1) to form a design layer. The second coating material described above is used as the second coating material. The second coating material can be applied by, for example, spraying, roller coating, troweling, or brushing. In the present invention, spraying or roller coating is preferred, and spray coating using a spray is particularly preferred. This method makes it possible to easily form a coating that is smooth and aesthetically pleasing, with little unevenness of the colored particles (D), a well-balanced (arranged) pattern, and minimal roughness. Furthermore, in the case of scaly particles (D'), it makes it possible to easily form a coating that is smooth and aesthetically pleasing, with little unevenness of the scaly particles ((d1), (d2), (d31)), a well-balanced (arranged) pattern, and minimal roughness.

[0056] The amount of the second coating material of the present invention to be applied is not particularly limited, but is preferably 0.05 to 1 kg / m per application. 2 (More preferably 0.1 to 0.8 kg / m 2 The number of times of application can be set depending on the desired design, but is preferably 1 to 2 times (more preferably 2 times). In such a case, the effect of the present invention can be fully exerted.

[0057] When applying the second coating material, the viscosity can be adjusted appropriately by mixing a diluent such as water. The dilution ratio is preferably 0 to 20% by weight. The viscosity of the second coating material to be applied is preferably 1 to 50 Pa s (more preferably 2 to 40 Pa s), and the thixotropy index is preferably 3 or more (even more preferably 3.5 to 15).

[0058] The second coating material may be dried preferably at room temperature (0 to 40° C.). When the second coating material is applied multiple times, it is desirable to apply the subsequent second coating material after the previous coating film of the second coating material has dried.

[0059] The present invention is characterized in that the color difference (ΔE) between the base layer formed in step (1) and the base-colored scaly particles (d1) contained in the second coating material in step (2) is 0.5 to 15 (preferably 1.0 to 12, more preferably 1.5 to 10). In such a case, a coating film exhibiting uniform color and excellent aesthetics can be obtained. If the color difference (ΔE) is less than 0.5, unevenness may occur in the formed pattern or color. On the other hand, if the color difference (ΔE) is more than 15, the hue of the base layer may be noticeable, resulting in poor design.

[0060] In the coating formation method of the present invention, a clear layer can be provided by applying a clear coating material to the outermost surface (on the design layer) for the purposes of surface protection, improved weather resistance, stain resistance, etc., as long as it does not impair the effects of the present invention. Such a clear layer may be either colorless and transparent or colored and transparent, and may be either glossy or matte (including 70% gloss, 50% gloss, 30% gloss, etc.).

[0061] <Laminate> The laminate of the present invention is a laminate having a laminate coating in which a base layer and a design layer are laminated in this order on a substrate. The substrate described above is used as the substrate. The base layer is formed from the first coating material described above, and the design layer is formed from the second coating material described above. This laminate (laminate coating) has a design layer laminated on the entire surface of the base layer, and the base layer can be seen through the gaps between the colored particles (D) that form the design layer. The laminate of the present invention is characterized in that the color difference (ΔE) between the base layer and the base-color scale-like particles (d1) contained in the design layer is 0.5 to 15 (preferably 1.0 to 12, more preferably 1.5 to 10). In this case, an accent pattern in which accent particles (d3) are scattered within the base pattern formed by the base-color scale-like particles (d1) is formed, resulting in a design layer with little unevenness in the pattern and color originating from the scale-like particles and a uniform appearance. If the color difference (ΔE) is less than 0.5, unevenness in the formed pattern and color may occur. If the color difference (ΔE) exceeds 15, the hue of the base layer becomes conspicuous, which may result in poor design. [Example]

[0062] The following examples will clarify the features of the present invention.

[0063] <Manufacturing the first coating material> After preparing the following white coating materials W1 to W3, each color pigment (black, yellow, red, etc.) was added to tone the color to the hue shown in Table 1, resulting in first coating materials 1 to 7. (White coating material W1) White coating material 1 was prepared by mixing 200 parts by weight of acrylic silicone resin emulsion (solid content: 50% by weight, medium: water) with 60 parts by weight of titanium oxide, 200 parts by weight of powder component [silica powder with particle diameter of 20 to 400 μm (content of particle diameter of 53 to 300 μm: 75% by weight)], and additives (thickener, dispersant, antifoaming agent, film-forming aid, etc.) in a conventional manner. (White coating material W2) White coating material W2 was prepared in the same manner as white coating material 1, except that silica powder with a particle size of 20 to 400 μm (content of particles with a particle size of 53 to 300 μm: 45% by weight) was used as the powder component. (White covering material W3) White coating material W3 was prepared in the same manner as white coating material 1, except that calcium carbonate (particle diameter: 20 to 38 μm) was used as the powder component.

[0064] [Table 1]

[0065] <Manufacturing the second coating material> Based on the formulation shown in Table 2, acrylic resin emulsion (solid content 50% by weight, medium: water), colored particles (D), and additives (thickener, antifoaming agent, film-forming aid, UV absorber, etc.) were mixed in a conventional manner to produce second coating materials 1 to 14. The colored particles (D) were prepared by premixing scaly particles (D') with the colored particles (D) according to the formulation shown in Table 3. The (D') component was sieved to calculate [(M) + (S)] / (L) and (M) / (S).

[0066] (D) Colored particles (D1): Light gray mica pieces [Minor diameter: over 0.3 mm and less than 2 mm, Minor diameter / Major diameter (average): 0.89, Minor diameter / Thickness (average): 10.5, L value = 88.8, a value = -0.9, b value = 4.4] (D2): Light gray mica pieces [Minor diameter: over 0.3 mm and less than 2 mm, Minor diameter / Major diameter (average): 0.89, Minor diameter / Thickness (average): 10.5, L value = 88.5, a value = -0.9, b value = 5.5] (D3): Light gray mica pieces [Minor diameter: over 1mm and less than 4mm, Minor diameter / Major diameter (average): 0.89, Minor diameter / Thickness (average): 10.5, L value = 88.8, a value = -0.9, b value = 4.4] (D4): Yellow mica pieces [Minor diameter: over 1mm and less than 4mm, Minor diameter / Major diameter (average): 0.88, Minor diameter / Thickness (average): 11.5, L value = 86.7, a value = 0.7, b value = 14.1] (D5): White mica piece [Minor diameter: over 1mm and less than 4mm, Minor diameter / Major diameter (average): 0.94, Minor diameter / Thickness (average): 11.0, L value = 91.5, a value = 0.5, b value = 4.4] (D6): Yellow mica pieces [Minor diameter: over 0.3 mm and less than 2 mm, Minor diameter / Major diameter (average): 0.92, Minor diameter / Thickness (average): 10.7, L value = 88.7, a value = 0.6, b value = 14.3] (D7): Gray mica pieces [Minor diameter: over 0.3 mm and less than 2 mm, Minor diameter / Major diameter (average): 0.87, Minor diameter / Thickness (average): 15.5, L value = 69.3, a value = -0.7, b value = 0.2]

[0067] [Table 2]

[0068] [Table 3]

[0069] (Examples 1 to 7, Comparative Examples 1 and 2) The first coating material was applied to the substrate (slate board: 45 x 30 cm) at an amount of 0.3 kg / m 2 The coating was then sprayed onto one half of the surface with a spray gun (diameter: 5.5 mm) at a rate of 0.5 kg / m². 2 and spray-painted the other half with a coating amount of 0.8 kg / m 2 The coating was sprayed onto the surface of the glass, and then dried and cured at 23°C for 24 hours to form a laminated coating. The combinations of the first and second coating materials are shown in Table 4.

[0070] <Evaluation> The following evaluations were carried out, and the results are shown in Table 4. Aesthetics The laminates with different coating amounts were visually inspected and evaluated for aesthetics. The evaluation criteria were A>B>C>D, with "A" representing a uniform color regardless of the viewing direction (angle) and "D" representing color unevenness.

[0071] [Table 4]

[0072] In Examples 1 to 7, a multilayer coating film with excellent aesthetics was obtained in which the (d3) component was scattered within a pattern layer with a uniform color formed by the (d1) component. In particular, in Examples 1, 2, and 5, a multilayer coating film with excellent aesthetics was obtained in which the (d3) component was scattered within a pattern layer with a uniform color regardless of the viewing direction (angle). On the other hand, in Comparative Example 1, areas with different coating amounts were visually perceived as different colors, resulting in color unevenness. Furthermore, in Comparative Example 3, the color harmony between the base layer and the design layer was poor.

[0073] (Examples 2, 8 to 17) A laminated coating was formed in the same manner as in Example 1. The combinations of the first coating material and the second coating material are shown in Table 5.

[0074] <Evaluation> The following evaluations were carried out, and the results are shown in Table 5. Aesthetics The aesthetics were evaluated in the same manner as above. ·Design Those with little deviation in the scale-like particles and a good balance of the pattern were given an "AA" rating, while those with poorer balance were given a "D" rating, and the evaluation was on a five-point scale of AA>A>B>C>D. Texture (touch) The coatings formed were rated on a five-point scale of AA>A>B>C>D, with those with a less rough feel being rated "AA" and those with a rough feel being rated "D".

[0075] [Table 5]

[0076] In Examples 2, 8 to 17, laminated coatings with excellent aesthetics were obtained in which component (d3) was scattered within a pattern layer with a uniform color formed by component (d1). Furthermore, in Examples 10 to 12, laminated coatings with excellent design (balance of the pattern of large, medium, and small particles and balance of accent particles) and texture were obtained.

Claims

1. A coating material set for forming a laminated coating, the coating material set including at least a first coating material and a second coating material, the first coating material being a coating material that forms a base layer, the second coating material being a coating material that includes a resin component and colored particles and that forms a design layer, the colored particles are scaly particles, The scale-like particles include large particles (L) having a short diameter of more than 2 mm, medium particles (M) having a short diameter of more than 0.7 mm and 2 mm or less, and small particles (S) having a short diameter of 0.7 mm or less, the colored particles include base color scale-like particles and accent color scale-like particles, the base color scaly particles are the color that is contained most in the colored particles, and the content of the base color scaly particles in the colored particles is 40 to 95% by weight; the accent color scale-like particles are of one or more colors different from the base color scale-like particles, and their content in the colored particles is 5 to 60 wt %; the color difference (ΔE) between the base layer and the base color scale-like particles is 1.0 to 10; The coating material set is characterized in that the color difference (ΔE) between the base color scale-like particles and the accent color scale-like particles is 2.5 or more.

2. 2. The coating material set according to claim 1, wherein a weight ratio of the medium particles (M) and small particles (S) to the large particles (L), [(M) + (S)] / (L), is 1 or more and 50 or less.

3. A coating forming method for applying a first coating material and a second coating material to a substrate in this order, wherein the first coating material is a coating material that forms a base layer, and the second coating material contains a resin component and colored particles and is a coating material that forms a design layer, the colored particles are scaly particles, the scale-like particles include large particles (L) having a minor axis of more than 2 mm, medium particles (M) having a minor axis of more than 0.7 mm and 2 mm or less, and small particles (S) having a minor axis of 0.7 mm or less; the colored particles include base color scale-like particles and accent color scale-like particles; the base color scaly particles are the color that is contained most in the colored particles, and the content of the base color scaly particles in the colored particles is 40 to 95% by weight; the accent color scale-like particles are of one or more colors different from the base color scale-like particles, and their content in the colored particles is 5 to 60 wt %; the color difference (ΔE) between the base layer and the base color scale-like particles is 1.0 to 10; The coating forming method is characterized in that the color difference (ΔE) between the base color scale-like particles and the accent color scale-like particles is 2.5 or more.

4. 4. The method for forming a coating according to claim 3, wherein the weight ratio of the medium particles (M) and small particles (S) to the large particles (L), [(M) + (S)] / (L), is 1 or more and 50 or less.

5. A laminate comprising a base layer and a design layer laminated in this order on a substrate, the base layer being formed from a first coating material, and the design layer being formed from a second coating material containing a resin component and colored particles. the colored particles are scaly particles, the scale-like particles include large particles (L) having a minor axis of more than 2 mm, medium particles (M) having a minor axis of more than 0.7 mm and 2 mm or less, and small particles (S) having a minor axis of 0.7 mm or less; the colored particles include base color scale-like particles and accent color scale-like particles; the base color scaly particles are the color that is contained most in the colored particles, and the content of the base color scaly particles in the colored particles is 40 to 95% by weight; the accent color scale-like particles are of one or more colors different from the base color scale-like particles, and their content in the colored particles is 5 to 60 wt %; the color difference (ΔE) between the base layer and the base color scale-like particles is 1.0 to 10; A laminate characterized in that the color difference (ΔE) between the base color scale-like particles and the accent color scale-like particles is 2.5 or more.

6. 6. The laminate according to claim 5, wherein the weight ratio [(M) + (S)] / (L) of the medium particles (M) and small particles (S) to the large particles (L) is 1 or more and 50 or less.

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