Film formation method

Abstract

To provide a decorative coating material which enables formation of a film that exhibits rich and matte fine appearance, and is excellent in crack resistance, substrate followability and contamination resistance.SOLUTION: A film formation method coats a decorative coating material and a surface finish material in this order, wherein the decorative coating material is obtained by dispersing liquid or gel color particles in an aqueous matte clear coating material, the aqueous matte clear coating material contains resin emulsion having a glass transition temperature of 30°C or lower, an extender pigment having an average particle diameter of more than 15 μm, and an extender pigment having an average particle diameter of 15 μm or less, and the surface finish material contains silica having an average particle diameter of 1 to 200 nm and a resin component in a solid content mass ratio of 0.5:1 to 5:1.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel film-forming method.

Background Art

[0002] Conventionally, on the wall surfaces of buildings, civil engineering structures, etc., coating has been performed with various decorative paints for the purposes of surface protection, improvement of aesthetics, etc. Among these, decorative paints in which liquid or gel-like color particles are dispersed in an aqueous medium are used in applications that require high aesthetics because a colorful film can be formed. In the finish using such a decorative paint, a matte finish with suppressed gloss is often required.

[0003] Regarding a method for forming such a film, for example, Patent Document 1 (Japanese Patent Laid-Open No. 9-57186) describes that after applying a decorative paint containing enamel dispersed particles, a clear paint with a specific hiding power is applied, and that a matte type or a stain-resistant type clear paint can be used as the clear paint (Claim 1, Paragraph 0038, Paragraph 0040, etc.). In such a method, in order to obtain a stain-resistant matte finish, the application of a specific clear paint is essential, but there is a risk of uneven gloss in the final finish appearance.

[0004] On the other hand, Patent Document 2 (Japanese Patent Laid-Open No. 2022-160152) describes that after applying an undercoat containing two types of extender pigments with a specific particle size, a paint in which liquid or gel-like color particles are suspended is applied as a decorative paint (Claim 1, Paragraph 0042, etc.), and that a decorative paint with a gloss value of 15 or less can be used as the decorative paint (Paragraph 0063). According to such a method, an appearance of a colorful matte finish can be obtained.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the above-mentioned Patent Document 2, the crack resistance, substrate followability, stain resistance, etc. of the coating film are not considered. Therefore, cracks and the like are likely to occur in the coating film, and the coating film may also be contaminated, which may damage the original finished appearance.

[0007] The present invention has been made in view of such points, and an object thereof is to provide a method capable of forming a coating film that exhibits a colorful and matte aesthetic appearance and is excellent in crack resistance, substrate followability, stain resistance, etc.

Means for Solving the Problems

[0008] In order to solve such problems, as a result of intensive studies, the inventor of the present invention came up with a coating film forming method in which a specific decorative coating material and a surface finishing material are applied in sequence, and the present invention was completed.

[0009] That is, the present invention has the following features. 1. A coating film forming method in which a decorative coating material and a surface finishing material are applied in sequence, wherein the decorative coating material is formed by dispersing liquid or gel-like color particles in an aqueous matte clear coating material, the aqueous matte clear coating material contains a resin emulsion having a glass transition temperature of 30°C or lower, an extender pigment having an average particle diameter of more than 15 μm, and an extender pigment having an average particle diameter of 15 μm or less, the surface finishing material contains silica having an average particle diameter of 1 to 200 nm and a resin component in a solid content mass ratio of 0.5:1 to 5:1 and is characterized by the above. 2. The liquid or gel-like color particles are particulate matter of a coloring material containing a resin, a coloring pigment, and an extender pigment The coating formation method according to claim 1, characterized in that...

Advantages of the Invention

[0010] According to the present invention, it is possible to form a film that exhibits a rich and matte aesthetic appearance and is excellent in crack resistance, substrate followability, stain resistance, etc.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments for carrying out the present invention will be described.

[0012] [Decorative Coating Material] The decorative coating material in the present invention is formed by dispersing liquid or gel-like color particles in an aqueous matte clear coating material. The liquid or gel-like color particles (hereinafter also simply referred to as "color particles") in the decorative coating material contribute to the formation of a richly colored film. On the other hand, the aqueous matte clear coating material serves as a medium for the color particles and is an essential component for making the formed film have a matte appearance.

[0013] The decorative coating material in the present invention can be used as a material defined in JIS K5667:2003 "Multicolor Pattern Paint". Such materials are classified into oil-in-water type (O / W type), water-in-water type (W / W type), etc. according to the combination of color particles and the medium (color particles / media). The decorative coating material preferably has a water-in-water type (W / W type) aspect.

[0014] In the present invention, the aqueous matte clear coating material is capable of forming a matte clear film and contains, as constituent components, a resin emulsion (a) having a glass transition temperature of 30°C or lower, an extender pigment (b) having an average particle diameter exceeding 15 μm, and an extender pigment (c) having an average particle diameter of 15 μm or less. In the present invention, since the aqueous matte clear coating material contains such components, it has a matte aesthetic appearance and can form a film excellent in crack resistance, substrate followability, etc. The aqueous matte clear coating material may be any material that can form a transparent film in which the color particles can be visually recognized.

[0015] The resin emulsion (a) with a glass transition temperature of 30°C or lower (hereinafter also referred to as the "(a) component") acts as a binder for the coating film and can form a clear coating film. Examples of the (a) component include acrylic resin emulsion, urethane resin emulsion, vinyl acetate resin emulsion, epoxy resin emulsion, silicone resin emulsion, fluororesin emulsion, acrylic vinyl acetate resin emulsion, acrylic urethane resin emulsion, acrylic silicone resin emulsion, etc., and one or more of these can be used. Among these, acrylic resin emulsion, acrylic urethane resin emulsion, acrylic silicone resin emulsion, fluororesin emulsion, etc. are preferred.

[0016] The glass transition temperature of the resin constituting the (a) component is 30°C or lower, preferably -10°C to 30°C. Since the (a) component has such a glass transition temperature, it is possible to form a coating film excellent in crack resistance, substrate followability, etc. In the present invention, the glass transition temperature is a value obtained from the FOX calculation formula. "α~β" is synonymous with "α or more and β or less".

[0017] In the aqueous flat clear coating material, as the extender pigment, an extender pigment (b) with an average particle diameter exceeding 15 μm (hereinafter also referred to as the "(b) component") and an extender pigment (c) with an average particle diameter of 15 μm or less (hereinafter also referred to as the "(c) component") are used. In the present invention, by using the (b) component and the (c) component with different average particle diameters as extender pigments in combination, it is possible to exhibit excellent performance in terms of crack resistance, substrate followability, etc. while giving the coating film a flat appearance.

[0018] (b) component and (c) component are not particularly limited as to the material, and various extender pigments can be used. For example, heavy calcium carbonate, gypsum, precipitated calcium carbonate, white carbon, talc, kaolin, clay, pottery clay, china clay, diatomaceous earth, baryte powder, barium sulfate, precipitated barium sulfate, silica sand, silica powder, quartz powder, gravel, glass beads, resin beads, or crushed products such as rocks, glass, shells, sintered bodies, plastics, and rubbers can be mentioned. These may be those subjected to surface treatment or the like. These can be used alone or in combination of two or more.

[0019] (b) component and (c) component preferably have a refractive index of 1.4 to 1.7 from the viewpoint of the clarity of the film. The refractive index can be measured using an Abbe refractometer.

[0020] (b) component has an average particle diameter of more than 15 μm, preferably 16 to 100 μm, more preferably 18 to 60 μm. (c) component has an average particle diameter of 15 μm or less, preferably 0.1 to 14 μm, more preferably 0.5 to 12 μm, still more preferably 1 to 10 μm. The average particle diameters of (b) component and (c) component are average values measured using a laser diffraction particle size distribution measuring device (measurement conditions: distribution standard: volume, refractive index: 1.60 - 0.10i, measurement temperature: 25 °C).

[0021] (b) component preferably has a mixing ratio of preferably 3 to 100 parts by mass, more preferably 5 to 90 parts by mass, still more preferably 10 to 80 parts by mass, based on 100 parts by mass of the solid content of (a) component. (c) component preferably has a mixing ratio of preferably 0.5 to 80 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 2 to 30 parts by mass, based on 100 parts by mass of the solid content of (a) component. Also, the mass ratio of (b) component to (c) component ((b) component:(c) component) is preferably 99:1 to 20:80, more preferably 98:2 to 50:50, still more preferably 97:3 to 60:40. If (b) component and (c) component are in such mixing ratios, a clear film exhibiting a sufficient mat appearance can be formed, which is also suitable in terms of improving physical properties such as crack resistance and substrate followability.

[0022] In the case of the aqueous matte clear coating material, in addition to the above-described components, known additives can be appropriately mixed. Examples of such additives include a dispersion stabilizer, a water-soluble resin, a pigment dispersant, an emulsifier, a thickener, a film-forming aid, a leveling agent, a coupling agent, a wetting agent, a plasticizer, an antifreezing agent, a pH adjuster, a drying adjuster, a preservative, a fungicide, an algicide, an antibacterial agent, an antifoaming agent, an adsorbent, a deodorant, an ultraviolet absorber, a light stabilizer, an antioxidant, a catalyst, a crosslinking agent, a solvent, water, and the like. The ratio of water (including the water which is a medium such as component (a)) in the aqueous matte clear coating material is preferably 80 to 800 parts by mass, more preferably 100 to 600 parts by mass, and still more preferably 120 to 500 parts by mass with respect to 100 parts by mass of the solid content of component (a).

[0023] In the aqueous matte clear coating material, a dispersion stabilizer can be included in order to stably disperse the color particles described later. The dispersion stabilizer is a component that stabilizes the coloring material in a granular form, and can be selected according to the type of the resin and the coloring material constituting the color particles. Specific examples of the dispersion stabilizer include magnesium salts, calcium salts, barium salts, aluminum salts, sodium salts, potassium salts, borate salts, silicate salts, phosphate salts, and the like. In addition, as the dispersion stabilizer, for example, water-soluble polymers, clays, and the like can also be used. Such a dispersion stabilizer can also be used as a gelling agent. 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 with respect to 100 parts by mass of the solid content of component (a).

[0024] The aqueous matte clear coating material forms a film exhibiting a matte appearance, and the 60-degree glossiness of the film is preferably 30 or less, more preferably 15 or less, and still more preferably 8 or less. The 60-degree glossiness of the aqueous matte clear coating material is a value obtained by measuring the specular glossiness (measurement angle: 60 degrees) when a sample is applied to one side of a black acrylic plate using a film applicator with a gap of 150 μm, the coated surface is placed horizontally, and dried for 48 hours in a standard state (temperature: 23 ° C, relative humidity: 50%).

[0025] The color particles in the decorative coating material are dispersed in the above-mentioned aqueous matte clear coating material. The decorative coating material can contain one or two or more kinds of color particles. When the decorative coating material contains two or more kinds of color particles of different colors, a color pattern formed by two or more kinds of color particles can be formed.

[0026] The color particles in the decorative coating material are particulate substances in which a coloring material containing a resin, a coloring pigment, and various additives as required is dispersed in a granular state in a liquid or gel state in the aqueous matte clear coating material. The resin contained in such a coloring material is preferably an aqueous resin. When the coloring material constituting the color particles contains an aqueous resin, the decorative coating material can be in a water-in-water (W / W type) mode.

[0027] As the aqueous resin in the coloring material, a resin emulsion and / or a water-soluble resin can be used. Among these, examples of the resin emulsion include an acrylic resin emulsion, a urethane resin emulsion, a vinyl acetate resin emulsion, a silicone resin emulsion, a fluororesin emulsion, an acrylic vinyl acetate resin emulsion, an acrylic urethane resin emulsion, an acrylic silicone resin emulsion, etc., and one or two or more of these can be used. Among these, from the viewpoints of weather resistance, water resistance, etc., an acrylic resin emulsion, an acrylic urethane resin emulsion, an acrylic silicone resin emulsion, a fluororesin emulsion, etc. are suitable. The glass transition temperature of the resin emulsion in the coloring material is not particularly limited, and is preferably -10 to 80°C, more preferably 10 to 60°C, and can also be set to be equal to or higher than the glass transition temperature of the component (a).

[0028] Examples of the water-soluble resin include polyvinyl alcohol, poly(meth)acrylic acid, polyethylene oxide, water-soluble urethane, biogum, galactomannan derivative, alginic acid or its derivative, cellulose derivative, gelatin, casein, albumin, etc., or those chemically modified by oxidation, methylation, carboxymethylation, hydroxyethylation, hydroxypropylation, sulfation, phosphorylation, cationization, etc. These can be used alone or in combination of two or more. Such water-soluble resin can contribute to the stabilization of the generation of color particles and can also be used as a gel former.

[0029] The coloring material preferably includes a resin emulsion and a water-soluble resin. By including both the resin emulsion and the water-soluble resin, color particles can be stably generated, and the weather resistance, water resistance, etc. of the coating film can also be enhanced. The ratio of the resin emulsion to the water-soluble resin in the coloring material is a solid content mass ratio (solid content of resin emulsion: solid content of water-soluble resin), preferably 99.5:0.5 to 70:30, more preferably 99:1 to 80:20.

[0030] The coloring pigment in the colorant is a component that imparts color and the like to the color particles. Examples of the coloring pigment include inorganic colored pigments such as ferric oxide (red iron oxide), yellow iron oxide, ultramarine, cobalt blue, and cobalt green; organic colored pigments such as azo-based, naphthol-based, pyrazolone-based, anthraquinone-based, perylene-based, quinacridone-based, disazo-based, isoindolinone-based, benzimidazole-based, phthalocyanine-based, and quinophthalone-based pigments; black pigments such as carbon black, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper-manganese-chromium composite oxide, black iron oxide, iron-chromium composite oxide, manganese-bismuth composite oxide, and manganese-yttrium composite oxide; white pigments such as titanium oxide, zinc oxide, and alumina; and other pearl pigments, aluminum pigments, bright pigments, phosphorescent pigments, and fluorescent pigments. These can be used alone or in combination of two or more. The average particle diameter of the coloring pigment is preferably less than 1 μm, more preferably 0.01 to 0.9 μm. The average particle diameter of the coloring pigment is an average value measured using a laser diffraction particle size distribution measuring device.

[0031] The mixing ratio of the coloring pigment in the colorant is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, based on 100 parts by mass of the solid content of the above resin.

[0032] As color particles in decorative coatings, particulate matter of a coloring material containing a resin, a coloring pigment, and an extender pigment is suitable. That is, it is desirable for the coloring material to contain an extender pigment. By the coloring material containing an extender pigment, the unevenness prevention property of the formed film can be enhanced. Examples of the extender pigment in the coloring material include heavy calcium carbonate, calcite, precipitated calcium carbonate, white carbon, talc, kaolin, clay, pottery clay, china clay, diatomaceous earth, barite powder, barium sulfate, precipitated barium sulfate, silica sand, silica powder, quartz powder, resin beads, and the like. These can be used alone or in combination of two or more. The refractive index of the extender pigment is preferably 1.4 to 1.7. The average particle diameter of the extender pigment is preferably less than 40 μm, more preferably 0.1 to 35 μm or less, still more preferably 0.5 to 25 μm, and particularly preferably 1 to 15 μm. The mixing ratio of the extender pigment in the coloring material is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and still more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the solid content of the above resin.

[0033] In addition to the above-described components, the coloring material can 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, fungicides, algaecides, antibacterial agents, defoamers, fibers, gel formers, adsorbents, deodorants, ultraviolet absorbers, light stabilizers, antioxidants, catalysts, crosslinking agents, solvents, water, and the like. The ratio of water (including water as a medium such as an aqueous resin) in the coloring material is preferably 80 to 800 parts by mass, more preferably 100 to 600 parts by mass with respect to 100 parts by mass of the solid content of the above resin.

[0034] The method of granulating the coloring material is not particularly limited, and known methods can be adopted. For example, a method according to the manufacturing method of the materials specified in JIS K5667:2003 "Multicolor Pattern Paint" can be adopted. Specifically, for example, a method of dispersing the coloring material in a medium (part or all of the components of the aqueous matte clear coating material) containing a dispersion stabilizer or the like can be adopted. The dispersion stabilizer is a component that stabilizes the coloring material in a granular form, and acts as a gelling agent for the coloring material, for example.

[0035] The particle size and shape of the color grains 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 material, the addition method and concentration of the dispersion stabilizer, the viscosity of the medium, etc. can be appropriately selected and adjusted. The average particle size of the color grains is preferably 0.05 to 20 mm (more preferably 0.1 to 18 mm). In the present invention, the average particle size of the color grains is a value obtained by drying the color grains on 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 the major axis (average value of 50 color grains).

[0036] To obtain a decorative coating material containing two or more types of color grains, for example, After respectively manufacturing color grain dispersion liquids (color grain dispersion liquids containing one type of color grains) in which one type of coloring material is dispersed in a medium, these are mixed, or A method of adding and dispersing two or more types of coloring materials having different color tones, etc. into the medium simultaneously or in sequence to obtain a color grain dispersion liquid (color grain dispersion liquid containing two or more types of color grains), etc. can be adopted. In such a method, as the medium, part or all of the aqueous matte clear coating material can be used. When a color grain dispersion liquid is manufactured using a part of the components of the aqueous matte clear coating material as the medium, the remaining components of the aqueous matte clear coating material may be mixed with the color grain dispersion liquid.

[0037] In a decorative coating material, the mass ratio of the color particles to the aqueous matte clear coating material (color particles: aqueous matte clear coating material) is preferably 1:99 to 80:20 (more preferably 10:90 to 75:25, still more preferably 30:70 to 70:30).

[0038] [Topcoat material] The topcoat material contains silica with an average particle diameter of 1 to 200 nm and a resin component in a solid content mass ratio of 0.5:1 to 5:1. In the present invention, by applying such a topcoat material, silica particles are fixed on the surface of the coating film of the decorative coating material, and while maintaining performances such as a colorful matte aesthetic appearance, crack resistance, and substrate followability, the stain resistance can be enhanced.

[0039] The silica in the topcoat material exhibits excellent stain resistance due to the high hardness of the particles themselves and the large number of silanol groups on the particle surface. The average particle diameter of the silica is 1 to 200 nm, preferably 3 to 100 nm. Within this range, a plurality of silicas having different average particle diameters can also be used in combination. When the average particle diameter of the silica is larger than 200 nm, the specific surface area becomes small and the silanol groups also decrease, resulting in insufficient stain resistance. When the average particle diameter is smaller than 1 nm, the silica itself becomes unstable, which is not practical. The average particle diameter mentioned here is the average value measured using a dynamic light scattering method particle size distribution measuring device.

[0040] The silica in the surface finishing material is preferably derived from a silica sol, and more preferably derived from a water-dispersible silica sol with a pH of 5.0 or more and less than 9.5 (preferably 6.0 or more and 9.0 or less). Such a neutral type of water-dispersible silica sol can be produced using a silicate compound as a raw material. Examples of the silicate compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, tetraphenoxysilane, or condensates thereof. In addition, alkoxysilane compounds other than the above silicate compounds, alcohols, glycols, glycol ethers, fluorinated alcohols, silane coupling agents, polyoxyalkylene group-containing compounds, etc. can also be used in combination.

[0041] The resin component in the surface finishing material plays a role in fixing the silica to the surface of the coating film of the decorative coating material, and various resins can be used. Specifically, for example, acrylic resin, urethane resin, vinyl acetate resin, silicone resin, fluororesin, acrylic vinyl acetate resin, acrylic urethane resin, acrylic silicone resin, etc. can be mentioned, and one or more of these can be used. Such a resin component is preferably a water-soluble resin and / or a resin emulsion. The glass transition temperature of such a resin component is not particularly limited, preferably -10 to 60 °C, more preferably 0 to 50 °C.

[0042] The solid content mass ratio (silica: resin component) of the silica and the resin component in the surface finishing material is 0.5:1 to 5:1, preferably 0.8:1 to 4:1, more preferably 1:1 to 3:1. Such a ratio is suitable in terms of a matte finish appearance, stain resistance, etc., and it becomes possible to stably exhibit the effects of the present invention over a long period.

[0043] The solid content of the surface finishing material is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass. The solid content of the surface finishing material is the solid content during use, and it can be a high solid content during manufacturing, storage, and transportation, and appropriately diluted during use to obtain the above solid content. If the solid content concentration of the surface finishing material is set within the above range, it is suitable in terms of finishability such as a matte appearance.

[0044] The surface finishing material may contain various components other than the above components as long as the effects of the present invention are not significantly impaired. Examples of such components include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusters, preservatives, fungicides, algicides, antibacterial agents, dispersants, antifoaming agents, crosslinking agents, fugitive pigments, light stabilizers, ultraviolet absorbers, antioxidants, solvents, water, and the like.

[0045] [Film-forming method] The film-forming method of the present invention can be applied to various coated surfaces. Examples of the coated surface include inner wall surfaces, outer wall surfaces, floor surfaces, ceiling surfaces, roof surfaces, etc. of buildings, civil engineering structures, and the like. Examples of the base materials constituting such coated surfaces include various plate-shaped base materials such as concrete, mortar, or cement boards, extruded plates, slate plates, PC plates, ALC plates, fiber-reinforced cement boards, metal siding boards, ceramic siding boards, ceramic plates, calcium silicate plates, gypsum boards, plastic boards, hard wood chip cement boards, vinyl chloride extruded siding boards, plywood, and the like. These may be those subjected to some surface treatment (filler treatment, putty treatment, surfacer treatment, sealer treatment, etc.), those on which a coating film has already been formed, those with wallpaper pasted, or the like. Further, when the coated surface is composed of a plurality of plate-shaped base materials, the joints between the plate-shaped base materials are preferably filled with joint materials (sealing materials, dry joints, etc.).

[0046] Before applying the decorative coating material, surface treatment of the surface to be coated can be carried out as required. Examples of the surface treatment include, for example, cleaning treatment, degreasing treatment, filler treatment, putty treatment, surfacer treatment, sealer treatment, etc. Such surface treatment can be appropriately carried out in consideration of, for example, the type and condition of the surface to be coated.

[0047] Before applying the decorative coating material, a step of applying one or more kinds of colored undercoat materials can be carried out. As the colored undercoat material, for example, those containing a resin and a coloring pigment and capable of forming a uniform single-color film by its coloring can be used. The color tone of the colored undercoat material can be set in consideration of the color tone of the decorative coating material, and for example, it can be set to an approximate color of the decorative coating material. As the colored undercoat material, for example, those forming a flat film, those forming various uneven patterns, etc. can be used.

[0048] As the coating method of the colored undercoat material, for example, spray coating, roller coating, trowel coating, brush coating, etc. can be adopted. The coating amount of the colored undercoat material is preferably 0.05~1 kg / m 2 , more preferably 0.1~0.8 kg / m 2 . It is desirable to uniformly coat the entire surface to be coated with the colored undercoat material. The coating or drying of the colored undercoat material is preferably carried out at room temperature (0~40°C).

[0049] In the present invention, after carrying out the above surface treatment, coating of the colored undercoat material, etc. as required, the decorative coating material can be applied. When the colored undercoat material is applied, it is desirable to apply the decorative coating material after the film of the colored undercoat material has dried.

[0050] As the coating method of the decorative coating material, for example, spray coating, roller coating, brush coating, etc. can be adopted. In roller coating, for example, a porous roller, a sponge roller, etc. can be used. The decorative coating material can be applied one or a plurality of times.

[0051] The coating amount of the decorative coating material is preferably 0.1 kg / m per application 2More preferably, it is 0.2 kg / m or more. By setting the lower limit of the coating amount of the decorative coating material to the above value, a film with a rich and colorful aesthetic appearance can be formed with a relatively small number of coating passes (one or two). The upper limit of the coating amount of the decorative coating material is preferably 1.5 kg / m or less per application, more preferably 1.2 kg / m or less. By setting the upper limit of the coating amount of the decorative coating material to the above value, it is possible to sufficiently suppress the downward deviation of color particles during or after drying of the decorative coating material. 2 or more. By setting the lower limit of the coating amount of the decorative coating material to the above value, a film with a rich and colorful aesthetic appearance can be formed with a relatively small number of coating passes (one or two). The upper limit of the coating amount of the decorative coating material is preferably 1.5 kg / m or less per application, more preferably 1.2 kg / m or less. By setting the upper limit of the coating amount of the decorative coating material to the above value, it is possible to sufficiently suppress the downward deviation of color particles during or after drying of the decorative coating material. 2 or less, more preferably 1.2 kg / m or less. By setting the upper limit of the coating amount of the decorative coating material to the above value, it is possible to sufficiently suppress the downward deviation of color particles during or after drying of the decorative coating material. 2 or less. By setting the upper limit of the coating amount of the decorative coating material to the above value, it is possible to sufficiently suppress the downward deviation of color particles during or after drying of the decorative coating material.

[0052] When applying the decorative coating material, a diluent such as water can be mixed to appropriately adjust the viscosity. The dilution ratio is preferably 0 to 10% by mass. The viscosity of the decorative coating material to be used for painting 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).

[0053] The drying of the decorative coating material is preferably performed at room temperature (0 to 40°C). When applying the decorative coating material multiple times, it is desirable to apply the subsequent decorative coating material after the film of the previous decorative coating material has dried.

[0054] In the present invention, a surface finishing material is applied to the surface of the film of the above decorative coating material. It is desirable to apply the surface finishing material after the film of the decorative coating material has dried.

[0055] As a method for applying the surface finishing material, for example, spray painting, roller painting, brush painting, etc. can be adopted. The coating amount of the surface finishing material is preferably 0.005 to 0.5 kg / m, more preferably 0.01 to 0.3 kg / m. Within this range, multiple coats may be applied. By setting the lower limit of the coating amount of the surface finishing material to the above value, it is suitable in terms of stain resistance and the like. By setting the upper limit of the coating amount of the surface finishing material to the above value, it is possible to sufficiently ensure the performance such as the aesthetic appearance, crack resistance, and substrate followability of the finished appearance. 2 more preferably 0.01 to 0.3 kg / m 2 is. Within this range, multiple coats may be applied. By setting the lower limit of the coating amount of the surface finishing material to the above value, it is suitable in terms of stain resistance and the like. By setting the upper limit of the coating amount of the surface finishing material to the above value, it is possible to sufficiently ensure the performance such as the aesthetic appearance, crack resistance, and substrate followability of the finished appearance.

[0056] The drying of the surface finishing material may preferably be carried out at room temperature (0 to 40°C). When applying the surface finishing material multiple times, it is desirable to apply the subsequent surface finishing material after the previous one has dried.

[0057] In the present invention, such coating can form a film exhibiting a rich and matte aesthetic appearance.

Examples

[0058] Examples and comparative examples are shown below to clarify the features of the present invention, but the present invention should not be construed as being limited to these examples.

[0059] (Manufacture of Decorative Coating Material 1) To the a mixture of the aqueous matte clear 1 with the formulation shown in Table 1, the colorant 1 (100 parts by mass) with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 1 was added to obtain a color particle dispersion liquid 1-1 in which yellow gel-like color particles with an average particle size of 1.5 mm were dispersed. On the other hand, to the a mixture of the aqueous matte clear 1 with the formulation shown in Table 1, the colorant 2 (100 parts by mass) with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 1 was added to obtain a color particle dispersion liquid 1-2 in which brown gel-like color particles with an average particle size of 1.5 mm were dispersed. By mixing these color particle dispersion liquids 1-1 and 1-2 at a mass ratio of 80:20, Decorative Coating Material 1 was manufactured (Table 3).

[0060] In the manufacture of the decorative coating material, the following were used as raw materials. · Resin 1: Acrylic silicone resin emulsion (glass transition temperature 20°C, solid content 40% by mass) · Resin 2: Acrylic silicone resin emulsion (glass transition temperature 38°C, solid content 40% by mass) · Resin 3: Acrylic resin emulsion (glass transition temperature 28°C, solid content 40% by mass) · Resin 4: Acrylic resin emulsion (glass transition temperature -5°C, solid content 40% by mass) · Resin 5: Water-soluble resin (aqueous solution of galactomannan derivative, solid content 3% by mass) · Dispersant: Anionic dispersant · Extender pigment 1: Resin beads (average particle size 38 μm, refractive index 1.5) · Extender pigment 2: Heavy calcium carbonate (average particle size 26 μm, refractive index 1.6) · Extender pigment 3: Silica powder (average particle size 58 μm, refractive index 1.6) · Extender pigment 4: Diatomaceous earth (average particle size 6 μm, refractive index 1.5) · Extender pigment 5: Heavy calcium carbonate (average particle size 4 μm, refractive index 1.6) · Extender pigment 6: Talc (average particle size 5 μm, refractive index 1.6) · Color pigment 1: Yellow color pigment mixture {mixed dispersion of titanium oxide (average particle size 0.3 μm), cadmium yellow (average particle size 0.2 μm), yellow iron oxide (average particle size 0.5 μm), black iron oxide (average particle size 0.8 μm), solid content 60% by mass} · Color pigment 2: Brown color pigment mixture {mixed dispersion of cadmium yellow (average particle size 0.2 μm), yellow iron oxide (average particle size 0.5 μm), black iron oxide (average particle size 0.8 μm), solid content 60% by mass} · Film-forming aid: Ester-based film-forming aid, ether-based film-forming aid · Dispersion stabilizer: 5% by mass aqueous solution of gelling agent · Thickener: Urethane-based thickener · Additive: Preservative, fungicide, algicide, light stabilizer · Defoamer: Silicon-based defoamer

[0061] (Manufacture of decorative coating material 2) To the a mixture of the aqueous matte clear 2 with the formulation shown in Table 1, 100 parts by mass of the colorant 1 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 2 was added to obtain a color particle dispersion liquid 2-1 in which yellow gel-like color particles with an average particle size of 1.3 mm were dispersed. On the other hand, to the a mixture of the aqueous matte clear 2 with the formulation shown in Table 1, 100 parts by mass of the colorant 2 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 2 was added to obtain a color particle dispersion liquid 2-2 in which brown gel-like color particles with an average particle size of 1.5 mm were dispersed. By mixing these color particle dispersion liquids 2-1 and 2-2 at a mass ratio of 80:20, a decorative coating material 2 was produced (Table 3).

[0062] (Production of Decorative Coating Material 3) To the a mixture of the aqueous matte clear 3 with the formulation shown in Table 1, 100 parts by mass of the colorant 1 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 3 was added to obtain a color particle dispersion liquid 3-1 in which yellow gel-like color particles with an average particle size of 1.6 mm were dispersed. On the other hand, to the a mixture of the aqueous matte clear 3 with the formulation shown in Table 1, 100 parts by mass of the colorant 2 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 3 was added to obtain a color particle dispersion liquid 3-2 in which brown gel-like color particles with an average particle size of 1.4 mm were dispersed. By mixing these color particle dispersion liquids 3-1 and 3-2 at a mass ratio of 80:20, a decorative coating material 3 was produced (Table 3).

[0063] (Production of Decorative Coating Material 4) To the a mixture of the water-based matte clear 1 with the formulation shown in Table 1, 100 parts by mass of the colorant 3 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 1 was added, whereby a color particle dispersion liquid 4-1 in which yellow gel-like color particles with an average particle diameter of 1.6 mm were dispersed was obtained. On the other hand, to the a mixture of the water-based matte clear 1 with the formulation shown in Table 1, 100 parts by mass of the colorant 4 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 1 was added, whereby a color particle dispersion liquid 4-2 in which brown gel-like color particles with an average particle diameter of 1.5 mm were dispersed was obtained. By mixing these color particle dispersion liquids 4-1 and 4-2 at a mass ratio of 80:20, a decorative coating material 4 was produced (Table 3).

[0064] (Production of Decorative Coating Material 5) To the a mixture of the water-based matte clear 4 with the formulation shown in Table 1, 100 parts by mass of the colorant 3 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 4 was added, whereby a color particle dispersion liquid 5-1 in which yellow gel-like color particles with an average particle diameter of 1.8 mm were dispersed was obtained. On the other hand, to the a mixture of the water-based matte clear 4 with the formulation shown in Table 1, 100 parts by mass of the colorant 4 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 4 was added, whereby a color particle dispersion liquid 5-2 in which brown gel-like color particles with an average particle diameter of 1.7 mm were dispersed was obtained. By mixing these color particle dispersion liquids 5-1 and 5-2 at a mass ratio of 80:20, a coating material 5 was produced (Table 3).

[0065] (Production of Coating Material 6) To the a mixture of the water-based matte clear 5 with the formulation shown in Table 1, 100 parts by mass of the colorant 3 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 5 was added, whereby A color particle dispersion liquid 6-1 in which yellow gel-like color particles with an average particle size of 1.8 mm were dispersed was obtained. On the other hand, 100 parts by mass of a colorant 4 having the formulation shown in Table 2 was added to an a mixture of an aqueous matte clear 5 having the formulation shown in Table 1, and the mixture was stirred and dispersed. Then, by adding a b mixture of the aqueous matte clear 5, a color particle dispersion liquid 6-2 in which brown gel-like color particles with an average particle size of 1.6 mm were dispersed was obtained. By mixing these color particle dispersion liquids 6-1 and 6-2 at a mass ratio of 80:20, a decorative coating material 6 was produced (Table 3).

[0066] (Production of Decorative Coating Material 7) To an a mixture of an aqueous matte clear 6 having the formulation shown in Table 1, 100 parts by mass of a colorant 3 having the formulation shown in Table 2 was added and stirred and dispersed. Then, by adding a b mixture of the aqueous matte clear 6, a color particle dispersion liquid 7-1 in which yellow gel-like color particles with an average particle size of 1.7 mm were dispersed was obtained. On the other hand, 100 parts by mass of a colorant 4 having the formulation shown in Table 2 was added to an a mixture of an aqueous matte clear 6 having the formulation shown in Table 1, and the mixture was stirred and dispersed. Then, by adding a b mixture of the aqueous matte clear 6, a color particle dispersion liquid 7-2 in which brown gel-like color particles with an average particle size of 1.5 mm were dispersed was obtained. By mixing these color particle dispersion liquids 7-1 and 7-2 at a mass ratio of 80:20, a decorative coating material 7 was produced (Table 3).

[0067] (Production of Decorative Coating Material 8) To an a mixture of an aqueous matte clear 7 having the formulation shown in Table 1, 100 parts by mass of a colorant 3 having the formulation shown in Table 2 was added and stirred and dispersed. Then, by adding a b mixture of the aqueous matte clear 7, a color particle dispersion liquid 8-1 in which yellow gel-like color particles with an average particle size of 1.6 mm were dispersed was obtained. On the other hand, 100 parts by mass of a colorant 4 having the formulation shown in Table 2 was added to an a mixture of an aqueous matte clear 7 having the formulation shown in Table 1, and the mixture was stirred and dispersed. Then, by adding a b mixture of the aqueous matte clear 7, a color particle dispersion liquid 8-2 in which brown gel-like color particles with an average particle size of 1.6 mm were dispersed was obtained. By mixing these color particle dispersion liquids 8-1 and 8-2 at a mass ratio of 80:20, a decorative coating material 8 was produced (Table 3).

[0068] (Manufacture of Decorative Coating Material 9) To the a mixture of the water-based matte clear 1 with the formulation shown in Table 1, 100 parts by mass of the colorant 5 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 1 was added, to obtain a color particle dispersion liquid 9-1 in which yellow gel-like color particles with an average particle diameter of 1.5 mm were dispersed. On the other hand, to the a mixture of the water-based matte clear 1 with the formulation shown in Table 1, 100 parts by mass of the colorant 6 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 1 was added, to obtain a color particle dispersion liquid 9-2 in which brown gel-like color particles with an average particle diameter of 1.5 mm were dispersed. By mixing these color particle dispersion liquids 9-1 and 9-2 at a mass ratio of 80:20, the decorative coating material 9 was manufactured (Table 3).

[0069] (Manufacture of Decorative Coating Material 10) To the a mixture of the water-based matte clear 1 with the formulation shown in Table 1, 100 parts by mass of the colorant 7 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 1 was added, to obtain a color particle dispersion liquid 10-1 in which yellow gel-like color particles with an average particle diameter of 1.6 mm were dispersed. On the other hand, to the a mixture of the water-based matte clear 1 with the formulation shown in Table 1, 100 parts by mass of the colorant 8 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the water-based matte clear 1 was added, to obtain a color particle dispersion liquid 10-2 in which brown gel-like color particles with an average particle diameter of 1.2 mm were dispersed. By mixing these color particle dispersion liquids 10-1 and 10-2 at a mass ratio of 80:20, the decorative coating material 10 was manufactured (Table 3).

[0070] (Manufacture of Decorative Coating Material 11) To the a mixture of the aqueous matte clear 8 with the formulation shown in Table 1, 100 parts by mass of the colorant 1 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 8 was added, thereby obtaining a color particle dispersion liquid 11-1 in which yellow gel-like color particles with an average particle diameter of 1.5 mm were dispersed. On the other hand, to the a mixture of the aqueous matte clear 8 with the formulation shown in Table 1, 100 parts by mass of the colorant 2 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 8 was added, thereby obtaining a color particle dispersion liquid 11-2 in which brown gel-like color particles with an average particle diameter of 1.6 mm were dispersed. By mixing these color particle dispersion liquids 11-1 and 11-2 at a mass ratio of 80:20, a decorative coating material 11 was produced (Table 3).

[0071] (Production of Decorative Coating Material 12) To the a mixture of the aqueous matte clear 9 with the formulation shown in Table 1, 100 parts by mass of the colorant 1 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 9 was added, thereby obtaining a color particle dispersion liquid 12-1 in which yellow gel-like color particles with an average particle diameter of 1.5 mm were dispersed. On the other hand, to the a mixture of the aqueous matte clear 9 with the formulation shown in Table 1, 100 parts by mass of the colorant 2 with the formulation shown in Table 2 was added and stirred for dispersion, and then the b mixture of the aqueous matte clear 9 was added, thereby obtaining a color particle dispersion liquid 12-2 in which brown gel-like color particles with an average particle diameter of 1.5 mm were dispersed. By mixing these color particle dispersion liquids 12-1 and 12-2 at a mass ratio of 80:20, a decorative coating material 12 was produced (Table 3).

[0072]

Table 1

[0073]

Table 2

[0074]

Table 3

[0075] (Production of Surface Finishing Material 1) Silica sol 1 (aqueous dispersion silica sol, pH 7.6, solid content 20% by mass, average particle diameter 27 nm) and resin 4 (acrylic resin emulsion, glass transition temperature 18 °C, solid content 45% by mass) were mixed so that the solid content mass ratio became 1.2:1, and a film-forming aid, a thickener, an antifoaming agent, and water were added thereto to produce a surface finishing material 1 with a solid content of 2% by mass.

[0076] (Production of surface finishing material 2) Silica sol 1 (the same as above) and resin 4 (the same as above) were mixed so that the solid content mass ratio became 2.0:1, and a film-forming aid, a thickener, an antifoaming agent, and water were added thereto to produce a surface finishing material 2 with a solid content of 2% by mass.

[0077] (Production of surface finishing material 3) Silica sol 1 (the same as above) and resin 4 (the same as above) were mixed so that the solid content mass ratio became 2.8:1, and a film-forming aid, a thickener, an antifoaming agent, and water were added thereto to produce a surface finishing material 3 with a solid content of 2% by mass.

[0078] (Production of surface finishing material 4) Silica sol 2 (aqueous dispersion silica sol, pH 7.8, solid content 12% by mass, average particle diameter 12 nm) and resin 4 (the same as above) were mixed so that the solid content mass ratio became 2.0:1, and a film-forming aid, a thickener, an antifoaming agent, and water were added thereto to produce a surface finishing material 4 with a solid content of 2% by mass.

[0079] (Production of surface finishing material 5) Silica sol 1 (the same as above) and resin 5 (acrylic silicone resin emulsion, glass transition temperature 35 °C, solid content 45% by mass) were mixed so that the solid content mass ratio became 1.2:1, and a film-forming aid, a thickener, an antifoaming agent, and water were added thereto to produce a surface finishing material 5 with a solid content of 2% by mass.

[0080] (Production of surface finishing material 6) Silica sol 1 (the same as above) and resin 4 (the same as above) were mixed so that the solid content mass ratio became 0.3:1, and a film-forming aid, a thickener, an antifoaming agent, and water were added thereto to produce a surface finishing material 6 with a solid content of 2% by mass.

[0081] (Test method) The tests were carried out and evaluated by the following methods. Note that all painting and drying were carried out under standard conditions (temperature 23°C, relative humidity 50%).

[0082] (1) Evaluation 1 For a slate board (900 mm × 900 mm × 3 mm) that had been pre-treated with a sealer, an acrylic resin-based colored undercoat was spray-coated at an application rate of 0.2 kg / m 2 and dried for 24 hours. Then, a decorative coating was spray-coated at an application rate of 0.6 kg / m 2 and dried for 24 hours. Next, a surface finishing material was spray-coated at an application rate of 0.1 kg / m 2 and dried and cured for 7 days. The appearance of the test board obtained by the above method was visually observed. The evaluation was carried out in three grades (excellent: A > B > C: poor), where those with suppressed gloss unevenness and excellent finished appearance were rated as "A", and those with recognized gloss unevenness were rated as "C".

[0083] (2) Evaluation 2 For the test board cut out to 100 mm × 300 mm from the test board obtained in Evaluation 1 above, a total of 10 cycles of a temperature and humidity cycling test with one cycle being 18 hours of water immersion, 3 hours of standing at -20°C, and 3 hours of standing at 50°C were carried out. After that, the coating appearance was confirmed and the state of crack occurrence was evaluated. The evaluation was carried out in three grades (excellent: A > B > C: poor), where those without recognized crack occurrence were rated as "A", and those with clearly recognized crack occurrence were rated as "C".

[0084] (3) Evaluation 3 Two slate boards of 100 mm × 300 mm × 6 mm were provided side by side, and a test substrate was made by filling a connecting part (width 10 mm) between the boards with a modified silicone-based sealing material. For the entire surface of this test substrate, an acrylic resin-based colored undercoat was spray-coated at an application rate of 0.2 kg / m 2 and dried for 24 hours. Then, a decorative coating was spray-coated at an application rate of 0.6 kg / m 2 and dried for 24 hours. Next, a surface finishing material was spray-coated at an application rate of 0.1 kg / m 2It was spray-painted and air-dried for 7 days. For the specimens obtained by the above method, a total of 10 cycles of temperature cycling tests were carried out, with each cycle consisting of 18 hours of water immersion, 3 hours of standing at -20°C, and 3 hours of standing at 50°C. After that, the appearance of the coating was checked and the substrate followability was evaluated. The evaluation was carried out in three grades (excellent: A > B > C: poor), where those with no abnormalities in the coating appearance and excellent substrate followability were rated as "A", and those with obvious abnormalities such as cracks were rated as "C".

[0085] (4) Evaluation 4 For the test panels cut from the ones obtained in the above Evaluation 1 to 100 mm × 300 mm, they were exposed outdoors at a 45-degree angle southward for 4 months, and the contamination states before and after exposure were visually observed. The evaluation was carried out in three grades (excellent: A > B > C: poor), where those with no observed contamination were rated as "A", and those with obvious contamination were rated as "C".

[0086] (Test Results) The combinations of the decorative coating materials and surface finishing materials used and their test results are shown in Tables 4 to 5. In the examples, good results were obtained in each test.

[0087]

Table 4

[0088]

Table 5

Claims

1. A coating method for coating a decorative coating material and a surface finishing material in sequence, comprising: The decorative coating material is Liquid or gel-like color particles are dispersed in a water-based matte clear coating material. The water-based matte clear coating material includes a resin emulsion having a glass transition temperature of 30° C. or less, an extender pigment having an average particle size of more than 15 μm, and an extender pigment having an average particle size of 15 μm or less, The surface finishing material contains silica having an average particle size of 1 to 200 nm and a resin component in a solid content mass ratio of 0.5:1 to 5:

1. The coating forming method according to the present invention is characterized in that

2. The liquid or gel color particles are coloring material particles containing resin, color pigment, and extender pigment.

2. The method for forming a coating according to claim 1.

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