Method for forming a multi-layered glitter coating film

Abstract

To provide a method for forming a multilayer coating film, which can form a coating film with less unevenness and excellent brilliance even under the condition of drying at room temperature. [Solution] The method for producing a multi-layer glitter coating film comprises step (1) of applying a colored coating material (I) containing a color pigment and a resin component onto a substrate surface so that the thickness of the colored coating film is equal to or greater than the hiding film thickness, and then drying to form a colored coating film, and step (2) of applying a glittering coating material (II) containing a glittering pigment and a resin component onto the colored coating film obtained in step (1), and then drying to form a glittering coating film, wherein the colored coating film does not contain the glittering pigment or has a lower glittering pigment content than the glittering coating film, and the glittering coating film contains the glittering pigment in the range of 0.05 to 15 mass % and is less than the hiding film thickness.

Description

[Technical Field]

[0001] The present invention relates to a method for forming a multi-layer coating film suitable for forming an appearance with excellent metallic or pearlescent luster. [Background technology]

[0002] Traditionally, calm and unassuming exteriors have been preferred for buildings, but the exterior materials and colors used for buildings are becoming more diverse. As an example, metallic exterior materials, which have optical phenomena such as gloss and reflection, are popular as exterior materials that can maintain harmony with the landscape without using flashy colors. In recent years, there has been an increase in high-design metallic buildings using exterior materials such as metal panels, and there is a growing need for metallic paints to be used in their renovation.

[0003] Patent Documents 1 and 2 disclose metallic paints that can be applied to buildings, which contain a scaly metallic pigment and a color pigment, and in which the non-volatile content and pigment volume concentration contained in the paint composition are within specific ranges.

[0004] Furthermore, Patent Document 3 discloses a coating composition that contains a specific amount of a non-leafing aluminum pigment and has a viscosity within a specific range when applied. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6121015 [Patent Document 2] Patent No. 6182686 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-87144 Summary of the Invention [Problem to be solved by the invention]

[0006] The coating compositions described in Patent Documents 1 to 3 can produce a highly luminous metallic coating film even when roller coating is performed, but they have the problem that metallic unevenness can be noticeable, requiring skilled painting.

[0007] For example, when a coating composition is used to paint an existing building, it is necessary to obtain a coating film with sufficient coating properties even when dried at room temperature. However, when a coating film is formed using a conventional metallic coating composition by drying at room temperature, the orientation of the metallic pigment is disturbed due to the slow evaporation rate of the solvent, which is likely to result in unevenness.

[0008] An object of the present invention is to provide a coating method that can form a coating film with little unevenness and excellent brilliance even under room temperature drying conditions. [Means for solving the problem]

[0009] The present inventors have conducted extensive research into a coating method for easily obtaining a glossy coating film having a metallic and pearlescent appearance, and as a result have arrived at the idea of ​​dividing the coating process for obtaining a glossy coating film into a colored paint coating process and a glossy paint coating process.

[0010] That is, the present invention relates to the following embodiments: Item 1. A process (1) of applying a colored coating material (I) containing a color pigment and a resin component to a substrate surface so that the thickness of the colored coating film is equal to or greater than the hiding film thickness, and drying the coating to form a colored coating film; Step (2) of applying a lustrous paint (II) containing a lustrous pigment and a resin component onto the colored coating film obtained in step (1) and drying the paint to form a lustrous coating film; The colored coating film does not contain a glittering pigment or has a lower glittering pigment content than the glittering coating film, A method for producing a glittering multi-layer coating film, wherein the glittering coating film contains a glittering pigment in the range of 0.05 to 15% by mass and has a thickness less than the hiding film thickness. Item 2. The method for forming a glittering multilayer coating film according to Item 1, wherein the substrate surface is a substrate surface of a building. Item 3. The method for forming a glittering multi-layer coating film according to Item 1 or 2, wherein the colored coating material (I) is a room temperature drying type coating material. Item 4. Colored paint (I) has lightness (L * ) is in the range of 40 to 95, and saturation (C * 4. The method for forming a glittering multilayer coating film according to any one of Items 1 to 3, wherein the paint forms a colored coating film having a color value of 40 or less. Item 5. The method for forming a glittering multilayer coating film according to any one of Items 1 to 4, wherein the colored coating film made of the colored coating material (I) is formed by roller coating. Item 6. The method for forming a glittering multilayer coating film according to any one of Items 1 to 5, wherein the glittering coating material (II) is a multi-component coating material containing a main component and a curing agent component. Item 7. The method for forming a glittering multilayer coating film according to any one of Items 1 to 6, wherein the glittering pigment is an aluminum flake pigment and / or a light interference pigment. Item 8. The method for forming a glittering multilayer coating film according to Item 7, wherein the glittering pigment comprises an aluminum flake pigment, and the aluminum flake pigment is a non-leafing type or a leafing type. Item 9. The method for forming a glittering multi-layer coating film according to Item 7 or 8, wherein the glittering pigment comprises an aluminum flake pigment, and the average particle size of the aluminum flake pigment is within the range of 5 to 250 μm. Item 10. The method for forming a glittering multi-layer coating film according to Items 7 to 9, wherein the glittering pigment comprises a light interference pigment, and the average particle size of the light interference pigment is in the range of 5 to 250 μm. Item 11. The method for forming a glittering multilayer coating film according to any one of Items 7 to 10, wherein the glittering pigment contains both an aluminum flake pigment and a light interference pigment in a mass ratio of the former to the latter ranging from 10 / 90 to 90 / 10. Item 12. The method for forming a glittering multilayer coating film according to any one of Items 6 to 11, wherein the glittering coating material (II) is a multi-component coating material containing a main component including a hydroxyl group-containing acrylic resin and a glittering pigment, and a curing agent component including a polyisocyanate. Item 13. The method for forming a glittering multilayer coating film according to any one of Items 6 to 11, wherein the glittering coating material (II) is a multi-component coating material containing a main component including a hydrolyzable silyl group-containing acrylic resin, a polysiloxane resin, an epoxy resin, and a glittering pigment, and a curing agent component including an amino group-containing alkoxysilane compound. Item 14. The method for forming a glittering multilayer coating film according to Item 13, wherein the glittering coating material (II) further contains an organic solvent and / or a curing catalyst. Item 15. The method for forming a glittering multilayer coating film according to any one of Items 1 to 14, wherein the glittering coating film of the glittering paint (II) is formed by a roller. Item 16. The method according to any one of items 1 to 15, further comprising step (3) of applying a clear coating (III) different from the bright coating (II) on the bright coating film formed in step (2). The method for forming a multi-layered glitter coating film is described above. Item 17. A clear coating film made of the clear coating (III) is formed by a roller. 17. A method for forming a glittering multilayer coating film according to 16. [Effects of the Invention]

[0011] According to the method for forming a multilayer coating film of the present invention, by applying a thin layer of a lustrous paint containing a lustrous pigment and a resin component onto a colored coating film so that the base is visible, the lower colored coating film and the upper lustrous coating film fuse together, and even under room temperature drying conditions, the resulting product has a metallic or pearlescent shine and is free of unevenness. A bright coating film can be easily obtained. DETAILED DESCRIPTION OF THE INVENTION

[0012] The method for forming a glittering multilayer coating film of the present invention will be described below.

[0013] <Base material> In the present invention, examples of substrates on which a multilayer coating film can be provided include metal-based inorganic substrates such as steel plate, galvanized steel, stainless steel, and aluminum; non-metallic inorganic substrates such as concrete, mortar, slate, siding, brick, gypsum, and wood; and organic substrates such as plastic and rubber; and combinations thereof. Specific examples of substrates include buildings. Specific examples of buildings include houses, public facilities, buildings, warehouses, gates, fences, and objet d'art.

[0014] In the present invention, the substrate may be directly coated with the colored coating material (I) described below, or may be coated in advance with a sealer, primer, surface conditioner, intermediate coating material, anti-rust coating material, etc. to form an undercoat coating film. The shape of the undercoat coating film may be flat or uneven.

[0015] <Process (1)> In the present invention, step (1) is a step of applying a colored coating material (I) to the substrate and drying it to provide a colored coating film.

[0016] <Colored paint (I)> The colored coating material (I) used in step (1) can be any of various conventionally known coating materials such as organic solvent-based, water-based, and solventless coating materials, as long as it contains a colored pigment and a resin component.

[0017] The color pigment may be any color pigment known in the coating field, depending on the intended purpose and preference. Examples of color pigments include titanium dioxide, carbon black, red iron oxide, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, threne pigments, perylene pigments, dioxazine pigments, diketopyrrolopyrrole pigments, and any combination thereof. The pigment may also include extender pigments such as baryta powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, and silica.

[0018] In the present invention, the role of the colored coating (I) is to impart color, so it is preferable that the colored coating film does not contain a luster pigment, that the luster pigment content is lower than that of the luster coating film, or that the luster pigment content in the colored coating film is 0.5 mass % or less.

[0019] As the resin component, resins and curing agents known in the coating field can be used without limitation. Specific examples include acrylic resins, urethane resins, polysiloxane resins, alkyd resins, fluororesins, polyester resins, epoxy resins, polyisocyanates, polyamines, amino group-containing alkoxysilanes, and combinations thereof. Particularly preferred resin components include acrylic resins, urethane resins, polysiloxane resins, and combinations thereof. The resin component also includes modified resins composed of multiple of these resins.

[0020] The colored coating material (I) may contain paint additives such as organic solvents, water, curing catalysts, reactive diluents, adhesion promoters, ultraviolet absorbers, light stabilizers, anti-algae agents, antifoaming agents, anti-settling agents, dispersants, and wetting agents.

[0021] In the present invention, the colored coating material (I) is preferably a room temperature drying coating material, such as a lacquer coating material, an alkyd resin coating material, a two-component urethane resin coating material containing a hydroxyl group-containing resin and a polyisocyanate, or a two-component epoxy coating material containing an epoxy group-containing resin and an amino group-containing resin.

[0022] In step (1), the colored coating material (I) is applied to the surface of the substrate so that the base is concealed, i.e., the thickness of the colored coating film is equal to or greater than the concealing film thickness, and then dried. In this specification, the concealing film thickness is a term well known in the paint field, and refers to the minimum film thickness at which the color of the base becomes unrecognizable. Specifically, the concealing film thickness is measured on a concealing rate test paper specified in JIS K5600-4-1 (1999), When paint is applied at different thicknesses and dried and cured, it is the minimum dry film thickness at which the white and black areas printed on the hiding power test paper cannot be distinguished visually.

[0023] In the present invention, the colored coating material (I) is preferably a coating material that forms a colored coating film with medium brightness and low chroma. Specifically, the brightness (L * ) is in the range of 40 to 95, and saturation (C * ) is preferably in the range of 40 or less. When the lightness and chroma of the colored coating film are within the above-mentioned ranges, the brilliance and color development of the multilayer coating film fused with the glitter coating film formed from the glitter paint (II) described below become more prominent. In detail, to achieve a metallic brilliance, the lightness (L*) of the colored coating film should be 40 to 80. To achieve a pearlescent shine, the brightness (L*) of the colored coating film must be within the range of 80 to 95. It is preferable to adjust it as follows.

[0024] In this specification, lightness (L * ) and saturation (C * ) is CIE 1976 L * a * b * It can be expressed using the color system (JIS Z8729). * a * b * In the color system, Lightness to L * and saturation is expressed as a * and b * Lightness L * takes a value between 0 and 100, and the larger the value, the brighter the light. * For example, the closer to 0, the closer to black it is, and the closer to 100, the closer to white it is. * represents the red-green directional component. The larger the negative value, the closer it is to green, and the larger the positive value, the closer it is to red. b * represents the blue-yellow direction component. The larger the negative value, the closer it is to blue, and the larger the positive value, the closer it is to yellow. * , b * The larger the numerical value (absolute value), the higher the saturation. * = 0 and b * = 0 is achromatic. As an index of saturation, C * =(a*2 +b *2 ) 1 / 2 will be adopted. L * , a * , b * can be measured using a commercially available colorimeter (for example, a color difference meter CR-400 manufactured by Konica Minolta, Inc.) The conditions for preparing a colored coating film for measuring lightness and saturation are as follows: a glass plate is used as the substrate, and the colored paint to be used as the sample is spray-painted so that the colored coating film has a hiding film thickness, and then dried at 23°C for one week.

[0025] The colored coating material (I) can be applied by a known coating method. Specifically, it can be applied using coating tools such as brush coating, flow coating, trowel coating, roller coating, spray coating, airless spray coating, lysine gun, and all-purpose gun. It is particularly preferable to apply the coating using a roller, which is a coating method that minimizes paint scattering to the surroundings. Drying after application is preferably carried out at room temperature, but forced drying or heat drying may be carried out as necessary. Room temperature refers to a temperature at which temperature manipulation such as forced heating or cooling is not performed, depending on the atmospheric temperature of the environment in which the coating is carried out, and is, for example, 5 to 40°C.

[0026] <Process (2)> In the method of the present invention, a glittering paint (II) is applied to the colored coating film formed in step (1) above and dried to form a glittering coating film. The glittering paint (II) is a paint that has a sparkling appearance due to the glittering pigment and also has transparency. In other words, in the present invention, when the glittering paint is applied to the colored coating film, the underlying colored coating film can be seen through the upper glittering coating film.

[0027] Therefore, in the present invention, it is not preferable to apply the glittering paint (II) in such a thick film that the underlying colored coating film is completely concealed, since this will result in a glittering multilayer coating film with insufficient glitter and color development.

[0028] In the present invention, the glittering paint (II) is applied so that the base can be seen through and the glittering paint film has a thickness less than the hiding film thickness. The amount of application is adjusted depending on the content of the glittering pigment and the application conditions, but the amount of application is 30 to 85 g / m2 in terms of the mass of the non-volatile content of the glittering paint (II). 2 , preferably 35 to 60 g / m 2 It is preferable that the temperature is in the range of

[0029] The bright paint (II) of the present invention can be any conventionally known paint, such as an organic solvent-based, water-based, or solventless paint, as long as it contains a bright pigment and a resin component. Among these, room temperature drying paints are preferred. In the case of room temperature drying paints, a multi-component paint containing a main component and a curing agent component may be used in terms of coating film properties such as weather resistance.

[0030] <Brilliant pigments> In the present invention, the luster pigment is used to impart a metallic or pearlescent sparkle to the coating film, and any pigment known in the coating field as a luster pigment can be used. Specific examples of the luster pigment include aluminum flake pigments, optical interference pigments, and vapor-deposited metal flake pigments.

[0031] Aluminum flake pigments are primarily used to impart a metallic-like sheen to coatings. They are generally produced by pulverizing and grinding aluminum in a ball mill or attritor mill in the presence of a grinding medium using a grinding aid. Grinding aids used in the production of aluminum flake pigments include higher fatty acids such as oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid, and myristic acid, as well as aliphatic amines, aliphatic amides, and aliphatic alcohols. The grinding medium used is an aliphatic hydrocarbon such as mineral spirits.

[0032] The above aluminum flake pigments can be roughly divided into leafing type and non-leafing type depending on the type of grinding aid, and either type can be used.In addition, those with no particular surface treatment can be used, but those with a resin-coated surface, those with a silica treatment, and those with a surface treatment using phosphoric acid, molybdic acid, or a silane coupling agent can also be used.Those that have undergone one of the above various surface treatments can be used, but those that have undergone multiple types of treatments can also be used. Furthermore, the aluminum flake pigment may be a colored aluminum pigment in which the surface of the aluminum flake pigment is coated with a colored pigment and then further coated with a resin, or in which the surface of the aluminum flake pigment is coated with a metal oxide such as iron oxide.

[0033] From the viewpoint of brightness and luster, it is preferable to use the aluminum flake pigment having an average particle size in the range of 5 to 250 μm, particularly 7 to 200 μm.

[0034] In this specification, the average particle size of the bright pigment is the 50% volume average particle size D50, which means the median diameter of the volume-based particle size distribution measured by a laser diffraction scattering method using a Microtrac particle size distribution analyzer MT3300 (trade name, manufactured by Nikkiso Co., Ltd.).

[0035] Optical interference pigments are used in combination with the aluminum flake pigments to impart a pearlescent or metallic appearance to the coating film. Specifically, they are lustrous pigments in which the surface of a transparent or semi-transparent, scaly substrate such as mica, artificial mica, glass, iron oxide, aluminum oxide, or various metal oxides is coated with a metal oxide having a refractive index different from that of the substrate. Specifically, a transparent substrate is a substrate that transmits at least 90% of visible light. A translucent substrate is a substrate that transmits at least 10 to less than 90% of visible light. Examples of the metal oxide include titanium oxide and iron oxide, and the optical interference pigment can exhibit various different interference colors depending on the thickness of the metal oxide.

[0036] Specific examples of the light interference pigment include metal oxide-coated mica pigments, metal oxide-coated alumina flake pigments, metal oxide-coated glass flake pigments, and metal oxide-coated silica flake pigments.

[0037] Metal oxide-coated mica pigments are pigments that use natural or artificial mica as a base material, with the surface of the base material coated with a metal oxide. Natural mica is a scaly base material made by crushing mica ore. Artificial mica is synthesized by heating industrial raw materials such as SiO2, MgO, Al2O3, K2SiF6, and Na2SiF6, melting them at a high temperature of approximately 1500°C, and then cooling and crystallizing them. Compared to natural mica, artificial mica contains fewer impurities and is more uniform in size and thickness. Specific examples of artificial mica base materials known include fluorphlogopite, potassium tetrasilicic mica, sodium tetrasilicic mica, Na taeniolite, and LiNa taeniolite.

[0038] Metal oxide-coated alumina flake pigments are pigments that use alumina flakes as a base material and the surface of the base material is coated with metal oxide. Alumina flakes refer to scaly (thin) aluminum oxide, and are colorless and transparent. The alumina flakes do not necessarily have to be composed solely of aluminum oxide, but may also contain oxides of other metals.

[0039] Metal oxide-coated glass flake pigments are pigments whose base material is scaly glass and whose surface is coated with metal oxide. The smooth surface of the base material of the metal oxide-coated glass flake pigments produces strong light reflection.

[0040] The metal oxide-coated silica flake pigment is a pigment in which scaly silica, which is a base material having a smooth surface and a uniform thickness, is coated with a metal oxide.

[0041] From the viewpoint of brilliance and gloss, it is preferable to use the above-mentioned light interference pigment having an average particle size of 5 to 250 μm, particularly 7 to 200 μm. Examples of commercially available products that can be used as the above-mentioned light interference pigment include the "Iriodin" series (product name, manufactured by Merck Japan), the "Xiralic" series (product name, manufactured by Merck Japan), and the "Twinkle Pearl" series (product name, manufactured by Nihon Koken Kogyo Co., Ltd.).

[0042] The vapor-deposited metal flake pigment is obtained by vapor-depositing a metal film such as aluminum or chromium on a base substrate such as a film, peeling off the base substrate, and then pulverizing the vapor-deposited metal film.

[0043] In the present invention, the bright pigment preferably contains an aluminum flake pigment and / or an optical coherence pigment. When both are used in combination to obtain a coating film that has a glittering brightness while suppressing unevenness, the mass ratio of the aluminum flake pigment to the optical coherence pigment is suitably within the range of 10 / 90 to 90 / 10, preferably 20 / 80 to 80 / 20.

[0044] In the present invention, the glittering coating film contains 0.05 to 15% by mass of glittering pigment. This is from the viewpoint of the glittering feeling and gloss of the finally formed multi-layer coating film. The preferred amount of glittering pigment contained in the glittering coating film is in the range of 0.5 to 10% by mass. If the glittering pigment content in the glittering coating film is less than 0.05% by mass, the glittering feeling of the multi-layer coating film will be reduced. If the glittering pigment content in the glittering coating film exceeds 15% by mass, unevenness will occur in the multi-layer coating film and / or the color development or glitter selection will be insufficient. There are cases where this is the case.

[0045] Furthermore, it is preferable that the glittering paint (II) does not contain the above-mentioned color pigment, or if it does contain it, the content thereof is in the range of 5 parts by mass or less based on 100 parts by mass of the non-volatile content of the glittering paint film. By using the above-mentioned pigment composition of the glittering paint film formed from the glittering paint (II), a glittering paint film appearance with excellent color development and glittering feeling can be obtained, and the color of the underlying colored paint film can be made to the maximum, and by changing the type of colored paint film, it is possible to provide a wide range of users with a wide variety of appearances by combining glittering feeling and color.

[0046] In this specification, "non-volatile content" refers to the residue remaining after removing volatile components such as water and organic solvents, and is the component that will form the coating film. For example, the drying conditions for the sample when measuring the mass of non-volatile content include heating 1 gram of sample in a dryer at 110°C for 1 hour.

[0047] <Resin component> As the resin component contained in the bright coating material (II), resins and curing agents known in the coating field can be used without limitation. Specific examples include acrylic resins, urethane resins, polysiloxane resins, alkyd resins, fluororesins, polyester resins, epoxy resins, polyisocyanates, polyamines, amino group-containing alkoxysilanes, and combinations thereof. The resin component also includes modified resins consisting of multiple of these resins.

[0048] Acrylic resin: The resin component preferably contains an acrylic resin from the viewpoint of weather resistance, and it is particularly preferable that the acrylic resin is an acrylic resin having a hydrolyzable silyl group and / or a hydroxyl group.

[0049] In this specification, the term "hydrolyzable silyl group" refers to a group that generates a silanol group by hydrolysis, and that the silanol group undergoes dehydration condensation to form a siloxane bond. The term is not particularly limited as long as it is a silyl group that has both or either a monovalent hydrolyzable atom (an atom that generates a silanol group by reacting with water) directly bonded to a silicon atom and a monovalent hydrolyzable group (a group that generates a silanol group by reacting with water) directly bonded to a silicon atom.

[0050] Specific examples of the hydrolyzable silyl group include halogenated silyl groups such as chlorosilyl and bromosilyl groups, alkoxysilyl groups such as methoxysilyl, ethoxysilyl, propoxysilyl and butoxysilyl groups, and any combination thereof.

[0051] Examples of acrylic resins having a hydrolyzable silyl group and / or a hydroxyl group include those containing monomer units of a hydrolyzable silyl group-containing polymerizable unsaturated compound and / or a hydroxyl group-containing polymerizable unsaturated compound and monomer units of a (meth)acryloyl group-containing compound. The (meth)acryloyl group-containing compound excludes hydrolyzable silyl group-containing polymerizable unsaturated compounds that contain a (meth)acryloyl group.

[0052] When the acrylic resin has a hydrolyzable silyl group, it may contain 1 to 50 mass %, preferably 2 to 30 mass %, of a hydrolyzable silyl group-containing polymerizable unsaturated compound based on all monomer units of the acrylic resin.On the other hand, when the acrylic resin has a hydroxyl group, it may contain 1 to 50 mass %, preferably 2 to 30 mass %, of a hydroxyl group-containing polymerizable unsaturated compound based on all monomer units of the acrylic resin.

[0053] In addition, when the acrylic resin has both a hydrolyzable silyl group and a hydroxyl group, the ratio of the hydrolyzable silyl group-containing polymerizable unsaturated monomer units to the total monomer units of the acrylic resin is 1:1 or more. The content of the compound is preferably 1 to 50 mass %, more preferably 2 to 30 mass %, and the content of the hydroxyl group-containing polymerizable unsaturated compound is preferably 0.1 to 40 mass %, more preferably 1 to 20 mass %.

[0054] Examples of the hydrolyzable silyl group-containing polymerizable unsaturated compound include vinylalkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinyltris(methoxyethoxy)silane; vinylchlorosilanes such as vinyltrichlorosilane, divinyldichlorosilane, and vinylmethyldichlorosilane; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, and (meth)acryloxyalkoxysilanes such as hydroxysilane, β-(meth)acryloxyethyltrimethoxysilane, β-(meth)acryloxyethyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, and γ-(meth)acryloxypropyldiethylmethoxysilane; and any combination thereof.

[0055] In this specification, the term "(meth)acryloxy group" refers to an acryloxy group, a methacryloxy group, or both an acryloxy group and a methacryloxy group.

[0056] Examples of the hydroxyl group-containing polymerizable unsaturated compound include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; compounds obtained by ring-opening polymerization of the above hydroxyalkyl (meth)acrylates with lactones such as ε-caprolactone; and hydroxyl group-containing (meth)acrylates such as monoesters of polyhydric alcohols such as polyethylene glycol mono(meth)acrylate with acrylic acid or methacrylic acid; and any combinations thereof.

[0057] On the other hand, a "(meth)acryloyl" group refers to an acryloyl group, a methacryloyl group, or both an acryloyl group and a methacryloyl group, and a "(meth)acrylic acid" refers to an acrylic acid, a methacrylic acid, or both an acrylic acid and a methacrylic acid.

[0058] Examples of the (meth)acryloyl group-containing compound include linear, branched, or cyclic alkyl group-containing (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tridecyl (meth)acrylate; N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, methoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, and ethoxyethyl (meth)acrylate. Alkoxyalkyl (meth)acrylates such as ethoxypropyl (meth)acrylate; alkoxy group-containing (meth)acrylates such as polyalkylene glycol monoalkoxy (meth)acrylates such as polyethylene glycol monomethoxy (meth)acrylate; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate; carboxyl group-containing (meth)acrylates such as half esters of acrylic acid, methacrylic acid, and hydroxyalkyl (meth)acrylates with acid anhydrides; sulfonic acid group-containing (meth)acrylates such as 2-acrylamido-2-methylpropanesulfonic acid; phosphate group-containing (meth)acrylates such as acid phosphooxyethyl (meth)acrylate and mono-[(2-hydroxyethyl)(meth)acrylic acid] phosphate ester; N,N amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, Nt-butylaminoethyl (meth)acrylate, and N,N-dimethylaminobutyl (meth)acrylate; quaternary ammonium base-containing (meth)acrylates such as (meth)acryloyloxyethyl trimethylammonium chloride and methacrylic acid dimethylaminoethyl methyl chloride; and fluoroalkyl (meth)acrylates such as hexafluoroisopropyl (meth)acrylate, perfluorooctylmethyl (meth)acrylate, and perfluorooctylethyl (meth)acrylate; and any combination thereof.

[0059] The acrylic resin having a hydrolyzable silyl group may contain, as a monomer unit of the hydrolyzable silyl group-containing polymerizable unsaturated compound, a polymerizable unsaturated compound having a hydrolyzable silyl group and a (meth)acryloyl group, such as a (meth)acryloxyalkoxysilane, for example, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, β-(meth)acryloxyethyltrimethoxysilane, β-(meth)acryloxyethyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, or γ-(meth)acryloxypropyldiethylmethoxysilane.

[0060] From the viewpoint of coating workability, the acrylic resin preferably contains a (meth)acryloyl group-containing compound that contains, as a monomer unit, a linear, branched, or cyclic alkyl ester of (meth)acrylic acid having about 4 to 18 carbon atoms.

[0061] Examples of linear, branched, or cyclic alkyl esters of (meth)acrylic acid having about 4 to 18 carbon atoms include n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tridecyl (meth)acrylate, and the like, as well as combinations thereof.

[0062] The acrylic resin may contain other polymerizable unsaturated compounds as monomer units. Other polymerizable unsaturated compounds are compounds other than (meth)acryloyl group-containing compounds, and specific examples thereof include aromatic vinyl compounds such as styrene and vinyl toluene; vinyl ethers such as cyclohexyl vinyl ether, nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, and t-butyl vinyl ether; allyl ethers such as ethyl allyl ether and hexyl allyl ether; and other vinyl carboxylic acid esters; olefins such as ethylene, propylene, and isobutylene; and fluorovinyl ethers such as fluoroalkyl trifluorovinyl ether and perfluoroalkyl trifluorovinyl ether.

[0063] The acrylic resin can be produced by any known method, for example, a radical polymerization method using an azo compound, peroxide, or the like as an initiator, and is commercially available.

[0064] The weight average molecular weight of the acrylic resin is not particularly limited, but is in the range of 1,000 to 100,000, and preferably in the range of 2,000 to 80,000, from the viewpoints of gloss, brilliance, and room temperature curing properties.

[0065] In this specification, the weight average molecular weight can be a value measured using, for example, a gel permeation chromatograph apparatus "HLC8120GPC" (trade name, manufactured by Tosoh Corporation), four columns "TSKgel G-4000HXL," "TSKgel G-3000HXL," "TSKgel G-2500HXL," and "TSKgel G-2000HXL" (trade names, all manufactured by Tosoh Corporation), a differential refractometer as a detector, under the following conditions: mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 1 mL / min.

[0066] Polysiloxane resin: From the viewpoint of weather resistance, the resin component preferably contains a polysiloxane resin, which is preferably a hydrolyzable silyl group-containing organopolysiloxane having a hydrolyzable silyl group and a polysiloxane skeleton in the resin.

[0067] The hydrolyzable silyl group-containing organopolysiloxane is, for example, a compound represented by the following formula (1): (1):SiX n Y 4-n Formula (1) (In the formula, X may be the same or different and represent a hydroxyl group or an alkoxy group; Y may be the same or different and represent a monovalent hydrocarbon group which may have a substituent; and n represents an integer of 1 to 4.) Examples of suitable organosilanes include resins formed by chemically bonding two or more identical or different organosilanes represented by the following formula:

[0068] When the hydrolyzable silyl group-containing organopolysiloxane is one in which the organosilanes represented by formula (1) are bonded in a linear or branched chain configuration, the hydrolyzable silyl group-containing organopolysiloxane resin preferably has a hydrocarbon group directly bonded to a silicon atom.

[0069] Examples of organosilanes represented by formula (1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β ... Trimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxy Silane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, γ-acyanopropyltriethoxysilane, 4-acyanobutyltriethoxysilane, p-aminophenyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, N-(6-aminohexyl)aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl)phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyl Examples of suitable silanes include methyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, trifluoropropyltrimethoxysilane, and the like, as well as any combination thereof.

[0070] From the viewpoint of coating workability, the hydrolyzable silyl group-containing organopolysiloxane preferably has methyl groups and / or phenyl groups directly bonded to silicon atoms.

[0071] Epoxy resin: The resin component preferably contains an epoxy resin. Such an epoxy resin is a compound having at least two epoxy groups in the molecule, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol-epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin-epichlorohydrin adduct, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A diglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol B diglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol ... hydrogenated bisphenol B diglycidyl ether, resorcinol diglycidyl ether, resorcinol di Examples of suitable epoxy resins include bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, dihydroxyanthracene type epoxy resins, polypropylene glycol diglycidyl ether, diphenyl sulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorene diglycidyl ether, biscresol fluorene diglycidyl ether, bisphenoxyethanol fluorene diglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-diglycidylaniline, N,N-diglycidyltoluidine; and compounds in which a glycidyl group-containing component is grafted onto an acrylic polymer.

[0072] When the resin component has a crosslinkable reactive group such as a hydroxyl group, a hydrolyzable silyl group, or an epoxy group, the resin component preferably contains a compound capable of reacting with the crosslinkable functional group as a curing agent, such as polyisocyanate, amino-containing alkoxysilane, or polyamine.

[0073] Polyisocyanates: Among these, polyisocyanates include, for example, aliphatic, aromatic, or araliphatic polyisocyanates. Specific examples include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), methylcyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, lysine diisocyanate, and the like, as well as modified versions of these isocyanate compounds. Specific examples of modified versions include biuret modified versions, isocyanurate modified versions, adduct modified versions (e.g., trimethylolpropane adducts), allophanate modified versions, uretdione modified versions, and combinations thereof. In particular, from the viewpoint of weather resistance, various modified versions of hexamethylene diisocyanate are preferred.

[0074] Amino group-containing alkoxysilane compounds: The amino group-containing alkoxysilane compound is a compound having an amino group and an alkoxysilyl group in the molecule, and specific examples thereof include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3-aminopropylmethyldiethoxysilane. Examples of the compound include aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-methylaminopropyltriethoxysilane, etc. The compounds also include hydrolysis condensates of these compounds.

[0075] The resin component contained in the above-mentioned bright coating material (II) is preferably a composition containing a hydroxyl group-containing acrylic resin and a polyisocyanate, or a composition containing a hydrolyzable silyl group-containing acrylic resin, a polysiloxane resin, an epoxy resin, and an amino group-containing alkoxysilane.

[0076] When the resin component contained in the lustrous coating material (II) is a composition containing a hydroxyl group-containing acrylic resin and a polyisocyanate, the ratio of the isocyanate groups contained in the polyisocyanate to the hydroxyl groups contained in the resin component is preferably in the range of 0.5 to 1.5 equivalents.

[0077] On the other hand, when the bright coating material (II) is a composition containing a hydrolyzable silyl group-containing acrylic resin, a polysiloxane resin, an epoxy resin, and an amino group-containing alkoxysilane as resin components, the ratio of the nonvolatile content contained in each component to the total nonvolatile content contained in the hydrolyzable silyl group-containing acrylic resin, the polysiloxane resin, and the epoxy resin is the hydrolyzable silyl group-containing acrylic resin is in the range of 20 to 90% by mass, preferably 30 to 80% by mass; The polysiloxane resin is in the range of 5 to 40% by mass, preferably 10 to 35% by mass, The epoxy resin is in the range of 5 to 40 mass %, preferably 10 to 35 mass % It is preferable that the

[0078] The amount of the amino group-containing alkoxysilane compound used is preferably such that the equivalent of active hydrogen in the amino group is within a range of 0.1 to 2.0, preferably 0.3 to 1.2, per equivalent of the epoxy group contained in the resin component.

[0079] <Glitter paint (II)> In the present invention, the above-mentioned lustrous paint (II) may contain, in addition to the above-mentioned resin component and lustrous pigment, paint additives such as organic solvents, water, fillers, modifying resins, curing catalysts, reactive diluents, adhesion promoters, ultraviolet absorbers, light stabilizers, anti-algae agents, defoamers, anti-settling agents, dispersants, wetting agents, and dehydrating agents.

[0080] Among these, the organic solvent may be a weak solvent. "Weak solvent" is a term well known in the art and generally refers to a solvent with weak dissolving power. The weak solvents mentioned above include those listed as Class 3 organic solvents in the classification of organic solvents under the Industrial Safety and Health Act. Specific examples of Class 3 organic solvents include gasoline, coal tar naphtha (also known as solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine, mineral spirits (also known as mineral thinner, petroleum spirits, white spirits, and mineral turpentine), and combinations thereof.

[0081] In the present invention, from the viewpoint of the environment during coating, it is preferable that the ratio of weak solvents to all organic solvents contained in the glittering coating material (II) is 40 mass % or more, and preferably 70 mass % or more.

[0082] Usable organic solvents other than weak solvents include known solvents, such as hydrocarbon solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, and cyclobutane; aromatic solvents such as toluene and xylene; ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono- Examples of the solvent include ether solvents such as n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and dioxane; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, methyl acetoacetate, ethylene glycol monomethyl ether acetate, and butyl carbitol acetate; ketone solvents such as acetone, acetylacetone, diacetone alcohol, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; and combinations thereof.

[0083] Examples of the curing catalyst include organic tin compounds such as diacetyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, diacetyltin dioctoate, tin octoate, dibutyltin diacetate, and dibutyltin dioctoate; aluminum trimethoxide, aluminum tris(acetylacetonate), aluminum tri-n-butoxide, aluminum tris(ethyl acetoacetate), aluminum diisopropoxy(ethyl acetoacetate), aluminum tris ... Organoaluminum compounds such as titanium tetra(monoethylethoxide), titanium tetra(monoethylethoxide), titanium tetra(monobutylethoxide), titanium tetrakis(acetylacetonate), tetra-n-butyltitanate, and other organic titanium compounds; zirconium tetra(monomethylethoxide), zirconium tetra(monoethylethoxide), zirconium tetra(monobutylethoxide), zirconium n-propylate, zirconium n-propyl butyrate, zirconium tetrakis(acetylacetonate), and other organic zirconium compounds; zinc naphthenate, and other organic zinc compounds; cobalt octylate, cobalt naphthenate, and other organic cobalt compounds; trimethylamine, triethylamine, 2-(dimethylamino)ethyl methacrylate, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, 1-methylpiperidine, 1-methylpyrrolidine, and other Examples of suitable catalysts include amine catalysts such as aliphatic amines, pyridine, 4-dimethylaminopyridine, 4-(1-piperidyl)pyridine, N-methylimidazole, and N,N-dimethylaniline; lead, tin, zinc, and iron complexes of carboxylic acids; and boric acid compounds such as boric acid esters such as trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, triphenyl borate, tri(4-chlorophenyl) borate, and trihexafluoroisopropyl borate, and these can be used alone or in combination of two or more. Among these, amine catalysts are preferred from the viewpoint of gloss.

[0084] The form of the glittering paint (II) can be selected depending on the type of resin component. Specifically, when the resin component is a composition containing a hydroxyl-containing acrylic resin and a polyisocyanate, the glittering paint (II) can be a multi-component paint containing a base component containing a hydroxyl-containing acrylic resin and a glittering pigment, and a curing agent component containing a polyisocyanate. Furthermore, when the resin component is a composition containing a hydrolyzable silyl-containing acrylic resin, a polysiloxane resin, an epoxy resin, and an amino-containing alkoxysilane compound, the glittering paint (II) can be a multi-component paint containing a base component containing an acrylic resin, a polysiloxane resin, an epoxy resin, and a glittering pigment, and a curing agent component containing an amino-containing alkoxysilane compound. By using such a multi-component paint, the storage stability of each of the main component and the curing agent component is good, and the lustrous paint (II) obtained by mixing the two components can form a coating film with excellent lustre and weather resistance and little unevenness.

[0085] When the above-mentioned bright paint (II) is a multi-component paint, the painter should mix the main component and The curing agent component and, if necessary, a diluent are mixed by stirring to prepare a bright coating material (II) for coating.

[0086] The mass ratio of the main component to the curing agent component is not particularly limited, but is generally within the range of 99 / 1 to 70 / 30, preferably 95 / 5 to 80 / 20, in terms of the mass ratio of the main component / curing agent component.

[0087] The application of the above-mentioned glittering paint (II) can be carried out by a known application method. Specifically, for example, it can be carried out using application tools such as brush coating, flow coating, trowel coating, roller coating, spray coating, airless spray coating, lysine gun, and all-purpose gun. In particular, it is preferable to apply using a roller, which is a coating means that causes little paint to scatter to the surroundings. Drying after application can be carried out at room temperature, but forced drying or heat drying, etc. may also be carried out as necessary.

[0088] <Process (3)> In the present invention, a clear coating (III) is applied on the glossy coating film formed in step (2). The clear coating (III) may further comprise a step (3) of repainting the same. Since the clear coating (III) is used to protect the coating film, any conventionally known clear coating can be used without any particular restrictions as long as it has excellent durability and transparency. is different from the bright paint (II), but the resin component contained in the clear paint (III) is bright. The same resins as those listed in the explanation of the resin components contained in the clear coating (II) can be used. The application of the clear coating (III) can be carried out by a known application method, such as brush application or flow application. The coating can be carried out using coating tools such as undercoating, trowel coating, roller coating, spray coating, airless spray coating, lysine gun, universal gun, etc., and coating using a roller is particularly preferred. Drying after coating can be carried out at room temperature, but forced drying or heat drying may also be carried out as necessary. [Example]

[0089] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" mean "parts by mass" and "% by mass," respectively.

[0090] <Production of acrylic resin> Manufacturing Example 1 44.7 parts of mineral spirits were placed in a flask equipped with a condenser and thermometer, and the temperature was raised to 95°C while stirring under a nitrogen stream. The following components were added dropwise to the flask over 4 hours with stirring, and after aging for 1 hour, the solution was diluted with mineral spirits to a non-volatile concentration of 60%, producing acrylic silicone resin solution (A-1). The weight average molecular weight of the acrylic resin was 25,000. Styrene 10.0 parts i-Butyl methacrylate 62.2 parts 2-hydroxyethyl acrylate 2 parts 2-Ethylhexyl acrylate 15.8 parts γ-(meth)acryloxypropyltrimethoxysilane 10.0 parts Manufacturing Example 2 An acrylic polyol resin solution (A-2) was produced in the same manner as in Production Example 1, except that the monomer to be added dropwise in Production Example 1 was as follows: The weight average molecular weight was 25,000. 30 parts styrene Hydroxyethyl methacrylate 10 parts Isobutyl methacrylate 30 parts 2 Hydroxyethyl acrylate 30 parts.

[0091] <<Production of lustrous paint>> Manufacturing Examples 3 to 25 The base component and curing agent component were prepared so as to have the blending ratio shown in Table 1, and the two were mixed to produce the glittering paints (II-1) to (II-23). ​​Note that the blending amount of the acrylic resin solution in Table 1 indicates the mass of the non-volatile content of the acrylic resin solution.

[0092] [Table 1]

[0093] [Table 2]

[0094] "coating" Example 1 A 60cm x 90cm zinc-plated steel plate that had been pre-sealed was painted with a roller using a weak solvent soluble modified epoxy paint "Supersaurus 2" (product name of Kansai Paint Co., Ltd.) gray at 120g / m 2 After curing at 23°C for one day, the colored paint (I-1) shown in Table 3 was applied with a roller at a rate of 100 g / m 2The coating was then dried at 23°C for one day to conceal the base. Next, the glitter paint (II-1) was applied on top of the coating so that the glitter paint film obtained by applying and drying the glitter paint was thinner than the concealing film thickness (coating amount of non-volatile matter of the paint: 45 g / m 2 ) The coating was applied by roller and dried at 23°C for 7 days to prepare test panels.

[0095] Examples 2, 4 to 19, 24, 26, 28, 30, 32, 34 to 39 Test panels were obtained in the same manner as in Example 1 above, except that the paint combinations used were as shown in Table 4.

[0096] Example 3 A weak solvent soluble modified epoxy paint "Supersaurus 2" (product name of Kansai Paint Co., Ltd.) gray was applied with a roller at a rate of 120 g / m2 onto a 60 cm x 90 cm zinc-plated steel plate that had been pre-sealed. 2 After curing at 23°C for one day, the colored paint (I-1) shown in Table 3 was applied with a roller at a rate of 100 g / m 2 The coating was then dried at 23°C for one day to conceal the base. Next, the glitter paint (II-1) was applied on top of the coating so that the glitter paint film obtained by applying and drying the glitter paint was thinner than the concealing film thickness (coating amount of non-volatile matter of the paint: 45 g / m 2 ) roller coating, dried at 23°C for 7 days, and then applied clear paint (III) (Note 14) as a top coat at a coating weight of 45 g / m2 2 The coating was then dried at 23°C for 7 days to obtain test panels. (Note 14) Clear paint (III): A clear paint with a composition obtained by removing the lustrous pigment from the lustrous paint (II-1) in Production Example 3.

[0097] Examples 20 to 23, 25, 27, 29, 31 and 33 Test panels were obtained in the same manner as in Example 3 above, except that the paint combinations used were as shown in Table 4.

[0098] Comparative Examples 1 to 3 Test panels were obtained in the same manner as in Example 1 above, except that the paint combinations used were as shown in Table 4.

[0099] Comparative Example 4 A galvanized steel plate measuring 60cm x 90cm that has been pre-sealed is Apply 120g / m2 of "Supersaurus 2" (product name of Kansai Paint Co., Ltd.), a soluble modified epoxy paint, in gray, with a roller. 2 After curing at 23°C for one day, apply a lustrous paint (II-22) on top of it with a coating amount of 45g / m of non-volatile matter. 2 The coating was then dried at 23°C for 7 days to prepare a test panel.

[0100] Comparative Example 5 On the test plate of Comparative Example 4, a clear coating (III) (Note 9) was further applied as a top coat at a coating amount of 45 g / m2 of non-volatile matter. 2 The coating was then dried at 23°C for 7 days to obtain test panels.

[0101] Comparative Example 6 A test panel was obtained in the same manner as in Comparative Example 4 above, except that the glittering paint (II-22) used in Comparative Example 4 was changed to the glittering paint (II-23).

[0102] [Table 3]

[0103] Evaluation Test The test panels obtained in the above Examples and Comparative Examples were evaluated according to the following criteria. The results are shown in Table 4. In Table 4, "-" means "none" (no coating film was present because no coating was applied).

[0104] [Table 4]

[0105] (*) Brilliant feeling The brightness of each test panel was visually evaluated according to the following criteria. ◎: Very good metallic or pearl-like sparkle, 〇: Good metallic or pearly sparkle, △: Metallic or pearly sparkle is slightly poor. ×: Metallic or pearly sparkle is poor.

[0106] (*) Irregularities The glitter of each test panel was visually evaluated for unevenness according to the following criteria. ◎: No unevenness in brightness at all, ◯: Slight unevenness in brightness is observed but not noticeable. △: Clear unevenness in brightness is observed. ×: The unevenness of the glitter is quite noticeable.

[0107] (*) Color development The color development of each test plate was visually evaluated according to the following criteria. ◎: Very good color development, 〇: Good color development, △: Color development is slightly poor, ×: Insufficient color development.

[0108] (*) Gloss The gloss of each test plate was visually evaluated according to the following criteria. ◎: Very good gloss, 〇: Good gloss, △: Gloss is slightly poor, ×: Lack of gloss.

[0109] (*)Weather resistance Each test plate was subjected to an accelerated weather resistance test (xenon weather meter) in accordance with JIS K 5600-7-7 for 3000 hours, and then the appearance was visually observed. ◎: No change at all before and after the test. ○: Some gloss loss or discoloration is observed after the test. △: Loss of gloss or discoloration is observed after the test. ×: Significant loss of gloss or discoloration was observed after the test.

[0110] 《Consideration》 Based on the results of Table 4, the effects of the present invention will be discussed below. Examples 1 to 39 are multi-layer coating films within the range specified by the present invention. Comparative Examples 1 to 6 are multi-layer coating films that deviate from the present invention in that the amount of the glittering pigment contained in the glittering paint is large. From the results of the finish test of the multi-layer coating film created as described above, the following can be said: By applying a glitter paint containing a small amount of glitter pigment so that it is transparent on top of the colored coating film, the colored coating film and the glittering coating film are fused together, resulting in a multi-layer coating film that combines glitter, color development, and gloss and has reduced unevenness (Examples 1 to 39). However, when a lustrous paint containing a larger amount of lustrous pigment than that specified in the present invention is applied, the lustrous pigment provides a sufficient lustrous appearance, but unevenness is noticeable and the gloss is insufficient. Furthermore, although the base is visible, the color development is poor. (Comparative Examples 1 to 6) Furthermore, when a clear coating is applied over a bright coating containing a large amount of bright pigment as an underlying layer, the brightness, gloss, and weather resistance are good, but unevenness is noticeable and color development is insufficient (Comparative Example 5).

Claims

1. A step (1) of applying a colored coating material (I) containing a color pigment and a resin component to a substrate surface so that the thickness of the colored coating film is equal to or greater than the hiding film thickness, and drying the applied coating film; and Step (2) of applying a lustrous paint (II) containing a lustrous pigment and a resin component onto the colored coating film obtained in step (1) and drying the paint to form a lustrous coating film; The colored coating film does not contain a glittering pigment or has a lower glittering pigment content than the glittering coating film, The glittering coating film contains a glittering pigment in the range of 0.05 to 1.9 mass %, A glossy coating film is formed by rolling and drying at room temperature. A method for producing a glossy multilayer coating film having a thickness less than the hiding film thickness.

2. 2. The method for forming a glittering multilayer coating film according to claim 1, wherein the substrate surface is the substrate surface of a building.

3. 3. The method for forming a glittering multi-layer coating film according to claim 1, wherein the colored coating material (I) is a room temperature drying type coating material.

4. The method for forming a glittering multilayer coating film according to any one of claims 1 to 3, wherein the colored coating material (I) is a coating material that forms a colored coating film having a lightness (L *) in the range of 40 to 95 and a chroma (C *) of 40 or less.

5. The method for forming a glittering multilayer coating film according to any one of claims 1 to 4, wherein the colored coating film made of the colored coating material (I) is formed by a roller.

6. The method for forming a glittering multilayer coating film according to any one of claims 1 to 5, wherein the glittering paint (II) is a multi-component paint containing a main component and a curing agent component.

7. The method for forming a glittering multilayer coating film according to any one of claims 1 to 6, wherein the glittering pigment is an aluminum flake pigment and / or a light interference pigment.

8. 8. The method for forming a glittering multilayer coating film according to claim 7, wherein the glittering pigment comprises an aluminum flake pigment, and the aluminum flake pigment is of a non-leafing type or a leafing type.

9. 9. The method for forming a glittering multilayer coating film according to claim 7 or 8, wherein the glittering pigment comprises an aluminum flake pigment, and the average particle size of the aluminum flake pigment is in the range of 5 to 250 μm.

10. The method for forming a glittering multilayer coating film according to claims 7 to 9, wherein the glittering pigment comprises a light interference pigment, and the average particle size of the light interference pigment is in the range of 5 to 250 μm.

11. The method for forming a glittering multilayer coating film according to any one of claims 7 to 10, wherein the glittering pigment comprises an aluminum flake pigment and a light interference pigment in a mass ratio of the former to the latter in the range of 10 / 90 to 90 / 10.

12. The method for forming a glittering multilayer coating film according to any one of claims 6 to 11, wherein the glittering paint (II) is a multi-component system containing a main component containing a hydroxyl group-containing acrylic resin and a glittering pigment, and a curing agent component containing a polyisocyanate.

13. The method for forming a glittering multilayer coating film according to any one of claims 6 to 11, wherein the glittering coating material (II) is a multi-component coating material containing a main component containing a hydrolyzable silyl group-containing acrylic resin, a polysiloxane resin, an epoxy resin and a glittering pigment, and a curing agent component containing an amino group-containing alkoxysilane compound.

14. The method for forming a glittering multilayer coating film according to claim 13, wherein the glittering paint (II) further contains an organic solvent and / or a curing catalyst.

15. The method for forming a glittering multilayer coating film according to any one of claims 1 to 14, wherein the glittering coating film of the glittering paint (II) is formed by a roller.

16. The method for forming a glittering multilayer coating film according to any one of claims 1 to 15, further comprising step (3) of applying a clear coating (III) different from the glittering coating (II) on the glittering coating film formed in step (2).

17. The method for forming a glittering multilayer coating film according to claim 16, wherein the clear coating film of the clear coating material (III) is formed by a roller.

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