Aqueous coating material, method for forming coating film, and top coating set

Abstract

Provided is an aqueous coating material which exhibits excellent ambient temperature curing properties and can exhibit excellent performance in terms of cracking resistance and also weathering resistance and so forth. This aqueous covering material contains an acrylic silicon resin emulsion (A) and a pigment (B) and exhibits ambient temperature curing properties, and is characterized in that: the residual proportion of silica among solid resin content in the acrylic silicon resin emulsion (A) is 1-40 mass%; the glass transition temperature of the acrylic silicon resin emulsion (A) is 30ºC or lower; two or more (meth)acrylic acid esters (s) having an alkyl group with 4 or more carbon atoms are contained as monomers that constitute the acrylic silicon resin emulsion (A); and the glass transition temperature of a homopolymer of the (meth)acrylic acid ester (s) having an alkyl group with 4 or more carbon atoms is 0ºC or lower.

Description

Water-based coating material, coating film forming method, and topcoat material set

[0001] The present invention relates to a novel aqueous coating material, a coating film forming method, and a topcoat material set.

[0002] Conventionally, surfaces of buildings, civil engineering structures, etc. have been finished with coating materials. Such coating materials not only impart aesthetic appeal through various colors and textures, but also protect the substrate from wind, rain, direct sunlight, etc., and therefore are required to exhibit excellent weather resistance. In recent years, in consideration of their non-polluting and safety, the use of water-based coating materials using resin emulsions as binders has increased.

[0003] One method for improving the weather resistance of aqueous coating materials is to use an acrylic silicone resin emulsion as a binder. For example, Patent Document 1 describes an aqueous coating material containing a resin emulsion having a specific silicon content, acid value, and hydroxyl value, its crosslinking agent, and a pigment.

[0004] Incidentally, aqueous coating materials applied to buildings, civil engineering structures, and the like are required to have the ability to form and cure a film (room temperature curing ability) in a temperature range of approximately 5 to 40° C., since the coating work is carried out outdoors. However, the above-mentioned patent documents do not sufficiently consider room temperature curing ability, and when coating is carried out at room temperature, there is a risk that cracks will occur in the coating film (film) or that the weather resistance of the coating film will be insufficient.

[0005] In particular, among the substrates that make up the framework of buildings, civil engineering structures, and the like, cement-based substrates such as concrete and mortar may crack over time due to the shrinkage of the substrate itself, the load on the substrate, etc. In addition, in building materials such as lightweight concrete boards, aerated concrete boards, and siding boards, the joints between the building materials tend to be easily displaced due to changes in temperature, humidity, etc. Water-based topcoat materials applied to buildings, civil engineering structures, etc., also require crack resistance for such coated surfaces.

[0006] Japanese Patent Application Publication No. 8-12930

[0007] The present invention has been made in consideration of the above-mentioned problems, and aims to provide an aqueous coating material that has excellent room temperature curing properties and can exhibit excellent performance in terms of crack resistance, weather resistance, etc.

[0008] The present invention has been made in view of the above-mentioned problems, and has as its object to provide a method for forming a coating that can exhibit excellent performance in terms of crack resistance, weather resistance, etc.

[0009] As a result of extensive research into achieving the above object, the inventors came up with the idea of ​​an aqueous coating material containing an acrylic silicone resin emulsion having a specific silica residual ratio and a specific resin composition, and a pigment, which led to the completion of the present invention.

[0010] As a result of intensive research into achieving the above-mentioned objective, the inventor came up with the idea of ​​a coating formation method in which a specific first topcoat material is applied, and then an acrylic silicone resin emulsion having a specific resin composition and a specific second topcoat material containing a pigment are applied, leading to the completion of the present invention.

[0011] That is, the present invention has the following features. 1. An aqueous coating material having room temperature curing properties, containing an acrylic silicone resin emulsion (A) and a pigment (B), wherein the silica residual ratio in the resin solid content of the acrylic silicone resin emulsion (A) is 1 to 40 mass %, the acrylic silicone resin emulsion (A) has a glass transition temperature of 30°C or lower, and the acrylic silicone resin emulsion (A) contains, as a monomer, two or more (meth)acrylic acid alkyl esters (s) having an alkyl group with 4 or more carbon atoms, and the glass transition temperature of a homopolymer of the (meth)acrylic acid alkyl esters (s) having an alkyl group with 4 or more carbon atoms is 0°C or lower. In the present invention, "room temperature" refers to 5 to 40°C. 2. The aqueous coating material according to 1., wherein the (meth)acrylic acid alkyl ester (s) having an alkyl group with 4 or more carbon atoms includes a (meth)acrylic acid alkyl ester (s1) having a branched alkyl group with 5 or more carbon atoms. 3. 2., wherein the branched alkyl group includes a methyl group. The aqueous coating material described in 1. 4. The aqueous coating material described in 1., characterized in that it contains a crosslinking agent (C), the acrylic silicone resin emulsion (A) has a reactive functional group, and the crosslinking agent (C) has a functional group capable of reacting with the reactive functional group. 5. A film formation method in which a first topcoat material and a second topcoat material are applied to a surface to be coated in order to form a topcoat material film, the first topcoat material forms a film with an elongation rate of 20% or more at -10 ° C, and the second topcoat material is an aqueous coating material described in any of 1. to 4., and the second topcoat material forms a film with an elongation rate at -10 ° C that is smaller than the elongation rate of the first topcoat material at -10 ° C. The film formation method, characterized in that it forms a film with an elongation rate at -10 ° C that is smaller than the elongation rate of the first topcoat material at -10 ° C. 6. The first topcoat material contains a resin emulsion and a pigment, and as a monomer constituting the resin emulsion, it contains two or more (meth)acrylic acid alkyl esters (s) having an alkyl group with 4 or more carbon atoms, and the glass transition temperature of the homopolymer of the (meth)acrylic acid alkyl esters (s) having an alkyl group with 4 or more carbon atoms is 0 ° C. or less. 5. The coating formation method described in.7. The coating formation method described in 6., characterized in that the (meth)acrylic acid alkyl ester (s) having an alkyl group having 4 or more carbon atoms contains a (meth)acrylic acid alkyl ester (s1) having a branched alkyl group having 5 or more carbon atoms. 8. The aqueous coating material described in 7., characterized in that the branched alkyl group contains a methyl group. 9. A topcoat material set consisting of the first topcoat material and the second topcoat material used in the coating formation method described in 5.

[0012] The aqueous coating material of the present invention has excellent room temperature curing properties and can exhibit excellent performance in terms of crack resistance, weather resistance, and the like.

[0013] According to the coating formation method of the present invention, a coating that exhibits excellent performance in terms of crack resistance, weather resistance, etc. can be formed.

[0014] Hereinafter, an embodiment of the present invention will be described.

[0015] [Aqueous Coating Material] The aqueous coating material of the present invention is characterized by containing a specific acrylic silicone resin emulsion (A) and a pigment (B). Such an aqueous coating material is capable of forming a colored coating film by room temperature curing. Specifically, the acrylic silicone resin emulsion (A) has a residual silica ratio of 1 to 40 mass% in the resin solids, a glass transition temperature (hereinafter also referred to as "Tg") of 30°C or less, and contains two or more (meth)acrylic acid alkyl esters (s) having an alkyl group with 4 or more carbon atoms as monomers constituting the acrylic silicone resin emulsion (A), and the glass transition temperature of a homopolymer of the (meth)acrylic acid alkyl esters (s) having an alkyl group with 4 or more carbon atoms is 0°C or less. In this invention, "monomer" is a general term for compounds having a polymerizable unsaturated double bond (excluding compounds having a silicon atom).

[0016] Generally, a resin emulsion is formed by emulsifying and dispersing a resin in an aqueous medium (a medium containing water). The glass transition temperature of the resin is a value calculated by the Fox formula based on the intrinsic Tg (Tg of the homopolymer of each monomer) of each monomer constituting the resin and the composition ratio. In the present invention, an acrylic silicone resin emulsion (A) is used as the resin emulsion. The acrylic silicone resin emulsion (A) is formed by emulsifying and dispersing an acrylic silicone resin in an aqueous medium. The glass transition temperature of the acrylic silicone resin emulsion (A) is a value calculated by the Fox formula based on the intrinsic Tg of each monomer constituting the acrylic silicone resin emulsion (A) and the composition ratio. However, in the present invention, alkoxysilane compounds are excluded from the calculation of the Tg of the acrylic silicone resin emulsion (A).

[0017] <Component (A)> Generally, resin emulsions can be cured at room temperature by setting the glass transition temperature below room temperature (5 to 40°C). Acrylic silicone resin emulsions can also be cured at room temperature by setting the glass transition temperature below room temperature.

[0018] However, in aqueous coating materials that use an acrylic silicone resin emulsion containing a large amount of silicone components as a binder and further mix in a pigment, even if the glass transition temperature of the acrylic silicone resin emulsion is set low, problems such as cracks occurring in the coating film or insufficient weather resistance of the coating film are likely to occur.

[0019] The present invention provides such an aqueous coating material, in which an acrylic silicone resin emulsion that meets the above-mentioned conditions is an essential component. The aqueous coating material of the present invention, which has such a specific configuration, can exhibit excellent performance in terms of crack resistance, weather resistance, etc. Furthermore, since the silica residual ratio in the resin solids of the acrylic silicone resin emulsion (A) is 1 to 40 mass%, the aqueous coating material of the present invention can exhibit stable performance even when using a binder containing a high proportion of silicon components, thereby allowing for a relative reduction in petroleum-derived organic components and contributing to decarbonization. Furthermore, the aqueous coating material of the present invention, due to its excellent weather resistance, can extend the life of the coated object and reduce the total number of maintenance cycles, thereby contributing to decarbonization and other efforts from this perspective as well.

[0020] The aqueous coating material of the present invention uses, as a binder, an acrylic silicone resin emulsion (A) (hereinafter referred to as "component (A)") having a silica residual ratio of 1 to 40 mass% in the resin solid content and a glass transition temperature of 30°C or lower.

[0021] As such component (A), a component (resin component) constituting the acrylic silicone resin can be used, which includes a monomer such as a (meth)acrylic acid alkyl ester containing a (meth)acrylic acid alkyl ester (s) having an alkyl group with 4 or more carbon atoms, and an alkoxysilane compound. In the present invention, alkyl acrylates and alkyl methacrylates are collectively referred to as (meth)acrylic acid alkyl esters. In addition, in the present invention, "α to β" is synonymous with "α or more and β or less."

[0022] Examples of (meth)acrylic acid alkyl esters include methyl methacrylate (Tg: 105°C), ethyl methacrylate (Tg: 65°C), n-propyl methacrylate (Tg: 35°C), isopropyl methacrylate (Tg: 81°C), n-butyl methacrylate (Tg: 20°C), tert-butyl acrylate (Tg: 43°C), tert-butyl methacrylate (Tg: 107°C), isobutyl methacrylate (Tg: 53°C), n-pentyl acrylate (Tg: 22°C), cyclohexyl acrylate (Tg: 15°C), cyclohexyl methacrylate (Tg: 83°C), stearyl acrylate (Tg: 35°C), and hexadecyl acrylate (Tg: 3 (Meth)acrylic acid alkyl esters having a homopolymer Tg of 15°C or higher, such as hexadecyl methacrylate (Tg: 15°C), tetradecyl acrylate (Tg: 24°C), isobornyl acrylate (Tg: 94°C), isobornyl methacrylate (Tg: 155°C), dicyclopentanyl acrylate (Tg: 120°C), dicyclopentanyl methacrylate (Tg: 175°C), and dicyclopentenyl acrylate (Tg: 120°C); (meth)acrylic acid alkyl esters having a homopolymer Tg of higher than 0°C and lower than 15°C, such as methyl acrylate (Tg: 8°C), n-propyl acrylate (Tg: 3°C), and n-lauryl acrylate (Tg: 10°C);Ethyl acrylate (Tg: -20°C), isopropyl acrylate (Tg: -3°C), n-butyl acrylate (Tg: -54°C), isobutyl acrylate (Tg: -26°C), n-pentyl methacrylate (Tg: -5°C), isoamyl acrylate (Tg: -45°C), n-hexyl acrylate (Tg: -57°C), n-hexyl methacrylate (Tg: -5°C), 2-ethylhexyl acrylate (Tg: -70°C), 2-ethylhexyl methacrylate (Tg: -10°C), n-octyl acrylate (Tg: -65°C), 2-octyl acrylate (Meth)acrylic acid alkyl esters having a homopolymer Tg of 0°C or less, such as acrylate (Tg: -44°C), isooctyl methacrylate (Tg: -45°C), isooctyl acrylate (Tg: -70°C), isononyl acrylate (Tg: -58°C), isodecyl acrylate (Tg: -60°C), isodecyl methacrylate (Tg: -41°C), tridecyl acrylate (Tg: -55°C), tridecyl methacrylate (Tg: -40°C), n-lauryl methacrylate (Tg: -65°C), and tetradecyl methacrylate (Tg: -72°C). These may be used alone or in combination of two or more, and the (meth)acrylic acid alkyl esters having a homopolymer Tg of 0°C or less include two or more types.

[0023] Examples of the alkoxysilane compound include polymerizable unsaturated double bond-containing silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane; epoxy group-containing silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane; amino group-containing silane coupling agents such as silane, N-2 (aminoethyl) 3-aminopropyl triethoxysilane, N-2 (aminoethyl) 3-aminopropyl methyl diethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropyl trimethoxysilane; ureido group-containing silane coupling agents such as 3-ureidopropyl triethoxysilane; chloroalkyl group-containing silane coupling agents such as 3-chloropropyltrimethoxysilane; sulfide group-containing silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide; isocyanate group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane; and other silane coupling agents (i),

[0024] tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and tetraacetoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrippropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrippropoxysilane, butyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldimethylsilane, alkylalkoxysilanes such as tetrafunctional alkoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane, methylphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, dimethyldiacetoxysilane, and diphenyldiacetoxysilane; or alkoxysilane-modified products obtained by modifying at least a portion of the alkoxyl groups of these tetrafunctional alkoxysilanes or alkylalkoxysilanes with a polyoxyalkylene group-containing compound, a fluorine-containing compound, or the like;

[0025] Examples of such cyclic siloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. These may be used alone or in combination of two or more.

[0026] The ratio of the alkoxysilane compound is preferably 2 to 100 parts by mass, more preferably 10 to 90 parts by mass, and even more preferably 20 to 85 parts by mass, relative to 100 parts by mass of the (meth)acrylic acid alkyl ester. Such a ratio of the alkoxysilane compound is suitable in terms of crack resistance, weather resistance, polymerization stability, etc.

[0027] The component (A) may contain other monomers (other monomers) as resin constituents. Examples of such other monomers include carboxyl group-containing monomers such as acrylic acid (Tg: 106°C), methacrylic acid (Tg: 185°C), itaconic acid (Tg: 100°C), and maleic acid (Tg: 130°C); aromatic monomers such as styrene (Tg: 100°C) and α-methylstyrene (Tg: 168°C); carbonyl group-containing monomers such as acrolein (Tg: 60°C) and diacetone acrylamide (Tg: 65°C); 2-hydroxyethyl acrylate (Tg: -15°C); hydroxyl group-containing monomers such as N,N-dimethylaminoethyl acrylate (Tg: 18°C), N,N-dimethylaminoethyl methacrylate (Tg: 18°C), and N,N-diethylaminoethyl methacrylate (Tg: 20°C); hydroxyl group-containing monomers such as N,N-dimethylaminoethyl acrylate (Tg: 18°C), N,N-dimethylaminoethyl methacrylate (Tg: 18°C), and N,N-diethylaminoethyl methacrylate (Tg: 20°C); Monomers containing: amide group-containing monomers such as acrylamide (Tg: 179°C) and N,N-dimethylaminopropylacrylamide (Tg: 134°C); nitrile group-containing monomers such as acrylonitrile (Tg: 125°C); epoxy group-containing monomers such as glycidyl methacrylate (Tg: 46°C); oxazoline group-containing monomers such as 2-isopropenyl-2-oxazoline (Tg: 100°C); 2-[2'-hydroxy-5'-methacryloyloxyethylphenyl]-2H-benzo Examples of suitable additives include ethylenically unsaturated double bond-containing ultraviolet absorbers such as triazole (Tg: 100°C), ethylenically unsaturated double bond-containing light stabilizers such as 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (Tg: 130°C), and other sulfonic acid-containing vinyl monomers, acid anhydrides, chlorine-containing monomers, fluorine-containing monomers, alkylene glycol monoallyl ethers, vinyl acetate, vinyl propionate, vinyl ethers, ethylene, propylene, isobutylene, etc. These can be used alone or in combination of two or more.

[0028] The ratio of the other monomer is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and even more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass of the (meth)acrylic acid alkyl ester. By using the other monomer within such a range, various functions (for example, crosslinkability, stability, dispersibility, etc.) can be imparted.

[0029] In the present invention, the monomer constituting component (A) can be a monomer obtained from a biological resource, i.e., a biomass-based monomer. The introduction of such a biomass-based monomer increases the biomass content of component (A) and thus the aqueous coating material, thereby enabling the reduction of the amount of petroleum-derived compounds used. The use of such materials can also contribute to decarbonization. Examples of biomass-based monomers that can be used include monomers produced using biologically derived alcohols, organic acids, hydrocarbons, etc. Since many biomass-based monomers, such as (meth)acrylic acid alkyl esters having alkyl groups with four or more carbon atoms, have been put to practical use, the present invention can effectively obtain an aqueous coating material with a high biomass content.

[0030] Component (A) can be produced by polymerizing the above-mentioned resin constituent components. Any known polymerization method can be used, including conventional emulsion polymerization, soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, multistage emulsion polymerization, and the like. Multistage emulsion polymerization can be carried out by a two-stage or three-stage or more emulsion polymerization method. During polymerization of component (A), for example, an emulsifier, initiator, dispersant, polymerization inhibitor, polymerization retarder, buffer, chain transfer agent, pH adjuster, and the like can be used.

[0031] Among these, various surfactants that can be used in emulsion polymerization can be used as the emulsifier, and these may be reactive types (reactive surfactants) having polymerizable unsaturated double bonds. Examples of emulsifiers that can be used include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Polymer emulsifiers such as polyurethane resins, polyacrylic acid resins, polyvinyl alcohol, and polyvinylpyrrolidone can also be used. These emulsifiers can be used alone or in combination.

[0032] The proportion of the emulsifier is preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the resin constituent components.

[0033] The component (A) in the present invention contains, as a monomer constituting an acrylic silicone resin, two or more types of (meth)acrylic acid alkyl ester (s) (hereinafter also referred to as "component (s)") having an alkyl group having 4 or more carbon atoms and having a homopolymer Tg of 0°C or less (preferably -15°C or less, more preferably -30°C or less).

[0034] Examples of the component (s) include n-butyl acrylate (Tg: -54°C), isobutyl acrylate (Tg: -26°C), n-pentyl methacrylate (Tg: -5°C), isoamyl acrylate (Tg: -45°C), n-hexyl acrylate (Tg: -57°C), n-hexyl methacrylate (Tg: -5°C), 2-ethylhexyl acrylate (Tg: -70°C), 2-ethylhexyl methacrylate (Tg: -10°C), n-octyl acrylate (Tg: -65°C), 2-octyl Examples of suitable monomers include isoamyl acrylate (Tg: -44°C), isooctyl methacrylate (Tg: -45°C), isooctyl acrylate (Tg: -70°C), isononyl acrylate (Tg: -58°C), isodecyl acrylate (Tg: -60°C), isodecyl methacrylate (Tg: -41°C), tridecyl acrylate (Tg: -55°C), tridecyl methacrylate (Tg: -40°C), n-lauryl methacrylate (Tg: -65°C), and tetradecyl methacrylate (Tg: -72°C). These monomers can be used in combination of two or more (preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3). Among these, for example, isoamyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, and n-lauryl methacrylate are suitable because they can be used as biomass-based monomers.

[0035] In the present invention, component (A) has such a specific structure, and is therefore able to exhibit excellent performance in terms of crack resistance, weather resistance, etc. The reason for such performance is not limited to the following, but it is thought that the coexistence of two or more alkyl groups with different chemical structures as described above in component (s) contributes to improved film-forming properties and imparted strength to the formed coating due to the action of those alkyl groups.

[0036] The number of carbon atoms in the alkyl group in component (s) is 4 or more, preferably 4 to 12, more preferably 4 to 10, and even more preferably 5 to 8. In the present invention, by using two or more types of component (s) having such carbon numbers, excellent performance can be exhibited in terms of crack resistance, weather resistance, etc.

[0037] The proportion of the (s) component can be preferably 20 to 80% by mass, more preferably 30 to 70% by mass, of the total amount of (meth)acrylic acid alkyl ester. Furthermore, of the two or more (s) components, the proportion of the (s) component with the highest proportion can be preferably 20 to 95% by mass, more preferably 25 to 85% by mass, and even more preferably 30 to 70% by mass, of the total amount of the (s) components. Such an embodiment of the (s) component is suitable in terms of room temperature curability, crack resistance, weather resistance, and the like.

[0038] In the present invention, the component (A) is preferably a (meth)acrylic acid alkyl ester (s1) (hereinafter also referred to as "component (s1)") in which at least one of the components (s) has a branched alkyl group having 5 or more carbon atoms. The number of carbon atoms in the alkyl group in component (s1) is preferably 5 or more, more preferably 5 to 12, even more preferably 5 to 10, and particularly preferably 5 to 8. In the present application, "branched alkyl group having 5 or more carbon atoms" refers to an alkyl group having a main chain and side chains, with the total number of carbon atoms in the main chain and side chains being 5 or more. Examples of component (s1) include isoamyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, and isodecyl methacrylate. It is desirable that component (A) contains at least one of such (s1) components as a monomer constituting the acrylic silicone resin, and more desirably contains two or more of such (s1) components. By including such component (s1) in component (A), it is possible to exhibit even more excellent performance in terms of crack resistance, blister resistance, weather resistance, etc. The reasons for exhibiting such performance are not limited to the following, but it is thought that the strength imparted to the coating after film formation due to the action of the branched alkyl group contributes to this.

[0039] The proportion of component (s1) in the total amount of component (s) is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30 to 100% by mass. Such an embodiment of component (s1) is advantageous in terms of improving physical properties such as crack resistance, blister resistance, and weather resistance.

[0040] In the present invention, the component (A) is preferably a (meth)acrylic acid alkyl ester (s11) (hereinafter also referred to as "component (s11)") in which at least one of the components (s) has a branched alkyl group having 5 or more carbon atoms, and the branched alkyl group has a methyl group. The number of carbon atoms in the alkyl group in the component (s11) is preferably 5 or more, more preferably 5 to 12, even more preferably 5 to 10, and particularly preferably 5 to 8. Examples of the component (s11) include isoamyl acrylate, 2-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, and isodecyl methacrylate. The component (A) preferably contains at least one such component (s11) as a monomer constituting the acrylic silicone resin, and more preferably contains two or more such components. By including such a component (s11), the component (A) can exhibit even more excellent performance in terms of crack resistance, blister resistance, weather resistance, and the like. In particular, component (s11) significantly contributes to water resistance, blister resistance, etc. in the early stages of film formation. The reason for such performance is not limited to the following, but it is thought that the effect of the branched alkyl group having a methyl group contributes to the early imparting of strength to the coating after film formation.

[0041] The proportion of component (s11) in the total amount of component (s) is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30 to 100% by mass. Such an embodiment of component (s11) is suitable for improving physical properties such as crack resistance, blister resistance, and weather resistance.

[0042] In the present invention, component (A) has a silica residual ratio of 1 to 40% by mass, preferably 5 to 35% by mass, and more preferably 10 to 30% by mass, based on the resin solids. When the silica residual ratio of component (A) is within the above range, the silicone component is contained in a large amount, and excellent weather resistance can be exhibited while ensuring physical properties such as crack resistance. If the silica residual ratio is below the above lower limit, it becomes difficult to obtain sufficient physical properties such as weather resistance, while if the silica residual ratio is above the above upper limit, crack resistance and other properties become insufficient, and weather resistance is also likely to be disadvantageous.

[0043] The silica remaining ratio is the ratio of silica (SiO ２ ) and remains as a mass ratio. Generally, alkoxysilanes react with water to undergo a hydrolysis reaction to form silanols, which then undergo condensation reactions between silanols or between silanols and alkoxy. When this reaction is carried to its ultimate state, silica (SiO ２ ) These reactions are expressed by the following general formula (reaction formula): RO(Si(OR) ２ O) ｎ R+(n+1)H ２ O → nSiO ２ +(2n+2)ROH The silica remaining ratio is calculated based on this reaction formula to represent the amount of remaining silica component.

[0044] In the component (A), the type and ratio of the alkoxysilane compound in the resin constituent components can be set so as to satisfy the above-mentioned silica residual ratio. As shown in the above general formula, n moles of Si corresponds to n moles of SiO ２Based on this, the residual silica ratio of component (A) can be set by the silicon atom ratio per molecule of the alkoxysilane compound used and its blending ratio. Examples of the alkoxysilane compound in component (A) include (1) an embodiment containing a silane coupling agent (i), (2) an embodiment containing alkoxysilanes (ii) and / or cyclic siloxanes (iii), and (3) an embodiment containing a silane coupling agent (i) and alkoxysilanes (ii) and / or cyclic siloxanes (iii). Of these, the above embodiments (2) or (3) (particularly embodiment (3)) are preferred in terms of increasing the proportion of the silicon component. In embodiment (3), the ratio of the silane coupling agent (i) in the total amount of the silane coupling agent (i), the alkoxysilanes (ii), and the cyclic siloxanes (iii) is preferably 1 to 30% by mass, more preferably 2 to 25% by mass.

[0045] The glass transition temperature (Tg) of component (A) is 30°C or lower, preferably -50°C to 25°C, more preferably -40°C to 20°C, and even more preferably -30°C to 15°C. Having the Tg of component (A) within the above range is preferable in terms of room temperature curing property, cracking resistance, weather resistance, stain resistance, and the like. If the Tg exceeds the above upper limit, it becomes difficult to obtain sufficient physical properties such as room temperature curing property and cracking resistance. In component (A), the types and ratios of monomers used as resin constituents can be set so as to satisfy the above glass transition temperature.

[0046] The average particle size of component (A) is preferably 300 nm or less, more preferably 20 to 250 nm, and even more preferably 50 to 200 nm. The average particle size referred to here is a value measured by dynamic light scattering.

[0047] The component (A) in the present invention can be an embodiment in which multiple resin phases are mixed, as long as the Tg is 30°C or less. For example, the component (A) may include a hard resin phase having a Tg of 15°C or more and a soft resin phase having a Tg of 0°C or less, and the Tg of the entire resin constituting the component (A) may be 30°C or less. The hard resin phase can be obtained by polymerizing one or more (preferably two or more) of the above-mentioned monomers so that the Tg is 15°C or more (more preferably 30°C or more, even more preferably 50°C or more). The hard resin phase desirably contains, as a resin constituent, a (meth)acrylic acid alkyl ester having a homopolymer Tg of 15°C or more (more preferably 30°C or more, even more preferably 50°C or more).

[0048] The soft resin phase can be obtained by polymerizing two or more of the above-mentioned monomers so that the Tg is 0° C. or lower (more preferably −15° C. or lower, and even more preferably −30° C. or lower). The soft resin phase desirably contains, as a resin constituent, a (meth)acrylic acid alkyl ester having a homopolymer Tg of 0° C. or lower (more preferably −15° C. or lower, and even more preferably −30° C. or lower).

[0049] The ratio of the hard resin phase to the soft resin phase in component (A) may be set within a range in which the Tg of the entire resin is 30°C or less. The ratio of the hard resin phase is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, based on the resin solid content of component (A). The ratio of the soft resin phase is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, based on the resin solid content of component (A). Such a mass ratio makes it easier to achieve the effects of the present invention described above more stably. Note that component (A) may, for example, have an embodiment containing two or more hard resin phases with different Tg's, or an embodiment containing two or more soft resin phases with different Tg's. Furthermore, the component (A) may have an embodiment that includes a resin phase different from the hard resin phase and soft resin phase described above (for example, a resin phase having a Tg intermediate between the hard resin phase and the soft resin phase (Tg greater than 0°C and less than 15°C)).

[0050] When component (A) contains a hard resin phase and a soft resin phase, as long as it satisfies the above-mentioned conditions, the hard resin phase and the soft resin phase may coexist in the same emulsion particle, or may exist in separate emulsion particles.Specifically, for example, it can be (I) a multilayer structure type acrylic silicone resin emulsion that contains a hard resin phase and a soft resin phase in the same emulsion particle, (II) a mixture of an acrylic silicone resin emulsion that contains a hard resin phase and an acrylic silicone resin emulsion that contains a soft resin phase, etc.

[0051] <Component (B)> The pigment (B) (hereinafter also referred to as "component (B)") is a component that contributes to at least one of color development, hiding power, gloss, aesthetics, strength, etc. As the component (B), for example, a color pigment (B1) (hereinafter also referred to as "component (B1)"), an extender pigment (B2) (hereinafter also referred to as "component (B2)"), etc. can be used.

[0052] The content of component (B) is preferably 5 to 650 parts by mass, more preferably 10 to 500 parts by mass, even more preferably 15 to 300 parts by mass, and particularly preferably 20 to 200 parts by mass, per 100 parts by mass of the solid content of component (A).

[0053] Examples of the color pigment (B1) include titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide, copper-manganese-chromium composite oxide, copper-magnesium composite oxide, bismuth-manganese composite oxide, red iron oxide, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, fast yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine blue, Prussian blue, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, aluminum pigments, and pearl pigments. These can be used alone or in combination of two or more.

[0054] The average particle size of the pigment (B1) is preferably 2 μm or less, and more preferably 0.01 to 1 μm. The average particle size of the pigment (B) is a value measured using a laser diffraction particle size distribution analyzer.

[0055] The content of component (B1) is preferably 250 parts by mass or less, more preferably 5 to 200 parts by mass, and even more preferably 10 to 150 parts by mass, per 100 parts by mass of the solid content of component (A). A content of component (B1) within this range is suitable in terms of the color development, hiding power, aesthetic appearance, etc. of the coating film, and is also advantageous in terms of manifesting the effects of the present invention.

[0056] Examples of the extender pigment (B2) include heavy calcium carbonate, light calcium carbonate, kaolin, clay, aluminum silicate, calcined clay, calcined kaolin, china clay, diatomaceous earth, hydrous finely powdered silicic acid, silica gel, zeolite, sodium sulfate, allophane, talc, mica, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate, silica powder, resin beads, aluminum hydroxide, porous calcium carbonate, siliceous shale, vermiculite, perlite, Oya stone powder, activated clay, activated carbon, shirasu balloon, etc. These can be used alone or in combination of two or more.

[0057] The average particle size of the extender pigment is preferably 0.1 to 100 μm, more preferably 0.3 to 50 μm.

[0058] The content of component (B2) is preferably 400 parts by mass or less, more preferably 10 to 350 parts by mass, even more preferably 15 to 300 parts by mass, and particularly preferably 20 to 200 parts by mass, per 100 parts by mass of the solid content of component (A). A content of component (B2) within this range is favorable in terms of the strength and aesthetics of the coating film, and is also advantageous in terms of achieving the effects of the present invention. Furthermore, the gloss of the coating can be set to a low gloss (e.g., semi-gloss, 30% gloss, matte, etc.).

[0059] <Component (C)> In the aqueous coating material of the present invention, a crosslinking agent (C) (hereinafter also referred to as "component (C)") can be mixed together with component (A). In this case, an acrylic silicone resin emulsion having a reactive functional group can be used as component (A), and a crosslinking agent having a functional group capable of reacting with the reactive functional group can be used as component (C). When such a component is present, in addition to the action of component (s) described above, the crosslinking reaction between component (A) and the crosslinking agent is thought to impart strength to the coating during and after film formation, thereby improving physical properties such as crack resistance, blister resistance, and weather resistance.

[0060] Suitable examples of the component (C) include water-soluble crosslinking agents, water-dispersible crosslinking agents, and self-emulsifying crosslinking agents.

[0061] In components (A) and (C), reactive functional groups usable in such crosslinking reactions include, for example, one or more selected from carboxyl groups, carbodiimide groups, epoxy groups, aziridine groups, oxazoline groups, hydroxyl groups, isocyanate groups, carbonyl groups, hydrazide groups, epoxy groups, amino groups, and alkoxysilyl groups. In components (A) and (C), such reactive functional groups may be used in combination. Examples of combinations of reactive functional groups include combinations of carboxyl groups and carbodiimide groups, carboxyl groups and epoxy groups, carboxyl groups and oxazoline groups, carboxyl groups and aziridine groups, hydroxyl groups and isocyanate groups, carbonyl groups and hydrazide groups, epoxy groups and amino groups, and alkoxysilyl groups. One or more of these combinations may be used. Suitable reactive functional groups in component (A) include, for example, carboxyl groups, carbonyl groups, and alkoxysilyl groups.

[0062] Specifically, when component (A) has a carboxyl group, component (C) can be, for example, a compound having one or more reactive functional groups selected from a carbodiimide group, an epoxy group, an oxazoline group, etc. Among these, examples of crosslinking agents having a carbodiimide group include those described in JP-A Nos. 10-60272, 10-316930, 11-60667, 2000-7642, 2000-119539, 2000-319351, 2013-112755, 2016-196612, 2016-196613, WO2017 / 6950, and the like. Examples of crosslinking agents having an epoxy group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyhydroxyalkane polyglycidyl ether, and sorbitol polyglycidyl ether. Examples of crosslinking agents having an oxazoline group include resins obtained by copolymerizing a polymerizable oxazoline compound, such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, or 2-isopropenyl-2-oxazoline, with a monomer copolymerizable with the compound. These compounds can be used alone or in combination of two or more.

[0063] The component (A) having a carboxyl group can be obtained by using a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, or maleic acid as a resin constituent.

[0064] When component (A) has a carbonyl group, for example, a compound having a hydrazide group can be used as component (C). Examples of crosslinking agents having a hydrazide group include malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and maleic acid dihydrazide. These can be used alone or in combination of two or more.

[0065] The component (A) having a carbonyl group can be obtained by using a carbonyl group-containing monomer such as acrolein or diacetone acrylamide as a resin constituent.

[0066] When component (A) has an alkoxysilyl group, for example, a compound having an alkoxysilyl group can be used as component (C). Examples of crosslinking agents having an alkoxysilyl group include the silane coupling agents and alkoxysilane compounds such as alkoxysilanes described above for component (A). These can be used alone or in combination of two or more.

[0067] The proportion of component (C) is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, calculated as solids, per 100 parts by mass of the resin solids of component (A).Such a proportion can sufficiently improve crack resistance, blister resistance, weather resistance, etc.

[0068] In addition to the above-mentioned components, various additives can also be mixed into the aqueous coating material of the present invention. Examples of such additives include pigment dispersants, viscosity modifiers, leveling agents, coupling agents, wetting agents, film-forming aids, plasticizers, antifreeze agents, pH adjusters, preservatives, antifungal agents, anti-algae agents, antibacterial agents, antifoaming agents, adsorbents, deodorizers, UV absorbers, light stabilizers, hydrophilizing agents, antioxidants, catalysts, solvents, and water. These can be used alone or in combination as needed.

[0069] Of these, the pigment dispersant is a component that contributes to stabilizing the dispersion of the component (B) and enabling the component (B) to exhibit its performance.

[0070] As the pigment dispersant, one or more commercially available or known dispersants can be used. For example, dispersants having a resin skeleton such as a styrene-maleic acid copolymer resin, a polyurethane resin, a polyester resin, or an acrylic resin can be used.

[0071] The pigment dispersant in the aqueous coating material of the present invention is preferably a pigment dispersant having an acid group and / or a basic group. Such a pigment dispersant can improve the dispersion stability of component (B). In addition, in aqueous coating materials that use an acrylic silicone resin emulsion containing a large amount of silicone as a binder, the pigment dispersant generally promotes excessive reaction of the silicone component, which can lead to problems such as cracking of the coating or insufficient weather resistance of the coating. However, in the present invention, even when such a pigment dispersant is used, by adopting component (A) having the above-mentioned specific resin structure, excellent performance can be achieved in terms of crack resistance, weather resistance, etc.

[0072] Examples of acid groups include carboxy groups, sulfonic acid groups, and phosphate groups. Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium salt groups. Component (C) can have one or more of these acid groups or basic groups. Suitable examples of component (C) include polycarboxylic acid-type dispersants such as polyacrylic acid, polymethacrylic acid, and styrene-maleic acid copolymer resins; sulfonic acid-type dispersants such as lignin sulfonic acid and naphthalene sulfonic acid; phosphate-type dispersants such as phosphate ester compounds; and polymer dispersants having an acid value and / or amine value.

[0073] The content of component (C) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, calculated as solid content, per 100 parts by mass of the solid content of component (A).

[0074] <Component (D)> In addition to the above components, the aqueous coating material of the present invention can be used by mixing an ether or ester solvent (D) (hereinafter also referred to as "component (D)"). Of the components (D), ether solvents are solvents having an ether bond in the molecule, and ester solvents are solvents having an ester bond in the molecule. In the present invention, the component (D) is an ether or ester solvent having a solubility in water of 0.5 to 50 g / 100 gH ２ The compound (D1) may contain an ether or ester solvent (D1) (hereinafter also referred to as "component (D1)") of the formula (D1) of O, and the solubility in water may be 0.5 to 50 g / 100 gH ２ The solubility of O in ether solvent and / or water is 0.5 to 50 g / 100 gH ２ An ester solvent of formula O can be used. By including such component (D1), the aqueous coating material of the present invention can exhibit better performance in terms of crack resistance, weather resistance, etc. When the aqueous coating material is a glossy type, gloss, etc. can also be improved. In the present invention, the solubility in water refers to the maximum mass (g) that can be dissolved in 100 g of water. The measurement temperature is 20°C.

[0075] As the component (D1), an ether solvent or an ester solvent having a water solubility within the above range can be used. A specific example of the compound is ethylene glycol monohexyl ether (water solubility 0.99 g / 100 gH ２ 0, boiling point 208°C), propylene glycol phenyl ether (solubility in water 1g / 100gH ２ 0, boiling point 243°C), ethylene glycol monobutyl ether acetate (solubility in water 1.1 g / 100 gH ２ 0, boiling point 188°C), diethylene glycol monohexyl ether (solubility in water 1.7 g / 100 gH ２ 0, boiling point 258°C), ethylene glycol monophenyl ether (solubility in water 2.6 g / 100 gH ２ 0, boiling point 245°C), tripropylene glycol monobutyl ether (solubility in water 3g / 100gH ２ 0, boiling point 274°C), diethylene glycol monophenyl ether (solubility in water 3.4 g / 100 gH ２0, boiling point 283°C), dipropylene glycol monobutyl ether (solubility in water 5g / 100gH ２ 0, boiling point 229°C), propylene glycol monobutyl ether (solubility in water 6g / 100gH ２ 0, boiling point 170°C), diethylene glycol monobutyl ether acetate (solubility in water 6.5 g / 100 gH ２ 0, boiling point 247°C), propylene glycol diacetate (solubility in water 8g / 100gH ２ 0, boiling point 161°C), propylene glycol monomethyl ether acetate (solubility in water 16g / 100gH ２ 0, boiling point 146°C), dipropylene glycol monopropyl ether (solubility in water 19 g / 100 gH ２ 0, boiling point 212°C), dipropylene glycol monomethyl ether acetate (solubility in water 19 g / 100 gH ２ 0, boiling point 209°C), ethylene glycol diethyl ether (solubility in water 20g / 100gH ２ 0, boiling point 121°C), ethylene glycol monoethyl ether acetate (solubility in water 23g / 100gH ２ These may be used alone or in combination of two or more.

[0076] The solubility of component (D1) in water is 0.5 to 50 g / 100 gH ２ O, preferably 0.8 to 25 g / 100 gH ２ 0, more preferably 1 to 10 g / 100 gH ２0. Furthermore, the boiling point of component (D1) is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 220°C or higher. Component (D1) satisfying these physical property values ​​is suitable in terms of realizing the effects of the present invention. The reasons why component (D1) achieves the effects of the present invention are not limited to the following, but are presumed to be due to the fact that component (D1) has intermediate properties between hydrophobicity and hydrophilicity, and these properties contribute to its increased affinity with the acrylic component and the silicone component. Component (D1) preferably has a hydrophobic group with 4 or more carbon atoms, more preferably a hydrophobic group with 6 or more carbon atoms, and particularly preferably has a phenyl group.

[0077] The content of component (D1) is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, even more preferably 3 to 25 parts by mass, and particularly preferably 4 to 20 parts by mass, per 100 parts by mass of the solid content of component (A). When the content of component (D1) is within this range, even more excellent performance can be exhibited in terms of room temperature curability, crack resistance, weather resistance, etc.

[0078] In the present invention, the component (D) may contain two or more types of component (D1). For example, the difference in solubility in water may be preferably 0.5 to 15 g / 100 g H ２ O (more preferably 0.8 to 10 g / 100 gH ２ 0, more preferably 1 to 5 g / 100 gH ２ In the present invention, an embodiment containing two kinds of components (D1) each having the formula (D1) or (D2) can be adopted. Such an embodiment is preferable in terms of improving the gloss effect of the present invention.

[0079] In the present invention, the component (D) is, in addition to the component (D1) described above, a compound having a solubility in water of 50 g / 100 gH ２ The component (D2) may contain an ether or ester solvent (D2) having a solubility in water of 50 g / 100 g H ２ Ether solvents with a solubility of more than 0 and / or water of 50 g / 100 g H ２Ester solvents having a molecular weight of more than 0 can be used, and specific examples of such compounds include ethylene glycol monomethyl ether (solubility in water: ∞, boiling point: 125°C), ethylene glycol monoethyl ether (solubility in water: ∞, boiling point: 135°C), ethylene glycol monopropyl ether (solubility in water: ∞, boiling point: 150°C), ethylene glycol monoisopropyl ether (solubility in water: ∞, boiling point: 143°C), ethylene glycol monobutyl ether (solubility in water: ∞, boiling point: 171°C), and ethylene glycol monoisobutyl ether (solubility in water: ∞, boiling point: 180°C). ∞, boiling point 161°C), ethylene glycol monotertiary butyl ether (solubility in water ∞, boiling point 153°C), ethylene glycol monomethyl ether acetate (solubility in water ∞, boiling point 145°C), ethylene glycol monoethyl ether acetate (solubility in water ∞, boiling point 156°C), ethylene glycol dimethyl ether (solubility in water ∞, boiling point 85°C), diethylene glycol monomethyl ether (solubility in water ∞, boiling point 194°C), diethylene glycol monoethyl ether (solubility in water ∞, boiling point 202°C), di Ethylene glycol monobutyl ether (solubility in water: ∞, boiling point: 230°C), diethylene glycol monoisobutyl ether (solubility in water: ∞, boiling point: 220°C), diethylene glycol monoethyl ether acetate (solubility in water: ∞, boiling point: 217°C), diethylene glycol dimethyl ether (solubility in water: ∞, boiling point: 162°C), diethylene glycol diethyl ether (solubility in water: ∞, boiling point: 189°C), triethylene glycol monomethyl ether (solubility in water: ∞, boiling point: 249°C), triethylene glycol monobutyl Ether (solubility in water: ∞, boiling point: 271°C), triethylene glycol monoethyl ether (solubility in water: ∞, boiling point: 255°C), propylene glycol monomethyl ether (solubility in water: ∞, boiling point: 120°C), propylene glycol monoethyl ether (solubility in water: ∞, boiling point: 133°C), propylene glycol monopropyl ether (solubility in water: ∞, boiling point: 150°C), dipropylene glycol monomethyl ether (solubility in water: ∞, boiling point: 190°C), dipropylene glycol dimethyl ether (solubility in water: 53g / 100gH ２0, boiling point 175°C), tripropylene glycol monomethyl ether (solubility in water ∞, boiling point 242°C), butylene glycol monomethyl ether (solubility in water ∞, boiling point 161°C), etc. These can be used alone or in combination of two or more.

[0080] The solubility of component (D2) in water is 50 g / 100 gH ２ The boiling point of component (D2) is preferably greater than 0, and is preferably ∞. Component (D2) also preferably has a boiling point of 150° C. or higher. Component (D2) that satisfies these physical property values ​​is suitable for improving the effects of the present invention.

[0081] In the present invention, the component (D) is, in addition to the component (D1) described above, a compound having a solubility in water of 0.5 g / 100 gH ２ The component (D3) may contain an ether or ester solvent (D3) having a solubility in water of less than 0.5 g / 100 g H ２ Solubility in ether solvents less than 0.0 and / or water is 0.5 g / 100 gH ２ Ester solvents having a solubility of less than 0 can be used, and specific examples of such compounds include diethylene glycol dibutyl ether (solubility in water: 0.3 g / 100 gH ２ 0, boiling point 255°C), diethylene glycol mono 2-ethylhexyl ether (solubility in water 0.3g / 100gH ２ 0, boiling point 272°C), ethylene glycol mono 2-ethylhexyl ether (solubility in water 0.2g / 100gH ２ 0, boiling point 229°C), ethylene glycol dibutyl ether (solubility in water 0.2 g / 100 gH ２ 0, boiling point 203°C), 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (solubility in water 0.09 g / 100 gH ２ 0, boiling point 255°C), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (solubility in water 0.04 g / 100 gH ２ These may be used alone or in combination of two or more.

[0082] The solubility of component (D3) in water is 0.5 g / 100 gH ２0, preferably less than 0.4 g / 100 gH ２ 0 or less, more preferably 0.01 to 0.4 g / 100 gH ２ The boiling point of component (D3) is preferably 200° C. or higher, and more preferably 220° C. or higher. A component (D3) that satisfies these physical property values ​​is suitable for improving the effects of the present invention.

[0083] In the present invention, the component (D) can be an embodiment containing the component (D1), an embodiment containing the component (D1) and the component (D2), an embodiment containing the component (D1) and the component (D3), an embodiment containing the component (D1), the component (D2), and the component (D3), etc. In each of these embodiments, two or more types of the component (D1) can be included.

[0084] When component (D2) is included as component (D), the amount of component (D2) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the solid content of component (A). In this case, the mass ratio of components (D1) to (D2) ((D1):(D2)) is preferably 95:5 to 10:90, more preferably 90:10 to 10:90, and even more preferably 80:20 to 20:80. Furthermore, when component (D3) is included as component (D), the amount of component (D3) is preferably 1 to 30 parts by mass, more preferably 2 to 30 parts by mass, per 100 parts by mass of the solid content of component (A). In this case, the mass ratio of component (D1) to component (D3) ((D1):(D3)) is preferably 95:5 to 5:95, more preferably 90:10 to 10:90, and even more preferably 80:20 to 20:80. Such an embodiment is suitable in terms of improving the effects of the present invention.

[0085] In addition to the above-mentioned components, the aqueous coating material of the present invention can also be mixed with resin emulsions other than component (A), water-soluble resins, etc. Examples of resin emulsions other than component (A) include acrylic resin emulsions, urethane resin emulsions, fluororesin emulsions, and epoxy resin emulsions. Acrylic silicone resin emulsions other than component (A) can also be used. Examples of water-soluble resins include polyurethane resins, polyacrylic acid resins, polyvinyl alcohol, and polyvinylpyrrolidone. These can be used alone or in combination as needed. Of these, resin emulsions such as urethane resin emulsions and fluororesin emulsions are preferred in terms of improving weather resistance, etc.

[0086] The aqueous coating material of the present invention can be produced by uniformly mixing the above-mentioned components (A), (B), and, if necessary, (C), various additives, etc., in a conventional manner.

[0087] [Method of Forming Coating] The aqueous coating material of the present invention is preferably applicable to surface finishing of coating surfaces of buildings, civil engineering structures, etc. Examples of surfaces to be coated in the present invention include exterior surfaces (e.g., exterior walls, roofs, etc.) of buildings, civil engineering structures, etc.

[0088] Examples of substrates that constitute the coating surface include concrete, mortar, porcelain tile, fiber-mixed cement board, cement calcium silicate board, slag cement perlite board, cement board, ALC board, siding board, gypsum board, plywood, extrusion molded board, steel plate, and plastic plate. When the coating surface is composed of multiple plate-shaped substrates, the joints between the plate-shaped substrates may be filled with a joint material such as a sealant or a dry joint material. The surfaces of these substrates may have been subjected to some kind of surface treatment (e.g., treatment with putty, sealer, surfacer, filler, etc.), or may already have a coating film formed thereon (e.g., a substrate with an existing coating film).

[0089] The surface to be coated may have an existing coating film, which may be formed, for example, by one or more coating agents.

[0090] As the coating agent, various types can be used, such as colored or uncolored, opaque or transparent, and examples include those containing one or more resins selected from vinyl acetate resin, alkyd resin, epoxy resin, acrylic resin, urethane resin, acrylic silicone resin, silicone resin, fluororesin, etc. The existing coating film is a coating film of one layer or two or more layers, and may be, for example, an elastic type, a hard type, etc.

[0091] The aqueous coating material of the present invention can be applied directly to such a surface, or can be applied after treating the surface by applying a primer or a surface preparation material (e.g., sealer, primer, surfacer, filler, putty, etc.) to the surface.

[0092] The aqueous coating material of the present invention can also be applied after forming an elastic coating by applying an elastic coating material to the surface to be coated.

[0093] Examples of elastic coating materials include those architectural finishing coating materials specified in JIS A6909:2021 that exhibit flexibility or waterproofing, architectural coating membrane waterproofing materials specified in JIS A6021:2022, etc. Specific examples of elastic coating materials include flexible exterior silicate-based thin-applied finishing coating materials (flexible exterior thin coating material Si), flexible exterior synthetic resin emulsion-based thin-applied finishing coating materials (flexible exterior thin coating material E), waterproof exterior synthetic resin emulsion-based thin-applied finishing coating materials (waterproof exterior thin coating material E), flexible polymer cement-based multilayer finishing coating materials (flexible multilayer coating material CE), waterproof polymer cement-based multilayer finishing coating materials (waterproof multilayer coating material CE), waterproof synthetic resin emulsion-based multilayer finishing coating materials (waterproof multilayer coating material E), and waterproof reactive hardening synthetic resin Examples of suitable finish coating materials include emulsion-based multi-layer coating materials (waterproof multi-layer coating material RE), waterproof synthetic resin solution-based multi-layer coating materials (waterproof multi-layer coating material RS), flexible synthetic resin emulsion-based repair finishing coating materials (flexible repair coating material E), flexible reaction-hardening synthetic resin emulsion-based repair finishing coating materials (flexible repair coating material RE), flexible polymer cement-based repair finishing coating materials (flexible repair coating material CE), acrylic rubber-based waterproof coating materials for roofs, urethane rubber-based waterproof coating materials for roofs, acrylic rubber-based waterproof coating materials for exterior walls, and urethane rubber-based exterior wall coating prevention materials.

[0094] The method for applying the elastic covering material is not particularly limited, and a method suitable for each material can be adopted. Examples of application tools that can be used include a spray, roller, trowel, and brush.

[0095] The amount of the elastic covering material applied is preferably 0.2 to 5 kg / m ２ , more preferably 0.3 to 4 kg / m ２ When applying, the elastic coating material can be diluted as needed.

[0096] Drying after application of the elastic coating material may be carried out at room temperature (5 to 40°C), or may be carried out with heating if necessary.

[0097] The elastic coating material can be applied directly to the surface to be coated, or can be applied after the surface has been treated with a primer or a surface preparation material (e.g., sealer, primer, surfacer, filler, putty, etc.).

[0098] It is desirable that the elastic coating (coating of the elastic coating material) be a single coating that forms a coating with an elongation percentage of 20% or more at -10°C. Such an elastic coating can exhibit advantageous effects, for example, in terms of its ability to follow the displacement of the coated surface and preventing the penetration of water, carbon dioxide, etc. into the coated surface. In the present invention, the elongation percentage at -10°C is a value measured according to the method specified in the "Elongation Test" of JIS A6909:2021. For the single coating of the elastic coating, a dry film thickness of 1 mm is subjected to the elongation test.

[0099] When applying the aqueous coating material of the present invention, various application tools can be used, such as a sprayer, roller, brush, etc. Among these, as the roller, for example, a fibrous roller with short, medium, or long pile (wool roller, etc.) can be used.

[0100] The amount of water to be mixed may be appropriately determined taking into consideration the type of coating equipment, the condition of the surface to be coated, the temperature during coating, etc., but is preferably 0 to 20% by mass of the total aqueous coating material.

[0101] The amount of the aqueous coating material of the present invention to be applied is preferably 0.05 to 1 kg / m ２ , more preferably 0.1 to 0.8 kg / m ２ , more preferably 0.15 to 0.6 kg / m ２ By applying the aqueous coating material in such an amount, it is possible to form a coating film that is sufficiently excellent in appearance, weather resistance, etc.

[0102] The aqueous coating material of the present invention can be used as a room-temperature curing aqueous coating material. Therefore, the application of the aqueous coating material of the present invention and drying after application can be carried out in an environment of room temperature (5 to 40°C). However, heating can be used if necessary. The drying time is preferably about 0.5 to 4 hours at room temperature. The number of coats can be one or two or more (preferably one to two). When two or more coats are applied, it is desirable that the total amount applied be within the above range.

[0103] The aqueous coating material of the present invention can be preferably used as a topcoat material.

[0104] The present invention is a coating formation method in which two specific topcoat materials (a first topcoat material and a second topcoat material) are applied (painted) to a surface to be coated in order to form a topcoat material coating.

[0105] <Topcoat material> In the present invention, the first topcoat material and the second topcoat material are applied to the surface to be coated in order to form a coating. Before applying the first topcoat material, as described above, one or more selected from the primer material, the base adjustment coating material, the elastic coating material, etc. can also be applied.

[0106] In the present invention, the first topcoat material is used to form a coating with an elongation rate of 20% or more at -10 ° C., and the second topcoat material can be the aqueous coating material of the present invention described above. In the present invention, by forming a coating by applying such a first topcoat material and a second topcoat material in sequence, it is possible to demonstrate excellent performance in terms of crack resistance, weather resistance, etc.

[0107] In the present invention, as the second topcoat material, in addition to the above conditions, a coating is used that forms an elongation rate at -10 ° C. smaller than the elongation rate at -10 ° C. of the first topcoat material.

[0108] The elongation rate of the second topcoat material at -10 ° C is preferably 30% or less, more preferably 1 to 30%, even more preferably 5 to 28%, and particularly preferably 10 to 26%. In the present invention, by using such a second topcoat material, it is possible to form a coating that exhibits excellent performance in terms of blister resistance, contamination resistance, etc. The elongation rate of the second topcoat material at -10 ° C is a value measured according to the method specified in the "elongation test" of JIS A6909:2021. The test specimen used in the elongation test is a waterproof multi-layer coating material E main material with a dry film thickness of 1 mm (its single coating meets the elongation rate provisions at -10 ° C specified in JIS A6909:2021), on the surface of which a second topcoat coating is coated and laminated with a dry film thickness of 80 μm.

[0109] The elongation rate of the second topcoat material at -10 ° C. can be adjusted by the Tg of the (A) component in the second topcoat material, the content of the (B) component, etc. The Tg of the (A) component is 30 ° C. or less, preferably -50 ° C. to 25 ° C., more preferably -40 ° C. to 20 ° C., and even more preferably -30 ° C. to 15 ° C. The content of the (B) component is preferably 5 to 500 parts by weight, more preferably 10 to 300 parts by weight, and even more preferably 10 to 200 parts by weight, relative to 100 parts by weight of the solid content of the (A) component.

[0110] <First topcoat material> In the present invention, the first topcoat material is one that forms a coating with an elongation rate of 20% or more at -10 ° C (preferably 20 to 50%, more preferably 22 to 40%). The elongation rate of this first topcoat material at -10 ° C is greater than the elongation rate of the second topcoat material at -10 ° C. This allows for the formation of a coating that exhibits excellent performance in terms of crack resistance, weather resistance, etc. The elongation rate of the first topcoat material at -10 ° C is a value measured according to the method specified in the "elongation test" of JIS A6909:2021. The test specimen used in the elongation test is a waterproof multi-layer coating material E main material with a dry film thickness of 1 mm (its single coating meets the elongation rate regulations at -10 ° C specified in JIS A6909:2021), with a first topcoat coating coated and laminated to a dry film thickness of 80 μm.

[0111] The first topcoat material can be a resin emulsion and a pigment. Such a first topcoat material can form a colored coating by room temperature curing. Among these, examples of resin emulsions include vinyl acetate resin emulsion, vinyl chloride resin emulsion, epoxy resin emulsion, alkyd resin emulsion, urethane resin emulsion, acrylic resin emulsion, acrylic silicone resin emulsion, fluororesin emulsion, etc., or a composite system thereof. These can be used alone or in combination of two or more types.

[0112] As the resin emulsion in the first topcoat material, an embodiment containing one or more selected from acrylic resin emulsion and acrylic silicone resin emulsion is suitable. As the acrylic resin emulsion, one containing (meth) acrylic acid alkyl ester as a resin constituent can be used. As the acrylic silicone resin emulsion, one containing (meth) acrylic acid alkyl ester and alkoxysilane compound as a resin constituent can be used. As the (meth) acrylic acid alkyl ester and alkoxysilane compound, the same as the second topcoat material (above-mentioned aqueous coating material of the present invention) can be used.

[0113] The resin emulsion in the first topcoat material, as a monomer constituting the resin, has a homopolymer Tg of 0 ° C or less (preferably -15 ° C or less, more preferably -30 ° C or less), and can contain two or more (meth)acrylic acid alkyl esters (s) having an alkyl group with 4 or more carbon atoms. In the present invention, by providing the resin emulsion in the first topcoat material with such a specific configuration, it is possible to demonstrate even better performance in terms of crack resistance, blister resistance, weather resistance, etc. The reasons for such performance are not limited to the following, but it is thought that the coexistence of two or more alkyl groups with different chemical structures, based on the action of those alkyl groups, enhances film-forming properties and imparts strength to the film after film formation, and further, the presence of alkyl groups similar to the second topcoat material contributes to enhanced adhesion, etc. As the (s) component, the same as that detailed in the second topcoat material can be used.

[0114] In addition, the resin emulsion in the first topcoat material, as a monomer constituting the resin, has a homopolymer Tg of 0 ° C or less (preferably -15 ° C or less, more preferably -30 ° C or less), and can also be an embodiment containing a (meth) acrylic acid alkyl ester (s1) having a branched alkyl group with 5 or more carbon atoms. As the (s1) component, the same as that detailed in the second topcoat material can be used. The resin emulsion in the first topcoat material preferably contains at least one (s1) component as a monomer constituting the resin, and more preferably contains two or more types, thereby enabling it to exhibit even more excellent performance in terms of crack resistance, blister resistance, weather resistance, etc. The reasons for such performance are not limited to the following, but are thought to be due to the strength imparted to the coating after film formation based on the action of the branched alkyl group, and the presence of an alkyl group similar to that of the second topcoat material, which contributes to increased adhesion.

[0115] In the resin emulsion in the first topcoat material, it is desirable that the branched alkyl group of the (s1) component contains a methyl group. Examples of (s1) components (hereinafter also referred to as "(s11) components") in which the branched alkyl group contains a methyl group include, for example, isoamyl acrylate, 2-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, isodecyl methacrylate, etc. The resin emulsion in the first topcoat material desirably contains at least one such (s11) component as a monomer constituting the resin, and more desirably contains two or more types. By including such an (s11) component in the resin emulsion in the first topcoat material, it is possible to demonstrate even more excellent performance in terms of crack resistance, blister resistance, weather resistance, etc. The reasons for such performance are not limited to the following, but it is thought that this is due to the fact that the strength is imparted early to the coating after film formation based on the action of the branched alkyl group having a methyl group.

[0116] The resin emulsion in the first topcoat material has a silica residual ratio in the resin solid content of preferably 0.5 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 4 to 25% by mass. This makes it more suitable in terms of crack resistance, weather resistance, etc.

[0117] The resin emulsion in the first topcoat material has a glass transition temperature (Tg) of preferably 30 ° C or less, more preferably -50 ° C to 30 ° C, and even more preferably -40 ° C to 25 ° C, which makes it more suitable in terms of room temperature curing and crack resistance. Specifically, the Tg of the acrylic resin emulsion is preferably -40 ° C to 30 ° C, more preferably -30 ° C to 25 ° C, and even more preferably -20 ° C to 20 ° C. The Tg of the acrylic silicone resin emulsion is preferably -50 to 20 ° C, more preferably -40 ° C to 10 ° C, and even more preferably -30 ° C to 5 ° C. In the resin emulsion in the first topcoat material, the type and ratio of monomers used as resin constituents can be set to meet the above glass transition temperature.

[0118] The average particle size of the resin emulsion in the first topcoat material is preferably 300 nm or less, more preferably 20 to 250 nm, and even more preferably 50 to 200 nm. The average particle size referred to here is a value measured by dynamic light scattering.

[0119] In the first topcoat material, in addition to the resin emulsion, it can contain pigment (B), which is an essential raw material of the aqueous coating material of the present invention. Pigment (B) is a component that contributes to at least one of color development, hiding power, strength, etc., and, as with the second topcoat material, for example, color pigment (B1), extender pigment (B2), etc. can be used.

[0120] The content of the (B) component is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, and even more preferably 20 to 100 parts by weight, per 100 parts by weight of the solids content of the resin emulsion. By mixing the (B) component, the color tone of the first topcoat material can also be set to an approximate color of the second topcoat material. As the coloring pigment (B1) and the extender pigment (B2), the same ones as those used in the second topcoat material (the aqueous coating material of the present invention described above) can be used.

[0121] The average particle size of component (B1) is preferably 2 μm or less, more preferably 0.01 to 1 μm. The content of component (B1) is preferably 250 parts by mass or less, more preferably 5 to 200 parts by mass, and even more preferably 10 to 100 parts by mass, per 100 parts by mass of the solids content of the resin emulsion. A content of component (B1) within this range is more suitable in terms of the color development and hiding power of the coating.

[0122] The average particle size of component (B2) is preferably 0.1 to 100 μm, more preferably 0.3 to 50 μm. The content of component (B2) is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less, per 100 parts by mass of the solid content of the resin emulsion. An embodiment that does not contain component (B2) is also suitable.

[0123] In the first topcoat material, a crosslinking agent (C) can be mixed with the resin emulsion. In this case, the resin emulsion can be a resin emulsion having a reactive functional group, and the (C) component can be a crosslinking agent capable of reacting with the reactive functional group. When such a component is present, the crosslinking reaction between the resin emulsion and the crosslinking agent provides strength to the coating during or after film formation, and can further improve physical properties such as crack resistance, blister resistance, and weather resistance.

[0124] As the (C) component, the same material as the second topcoat material (the aqueous coating material of the present invention described above) can be used.

[0125] The proportion of component (C) is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, calculated as solids, per 100 parts by mass of the resin solids of the resin emulsion. Such a proportion can sufficiently improve crack resistance, blister resistance, weather resistance, etc.

[0126] In the first topcoat material, in addition to the above-mentioned components, various additives can also be mixed. Such additives include, for example, pigment dispersants, viscosity adjusters, leveling agents, coupling agents, wetting agents, film-forming aids, plasticizers, antifreeze agents, pH adjusters, preservatives, antifungal agents, anti-algae agents, antibacterial agents, antifoaming agents, adsorbents, deodorizers, ultraviolet absorbers, light stabilizers, hydrophilizing agents, antioxidants, catalysts, solvents, and water. These can be used alone or in combination as needed. Of these, the pigment dispersant can be the same as that used in the second topcoat material (the aqueous coating material of the present invention described above), and its content is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, in terms of solids, per 100 parts by weight of the solids of the resin emulsion. In addition, the first topcoat material can also be mixed with an ether or ester solvent (D) (one or more selected from the group consisting of (D1) component, (D2) component, (D3) component, etc.) as in the second topcoat material.

[0127] In the first topcoat material, in addition to the above-mentioned components, water-soluble resins can also be mixed. Examples of water-soluble resins include polyurethane resins, polyacrylic acid resins, polyvinyl alcohol, polyvinylpyrrolidone, etc. These can be used alone or in combination as needed.

[0128] The first topcoat material can be manufactured by uniformly mixing the above-mentioned components and, if necessary, various additives, etc., using conventional methods.

[0129] The elongation rate of the first topcoat material at -10 ° C. can be adjusted by the Tg of the resin emulsion in the first topcoat material, the content of the (B) component, etc. The Tg of the resin emulsion in the first topcoat material is preferably 30 ° C. or less, more preferably -50 ° C. to 30 ° C., and even more preferably -40 ° C. to 25 ° C. The content of the (B) component is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, and even more preferably 20 to 100 parts by weight, relative to 100 parts by weight of the solids of the resin emulsion.

[0130] <Coating method> In the present invention, a topcoat film is formed by applying (painting) a topcoat material (first topcoat material and second topcoat material) to the surface to be coated. That is, the first topcoat material and the second topcoat material are applied in order to the surface to be coated to form a topcoat film. Before painting the first topcoat material, as described above, it is also possible to paint one or more selected from primer material, base adjustment coating material, elastic coating material, etc.

[0131] In the present invention, it is desirable to apply the first topcoat material, dry the coating, and then apply the second topcoat material. The first topcoat material and the second topcoat material can be the above-mentioned. In the present invention, by forming a laminated coating using these two specific topcoat materials, it is possible to demonstrate excellent performance in terms of crack resistance, weather resistance, etc.

[0132] When applying each topcoat material, known painting tools can be used. For example, sprayers, rollers, brushes, etc. can be used as painting tools. When applying, each topcoat material can be diluted as needed.

[0133] The amount of water to be mixed may be appropriately determined taking into consideration the type of coating equipment, the condition of the surface to be coated, the temperature during coating, etc., but is preferably 0 to 20% by mass.

[0134] Both the first and second topcoat materials can be used as water-based topcoats that cure at room temperature. Therefore, the application of each topcoat material or drying after application can be done in an environment of room temperature (5 to 40 ° C). However, heating is also possible if necessary. The drying time is preferably about 0.5 to 4 hours at room temperature.

[0135] The amount of the first and second topcoats applied is preferably 0.05 to 0.4 kg / m ２ , more preferably 0.08 to 0.3 kg / m ２ is.

[0136] In addition, the dry film thickness of the first and second topcoat materials is preferably 20 to 300 μm, more preferably 30 to 200 μm, respectively. This allows for the formation of a coating that exhibits excellent performance in weather resistance, crack resistance, etc., while taking advantage of the texture of the base before the topcoat material is applied.

[0137] The film thickness ratio of the first topcoat film to the second topcoat film {(dry film thickness of the first topcoat film): (dry film thickness of the second topcoat film)} is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 65:35 to 35:65. By being in this mode, better performance can be stably obtained in terms of weather resistance, crack resistance, etc.

[0138] In the coating method of the present invention, for example, after applying one or more types of coating selected from primer, base adjustment coating material, elastic coating material, etc. to the surface to be coated as needed, the first topcoat material and the second topcoat material can be applied in sequence. It is desirable to apply the second topcoat material after drying the coating of the first topcoat material (preferably after drying for 1 hour or more, more preferably 2 hours or more).

[0139] [Topcoat material set] In the present invention, the above-mentioned first topcoat material and second topcoat material can be used as a topcoat material set consisting of these two types. That is, as a topcoat material set for forming a topcoat material film on the coated surface, the above-mentioned first topcoat material and second topcoat material can be used.

[0140] The following examples will be given to clarify the features of the present invention, but the present invention is not limited to these examples.

[0141] (Production of Aqueous Coating Material) The following raw materials were used to produce the aqueous coating material in the examples.

[0142] Resin 1: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate-2-ethylhexyl acrylate-n-octyl acrylate-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 38:14:12.5:1.5:1.5:32.5), glass transition temperature 3°C, silica remaining ratio in the resin solid content 15% by mass, solid content 40% by mass) Resin 2: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate-2-octyl acrylate-n-octyl acrylate-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 33:18.5:13:1.5:1.5:32.5), glass transition temperature 3°C, silica remaining ratio in the resin solid content 15% by mass, solid content 40% by mass) Resin 3: Acrylic silicone resin emulsion (emulsion polymer mainly composed of methyl methacrylate-cyclohexyl methacrylate-2-ethylhexyl acrylate-isoamyl acrylate-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 8:27:17:12.5:1.5:1.5:32.5), glass transition temperature 3°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass)

[0143] Resin 4: Acrylic silicone resin emulsion (emulsion polymer mainly composed of methyl methacrylate-cyclohexyl methacrylate-2-ethylhexyl acrylate-isoamyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 8:25:16:14:1.5:1.5:1.5:32.5), glass transition temperature 3°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass) Resin 5: Acrylic silicone resin emulsion (emulsion polymer mainly composed of methyl methacrylate-cyclohexyl methacrylate-2-ethylhexyl acrylate-isoamyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 8:28:13:14:1.5:1.5:1.5:32.5), glass transition temperature 10°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass) Resin 6: Acrylic silicone resin emulsion (emulsion polymer mainly composed of methyl methacrylate-cyclohexyl methacrylate-2-ethylhexyl acrylate-isoamyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 8:15.5:13:15.5:1.5:1.5:1.5:43.5), glass transition temperature -4°C, residual silica ratio in resin solid content 20% by mass, solid content 40% by mass)

[0144] Resin 7: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate-2-ethylhexyl acrylate-2-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 32.5:12:18.5:1.5:1.5:1.5:32.5), glass transition temperature 3°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass) Resin 8: Acrylic silicone resin emulsion (emulsion polymer mainly composed of methyl methacrylate-cyclohexyl methacrylate-isoamyl acrylate-2-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 5:22.5:17:18.5:1.5:1.5:1.5:32.5), glass transition temperature 3°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass) Resin 9: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate, isobornyl acrylate, isoamyl acrylate, 2-octyl acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (mass ratio 23:5:18:17:1.5:1.5:1.5:32.5), glass transition temperature 3°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass)

[0145] Resin 10: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate-2-ethylhexyl acrylate-n-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 36.5:13:13.5:1.5:1.5:1.5:32.5), glass transition temperature 3°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass) Resin 11: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate-2-octyl acrylate-n-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 32:16:15:1.5:1.5:1.5:32.5), glass transition temperature 3°C, residual silica ratio in resin solid content 15% by mass, solid content 40% by mass)

[0146] Resin 12: Acrylic silicone resin emulsion (emulsion polymer having as main components cyclohexyl methacrylate-2-ethylhexyl acrylate-2-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 39.5:16.5:18:1.5:1.5:1.5:21.5), glass transition temperature 3°C, residual silica ratio in resin solids 10 mass%, solids content 40 mass%). In addition, for resins 1 to 12, γ-methacryloxypropyltrimethoxysilane was used as the silane coupling agent, and methyltrimethoxysilane was used as the alkoxysilanes.

[0147] Resin 13: Acrylic silicone resin emulsion (emulsion polymer having as main components cyclohexyl methacrylate-n-hexyl acrylate-2-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 36.5:19:18.5:1.5:1.5:1.5:21.5), glass transition temperature 3°C, residual silica ratio in resin solids 10 mass%, solids content 40 mass%). In addition, in Resin 13, γ-methacryloxypropyltrimethoxysilane was used as the silane coupling agent, and methyltrimethoxysilane and phenyltrimethoxysilane (mass ratio 19.5:2) were used as the alkoxysilanes. Resin 14: Acrylic silicone resin emulsion (emulsion polymer having as main components cyclohexyl methacrylate-n-butyl acrylate-2-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes-cyclic siloxanes (mass ratio 36:17:22:1.5:1.5:1.5:17.5:3), glass transition temperature 3°C, residual silica ratio in resin solids 10 mass%, solids content 40 mass%). In Resin 14, γ-methacryloxypropyltrimethoxysilane was used as the silane coupling agent, and methyltrimethoxysilane and phenyltrimethoxysilane (mass ratio 14.5:3) were used as the alkoxysilanes.

[0148] Resin 15: Acrylic silicone resin emulsion (emulsion polymer mainly composed of methyl methacrylate-cyclohexyl methacrylate-isoamyl acrylate-2-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 5:24:29:21:1.5:1.5:1.5:16.5), glass transition temperature -6°C, silica residual ratio in resin solid content 8% by mass, solid content 40% by mass) Resin 16: Acrylic resin emulsion (emulsion polymer mainly composed of methyl methacrylate-cyclohexyl methacrylate-2-ethylhexyl acrylate-n-butyl acrylate-diacetone acrylamide-methacrylic acid (mass ratio 15:41.5:20:20.5:1.5:1.5), glass transition temperature 8°C, solid content 40% by mass)

[0149] Resin 17: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate-n-octyl acrylate-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 37:27.5:1.5:1.5:32.5), glass transition temperature 3°C, silica remaining ratio in resin solid content 15% by mass, solid content 40% by mass) Resin 18: Acrylic silicone resin emulsion (an emulsion polymer mainly composed of cyclohexyl methacrylate-n-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio 35.8:27.2:1.5:1.5:1.5:32.5), glass transition temperature 3°C, silica remaining ratio in resin solid content 15% by mass, solid content 40% by mass) In addition, for resins 15, 17, and 18, γ-methacryloxypropyltrimethoxysilane was used as the silane coupling agent, and methyltrimethoxysilane was used as the alkoxysilane.

[0150] Resin 19: Urethane resin emulsion (aqueous dispersion of polycarbonate-based polyurethane resin, solid content 30% by mass)

[0151] Colored pigment 1: titanium oxide (average particle size 0.3 μm) Pigment dispersant 1: polycarboxylic acid type dispersant (aqueous solution of polycarboxylic acid ammonium salt, solid content 30% by mass) Colored liquid 1: aqueous dispersion of yellow iron oxide (average particle size 0.5 μm) [colored pigment ratio 50% by mass, solid content ratio of pigment dispersant {polycarboxylic acid type dispersant (styrene-maleic acid copolymer resin)} 2% by mass] Colored liquid 2: aqueous dispersion of carbon black (average particle size 0.1 μm) [colored pigment ratio 20% by mass, solid content ratio of pigment dispersant {polymer dispersant having an acid value and an amine value, and phosphate type dispersant (phosphate ester compound)} 2% by mass] Solvent 1: ether solvent (tripropylene glycol monobutyl ether, solubility in water 3 g / 100 gH ２ 0, boiling point 274°C) Solvent 2: ether solvent (dipropylene glycol monobutyl ether, solubility in water 5 g / 100 gH ２0, boiling point 229°C) Solvent 3: ether solvent (ethylene glycol monophenyl ether, solubility in water 2.6 g / 100 gH ２ 0, boiling point 245°C) Solvent 4: Ether solvent (ethylene glycol monotertiary butyl ether, solubility in water ∞, boiling point 153°C) Solvent 5: Ether solvent (diethylene glycol monobutyl ether, solubility in water ∞, boiling point 230°C) Solvent 6: Ether solvent (diethylene glycol dibutyl ether, solubility in water 0.3g / 100gH ２ 0, boiling point 255°C) Solvent 7: Ether solvent (ethylene glycol mono-2-ethylhexyl ether, solubility in water 0.2 g / 100 gH ２ 0, boiling point 229°C) Solvent 8: Ether solvent (diethylene glycol monophenyl ether, solubility in water 3.4 g / 100 gH ２ 0, boiling point 283°C), Solvent 9: Ester solvent (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, solubility in water 0.09 g / 100 gH ２ 0, boiling point 255°C) Thickener 1: Cellulose-based thickener Thickener 2: Polyurethane-based associative thickener Defoamer 1: Mineral oil-based defoamer Defoamer 2: Silicone-based defoamer Crosslinker 1: Adipic acid dihydrazide Crosslinker 2: Carbodiimide resin aqueous dispersion (solid content: 40% by mass) Crosslinker 3: γ-glycidoxypropyltrimethoxysilane

[0152] The full names of the abbreviations in the table are as follows: 2EHA: 2-ethylhexyl acrylate nOA: n-octyl acrylate 2OA: 2-octyl acrylate IAA: isoamyl acrylate nHA: n-hexyl acrylate nBA: n-butyl acrylate

[0153] <Aqueous Coating Material 1> A color pigment dispersion was prepared by mixing and stirring 27 parts by mass of water with 0.4 parts by mass of Thickener 1, 0.1 parts by mass of Antifoaming Agent 1, 2.5 parts by mass of Pigment Dispersant 1, and 70 parts by mass of Color Pigment 1. Next, 100 parts by mass of this color pigment dispersion was mixed with and stirred with 250 parts by mass (100 parts by mass in terms of solid content) of Resin 1, 18 parts by mass of Solvent 1, 2 parts by mass of Thickener 2, and 0.2 parts by mass of Antifoaming Agent 2, to prepare aqueous coating material 1.

[0154] <Aqueous coating material 2> Aqueous coating material 2 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 2 (100 parts by mass equivalent to solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, and 0.2 parts by mass of defoamer 2.

[0155] <Aqueous coating material 3> Aqueous coating material 3 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 3 (100 parts by mass equivalent to solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, and 0.2 parts by mass of defoamer 2.

[0156] <Aqueous coating material 4> Aqueous coating material 4 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 4 (100 parts by mass equivalent to solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0157] <Aqueous coating material 5> Aqueous coating material 5 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of Resin 5 (100 parts by mass equivalent to solids content), 18 parts by mass of Solvent 1, 2 parts by mass of Thickener 2, 0.2 parts by mass of Antifoaming Agent 2, and 1 part by mass of Crosslinking Agent 1.

[0158] <Aqueous coating material 6> Aqueous coating material 6 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 6 (100 parts by mass equivalent to solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0159] <Aqueous coating material 7> Aqueous coating material 7 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 7 (equivalent to 100 parts by mass of solids content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0160] <Aqueous coating material 8> Aqueous coating material 8 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 8 (100 parts by mass equivalent to solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0161] <Aqueous coating material 9> Aqueous coating material 9 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 9 (100 parts by mass equivalent to solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0162] <Aqueous coating material 10> Aqueous coating material 10 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 8 (equivalent to 100 parts by mass of solids content), 18 parts by mass of solvent 2, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0163] <Aqueous coating material 11> Aqueous coating material 11 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 8 (equivalent to 100 parts by mass of solids content), 12 parts by mass of solvent 2, 6 parts by mass of solvent 3, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0164] <Aqueous coating material 12> Aqueous coating material 12 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 8 (equivalent to 100 parts by mass of solids content), 12 parts by mass of solvent 2, 6 parts by mass of solvent 4, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0165] <Aqueous coating material 13> Aqueous coating material 13 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 8 (equivalent to 100 parts by mass of solids content), 12 parts by mass of solvent 2, 6 parts by mass of solvent 5, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0166] <Aqueous coating material 14> Aqueous coating material 14 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 8 (100 parts by mass equivalent to solids content), 12 parts by mass of solvent 2, 6 parts by mass of solvent 6, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0167] <Aqueous coating material 15> Aqueous coating material 15 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 8 (equivalent to 100 parts by mass of solids content), 12 parts by mass of solvent 2, 6 parts by mass of solvent 7, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0168] <Aqueous coating material 16> Aqueous coating material 16 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 9 (100 parts by mass equivalent to solids content), 12 parts by mass of solvent 2, 6 parts by mass of solvent 3, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0169] <Aqueous coating material 17> Aqueous coating material 17 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of Resin 10 (equivalent to 100 parts by mass of solids content), 18 parts by mass of Solvent 1, 2 parts by mass of Thickener 2, 0.2 parts by mass of Antifoaming Agent 2, and 1 part by mass of Crosslinking Agent 1.

[0170] <Aqueous coating material 18> Aqueous coating material 18 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 11 (equivalent to 100 parts by mass of solids content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0171] <Aqueous coating material 19> Aqueous coating material 19 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 3 (100 parts by mass equivalent to solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 3 parts by mass of crosslinker 2.

[0172] <Aqueous coating material 20> Aqueous coating material 20 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 12 (100 parts by mass in terms of solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0173] <Aqueous coating material 21> Aqueous coating material 21 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 13 (equivalent to 100 parts by mass of solids content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0174] <Aqueous coating material 22> Aqueous coating material 22 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 14 (100 parts by mass in terms of solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0175] <Aqueous coating material 23> Aqueous coating material 23 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 9 (100 parts by mass equivalent to solids content), 2 parts by mass of solvent 2, 2 parts by mass of solvent 8, 11 parts by mass of solvent 9, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0176] <Aqueous coating material 24> Aqueous coating material 24 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 9 (100 parts by mass equivalent to solids content), 2 parts by mass of solvent 2, 2 parts by mass of solvent 8, 11 parts by mass of solvent 9, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, 1 part by mass of crosslinker 1, and 10 parts by mass of coloring liquid 1.

[0177] <Aqueous coating material 25> Aqueous coating material 25 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 9 (100 parts by mass equivalent to solids content), 2 parts by mass of solvent 2, 2 parts by mass of solvent 8, 11 parts by mass of solvent 9, 2 parts by mass of thickener 2, 0.2 part by mass of defoamer 2, 1 part by mass of crosslinker 1, and 10 parts by mass of coloring liquid 2.

[0178] <Aqueous Coating Material 26> Aqueous coating material 26 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of Resin 9 (100 parts by mass equivalent to solids content), 2 parts by mass of Solvent 2, 2 parts by mass of Solvent 8, 11 parts by mass of Solvent 9, 2 parts by mass of Thickener 2, 0.2 part by mass of Antifoaming Agent 2, and 1 part by mass of Crosslinking Agent 3.

[0179] <Aqueous Coating Material 27> Aqueous coating material 27 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 220 parts by mass of Resin 10 (88 parts by mass in terms of solid content), 18 parts by mass of Solvent 1, 2 parts by mass of Thickener 2, 0.2 parts by mass of Antifoaming Agent 2, 1 part by mass of Crosslinking Agent 1, and 40 parts by mass of Resin 19 (12 parts by mass in terms of solid content).

[0180] <Aqueous Coating Material 28> Aqueous coating material 28 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1 with 220 parts by mass of Resin 9 (88 parts by mass in terms of solids content), 2 parts by mass of Solvent 2, 2 parts by mass of Solvent 8, 11 parts by mass of Solvent 9, 2 parts by mass of Thickener 2, 0.2 part by mass of Antifoaming Agent 2, 1 part by mass of Crosslinking Agent 1, and 40 parts by mass of Resin 19 (12 parts by mass in terms of solids content).

[0181] <Aqueous coating material 29> Aqueous coating material 29 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 17 (equivalent to 100 parts by mass of solids content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, and 0.2 parts by mass of defoamer 2.

[0182] <Aqueous coating material 30> Aqueous coating material 30 was produced by mixing and stirring 250 parts by mass of resin 17 (equivalent to 100 parts by mass of solid content) with 100 parts by mass of the same color pigment dispersion as in Example 1, 2 parts by mass of thickener 2, and 0.2 parts by mass of defoamer 2.

[0183] <Aqueous coating material 31> Aqueous coating material 31 was produced by mixing and stirring 100 parts by mass of the same color pigment dispersion as in Example 1, 250 parts by mass of resin 18 (equivalent to 100 parts by mass of solids content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, 0.2 parts by mass of defoamer 2, and 1 part by mass of crosslinker 1.

[0184] <Aqueous Coating Material 32> Aqueous coating material 32 was produced by mixing and stirring 250 parts by mass of resin 17 (100 parts by mass in terms of solid content), 18 parts by mass of solvent 1, 2 parts by mass of thickener 2, and 0.2 parts by mass of antifoaming agent 2.

[0185] (Test Method) Each aqueous coating material was tested by the following method.

[0186] [Test 1] A slate board with a roughened pattern (height difference of about 1.5 mm) formed by a thick synthetic resin emulsion-based finishing coating material was prepared as a test substrate. Each aqueous coating material was applied to this test substrate at an amount of 0.3 kg / m. ２ The coating was spray-painted at 1000 W / m² and the coated surface was placed horizontally in an incubator at 5°C and allowed to dry for 168 hours, after which the appearance of the coating was observed. The evaluation criteria were "A" for no cracks, "B" for slight cracks, and "C" for obvious cracks. "C" indicates a level that is problematic for practical use.

[0187] [Test 2] Each aqueous coating material was applied to one side of a glass plate using a film applicator with a gap of 150 μm, and the coated surface was placed horizontally and dried for 48 hours under standard conditions (air temperature 23°C, relative humidity 50%), after which the 20-degree specular gloss (measurement angle 20 degrees) was measured. The evaluation criteria were: a 20-degree specular gloss of 46 or more was rated "AA," 43 to 46 was rated "A," 40 to 43 was rated "B," and less than 40 was rated "C." Note that a level that is problematic for practical use was rated "C."

[0188] [Test 3] After the above Test 1, the test plate was dried under standard conditions (temperature 23°C, relative humidity 50%) for 14 days, and then exposed for 1000 hours in an accelerated weathering tester (xenon weather meter), after which the appearance of the coating film was observed. The evaluation criteria were "A" for no cracks, "B" for slight cracks, and "C" for obvious cracks. Note that "C" is a level that is problematic for practical use.

[0189] [Test 4] A slate board with a coating film (0.5 mm thick) made of a flexible synthetic resin emulsion-based repair finishing coating material was prepared as a test substrate. Each aqueous coating material was applied to this test substrate at an amount of 0.3 kg / m. ２ The test specimens were spray-painted with a coating of 1000 ppm or less at 2000 kJ / cm² and then placed horizontally in an incubator at 5°C and dried for 24 hours to prepare test specimens. The test specimens were then immersed in water at 23°C for 24 hours, and the appearance of the coating film was observed. The evaluation criteria were as follows: no blistering was rated "AA," very slight blistering was rated "A," slight blistering was rated "B," and clear blistering was rated "C." Note that "C" is a level that is problematic for practical use.

[0190] (Test Results) The test results are shown in Table 1. In Test 1, Examples 1 to 28 (particularly Examples 3 to 28) obtained good results and were excellent in crack resistance. In Test 2, Examples 1 to 28 (particularly Examples 11 to 16, 23 to 26, and 28) obtained good results and were excellent in gloss. Examples 3 to 28 (particularly Examples 4 to 16 and 18 to 28) also obtained good results in Test 3 and were excellent in crack resistance and weather resistance. In Test 4, Examples 1 to 28 (particularly Examples 2 to 16 and 18 to 28) obtained good results, exhibiting early development of coating film strength and excellent blister resistance. Comparative Examples 1 to 3 obtained unsatisfactory results in Test 1, so Test 3 was not performed for Comparative Examples 1 to 3. Comparative Example 4 did not contain pigments or the like, which is outside the scope of the present invention, so Tests 2 and 3 were not performed.

[0191]

[0192]

[0193]

[0194] <Topcoat material 1> To 27 parts by weight of water, 0.4 parts by weight of thickener 1, 0.1 parts by weight of antifoaming agent 1, 2.5 parts by weight of pigment dispersant 1, 70 parts by weight of colored pigment 1 were mixed and stirred to produce a colored pigment dispersion. Next, to 100 parts by weight of this colored pigment dispersion, 250 parts by weight of resin 1 (solid content equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2 were mixed and stirred to produce topcoat material 1. The elongation rate of this topcoat material 1 at -10 ° C was 17%.

[0195] <Topcoat material 2> Topcoat material 2 was produced by mixing and stirring 250 parts by weight of resin 2 (100 parts by weight of solids equivalent) for 100 parts by weight of colored pigment dispersion similar to topcoat material 1, 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, and 0.2 parts by weight of antifoaming agent 2. The elongation rate of this topcoat material 2 at -10 ° C was 18%.

[0196] <Topcoat material 3> Topcoat material 3 was produced by mixing and stirring 250 parts by weight of resin 3 (solids equivalent 100 parts by weight) for 100 parts by weight of the same color pigment dispersion as topcoat material 1, 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, and 0.2 parts by weight of antifoaming agent 2. The elongation rate of this topcoat material 3 at -10 ° C was 18%.

[0197] <Topcoat material 4> Topcoat material 1 was used to prepare 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 10 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 4 at -10 ° C was 18%.

[0198] <Topcoat material 5> Topcoat material 1, 100 parts by weight of the same color pigment dispersion as 250 parts by weight of resin 11 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, 1 part by weight of crosslinking agent 1, by mixing and stirring, topcoat material 5 was produced. The elongation rate of this topcoat material 5 at -10 ° C was 18%.

[0199] <Topcoat material 6> Topcoat material 1, 100 parts by weight of the same color pigment dispersion liquid as above, 250 parts by weight of resin 3 (solid content equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, 3 parts by weight of crosslinking agent 2, mixed and stirred to produce topcoat material 6. The elongation rate of this topcoat material 6 at -10 ° C was 20%.

[0200] <Topcoat material 7> Topcoat material 1, 100 parts by weight of the same color pigment dispersion liquid as above, 250 parts by weight of resin 4 (solid content equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, 1 part by weight of crosslinking agent 1, by mixing and stirring, topcoat material 7 was produced. The elongation rate of this topcoat material 7 at -10 ° C was 20%.

[0201] <Topcoat material 8> Topcoat material 1, 100 parts by weight of the same color pigment dispersion liquid as above, 250 parts by weight of resin 5 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, 1 part by weight of crosslinking agent 1, by mixing and stirring, topcoat material 8 was produced. The elongation rate of this topcoat material 8 at -10 ° C was 14%.

[0202] <Topcoat material 9> Topcoat material 1 was used to prepare 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 6 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 9 at -10 ° C was 26%.

[0203] <Topcoat material 10> Topcoat material 1 was prepared by mixing and stirring 100 parts by weight of the same colored pigment dispersion as above, 250 parts by weight of resin 12 (100 parts by weight of solids), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 10 at -10 ° C was 23%.

[0204] <Topcoat material 11> Topcoat material 1 was prepared by mixing and stirring 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 8 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 11 at -10 ° C was 20%.

[0205] <Topcoat material 12> Topcoat material 1 was prepared by mixing and stirring 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 9 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 12 at -10 ° C was 18%.

[0206] <Topcoat material 13> Topcoat material 1, 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 8 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 2, 6 parts by weight of solvent 8, 6 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, 1 part by weight of crosslinking agent 1, by mixing and stirring, topcoat material 13 was produced. The elongation rate of this topcoat material 13 at -10 ° C was 21%.

[0207] <Topcoat material 14> Topcoat material 1 was used to prepare 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 8 (solids equivalent 100 parts by weight), 12 parts by weight of solvent 2, 6 parts by weight of solvent 8, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The topcoat material 14 was produced by mixing and stirring. The elongation rate of this topcoat material 14 at -10 ° C. was 20%.

[0208] <Topcoat material 15> Topcoat material 1 was prepared by mixing and stirring 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 13 (100 parts by weight of solids), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 15 at -10 ° C was 18%.

[0209] <Topcoat material 16> Topcoat material 1 was prepared by mixing and stirring 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 14 (100 parts by weight of solids), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 16 at -10 ° C was 19%.

[0210] <Topcoat material 17> For 100 parts by weight of the same color pigment dispersion as coating material 1, 250 parts by weight of resin 17 (100 parts by weight of solids), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, and 0.2 parts by weight of antifoaming agent 2 were mixed and stirred to produce topcoat material 17. The elongation rate of this topcoat material 17 at -10 ° C was 18%.

[0211] <Topcoat material 18> Topcoat material 1 was prepared by mixing and stirring 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 18 (100 parts by weight of solids), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 18 at -10 ° C was 18%.

[0212] <Topcoat material 19> Topcoat material 1 was prepared by mixing and stirring 100 parts by weight of the same color pigment dispersion as above, 250 parts by weight of resin 15 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, and 1 part by weight of crosslinking agent 1. The elongation rate of this topcoat material 19 at -10 ° C was 32%.

[0213] <Topcoat material 20> Topcoat material 1, 100 parts by weight of the same colored pigment dispersion liquid, 125 parts by weight of resin 8 (solid content equivalent 50 parts by weight), 125 parts by weight of resin 16 (solid content equivalent 50 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, 1 part by weight of crosslinking agent 1, by mixing and stirring, topcoat material 20 was produced. The elongation rate of this topcoat material 20 at -10 ° C was 30%.

[0214] <Topcoat material 21> Topcoat material 1, 100 parts by weight of the same color pigment dispersion as 250 parts by weight of resin 16 (solids equivalent 100 parts by weight), 6 parts by weight of solvent 8, 12 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of antifoaming agent 2, 1 part by weight of crosslinking agent 1, by mixing and stirring, topcoat material 21 was produced. The elongation rate of this topcoat material 21 at -10 ° C was 38%.

[0215] The elongation rate of each topcoat material at -10 ° C is a value measured according to the method specified in the "elongation test" of JIS A6909: 2021. The test specimens used in the elongation test were waterproof multi-layer coating material E (a mixture of acrylic resin emulsion (Tg -28 ° C), titanium oxide (average particle size 0.3 μm), heavy calcium carbonate (average particle size 12 μm), etc.) corresponding to JIS A6909: 2021. The surface of the coating with a dry film thickness of 1 mm and an elongation rate of 38% at -10 ° C of the single coating was coated with a topcoat coating with a dry film thickness of 80 μm.

[0216] (Test method) Each topcoat material was tested by the following method.

[0217] [Test 5] As the test substrate, a waterproof multi-layer coating material E corresponding to JIS A6909:2021 (a mixture of acrylic resin emulsion (Tg -28 ° C), titanium oxide (average particle size 0.3 μm), heavy calcium carbonate (average particle size 12 μm), etc.) was used. A slate board with an uneven pattern (height difference of approximately 1.5 mm) formed by a single coating with an elongation rate of 38% at -10 ° C was prepared. A first topcoat material was applied to this test substrate at an amount of 0.15 kg / m ２ Spray paint at 1000 W / m², dry for 2 hours, and then apply the second top coat at a coating amount of 0.15 kg / m². ２The coating, drying, and curing were all carried out under standard conditions (temperature 23°C, relative humidity 50%).

[0218] The test specimens obtained by the above method were subjected to a total of 10 cycles of hot and cold cycling, 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 occurrence of defects (blistering, peeling, cracks, etc.) was evaluated. The evaluation was conducted on a four-level scale (excellent: A>B>C>D: poor), with "A" indicating no defects and "D" indicating clear defects. Note that "C" and "D" are levels that are problematic for practical use.

[0219] [Test 6] Test specimens obtained in the same manner as in Test 5 above were exposed for 1000 hours in an accelerated weathering tester (xenon weather meter), and then the coating appearance was observed. Evaluation was conducted on a four-level scale (excellent: A>B>C>D: poor), with "A" indicating no defects and "D" indicating clear defects. "C" and "D" are considered to be practically problematic.

[0220] (Test Results) The test results are shown in Table 6. Examples 29 to 47 showed good results in Tests 5 and 6, and were excellent in crack resistance, weather resistance, and the like.

[0221]

[0222] Note: All resins except "Resin 16" included in the "Resin Components" in Table 5 above contain acrylic silicone resin, and "Resin 16" does not contain silicone components.

[0223]

Claims

1. An aqueous coating material having room temperature curability, containing an acrylic silicone resin emulsion (A) and a pigment (B), wherein the silica residue ratio in the resin solid content of the acrylic silicone resin emulsion (A) is 1 to 40% by mass, the glass transition temperature of the acrylic silicone resin emulsion (A) is 30°C or lower, and as monomers constituting the acrylic silicone resin emulsion (A), two or more (meth)acrylic acid alkyl esters having an alkyl group with 4 or more carbon atoms are included, and the glass transition temperature of the homopolymer of the (meth)acrylic acid alkyl ester(s) having an alkyl group with 4 or more carbon atoms is 0°C or lower.

2. The aqueous coating material according to claim 1, wherein the (meth)acrylic acid alkyl ester(s) having an alkyl group with 4 or more carbon atoms includes (meth)acrylic acid alkyl ester(s1) having a branched alkyl group with 5 or more carbon atoms.

3. The aqueous coating material according to claim 2, wherein the branched alkyl group includes a methyl group.

4. The aqueous coating material according to claim 1, further comprising a crosslinking agent (C), wherein the acrylic silicone resin emulsion (A) has reactive functional groups, and the crosslinking agent (C) has functional groups capable of reacting with the reactive functional groups.

5. A film forming method for forming a topcoat film by sequentially applying a first topcoat material and a second topcoat material to a surface to be coated, wherein the first topcoat material forms a film having an elongation rate of 20% or more at -10°C, the second topcoat material is the aqueous coating material according to any one of claims 1 to 4, and the second topcoat material forms a film having an elongation rate at -10°C smaller than that of the first topcoat material at -10°C.

6. The film forming method according to claim 5, wherein the first topcoat material includes a resin emulsion and a pigment, and as monomers constituting the resin emulsion, two or more (meth)acrylic acid alkyl esters having an alkyl group with 4 or more carbon atoms are included, and the glass transition temperature of the homopolymer of the (meth)acrylic acid alkyl ester(s) having an alkyl group with 4 or more carbon atoms is 0°C or lower.

7. The film-forming method according to claim 6, characterized in that the (meth)acrylic acid alkyl ester(s) having an alkyl group with 4 or more carbon atoms contains a (meth)acrylic acid alkyl ester(s1) having a branched alkyl group with 5 or more carbon atoms.

8. The aqueous coating material according to claim 7, characterized in that the branched alkyl group contains a methyl group.

9. A topcoat material set comprising the first topcoat material and the second topcoat material used in the film-forming method according to claim 5.

Images