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

Abstract

A water-based coating material is provided, exhibiting good room-temperature curing properties and excellent performance in terms of crack resistance and weather resistance. The water-based coating material of this invention is a room-temperature curing water-based coating material containing an acrylic silicone resin emulsion (A) and a pigment (B). Its characteristics are: the residual silica content in the acrylic silicone resin emulsion (A) is 1-40% by mass; the glass transition temperature of the acrylic silicone resin emulsion (A) is below 30°C; the monomers constituting the acrylic silicone resin emulsion (A) include two or more alkyl (meth)acrylates (S) having 4 or more carbon atoms; and the glass transition temperature of the homopolymer of the alkyl (meth)acrylates (S) having 4 or more carbon atoms is below 0°C.

Description

Technical Field

[0001] This invention relates to a novel water-based coating material, a coating film formation method, and an upper coating material group. Background Technology

[0002] Traditionally, buildings and civil structures are surface-treated with coating materials. These materials provide aesthetic appeal through various colors and textures, and also protect the substrate from wind, rain, and direct sunlight, thus requiring excellent weather resistance. In recent years, considering their environmental friendliness and safety, water-based coating materials that use resin emulsions as adhesives have become increasingly popular.

[0003] As is well known, using acrylic silicone resin emulsion as a binder is a method to improve the weather resistance of water-based coating materials. For example, Patent Document 1 discloses a water-based coating material containing a resin emulsion with specific silicon content, acid value, and hydroxyl value, as well as its crosslinking agent, pigments, etc.

[0004] Furthermore, since water-based coatings are intended for outdoor application, they must be able to form and cure films within a temperature range of approximately 5–40°C (room temperature curing). However, the aforementioned patent documents do not adequately address this room temperature curing capability. If coating is applied at room temperature, the coating may crack or have insufficient weather resistance.

[0005] In particular, cement-based materials such as concrete and mortar, which form the main structure of buildings and civil engineering structures, may crack over time due to factors such as shrinkage of the substrate itself and the loads applied to it. Furthermore, the joints between building materials such as lightweight concrete slabs, aerated concrete slabs, and exterior wall cladding are susceptible to displacement due to changes in temperature and humidity. Water-based topcoat materials suitable for buildings and civil engineering structures must also possess crack resistance for such coated surfaces.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent document 1: Japanese Patent Application Publication No. 8-12930. Summary of the Invention

[0009] The problem the invention aims to solve

[0010] The present invention was made in view of the problems described above, and aims to provide a water-based coating material with good room temperature curing properties and excellent performance in terms of crack resistance and weather resistance.

[0011] The present invention was made in view of the problems described above, and aims to provide a coating forming method that can exhibit excellent performance in terms of crack resistance, weather resistance, etc.

[0012] Solution for solving the problem

[0013] In order to achieve the above objectives, the inventors, through in-depth research, conceived of an aqueous coating material comprising an acrylic silicone resin emulsion and pigments, having a specific residual silica ratio and a specific resin composition, thus completing the present invention.

[0014] In order to achieve the above objectives, the inventors, through in-depth research, devised a coating formation method, which involves first applying a specific first upper coating material, and then applying a specific second upper coating material having a specific resin composition and containing acrylic silicone resin emulsion and pigments, thereby completing the present invention.

[0015] That is, the present invention has the following features:

[0016] 1. An aqueous coating material comprising an acrylic silicone resin emulsion (A) and a pigment (B), and having room temperature curing properties, characterized in that the residual silica content in the resin solids of the acrylic silicone resin emulsion (A) is 1-40% by mass, the glass transition temperature of the acrylic silicone resin emulsion (A) is below 30°C, the monomers constituting the acrylic silicone resin emulsion (A) comprise two or more alkyl (meth)acrylates (s) having 4 or more carbon atoms, and the glass transition temperature of the homopolymer of the alkyl (meth)acrylates (s) having 4 or more carbon atoms is below 0°C.

[0017] It should be noted that in this invention, "room temperature" refers to 5–40°C.

[0018] 2. The water-based coating material according to 1, characterized in that the alkyl (meth)acrylate (s) having 4 or more carbon atoms comprises alkyl (meth)acrylate (s1) having 5 or more branched alkyl groups.

[0019] 3. The aqueous coating material according to 2, wherein the branched alkyl group comprises methyl.

[0020] 4. The aqueous coating material according to 1, characterized in that it comprises 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.

[0021] 5. A method for forming a coating, wherein a first upper coating material and a second upper coating material are sequentially applied to a surface to be coated to form an upper coating material coating, characterized in that the first upper coating material is a coating material for forming a coating with an elongation of 20% or more at -10°C, the second upper coating material is an aqueous coating material as described in any one of 1. to 4, and the second upper coating material is a coating material for forming a coating with an elongation at -10°C less than that of the first upper coating material at -10°C.

[0022] 6. The coating formation method according to 5, characterized in that the first upper coating material comprises a resin emulsion and a pigment, the monomer constituting the resin emulsion comprises two or more alkyl (meth)acrylates(s) having 4 or more carbon atoms, and the glass transition temperature of the homopolymer of the alkyl (meth)acrylates(s) having 4 or more carbon atoms is below 0°C.

[0023] 7. The coating forming method according to 6, characterized in that the alkyl (meth)acrylate (s) having 4 or more carbon atoms comprises alkyl (meth)acrylate (s1) having 5 or more branched alkyl groups.

[0024] 8. The aqueous coating material according to 7, wherein the branched alkyl group comprises methyl.

[0025] 9. An upper coating material group comprising a first upper coating material and a second upper coating material for the film forming method described in 5.

[0026] Invention Effects

[0027] The water-based coating material of the present invention has good room temperature curing properties and can exhibit excellent performance in terms of crack resistance and weather resistance.

[0028] According to the coating forming method of the present invention, a coating with excellent properties in terms of crack resistance and weather resistance can be formed. Detailed Implementation

[0029] The following describes the methods for implementing the present invention.

[0030] [Water-based coating material]

[0031] The waterborne coating material of the present invention is characterized by comprising a specific acrylic silicone resin emulsion (A) and a pigment (B). This waterborne coating material can be cured at room temperature to form a colored coating film. Specifically, the acrylic silicone resin emulsion (A) has a silica residue ratio of 1 to 40% by mass in its resin solids content, a glass transition temperature (hereinafter also referred to as "Tg") of 30°C or less, and the monomers constituting the acrylic silicone resin emulsion (A) comprise two or more alkyl (meth)acrylates (s) having 4 or more carbon atoms, and the homopolymer of the alkyl (meth)acrylates (s) having 4 or more carbon atoms has a glass transition temperature of 0°C or less.

[0032] It should be noted that, in this invention, monomer refers to the general term for compounds with polymerizable unsaturated double bonds (except for compounds with silicon atoms).

[0033] Generally speaking, resin emulsion refers to a substance formed by emulsifying and dispersing resin in an aqueous medium (a medium containing water).

[0034] Furthermore, the glass transition temperature of the resin is a value calculated using the Fox formula based on the inherent Tg (Tg of each monomer homopolymer) and composition ratio of the monomers constituting the resin.

[0035] In this invention, an acrylic silicone resin emulsion (A) is used as the resin emulsion. The acrylic silicone resin emulsion (A) is a substance formed by emulsifying and dispersing acrylic silicone resin in an aqueous medium.

[0036] The glass transition temperature of the acrylic silicone resin emulsion (A) is calculated using the Fox formula based on the inherent Tg and composition ratio of each monomer constituting the acrylic silicone resin emulsion (A). However, in this invention, alkoxysilane compounds should be excluded when calculating the Tg of the acrylic silicone resin emulsion (A).

[0037] <(A) Ingredient>

[0038] Generally, room temperature curing can be achieved by setting the glass transition temperature of the resin emulsion below room temperature (5–40°C). Room temperature curing can also be achieved by setting the glass transition temperature of the acrylic silicone resin emulsion below room temperature.

[0039] However, for water-based coating materials that use acrylic silicone resin emulsions containing a high amount of silicon as binders and are mixed with pigments, even if the glass transition temperature of the acrylic silicone resin emulsion is set low, problems such as coating cracking or insufficient weather resistance of the coating are likely to occur.

[0040] In this waterborne coating material, the present invention uses an acrylic silicone resin emulsion that meets the above conditions as an essential component. The waterborne coating material of the present invention, having this specific composition, exhibits excellent performance in terms of crack resistance and weather resistance.

[0041] Furthermore, in the water-based coating material of the present invention, the residual silica content in the acrylic silicone resin emulsion (A) is 1-40% by mass, which enables stable performance when using adhesives containing a high proportion of silicon. Therefore, it relatively reduces the organic matter content derived from petroleum and also contributes to decarbonization. Moreover, the water-based coating material of the present invention, with its excellent weather resistance, can extend the service life of the coated object and reduce the overall maintenance frequency, which also contributes to decarbonization.

[0042] In the water-based coating material of the present invention, an acrylic silicone resin emulsion (A) (hereinafter referred to as "component (A)") with a silica residue ratio of 1 to 40% by mass and a glass transition temperature of 30°C or less in the resin solids content is used as an adhesive.

[0043] As this component (A), monomers such as alkyl methacrylates (s) containing alkyl groups having 4 or more carbon atoms can be used as components constituting acrylic silicone resins (resin constituents), as well as substances containing alkoxysilane compounds. It should be noted that in this invention, alkyl acrylates and alkyl methacrylates are collectively referred to as alkyl methacrylates. Furthermore, in this invention, "α~β" is synonymous with "α or more, β or less".

[0044] Alkyl methacrylates can be, for example, homopolymers with a Tg of 15°C or higher, such as 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), and methacrylate. Cyclohexyl acrylate (Tg: 83℃), octadecyl acrylate (Tg: 35℃), hexadecyl acrylate (Tg: 35℃), hexadecyl methacrylate (Tg: 15℃), tetradecyl acrylate (Tg: 24℃), isobornyl acrylate (Tg: 94℃), isobornyl methacrylate (Tg: 155℃), dicyclopentyl acrylate (Tg: 120℃), dicyclopentyl methacrylate (Tg: 175℃), dicyclopentenyl acrylate (Tg: 120℃), etc.; alkyl (meth)acrylates with a Tg greater than 0℃ and less than 15℃, such as methyl acrylate (Tg: 8℃). Examples of homopolymers include n-propyl acrylate (Tg: 3℃), dipropylene glycol diacrylate (Tg: 10℃), etc.; alkyl (meth)acrylates with a Tg below 0℃, such as ethyl acrylate (Tg: -20℃), isopropyl acrylate (Tg: -3℃), n-butyl acrylate (Tg: -54℃), isobutyl acrylate (Tg: -26℃), n-amyl methacrylate (Tg: -5℃), isoamyl acrylate (Tg: -45℃), n-hexyl acrylate (Tg: -57℃), n-hexyl methacrylate (Tg: -5℃), 2-ethylhexyl acrylate (Tg: -70℃), and methacrylate. 2-Ethylhexyl acrylate (Tg: -10℃), n-octyl acrylate (Tg: -65℃), octyl 2-acrylate (Tg: -44℃), isooctyl methacrylate (Tg: -45℃), isooctyl acrylate (Tg: -70℃), isononyl acrylate (Tg: -58℃), isodecanyl acrylate (Tg: -60℃), isodecanyl methacrylate (Tg: -41℃), tridecyl acrylate (Tg: -55℃), tridecyl methacrylate (Tg: -40℃), n-dodecyl methacrylate (Tg: -65℃), tetradecyl methacrylate (Tg: -72℃), etc. One or more of these can be used, but the homopolymer must contain alkyl (meth)acrylates with a Tg below 0℃.

[0045] Alkoxysilane compounds can be, for example, silane coupling agents containing polymerizable unsaturated double bonds, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane; epoxy-containing silane coupling agents, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropyltrimethoxysilane. Amino-containing silane coupling agents such as alkyl, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.; mercapto-containing silane coupling agents such as γ-mercaptopropyltrimethoxysilane; urea-containing silane coupling agents such as 3-ureopropyltriethoxysilane; chloroalkyl-containing silane coupling agents such as 3-chloropropyltrimethoxysilane; sulfide-containing silane coupling agents such as bis(3-triethoxysilylpropyl)tetrasulfide; isocyanate-containing silane coupling agents such as 3-isocyanate-propyltriethoxysilane; etc. silane coupling agents (i).

[0046] Tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetraacetoxysilane, etc.; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldimethoxysilane. Alkylalkoxysilanes, including tetraalkoxysilanes, dimethyldiethoxysilanes, dimethyldiethoxysilanes, dimethyldiethoxysilanes, dimethyldiethoxysilanes, diethyldiethoxysilanes, diethyldiethoxysilanes, diethyldiethoxysilanes, diethyldiethoxysilanes, diethyldiethoxysilanes, dipropyldiethoxysilanes, dipropyldiethoxysilanes, dibutyldiethoxysilanes, dibutyldiethoxysilanes, diphenyldiethoxysilanes, diphenyldiethoxysilanes, diphenyldiethoxysilanes, dimethoxymethylphenylsilanes, methylphenyldiethoxysilanes, cyclohexylmethyldiethoxysilanes, dimethyldiacetoxysilanes, diphenyldiacetoxysilanes, and other alkylalkoxysilanes; or, alkoxysilane modified by modifying at least a portion of the alkoxy groups in these tetraalkoxysilanes or alkylalkoxysilanes with compounds containing polyoxyalkyl groups, fluorinated compounds, etc.; and other alkoxysilanes (ii).

[0047] Cyclic siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane (iii) may be used. One or more of these may be used.

[0048] The proportion of alkoxysilane compound relative to 100 parts by weight of (meth)acrylate is preferably 2 to 100 parts by weight, more preferably 10 to 90 parts by weight, and even more preferably 20 to 85 parts by weight. When the alkoxysilane compound is in this proportion, it is preferred in terms of crack resistance, weather resistance, and polymerization stability.

[0049] (A) The components may include monomers other than those mentioned above (other monomers) as components of the resin. Other monomers can include, for example, carboxyl-containing monomers such as acrylic acid (Tg: 106℃), methacrylic acid (Tg: 185℃), itaconic acid (Tg: 100℃), and maleic acid (Tg: 130℃); aromatic monomers such as styrene (Tg: 100℃) and α-methylstyrene (Tg: 168℃); carbonyl-containing monomers such as acrolein (Tg: 60℃) and diacetone acrylamide (Tg: 65℃); hydroxyl-containing monomers such as 2-hydroxyethyl acrylate (Tg: -15℃), 2-hydroxyethyl methacrylate (Tg: 55℃), 2-hydroxybutyl acrylate (Tg: -7℃), 2-hydroxybutyl methacrylate (Tg: 26℃), and 4-hydroxybutyl acrylate (Tg: -80℃); and N,N-dimethylaminoethyl acrylate (Tg: 18℃), N,N-dimethylaminoethyl methacrylate (Tg: 18℃), and N,N-diethylaminoethyl methacrylate. Monomers containing amino groups, such as esters (Tg: 20℃); monomers containing amide groups, such as acrylamide (Tg: 179℃) and N,N-dimethylaminopropylacrylamide (Tg: 134℃); monomers containing nitrile groups, such as acrylonitrile (Tg: 125℃); monomers containing epoxy groups, such as glycidyl methacrylate (Tg: 46℃); monomers containing oxazoline groups, such as 2-isopropen-2-oxazoline (Tg: 100℃); 2-[2'-hydroxy-5'-methyl... UV absorbers containing ethylene unsaturated double bonds, such as [-2H-benzotriazole (Tg: 100℃)]-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine (Tg: 130℃); and other vinyl monomers containing sulfonic acids, acid anhydrides, chlorinated monomers, fluorinated monomers, alkyl glycol monoallyl ethers, vinyl acetate, vinyl propionate, vinyl ethers, ethylene, propylene, isobutylene, etc. One or more of these can be used.

[0050] The proportion of other monomers relative to 100 parts by weight of alkyl methacrylate is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and even more preferably 0.3 to 10 parts by weight. By using other monomers within this range, it can be endowed with various functions (e.g., crosslinking properties, stability, dispersibility, etc.).

[0051] In this invention, monomers obtained from biological resources, i.e., bio-based monomers, can be used as the monomers constituting component (A). By introducing such bio-based monomers, the biomass value of component (A) and even aqueous coating materials can be increased, while reducing the amount of petroleum-derived compounds used. Using such materials also helps to achieve decarbonization. For example, monomers made from bio-derived alcohols, organic acids, hydrocarbons, etc., can be used as bio-based monomers. Since alkyl (meth)acrylates having 4 or more carbon atoms are widely used in actual production, this invention can effectively obtain aqueous coating materials with high biomass value as bio-based monomers.

[0052] (A) The component can be manufactured by polymerizing the above-mentioned resin components. Known polymerization methods can be used, including conventional emulsion polymerization, as well as soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, multi-stage emulsion polymerization, etc. In multi-stage emulsion polymerization, it can be manufactured using two-stage or three-stage or higher emulsion polymerization methods.

[0053] In the polymerization process of component (A), emulsifiers, initiators, dispersants, polymerization inhibitors, polymerization inhibitors, buffers, chain transfer agents, pH adjusters, etc., may be used.

[0054] As an emulsifier, various surfactants that can be used in emulsion polymerization can be used. These surfactants can be reactive types with polymerizable unsaturated double bonds (reactive surfactants).

[0055] As emulsifiers, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc., can be used. In addition, high molecular weight 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.

[0056] The proportion of emulsifier relative to the total amount of resin components is preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass.

[0057] As a monomer constituting acrylic silicone resin, component (A) of the present invention comprises two or more homopolymers with a Tg of 0°C or below (preferably -15°C or below, more preferably -30°C or below) and having an alkyl group having 4 or more carbon atoms, and is a (meth)acrylate alkyl ester(s) (hereinafter also referred to as "(s) component").

[0058] (s) Components may include, for example, n-butyl acrylate (Tg: -54℃), isobutyl acrylate (Tg: -26℃), n-amyl methacrylate (Tg: -5℃), isoamyl acrylate (Tg: -45℃), n-hexyl acrylate (Tg: -57℃), n-hexyl methacrylate (Tg: -5℃), 2-ethylhexyl acrylate (Tg: -70℃), 2-ethylhexyl methacrylate (Tg: -10℃), n-octyl acrylate (Tg: -65℃), 2-acrylic acid Octyl acrylate (Tg: -44℃), isooctyl methacrylate (Tg: -45℃), isooctyl acrylate (Tg: -70℃), isononyl acrylate (Tg: -58℃), isodecanyl acrylate (Tg: -60℃), isodecanyl methacrylate (Tg: -41℃), tridecyl acrylate (Tg: -55℃), tridecyl methacrylate (Tg: -40℃), n-dodecyl methacrylate (Tg: -65℃), tetradecyl methacrylate (Tg: -72℃), etc. Two or more of these can be used (preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3). Among these, isoamyl acrylate, n-hexyl acrylate, n-octyl acrylate, octyl 2-acrylate, n-dodecyl methacrylate, etc., are preferred because they can be used as bio-based monomers.

[0059] In this invention, because component (A) has this specific composition, it exhibits excellent performance in terms of crack resistance and weather resistance. Although the reasons for this performance are not limited to those described below, it is speculated that, as component (S), as mentioned above, the coexistence of two or more alkyl groups with different chemical structures not only improves film-forming properties but also gives the film coating a certain strength, etc., thanks to the effect of these alkyl groups.

[0060] The alkyl group in component (s) has 4 or more carbon atoms, preferably 4 to 12, more preferably 4 to 10, and even more preferably 5 to 8. In this invention, by using two or more components (s) having this number of carbon atoms, excellent performance can be achieved in terms of crack resistance, weather resistance, etc.

[0061] In the total amount of (meth)acrylate alkyl esters, the proportion of (s) component is preferably 20-80% by mass, more preferably 30-70% by mass. Furthermore, among two or more (s) components, the proportion of the (s) component with the highest proportion in the total amount of (s) component is preferably 20-95% by mass, more preferably 25-85% by mass, and even more preferably 30-70% by mass. When the (s) component is in this form, this form is preferred in terms of room temperature curing properties, crack resistance, and weather resistance.

[0062] In the present invention, preferably, at least one of the components (S) is an alkyl (meth)acrylate (S1) having a branched alkyl group having 5 or more carbon atoms (hereinafter also referred to as "(S1) component"). The alkyl group in the (S1) component preferably has 5 or more carbon atoms, more preferably 5 to 12, further preferably 5 to 10, and particularly preferably 5 to 8. It should be noted that, in this application, "branched alkyl group having 5 or more carbon atoms" refers to an alkyl group having a main chain and side chains, and the total number of carbon atoms in the main chain and side chains is 5 or more.

[0063] Component (s1) can be, for example, isoamyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, isooctyl methacrylate, isooctyl acrylate, isononyl acrylate, isodecanyl acrylate, isodecanyl methacrylate, etc. Preferably, component (A) contains at least one of these (s1) components as monomers constituting the acrylic silicone resin; more preferably, it contains two or more. Because component (A) contains this (s1) component, it can further exhibit excellent properties in terms of crack resistance, swelling resistance, and weather resistance. Although the reasons for this property are not limited to those described below, it is speculated that the film formed after coating has a certain strength due to the effect of branched alkyl groups, etc.

[0064] In the total amount of (s) component, the proportion of (s1) component is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30 to 100% by mass. When the (s1) component is in this form, this form is preferred in terms of improving properties such as crack resistance, swelling resistance, and weather resistance.

[0065] In the present invention, in component (A), preferably, at least one of the components (S) has a branched alkyl group having 5 or more carbon atoms, and the branched alkyl group is a methyl alkyl methacrylate (S11) (hereinafter also referred to as "(S11) component"). The alkyl group in the (S11) component preferably has 5 or more carbon atoms, more preferably 5 to 12, further preferably 5 to 10, and particularly preferably 5 to 8.

[0066] The (s11) component can be, for example, isoamyl acrylate, octyl 2-acrylate, isooctyl methacrylate, isooctyl acrylate, isononyl acrylate, isodecanyl acrylate, isodecanyl methacrylate, etc. Preferably, component (A) contains at least one of these (s11) components as monomers constituting the acrylic silicone resin; more preferably, it contains two or more. Because component (A) contains this (s11) component, it can further exhibit excellent properties in terms of crack resistance, swelling resistance, and weather resistance. In particular, the (s11) component plays an important role in water resistance and swelling resistance in the early stages of film formation. Although the reasons for this performance are not limited to those described below, it is speculated that the coating after film formation has a certain strength in the early stages due to the effect of the branched alkyl groups with methyl groups, etc.

[0067] In the total amount of (s) component, the proportion of (s11) component is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30 to 100% by mass. When the (s11) component is in this form, this form is preferred in terms of improving properties such as crack resistance, swelling resistance, and weather resistance.

[0068] In component (A) of this invention, the residual silica content in the resin solids is 1-40% by mass, preferably 5-35% by mass, and more preferably 10-30% by mass. Since the residual silica content in component (A) is within the above range, it contains a relatively high amount of silicon, thus ensuring excellent weather resistance while maintaining properties such as crack resistance. If the residual silica content is below the lower limit, sufficient properties in terms of weather resistance are difficult to obtain; if the residual silica content exceeds the upper limit, crack resistance is insufficient, and the weather resistance is also likely to be disadvantageous.

[0069] It should be noted that the residual silica ratio refers to the mass percentage of silica (SiO2) that remains after calcination of components with Si-O bonds at 900°C. Generally, alkoxysilanes have the property of undergoing hydrolysis with water to form silanols, followed by condensation reactions between silanols or between silanols and alkoxy groups. When this reaction proceeds to completion, silica (SiO2) is ultimately formed. These reactions can be represented by the following general formula (reaction equation):

[0070] RO(Si(OR)2O) n R+(n+1)H2O→nSiO2+(2n+2)ROH

[0071] The residual silica ratio is calculated based on this reaction formula to determine the amount of residual silica.

[0072] In component (A), the type and proportion of alkoxysilane compounds in the resin composition can be set to meet the aforementioned silica residual ratio. As shown in the general formula above, n moles of Si will generate n moles of SiO2. Based on this, the silica residual ratio in component (A) can be set according to the proportion of monomolecular silicon atoms in the alkoxysilane compounds used and their addition ratio.

[0073] For the alkoxysilane compound in component (A), it can be, for example, in the form of (1) containing a silane coupling agent (i); (2) containing alkoxysilanes (ii) and / or cyclic siloxanes (iii); or (3) containing a silane coupling agent (i) and alkoxysilanes (ii) and / or cyclic siloxanes (iii). Among these, the forms of (2) or (3) above (especially the form of (3)) are preferred in terms of increasing the proportion of silicon content.

[0074] In the above-described (3) form, in the total amount of silane coupling agent (i), alkoxysilane (ii), and cyclic siloxane (iii), preferably, the proportion of silane coupling agent (i) is 1 to 30% by mass, more preferably 2 to 25% by mass.

[0075] The glass transition temperature (Tg) of component (A) is below 30°C, preferably -50°C to 25°C, more preferably -40°C to 20°C, and even more preferably -30°C to 15°C. Because the Tg of component (A) is within the above range, it exhibits excellent performance in terms of room temperature curing properties, crack resistance, and even weather resistance and stain resistance. If the Tg exceeds the above upper limit, it is difficult to obtain sufficient properties in terms of room temperature curing properties and crack resistance. In component (A), the types and proportions of monomers used as resin components can be set to satisfy the above glass transition temperature.

[0076] (A) The average particle size of the component is preferably less than 300 nm, more preferably 20 to 250 nm, and even more preferably 50 to 200 nm. It should be noted that the average particle size here is a value measured by dynamic light scattering method.

[0077] As long as the Tg of component (A) in this invention is below 30°C, a mixture of multiple resin phases can be formed. For example, a resin containing a hard resin phase with a Tg of 15°C or higher and a soft resin phase with a Tg of 0°C or lower, and the total Tg of the resin constituting component (A) is below 30°C, can be used as such component (A).

[0078] The hard resin phase can be obtained by polymerizing one or more of the monomers mentioned above (preferably two or more) to achieve a Tg of 15°C or higher (more preferably 30°C or higher, and even more preferably 50°C or higher).

[0079] Preferably, the hard resin phase comprises alkyl (meth)acrylates with a Tg of 15°C or higher (more preferably 30°C or higher, and even more preferably 50°C or higher) as a resin component.

[0080] The soft resin phase can be obtained by polymerizing two or more of the monomers mentioned above, so that its Tg is below 0°C (more preferably below -15°C, and even more preferably below -30°C).

[0081] Preferably, the soft resin phase comprises alkyl (meth)acrylates with a Tg of less than 0°C (more preferably less than -15°C, and even more preferably less than -30°C) as a resin component.

[0082] The ratio of hard resin phase to soft resin phase in component (A) can be set within a range where the overall resin Tg is below 30°C. In the resin solids content of component (A), the proportion of hard resin phase is preferably 10-90% by mass, more preferably 20-80% by mass, and even more preferably 30-70% by mass. In the resin solids content of component (A), the proportion of soft resin phase is preferably 10-90% by mass, more preferably 20-80% by mass, and even more preferably 30-70% by mass. Using this mass ratio makes it easier to stably obtain the effects of the present invention described above. It should be noted that component (A) may, for example, have a form containing two or more hard resin phases with different Tgs, or a form containing two or more soft resin phases with different Tgs. Furthermore, component (A) may also have a form containing a resin phase different from the aforementioned hard and soft resin phases (e.g., a resin phase having a Tg between the hard and soft resin phases (Tg greater than 0°C and less than 15°C)).

[0083] When component (A) contains both a hard resin phase and a soft resin phase, as long as the above conditions are met, the hard resin phase and the soft resin phase can coexist within the same emulsion particle or exist separately in different emulsion particles. Specifically, for example, it can be (I) a multilayer acrylic silicone resin emulsion containing both a hard resin phase and a soft resin phase within the same emulsion particle; (II) an acrylic silicone resin emulsion containing a hard resin phase; and a mixture of acrylic silicone resin emulsions containing a soft resin phase, etc.

[0084] <(B) Component>

[0085] Pigment (B) (hereinafter also referred to as "(B) component") refers to at least one component that is beneficial to color development, hiding power, gloss, aesthetics, strength, etc. For example, coloring pigment (B1) (hereinafter also referred to as "(B1) component"), extender pigment (B2) (hereinafter also referred to as "(B2) component"), etc. can be used as (B) component.

[0086] The content of component (B) is preferably 5 to 650 parts by mass relative to the solid content of component (A) per 100 parts by mass, more preferably 10 to 500 parts by mass, even more preferably 15 to 300 parts by mass, and especially preferably 20 to 200 parts by mass.

[0087] Coloring pigments (B1) can be, for example, titanium dioxide, zinc oxide, carbon black, graphite, iron oxide black, iron-manganese composite oxides, iron-copper-manganese composite oxides, iron-chromium composite oxides, iron-chromium-cobalt composite oxides, copper-chromium composite oxides, copper-manganese-chromium composite oxides, copper-magnesium composite oxides, bismuth-manganese composite oxides, Bengal red, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, iron oxide yellow, titanium yellow, lightfast yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, indigo, cobalt blue, phthalocyanine blue, quinacridone violet, carbazole violet, aluminum pigments, pearlescent pigments, etc. One or more of these pigments can be used.

[0088] The average particle size of component (B1) is preferably less than 2 μm, more preferably 0.01 to 1 μm. It should be noted that the average particle size of pigment (B) is a value measured by a laser diffraction particle size distribution measuring device.

[0089] The content of component (B1) is preferably 250 parts by weight or less, more preferably 5 to 200 parts by weight, and even more preferably 10 to 150 parts by weight, relative to the solid content of 100 parts by weight of component (A). When the content of component (B1) is within this range, the coating film exhibits excellent color development, hiding power, and aesthetics, and is conducive to demonstrating the effects of the present invention.

[0090] Extender pigments (B2) can include, for example, heavy calcium carbonate, light calcium carbonate, kaolin, clay, aluminum silicate, calcined clay, calcined kaolin, pottery clay, Chinese clay, diatomaceous earth, hydrous microcrystalline silica, silica gel, zeolite, sodium sulfate, diatomite, 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, Ōtani stone powder, activated clay, activated carbon, and cenospheres. One or more of these can be used.

[0091] The average particle size of the extender pigment is preferably 0.1 to 100 μm, more preferably 0.3 to 50 μm.

[0092] The content of component (B2) is preferably 400 parts by weight or less, more preferably 10 to 350 parts by weight, further preferably 15 to 300 parts by weight, and especially preferably 20 to 200 parts by weight, relative to the solid content of component (A) per 100 parts by weight. When the content of component (B2) is within this range, the strength and aesthetics of the coating film are excellent, which is beneficial to demonstrating the effects of the present invention. In addition, the gloss of the coating can be set to low gloss (e.g., semi-gloss, three-quarter gloss, matte, etc.).

[0093] <(C) Component>

[0094] In the aqueous coating material of the present invention, a crosslinking agent (C) (hereinafter also referred to as "component (C)") can be mixed with component (A). In this case, an acrylic silicone resin emulsion having reactive functional groups can be used as component (A), and a crosslinking agent having functional groups capable of reacting with these reactive functional groups can be used as component (C). When such a component is present, in addition to the effects of component (S) described above, the crosslinking reaction between component (A) and the crosslinking agent enables the coating to have a certain strength during and after film formation, thereby improving properties such as crack resistance, swelling resistance, and weather resistance.

[0095] (C) The preferred components are, for example, water-soluble crosslinking agents, water-dispersible crosslinking agents, self-emulsifying crosslinking agents, etc.

[0096] In components (A) and (C), the reactive functional groups that can be used in this crosslinking reaction may be, for example, one or more selected from carboxyl, carbodiimide, epoxy, aziroxy, oxazoline, hydroxy, isocyanate, carbonyl, acylhydrazine, epoxy, amino, and alkoxysilyl.

[0097] In components (A) and (C), this reactive functional group can be used in combination. Examples of combinations of reactive functional groups include carboxyl and carbodiimide, carboxyl and epoxy, carboxyl and oxazoline, carboxyl and aziridine, hydroxyl and isocyanate, carbonyl and hydrazide, epoxy and amino, and alkoxysilyl groups. One or more of these combinations can be used.

[0098] (A) The preferred reactive functional groups in the component can be, for example, carboxyl, carbonyl, alkoxysilyl, etc.

[0099] Specifically, when component (A) has a carboxyl group, component (C) may, for example, be a compound having one or more reactive functional groups selected from carbodiimide, epoxy, oxazoline, etc. Among these, the crosslinking agent having a carbodiimide group may be, for example, the crosslinking agent described in Japanese Patent Application Publication No. 10-60272, Japanese Patent Application Publication No. 10-316930, Japanese Patent Application Publication No. 11-60667, Japanese Patent Application Publication No. 2000-7642, Japanese Patent Application Publication No. 2000-119539, Japanese Patent Application Publication No. 2000-319351, Japanese Patent Application Publication No. 2013-112755, Japanese Patent Application Publication No. 2016-196612, Japanese Patent Application Publication No. 2016-196613, WO2017 / 6950, etc. Crosslinking agents with epoxy groups can be, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, diglycerol diglycidyl ether, polyglycerol diglycidyl ether, diglycerol diglycidyl ether, polyhydroxyalkane polyglycidyl ether, sorbitol polyglycidyl ether, etc. Crosslinking agents with oxazoline groups can be, for example, resins copolymerized from polymerizable oxazoline compounds such as 2-ethylene-2-oxazoline, 2-ethylene-4-methyl-2-oxazoline, 2-ethylene-5-methyl-2-oxazoline, and 2-isopropene-2-oxazoline with monomers that can copolymerize with these compounds. One or more of these can be used.

[0100] As a component of resin, for example, a component (A) with a carboxyl group can be obtained by using carboxyl-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid.

[0101] When component (A) has a carbonyl group, component (C) may be a compound having an acylhydrazine group, for example. Crosslinking agents having an acylhydrazine group may be, for example, malonyl hydrazine, succinic hydrazine, glutaric hydrazine, adipic hydrazine, sebacic hydrazine, maleic hydrazine, etc. One or more of these may be used.

[0102] As a component of resin, a component (A) with a carbonyl group can be obtained, for example, by using carbonyl-containing monomers such as acrolein, diacetone acrylamide, etc.

[0103] When component (A) has an alkoxysilane group, component (C) may, for example, use a compound having an alkoxysilane group. The crosslinking agent having an alkoxysilane group may, for example, be an alkoxysilane compound such as the silane coupling agent described in component (A) above, or an alkoxysilane. One or more of these compounds may be used.

[0104] The proportion of component (C), based on solid content, is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, relative to the resin solid content of 100 parts by weight of component (A). Using this proportion can significantly improve crack resistance, swelling resistance, and weather resistance.

[0105] In the water-based coating material of the present invention, in addition to the above-mentioned components, various additives may be mixed in. Such additives may include, for example, pigment dispersants, viscosity modifiers, leveling agents, coupling agents, wetting agents, film-forming aids, plasticizers, antifreeze agents, pH adjusters, preservatives, mildew inhibitors, algaecides, antibacterial agents, defoamers, adsorbents, deodorizers, ultraviolet absorbers, light stabilizers, hydrophilic agents, antioxidants, catalysts, solvents, and water. One or more of these additives may be used as needed.

[0106] Among them, pigment dispersants help to stabilize the dispersion of the above-mentioned component (B) and enhance the performance of the above-mentioned component (B).

[0107] One or more of commercially available products or known substances can be used as pigment dispersants, such as pigment dispersants with styrene-maleic acid copolymer resin, polyurethane resin, polyester resin, acrylic resin, etc. as the resin skeleton.

[0108] The pigment dispersant in the aqueous coating material of the present invention is preferably a pigment dispersant having acid groups and / or base groups. Such a pigment dispersant can improve the dispersion stability of component (B), etc.

[0109] In addition, generally speaking, in water-based coating materials that use acrylic silicone resin emulsions containing a large amount of silicon as adhesives, problems such as coating cracking and insufficient weather resistance of the coating are prone to occur due to factors such as excessive promotion of the reaction of silicon components by pigment dispersants. However, in the present invention, even if such pigment dispersants are used, as long as component (A) with the above-mentioned specific resin composition is used, excellent performance in terms of crack resistance and weather resistance can be achieved.

[0110] The acid group can be, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Similarly, the base group can be, for example, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group, etc. Component (C) can have one or more of these acid groups or base groups. A preferred example of component (C) is a polycarboxylic acid type dispersant such as polyacrylic acid, polymethacrylic acid, or styrene-maleic acid copolymer resin; a sulfonic acid type dispersant such as lignin sulfonic acid or naphthalene sulfonic acid; a phosphoric acid type dispersant such as a phosphate ester compound; or a polymeric dispersant having an acid value and / or an amine value, etc.

[0111] The content of component (C) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, relative to the solid content of 100 parts by weight of component (A).

[0112] <(D) component>

[0113] In addition to the above-mentioned components, the aqueous coating material of the present invention may also be mixed with ether or ester solvents (D) (hereinafter also referred to as "(D) component"). In (D) component, ether solvents refer to solvents containing ether bonds in their molecules, and ester solvents refer to solvents containing ester bonds in their molecules.

[0114] In this invention, component (D) may include an ether or ester solvent (D1) (hereinafter also referred to as "(D1) component") with a solubility of 0.5 to 50 g / 100 g H2O in water. An ether solvent with a solubility of 0.5 to 50 g / 100 g H2O in water, and / or an ester solvent with a solubility of 0.5 to 50 g / 100 g H2O in water may be used. If this (D1) component is included, the water-based coating material of this invention can exhibit superior performance in terms of crack resistance and weather resistance. When the water-based coating material is a glossy material, it can also improve gloss, etc.

[0115] It should be noted that the solubility in water in this invention refers to the maximum mass (g) that can be dissolved in 100g of water. The measurement temperature was 20℃.

[0116] As component (D1), ether or ester solvents with solubility in water within the above-mentioned range can be used. Specific compounds include, for example, ethylene glycol monohexyl ether (solubility in water: 0.99 g / 100 g H2O, boiling point: 208 °C), propylene glycol phenyl ether (solubility in water: 1 g / 100 g H2O, boiling point: 243 °C), ethylene glycol monobutyl ether acetate (solubility in water: 1.1 g / 100 g H2O, boiling point: 188 °C), diethylene glycol monobutyl ether acetate, etc. Diethylene glycol monohexyl ether (solubility in water: 1.7 g / 100 g H₂O, boiling point: 258 °C), ethylene glycol monophenyl ether (solubility in water: 2.6 g / 100 g H₂O, boiling point: 245 °C), tripropylene glycol monobutyl ether (solubility in water: 3 g / 100 g H₂O, boiling point: 274 °C), diethylene glycol monophenyl ether (solubility in water: 3.4 g / 100 g H₂O, boiling point: 283 °C), dipropylene glycol monobutyl ether (solubility in water: ... The following are listed: 5 g / 100 g H₂O (solubility in water: 5 g / 100 g H₂O, boiling point: 229 °C), propylene glycol monobutyl ether (solubility in water: 6 g / 100 g H₂O, boiling point: 170 °C), diethylene glycol monobutyl ether acetate (solubility in water: 6.5 g / 100 g H₂O, boiling point: 247 °C), propylene glycol diacetate (solubility in water: 8 g / 100 g H₂O, boiling point: 161 °C), and propylene glycol monomethyl ether acetate (solubility in water: 16 g / 100 g H₂O). The following are some examples: dipropylene glycol monopropyl ether (solubility in water: 19 g / 100 g H₂O, boiling point: 212 °C), dipropylene glycol monomethyl ether acetate (solubility in water: 19 g / 100 g H₂O, boiling point: 209 °C), ethylene glycol diethyl ether (solubility in water: 20 g / 100 g H₂O, boiling point: 121 °C), and ethylene glycol monoethyl ether acetate (solubility in water: 23 g / 100 g H₂O, boiling point: 156 °C). One or more of these can be used.

[0117] The solubility of component (D1) in water is 0.5–50 g / 100 g H2O, preferably 0.8–25 g / 100 g H2O, and more preferably 1–10 g / 100 g H2O. 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. From the viewpoint of achieving the effects of the present invention, component (D1) satisfying these characteristic values ​​is preferred.

[0118] The reason why component (D1) can exert the effects of the present invention is not limited to the following description. It is speculated that component (D1) has intermediate properties of hydrophobicity and hydrophilicity, and these properties improve its affinity with acrylic and silicone components.

[0119] As component (D1), it is preferred to have a hydrophobic group having 4 or more carbon atoms, more preferably a hydrophobic group having 6 or more carbon atoms, and especially preferably a component having a phenyl group.

[0120] The content of component (D1) is preferably 1 to 40 parts by mass relative to the solid content of component (A) per 100 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. When the content of component (D1) is within this range, it can further exhibit excellent performance in terms of room temperature curing properties, crack resistance, and even weather resistance.

[0121] In this invention, two or more (D1) components may be included as (D) components. For example, two (D1) components may be used, preferably with a difference in solubility in water of 0.5 to 15 g / 100 g H2O (more preferably 0.8 to 10 g / 100 g H2O, and even more preferably 1 to 5 g / 100 g H2O). From the viewpoint of improving the gloss effect of this invention, this form is preferred.

[0122] In this invention, in addition to the above-mentioned component (D1), component (D) may also include an ether or ester solvent (D2) with a solubility in water greater than 50 g / 100 g H2O (hereinafter also referred to as "component (D2)").

[0123] As component (D2), ether solvents with a solubility in water greater than 50 g / 100 g H2O, and / or ester solvents with a solubility in water greater than 50 g / 100 g H2O, can be used. Specific compounds may include: ethylene glycol monomethyl ether (solubility in water is ∞, boiling point is 125°C), ethylene glycol monoethyl ether (solubility in water is ∞, boiling point is 135°C), ethylene glycol monopropyl ether (solubility in water is ∞, boiling point is 150°C), ethylene glycol monoisopropyl ether (solubility in water is ∞, boiling point is 143°C), ethylene glycol monobutyl ether (solubility in water is ∞, boiling point is 143°C), and ethylene glycol monobutyl ether (solubility in water is ∞, boiling point is 143°C). The following are listed: Ethylene glycol monoisobutyl ether (solubility in water is ∞, boiling point is 161℃), ethylene glycol monotert-butyl ether (solubility in water is ∞, boiling point is 153℃), ethylene glycol monomethyl ether acetate (solubility in water is ∞, boiling point is 145℃), ethylene glycol monoethyl ether acetate (solubility in water is ∞, boiling point is 156℃), ethylene glycol dimethyl ether (solubility in water is ∞, boiling point is 85℃), diethylene glycol monomethyl ether (solubility in water is ∞, boiling point is 194℃), diethylene glycol monoethyl ether (solubility in water is ∞, boiling point is 202℃), diethylene glycol monobutyl ether... Ether (solubility in water is ∞, boiling point is 230℃), diethylene glycol monoisobutyl ether (solubility in water is ∞, boiling point is 220℃), diethylene glycol monoethyl ether acetate (solubility in water is ∞, boiling point is 217℃), diethylene glycol dimethyl ether (solubility in water is ∞, boiling point is 162℃), diethylene glycol diethyl ether (solubility in water is ∞, boiling point is 189℃), triethylene glycol monomethyl ether (solubility in water is ∞, boiling point is 249℃), triethylene glycol monobutyl ether (solubility in water is ∞, boiling point is 271℃), triethylene glycol monoethyl ether (solubility in water is ∞) The following are some of the propylene glycol monomethyl ethers available: propylene glycol monomethyl ether (solubility in water is ∞, boiling point is 120℃), propylene glycol monoethyl ether (solubility in water is ∞, boiling point is 133℃), propylene glycol monopropyl ether (solubility in water is ∞, boiling point is 150℃), dipropylene glycol monomethyl ether (solubility in water is ∞, boiling point is 190℃), dipropylene glycol dimethyl ether (solubility in water is 53g / 100gH2O, boiling point is 175℃), tripropylene glycol monomethyl ether (solubility in water is ∞, boiling point is 242℃), and butanediol monomethyl ether (solubility in water is ∞, boiling point is 161℃). One or more of these propylene glycol monomethyl ethers may be used.

[0124] The solubility of component (D2) in water is greater than 50 g / 100 g H2O, preferably ∞. Furthermore, the boiling point of component (D2) is preferably 150 °C or higher. From the viewpoint of improving the effectiveness of the present invention, component (D2) satisfying these characteristic values ​​is preferred.

[0125] In this invention, in addition to the above-mentioned component (D1), component (D) may also include an ether or ester solvent (D3) with a solubility in water of less than 0.5 g / 100 g H2O (hereinafter also referred to as "component (D3)").

[0126] As component (D3), ether solvents with a solubility of less than 0.5 g / 100 g H2O in water, and / or ester solvents with a solubility of less than 0.5 g / 100 g H2O in water can be used. Specific compounds include, for example, diethylene glycol dibutyl ether (solubility in water is 0.3 g / 100 g H2O, boiling point is 255 °C), diethylene glycol mono-2-ethylhexyl ether (solubility in water is 0.3 g / 100 g H2O, boiling point is 272 °C), and ethylene glycol mono-2-ethylhexyl ether (solubility in water is 0.3 g / 100 g H2O, boiling point is 272 °C). The following are some of the ingredients that can be used: ethylene glycol dibutyl ether (0.2 g / 100 g H₂O, boiling point 229 °C), 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (0.09 g / 100 g H₂O, boiling point 255 °C), and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (0.04 g / 100 g H₂O, boiling point 282 °C). One or more of these ingredients may be used.

[0127] The solubility of component (D3) in water is less than 0.5 g / 100 g H2O, preferably less than 0.4 g / 100 g H2O, and more preferably 0.01 to 0.4 g / 100 g H2O. Furthermore, the boiling point of component (D3) is preferably 200°C or higher, more preferably 220°C or higher. From the viewpoint of improving the effect of the present invention, component (D3) satisfying these characteristic values ​​is preferred.

[0128] In this invention, the (D) component can be in the form of including (D1), including (D1) and (D2), including (D1) and (D3), including (D1), (D2), and (D3). In these forms, more than two (D1) components may also be included.

[0129] When component (D2) is included as component (D), the content of component (D2) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to the solid content of 100 parts by mass of component (A). In this case, the mass ratio of component (D1) to component (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 content of component (D3) is preferably 1 to 30 parts by mass, more preferably 2 to 30 parts by mass, relative to the solid content of 100 parts by mass 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. From the viewpoint of improving the effectiveness of the present invention, this form is preferred.

[0130] In the aqueous coating material of the present invention, in addition to the above-mentioned components, resin emulsions, water-soluble resins, etc., other than component (A) may also be mixed.

[0131] Resin emulsions other than component (A) can be, for example, acrylic resin emulsions, polyurethane resin emulsions, fluoropolymer resin emulsions, epoxy resin emulsions, etc. Acrylic silicone resin emulsions other than component (A) can also be used.

[0132] Water-soluble resins can be, for example, polyurethane resins, polyacrylic acid resins, polyvinyl alcohol, polyvinylpyrrolidone, etc. One or more of these can be used as needed. From the perspective of improving weather resistance, polyurethane resin emulsions, fluoropolymer emulsions, etc., are preferred.

[0133] The water-based coating material of the present invention can be manufactured by uniformly mixing the above-mentioned components (A) and (B), as well as components (C) and various additives as necessary.

[0134] [Coating Formation Method]

[0135] The water-based coating material of the present invention can preferably be used, for example, for surface treatment of the coating surface of buildings or civil structures. In the present invention, the coating surface to be coated can be, for example, the exterior wall surface (e.g., exterior wall, roof, etc.) of buildings or civil structures.

[0136] The substrates constituting the coated surface can be, for example, concrete, mortar, ceramic tiles, fiber-reinforced cement board, cement calcium silicate board, slag cement perlite board, cement board, ALC board, exterior wall cladding, gypsum board, plywood, extruded polystyrene board, steel plate, plastic board, etc. When the coated surface is composed of multiple plate-shaped substrates, the joints between the plate-shaped substrates can be filled with sealant, dry caulking material, or other joint filling materials.

[0137] The surfaces of these substrates can be surfaces that have undergone some kind of surface treatment (e.g., treated with putty, sealant, topcoat, filler, etc.) or surfaces that have already formed a coating (e.g., surfaces with an existing coating).

[0138] The surface to be coated can be a surface with an existing coating. Such an existing coating may be formed, for example, by one or more coating agents.

[0139] As a coating agent, various coating agents can be used, such as colored or uncolored, opaque or transparent, for example, coating agents containing one or more resins selected from vinyl acetate resin, alkyd resin, epoxy resin, acrylic resin, polyurethane resin, acrylic silicone resin, silicone resin, fluoropolymer resin, etc. Existing coatings are single-layer or two-layer or more, for example, they can be any of the elastic type, rigid type, etc.

[0140] The water-based coating material of the present invention can be applied directly to the coated surface, or an undercoating material or a base coat (e.g., sealant, primer, topcoat, filler, putty, etc.) can be applied to the coated surface to treat it before coating.

[0141] In addition, the water-based coating material of the present invention can also be coated on the surface to be coated to form an elastic film before coating.

[0142] Elastic coating materials can be, for example, flexible or waterproof materials among the surface coating materials for building use specified in JIS A6909:2021, and waterproof coating materials for building use specified in JIS A6021:2022. Specifically, elastic coating materials can be, for example, flexible exterior wall silicate-based thin-coat surface coating materials (flexible exterior wall thin-coat material Si), flexible exterior wall synthetic resin emulsion-based thin-coat surface coating materials (flexible exterior wall thin-coat material E), waterproof exterior wall synthetic resin emulsion-based thin-coat surface coating materials (waterproof exterior wall thin-coat material E), flexible polymer cementitious-based multi-layer surface coating materials (flexible multi-layer coating material CE), waterproof polymer cementitious-based multi-layer surface coating materials (waterproof multi-layer coating material CE), waterproof synthetic resin emulsion-based multi-layer surface coating materials (waterproof multi-layer coating material E), and waterproof reaction-curing synthetic resin emulsion-based... Multi-layer surface coating materials (waterproof multi-layer coating material RE), waterproof synthetic resin solution-based multi-layer surface coating materials (waterproof multi-layer coating material RS), flexible synthetic resin emulsion-based repair surface coating materials (flexible repair coating material E), flexible reaction-curing synthetic resin emulsion-based repair surface coating materials (flexible repair coating material RE), flexible polymer cement-based repair surface coating materials (flexible repair coating material CE), acrylic rubber-based roofing waterproof coating materials, polyurethane rubber-based roofing waterproof coating materials, acrylic rubber-based exterior wall waterproof coating materials, polyurethane rubber-based exterior wall waterproof coating materials, etc.

[0143] There are no particular restrictions on the coating method for elastic coating materials; appropriate coating methods can be used depending on the material. Coating tools can include, for example, spray guns, rollers, trowels, and brushes.

[0144] The preferred application rate of the elastic coating material is 0.2–5 kg / m². 2 More preferably 0.3–4 kg / m 2 During coating, the elastic coating material can be diluted appropriately as needed.

[0145] The drying of elastic coating materials can be carried out at room temperature (5-40℃), or heating can be carried out as needed.

[0146] Elastic coating materials can be applied directly to the surface to be coated, or an undercoating material or primer (such as sealant, primer, topcoat, filler, putty, etc.) can be applied to the surface to be coated and then the surface is treated before coating.

[0147] The elastic coating (the coating of the elastic coating material) is preferably a coating in which the monomer coating can form an elongation of 20% or more at -10°C. Such an elastic coating can play a beneficial role, for example, in adapting to the displacement of the coated surface and preventing water, carbon dioxide, etc. from penetrating into the interior of the coated surface.

[0148] It should be noted that, in this invention, the elongation at -10°C is the value measured according to the method specified in JIS A6909:2021 "Elongation Test". An elastically coated monomer film with a dry film thickness of 1 mm should be used for the elongation test.

[0149] When applying the water-based coating material of the present invention, various coating tools such as spray guns, rollers, and brushes can be used. Among them, rollers can be made of short, medium, or long fibers (such as wool rollers).

[0150] Water can also be used for dilution during coating. The amount of water mixed should be set according to the type of coating tool, the condition of the surface to be coated, and the temperature during coating, and is preferably 0-20% by mass relative to the overall water-based coating material.

[0151] The preferred application rate of the water-based coating material of the present invention is 0.05–1 kg / m². 2 More preferably, it is 0.1–0.8 kg / m 2 More preferably, it is 0.15–0.6 kg / m³. 2 Applying this amount of water-based coating material can create a coating film with excellent aesthetics and weather resistance.

[0152] The water-based coating material of the present invention can be used as a room-temperature curing water-based coating material. Therefore, the coating and drying of the water-based coating material of the present invention can be carried out at room temperature (5-40°C). However, heating can also be performed as needed.

[0153] The drying time is preferably about 0.5 to 4 hours at room temperature.

[0154] The application can be done once or twice or more (preferably once or twice). When the application is done twice or more, the total amount applied should preferably be within the range mentioned above.

[0155] The water-based coating material of the present invention can preferably be used as an upper coating material.

[0156] The present invention is a coating formation method, wherein two specific upper coating materials (a first upper coating material and a second upper coating material) are sequentially applied (coated) to a surface to be coated to form an upper coating material coating.

[0157] <Top Coating Material>

[0158] In this invention, a first upper coating material and a second upper coating material are sequentially applied to the surface to be coated to form a film. Before applying the first upper coating material, as described above, one or more materials selected from the lower coating material, the undercoating material, the elastic coating material, etc., may be applied first.

[0159] In this invention, a coating material capable of forming a film with an elongation of 20% or more at -10°C can be used as the first upper coating material, and the aqueous coating material of this invention described above can be used as the second upper coating material. In this invention, by sequentially applying this first upper coating material and the second upper coating material to form a film, excellent performance can be achieved in terms of crack resistance, weather resistance, etc.

[0160] In addition to the conditions described above, a coating material capable of forming a film at -10°C with an elongation at less than that of the first upper coating material at -10°C is used as the second upper coating material.

[0161] The elongation of the second upper coating material at -10°C is preferably 30% or less, more preferably 1 to 30%, further preferably 5 to 28%, and especially preferably 10 to 26%. In this invention, using such a second upper coating material, a film with excellent properties in terms of anti-swelling and anti-fouling can be formed.

[0162] It should be noted that the elongation at -10°C of the second upper coating material is a value measured according to the method specified in "Elongation Test" of JIS A6909:2021. The specimen used for the elongation test is a specimen in which a second upper coating material with a dry film thickness of 80 μm is coated and laminated on the surface of the main material of the waterproof multilayer coating material E with a dry film thickness of 1 mm (whose monomer film meets the elongation requirement at -10°C specified in JIS A6909:2021).

[0163] The elongation of the second upper coating material at -10℃ can be adjusted by the Tg of component (A) and the content of component (B) in the second upper coating material.

[0164] (A) The Tg of the component is below 30°C, preferably -50°C to 25°C, more preferably -40°C to 20°C, and even more preferably -30°C to 15°C.

[0165] The content of component (B) is preferably 5 to 500 parts by mass relative to the solid content of component (A) per 100 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 10 to 200 parts by mass.

[0166] <First upper coating material>

[0167] In this invention, a coating material capable of forming a film with an elongation of 20% or more (preferably 20-50%, more preferably 22-40%) at -10°C is used as the first upper coating material. Furthermore, the elongation of this first upper coating material at -10°C is greater than that of the second upper coating material at -10°C. Therefore, a film with excellent properties in terms of crack resistance and weather resistance can be formed.

[0168] It should be noted that the elongation at -10°C of the first upper coating material is a value measured according to the method specified in "Elongation Test" of JIS A6909:2021. The specimen used for the elongation test is a specimen in which a first upper coating material film with a dry film thickness of 80 μm is coated and laminated on the surface of the main material of the waterproof multilayer coating material E with a dry film thickness of 1 mm (whose monomer film meets the elongation at -10°C specified in JIS A6909:2021).

[0169] A coating material comprising resin emulsion and pigment can be used as the first upper coating material. This first upper coating material can form a colored film by curing at room temperature.

[0170] The resin emulsion can be, for example, vinyl acetate resin emulsion, vinyl chloride resin emulsion, epoxy resin emulsion, alkyd resin emulsion, polyurethane resin emulsion, acrylic resin emulsion, acrylic silicone resin emulsion, fluoropolymer resin emulsion, or a composite system thereof. One or more of these can be used.

[0171] The resin emulsion in the first upper coating material is preferably one or more forms selected from acrylic resin emulsion and acrylic silicone resin emulsion.

[0172] As a resin component, a resin emulsion containing (meth)acrylate alkyl esters can be used as an acrylic resin emulsion.

[0173] As a resin component, a resin emulsion containing (meth)acrylate and alkoxysilane compounds can be used as an acrylic silicone resin emulsion. The same coating material as the second upper coating material (the aqueous coating material of the present invention described above) can be used as (meth)acrylate and alkoxysilane compounds.

[0174] As monomers constituting the resin, the resin emulsion in the first upper coating material may contain two or more homopolymers with a Tg of 0°C or below (preferably -15°C or below, more preferably -30°C or below) and alkyl (meth)acrylates(s) having an alkyl group having 4 or more carbon atoms. In this invention, the resin emulsion in the first upper coating material has this specific composition, thus exhibiting superior performance in terms of crack resistance, swelling resistance, and weather resistance. While the reasons for this performance are not limited to those described below, it is speculated that the coexistence of two or more alkyl groups with different chemical structures, based on the effect of these alkyl groups, not only improves film-forming properties but also gives the film a certain strength. Furthermore, the presence of alkyl groups similar to those in the second upper coating material also improves adhesion and other factors.

[0175] As component (s), the same coating material as described in the detailed description of the second upper coating material can be used.

[0176] In addition, as a monomer constituting the resin, the resin emulsion in the first upper coating material may also be in the form of a (meth)acrylate alkyl ester (s1) containing a homopolymer with a Tg of 0°C or less (preferably -15°C or less, more preferably -30°C or less) and having a branched alkyl group having 5 or more carbon atoms.

[0177] As component (s1), the same coating material as described in the detailed description of the second upper coating material may also be used.

[0178] As a monomer constituting the resin, the resin emulsion in the first upper coating material preferably contains at least one (s1) component, more preferably two or more, thus enabling it to further exhibit excellent performance in terms of crack resistance, swelling resistance, and weather resistance. Although the reasons for this performance are not limited to those described below, it is speculated that the film formed after coating has a certain strength due to the effect of branched alkyl groups, and that the presence of alkyl groups similar to those in the second upper coating material also improves adhesion.

[0179] In the resin emulsion of the first upper coating material, the branched alkyl group in the (s1) component preferably includes a methyl group. The branched alkyl group containing a methyl group (hereinafter also referred to as the "(s11) component") can be, for example, isoamyl acrylate, octyl 2-acrylate, isooctyl methacrylate, isooctyl acrylate, isononyl acrylate, isodecanyl acrylate, isodecanyl methacrylate, etc. As a monomer constituting the resin, the resin emulsion of the first upper coating material preferably contains at least one such (s11) component, more preferably two or more. Because the resin emulsion of the first upper coating material contains such a (s11) component, it can further exhibit excellent performance in terms of crack resistance, swelling resistance, and weather resistance. Although the reasons for this performance are not limited to those described below, it is speculated that it is due to factors such as the effect of the branched alkyl group containing a methyl group, which gives the film a certain strength in the early stages after film formation.

[0180] In the resin emulsion of the first upper coating material, the residual proportion of silica in the resin solid content is preferably 0.5 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 4 to 25% by mass. Therefore, it is more preferable in terms of crack resistance and weather resistance.

[0181] The glass transition temperature (Tg) of the resin emulsion in the first upper coating material is preferably below 30°C, more preferably -50°C to 30°C, and even more preferably -40°C to 25°C. Therefore, it is more preferred in terms of room temperature curing properties and crack resistance.

[0182] Specifically, the Tg of the acrylic resin emulsion is preferably -40℃ to 30℃, more preferably -30℃ to 25℃, and even more preferably -20℃ to 20℃.

[0183] The Tg of the acrylic silicone resin emulsion is preferably -50 to 20°C, more preferably -40 to 10°C, and even more preferably -30 to 5°C.

[0184] In the resin emulsion of the first upper coating material, the types and proportions of monomers used as resin components can be set to satisfy the aforementioned glass transition temperature.

[0185] The average particle size of the resin emulsion in the first upper coating material is preferably less than 300 nm, more preferably 20–250 nm, and even more preferably 50–200 nm. It should be noted that the average particle size here is a value measured by dynamic light scattering.

[0186] In addition to the resin emulsion, the first upper coating material may also contain pigment (B), which is an essential raw material for the aqueous coating material of the present invention.

[0187] Pigment (B) is a component that contributes to at least one of the following: color development, hiding power, strength, etc., and is the same as the second upper coating material. For example, coloring pigment (B1), extender pigment (B2), etc. can be used.

[0188] The content of component (B) 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 the solid content of 100 parts by weight of the resin emulsion. By mixing component (B), the hue of the first upper coating material can also be set to a similar color to that of the second upper coating material. The same pigments as those in the second upper coating material (the aqueous coating material of the present invention described above) can be used as the coloring pigment (B1) and the extender pigment (B2).

[0189] 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) relative to the solid content of 100 parts by weight of the resin emulsion is preferably 250 parts by weight or less, more preferably 5 to 200 parts by weight, and even more preferably 10 to 100 parts by weight. When the content of component (B1) is within this range, it is more preferable from the viewpoint of color development and hiding power of the coating.

[0190] 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 weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less, relative to the solid content of 100 parts by weight of the resin emulsion. Component (B2) may also be absent.

[0191] In the first upper coating material, a crosslinking agent (C) can be mixed with a resin emulsion. In this case, a resin emulsion with reactive functional groups can be used as the resin emulsion, and a crosslinking agent capable of reacting with these reactive functional groups can be used as component (C). When this component is present, the crosslinking reaction between the resin emulsion and the crosslinking agent can give the coating a certain strength during and after film formation, thereby further improving properties such as crack resistance, swelling resistance, and weather resistance.

[0192] As component (C), the same components as the second upper coating material (the aqueous coating material of the present invention described above) can be used.

[0193] The proportion of component (C) relative to the resin solid content of 100 parts by weight of the resin emulsion is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on the solid content. Using this proportion can significantly improve crack resistance, swelling resistance, and weather resistance.

[0194] In addition to the components mentioned above, various additives may be mixed into the first upper coating material. Such additives may include, for example, pigment dispersants, viscosity modifiers, leveling agents, coupling agents, wetting agents, film-forming aids, plasticizers, antifreeze agents, pH adjusters, preservatives, mildew inhibitors, algaecides, antibacterial agents, defoamers, adsorbents, deodorizers, ultraviolet absorbers, light stabilizers, hydrophilic agents, antioxidants, catalysts, solvents, and water. One or more of these additives may be used as needed. As a pigment dispersant, the same dispersant as that used in the second upper coating material (the aqueous coating material of the present invention described above) may be used, and its content, relative to the solid content of 100 parts by weight of the resin emulsion, is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. Furthermore, similarly to the second upper coating material, ether or ester solvents (D) (selected from one or more of components (D1), (D2), and (D3)) may also be mixed into the first upper coating material.

[0195] In addition to the components mentioned above, the first upper coating material may also contain water-soluble resins. Examples of water-soluble resins include polyurethane resins, polyacrylic acid resins, polyvinyl alcohol, and polyvinylpyrrolidone. One or more of these resins may be used as needed.

[0196] The first upper coating material can be manufactured by uniformly mixing the above-mentioned components, as well as various additives as necessary, using conventional methods.

[0197] The elongation of the first upper coating material at -10°C can be adjusted by the Tg of the resin emulsion in the first upper coating material, the content of component (B), etc.

[0198] The Tg of the resin emulsion in the first upper coating material is preferably below 30°C, more preferably -50°C to 30°C, and even more preferably -40°C to 25°C.

[0199] The content of component (B) 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 the solid content of 100 parts by weight of the resin emulsion.

[0200] <Coating Formation Method>

[0201] In this invention, an upper coating material film is formed by applying (coating) an upper coating material (a first upper coating material and a second upper coating material) to the surface to be coated. That is, an upper coating material film is formed by sequentially applying the first upper coating material and the second upper coating material to the surface to be coated. Before applying the first upper coating material, as described above, one or more materials selected from the lower coating material, an undercoating coating, an elastic coating material, etc., may be pre-coated.

[0202] In this invention, it is preferable to apply the first upper coating material and allow it to dry before applying the second upper coating material. The first and second upper coating materials can be the aforementioned coating materials. In this invention, by using these two specific upper coating materials to form a laminated film, excellent performance in terms of crack resistance and weather resistance is achieved.

[0203] When applying the coating material to each upper surface, known painting tools can be used. These tools may include spray guns, rollers, and brushes. During application, the coating material can be diluted appropriately as needed.

[0204] The amount of water mixed can be set according to the type of coating tool, the condition of the surface to be coated, and the temperature during coating, preferably 0 to 20% by mass.

[0205] Both the first and second top coating materials can be used as room-temperature curing water-based top coating materials. Therefore, the application and drying of each top coating material can be carried out at room temperature (5–40°C). However, heating can also be performed as needed. The drying time at room temperature is preferably about 0.5–4 hours.

[0206] The preferred application amounts of the first and second upper coating materials are 0.05–0.4 kg / m³. 2 More preferably, it is 0.08–0.3 kg / m 2 .

[0207] Furthermore, the dry film thicknesses of the first upper coating material and the second upper coating material are preferably 20–300 μm, more preferably 30–200 μm. In this way, the texture of the substrate before the upper coating material is applied can be preserved, and a coating with excellent properties in terms of weather resistance and crack resistance can be formed.

[0208] The film thickness ratio of the first upper coating material film to the second upper coating material film {(dry film thickness of the first upper coating material film):(dry film thickness of the second upper coating material film)} is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 65:35 to 35:65. This configuration allows for consistently superior performance in terms of weather resistance and crack resistance.

[0209] In the film-forming method of the present invention, for example, on the surface to be coated, after applying one or more materials selected from the lower coating material, the undercoating material, the elastic coating material, etc., as needed, a first upper coating material and a second upper coating material may be applied sequentially. The second upper coating material is preferably applied after the film of the first upper coating material has been dried (preferably after drying for more than 1 hour, more preferably after drying for more than 2 hours).

[0210] [Upper coating material group]

[0211] In this invention, the first upper coating material and the second upper coating material described above can be used as an upper coating material set, which consists of two coating materials. That is, as an upper coating material set for forming an upper coating material film on the coated surface, a coating material composed of the first upper coating material and the second upper coating material described above can be used.

[0212] Example

[0213] The features of the present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.

[0214] (Manufacturing of water-based coating materials)

[0215] The following raw materials were used in the manufacture of the water-based coating material in this embodiment:

[0216] Resin 1: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-2-ethylhexyl acrylate-n-octyl acrylate-methacrylic acid-silane coupling agent-alkoxysilane (mass ratio of 38:14:12.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0217] Resin 2: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-octyl 2-acrylate-n-octyl acrylate-methacrylic acid-silane coupling agent-alkoxysilane (mass ratio of 33:18.5:13:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0218] Resin 3: Acrylic silicone resin emulsion (an emulsified polymer with methyl methacrylate-cyclohexyl methacrylate-2-ethylhexyl acrylate-isoamyl acrylate-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio of 8:27:17:12.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0219] Resin 4: Acrylic silicone resin emulsion (an emulsified polymer with methyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, isoamyl acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (mass ratio of 8:25:16:14:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0220] Resin 5: Acrylic silicone resin emulsion (an emulsified polymer with methyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, isoamyl acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (mass ratio of 8:28:13:14:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 10℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0221] Resin 6: Acrylic silicone resin emulsion (an emulsified polymer with methyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, isoamyl acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (in a mass ratio of 8:15.5:13:15.5:1.5:1.5:1.5:43.5) as the main components, with a glass transition temperature of -4℃, a silica residue of 20% by mass, and a solid content of 40% by mass).

[0222] Resin 7: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-2-ethylhexyl acrylate-octyl 2-acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio of 32.5:12:18.5:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0223] Resin 8: Acrylic silicone resin emulsion (an emulsified polymer with methyl methacrylate, cyclohexyl methacrylate, isoamyl acrylate, octyl 2-acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (in a mass ratio of 5:22.5:17:18.5:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3°C, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0224] Resin 9: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate, isobornyl acrylate, isoamyl acrylate, octyl 2-acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (mass ratio of 23:5:18:17:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0225] Resin 10: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-2-ethylhexyl acrylate-n-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio of 36.5:13:13.5:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0226] Resin 11: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-octyl 2-acrylate-n-octyl acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio of 32:16:15:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0227] Resin 12: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-2-ethylhexyl acrylate-octyl 2-acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio of 39.5:16.5:18:1.5:1.5:1.5:21.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 10% by mass, and a solid content of 40% by mass).

[0228] It should be noted that in resins 1 to 12, γ-methacryloyloxypropyltrimethoxysilane was used as a silane coupling agent, and methyltrimethoxysilane was used as an alkoxysilane.

[0229] Resin 13: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-n-hexyl acrylate-octyl 2-acrylate-diacetone acrylamide-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio of 36.5:19:18.5:1.5:1.5:1.5:21.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 10% by mass, and a solid content of 40% by mass).

[0230] It should be noted that in resin 13, γ-methacryloxypropyltrimethoxysilane was used as a silane coupling agent, and methyltrimethoxysilane and phenyltrimethoxysilane (in a mass ratio of 19.5:2) were used as alkoxysilanes.

[0231] Resin 14: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate, n-butyl acrylate, octyl 2-acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, alkoxysilanes, and cyclic siloxanes (mass ratio of 36:17:22:1.5:1.5:1.5:17.5:3) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 10% by mass, and a solid content of 40% by mass).

[0232] It should be noted that in resin 14, γ-methacryloxypropyltrimethoxysilane was used as a silane coupling agent, and methyltrimethoxysilane and phenyltrimethoxysilane (in a mass ratio of 14.5:3) were used as alkoxysilanes.

[0233] Resin 15: Acrylic silicone resin emulsion (an emulsified polymer with methyl methacrylate, cyclohexyl methacrylate, isoamyl acrylate, octyl 2-acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (in a mass ratio of 5:24:29:21:1.5:1.5:1.5:16.5) as the main components, with a glass transition temperature of -6℃, a silica residue ratio of 8% by mass, and a solid content of 40% by mass).

[0234] Resin 16: Acrylic resin emulsion (an emulsified polymer with methyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, n-butyl acrylate, diacetone acrylamide, and methacrylic acid (in a mass ratio of 15:41.5:20:20.5:1.5:1.5) as the main components, with a glass transition temperature of 8°C and a solid content of 40% by mass).

[0235] Resin 17: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate-n-octyl acrylate-methacrylic acid-silane coupling agent-alkoxysilanes (mass ratio of 37:27.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3℃, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0236] Resin 18: Acrylic silicone resin emulsion (an emulsified polymer with cyclohexyl methacrylate, n-octyl acrylate, diacetone acrylamide, methacrylic acid, silane coupling agent, and alkoxysilanes (mass ratio of 35.8:27.2:1.5:1.5:1.5:32.5) as the main components, with a glass transition temperature of 3°C, a silica residue ratio of 15% by mass, and a solid content of 40% by mass).

[0237] It should be noted that in resins 15, 17, and 18, γ-methacryloyloxypropyltrimethoxysilane was used as a silane coupling agent, and methyltrimethoxysilane was used as an alkoxysilane.

[0238] Resin 19: Polyurethane resin emulsion (aqueous dispersion of polycarbonate-based polyurethane resin, with a solid content of 30% by mass).

[0239] Coloring pigment 1: Titanium oxide (average particle size 0.3 μm);

[0240] Pigment dispersant 1: Polycarboxylate dispersant (aqueous solution of polycarboxylate ammonium salt, solid content 30% by mass);

[0241] Coloring solution 1: Aqueous dispersion of iron oxide yellow (average particle size 0.5 μm) [the proportion of coloring pigment is 50% by mass, and the solid content of pigment dispersant {polycarboxylic acid type dispersant (styrene-maleic acid copolymer resin)} is 2% by mass];

[0242] Coloring solution 2: Aqueous dispersion of carbon black (average particle size of 0.1 μm) [the proportion of coloring pigment is 20% by mass, and the solid content of pigment dispersant {high molecular weight dispersant with acid value and amine value, and phosphoric acid type dispersant (phosphate ester compound)} is 2% by mass];

[0243] Solvent 1: Ether solvent (tripropylene glycol monobutyl ether, solubility in water is 3g / 100gH2O, boiling point is 274℃);

[0244] Solvent 2: Ether solvent (dipropylene glycol monobutyl ether, solubility in water is 5g / 100gH2O, boiling point is 229℃);

[0245] Solvent 3: Ether solvent (ethylene glycol monophenyl ether, solubility in water is 2.6 g / 100 g H2O, boiling point is 245 °C);

[0246] Solvent 4: Ether solvent (ethylene glycol monotert-butyl ether, solubility in water is ∞, boiling point is 153℃);

[0247] Solvent 5: Ether solvent (diethylene glycol monobutyl ether, solubility in water is ∞, boiling point is 230℃);

[0248] Solvent 6: Ether solvent (diethylene glycol dibutyl ether, solubility in water is 0.3 g / 100 g H2O, boiling point is 255 °C);

[0249] Solvent 7: Ether solvent (ethylene glycol mono-2-ethylhexyl ether, solubility in water is 0.2 g / 100 g H2O, boiling point is 229 °C);

[0250] Solvent 8: Ether solvent (diethylene glycol monophenyl ether, solubility in water is 3.4 g / 100 g H2O, boiling point is 283 °C);

[0251] Solvent 9: Ester solvent (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, solubility in water is 0.09 g / 100 g H2O, boiling point is 255 °C);

[0252] Thickener 1: Cellulose-based thickener;

[0253] Thickener 2: Polyurethane-based associative thickener;

[0254] Defoamer 1: Mineral oil-based defoamer;

[0255] Defoamer 2: Silicone-based defoamer;

[0256] Crosslinking agent 1: Adipate dihydrazide;

[0257] Crosslinking agent 2: Carbodiimide resin aqueous dispersion (solid content: 40% by mass);

[0258] Crosslinking agent 3: γ-glycidoxypropyltrimethoxysilane.

[0259] In addition, the official names of the abbreviations in the table are as follows:

[0260] 2EHA: 2-Ethylhexyl acrylate;

[0261] nOA: n-octyl acrylate;

[0262] 2OA: Octyl 2-acrylate;

[0263] IAA: Isoamyl acrylate;

[0264] nHA: n-Hexyl acrylate;

[0265] nBA: n-Butyl acrylate.

[0266] <Water-based coating material 1>

[0267] A coloring pigment dispersion was prepared by mixing and stirring 27 parts by weight of water with 0.4 parts by weight of thickener 1, 0.1 parts by weight of defoamer 1, 2.5 parts by weight of pigment dispersant 1, and 70 parts by weight of coloring pigment 1.

[0268] Next, 100 parts by weight of the coloring pigment dispersion was mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 1, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2 and 0.2 parts by weight of defoamer 2 to produce water-based coating material 1.

[0269] <Water-based coating material 2>

[0270] A water-based coating material 2 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 2, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2 and 0.2 parts by weight of defoamer 2.

[0271] <Water-based coating material 3>

[0272] A water-based coating material 3 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 3, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, and 0.2 parts by weight of defoamer 2.

[0273] <Water-based coating material 4>

[0274] A water-based coating material 4 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 4, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0275] <Water-based coating material 5>

[0276] A water-based coating material 5 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 5, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0277] <Water-based coating material 6>

[0278] A water-based coating material 6 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 6, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0279] <Water-based coating material 7>

[0280] A water-based coating material 7 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 7, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0281] <Water-based coating material 8>

[0282] A water-based coating material 8 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0283] <Water-based coating material 9>

[0284] A water-based coating material 9 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 9, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0285] <Water-based coating material 10>

[0286] A water-based coating material 10 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 18 parts by weight of solvent 2, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0287] <Water-based coating material 11>

[0288] A water-based coating material 11 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 8, 12 parts by weight of solvent 2, 6 parts by weight of solvent 3, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0289] <Water-based coating material 12>

[0290] A water-based coating material 12 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 12 parts by weight of solvent 2, 6 parts by weight of solvent 4, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0291] <Water-based coating material 13>

[0292] A water-based coating material 13 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 12 parts by weight of solvent 2, 6 parts by weight of solvent 5, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0293] <Water-based coating material 14>

[0294] A water-based coating material 14 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 8, 12 parts by weight of solvent 2, 6 parts by weight of solvent 6, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0295] <Water-based coating material 15>

[0296] A water-based coating material 15 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 12 parts by weight of solvent 2, 6 parts by weight of solvent 7, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0297] <Water-based coating material 16>

[0298] A water-based coating material 16 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 9, 12 parts by weight of solvent 2, 6 parts by weight of solvent 3, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0299] <Water-based coating material 17>

[0300] A water-based coating material 17 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 10, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0301] <Water-based coating material 18>

[0302] A water-based coating material 18 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 11, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0303] <Water-based coating material 19>

[0304] A water-based coating material 19 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 3, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 3 parts by weight of crosslinking agent 2.

[0305] <Water-based coating material 20>

[0306] A water-based coating material 20 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 12, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0307] <Water-based coating material 21>

[0308] A water-based coating material 21 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 13, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0309] <Water-based coating material 22>

[0310] A water-based coating material 22 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 14, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0311] <Water-based coating material 23>

[0312] A water-based coating material 23 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 9, 2 parts by weight of solvent 2, 2 parts by weight of solvent 8, 11 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0313] <Water-based coating material 24>

[0314] A water-based coating material 24 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 9, 2 parts by weight of solvent 2, 2 parts by weight of solvent 8, 11 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, 1 part by weight of crosslinking agent 1, and 10 parts by weight of coloring liquid 1.

[0315] <Water-based coating material 25>

[0316] A water-based coating material 25 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 9, 2 parts by weight of solvent 2, 2 parts by weight of solvent 8, 11 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, 1 part by weight of crosslinking agent 1, and 10 parts by weight of coloring liquid 2.

[0317] <Water-based coating material 26>

[0318] A water-based coating material 26 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight based on solid content) of resin 9, 2 parts by weight of solvent 2, 2 parts by weight of solvent 8, 11 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 3.

[0319] <Water-based coating material 27>

[0320] A water-based coating material 27 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 220 parts by weight (88 parts by weight in terms of solid content) of resin 10, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, 1 part by weight of crosslinking agent 1, and 40 parts by weight (12 parts by weight in terms of solid content).

[0321] <Water-based coating material 28>

[0322] A water-based coating material 28 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 220 parts by weight (88 parts by weight in terms of solid content) of resin 9, 2 parts by weight of solvent 2, 2 parts by weight of solvent 8, 11 parts by weight of solvent 9, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, 1 part by weight of crosslinking agent 1, and 40 parts by weight (12 parts by weight in terms of solid content).

[0323] <Water-based coating material 29>

[0324] A water-based coating material 29 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 17, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, and 0.2 parts by weight of defoamer 2.

[0325] <Water-based coating material 30>

[0326] A water-based coating material 30 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 17, 2 parts by weight of thickener 2, and 0.2 parts by weight of defoamer 2.

[0327] <Water-based coating material 31>

[0328] A water-based coating material 31 was prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as in Example 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 18, 18 parts by weight of solvent 1, 2 parts by weight of thickener 2, 0.2 parts by weight of defoamer 2, and 1 part by weight of crosslinking agent 1.

[0329] <Water-based coating material 32>

[0330] 250 parts by weight (100 parts by weight based on solid content) of resin, 17 and 18 parts by weight of solvent, 2 parts by weight of thickener, and 0.2 parts by weight of defoamer were mixed and stirred to produce an aqueous coating material 32.

[0331] (Experimental Methods)

[0332] The following methods were used to test various water-based coating materials.

[0333] [Experiment 1]

[0334] A stone slab with a textured surface (height difference of approximately 1.5 mm) made of a synthetic resin emulsion-based thick-coat surface material was prepared as the test substrate. A spray gun was used to apply a coating at a rate of 0.3 kg / m² onto this test substrate. 2 For each water-based coating material, the coated surface was placed horizontally in a thermostat at 5°C and the coating appearance was observed after 168 hours of drying. The evaluation criteria were: a coating without cracks was rated "A", a coating with slight cracks was rated "B", and a coating with obvious cracks was rated "C". It should be noted that the level of problems encountered in actual use was "C".

[0335] [Experiment 2]

[0336] Various water-based coating materials were applied to one side of a glass plate using a thin-film coater with a gap of 150 μm. The coated surface was placed horizontally, and the 20-degree specular gloss (measured at a 20-degree angle) was measured after drying for 48 hours under standard conditions (air temperature 23℃, relative humidity 50%). The evaluation criteria were as follows: coatings with a 20-degree specular gloss of 46 or higher were rated "AA"; coatings with a gloss of 43 or higher but less than 46 were rated "A"; coatings with a gloss of 40 or higher but less than 43 were rated "B"; and coatings with a gloss of less than 40 were rated "C". It should be noted that the level of problems encountered in actual use was "C".

[0337] [Experiment 3]

[0338] After drying the test panels from Test 1 under standard conditions (23°C, 50% relative humidity) for 14 days, they were exposed to accelerated weathering (xenon lamp weathering tester) for 1000 hours, and the appearance of the coating was observed. The evaluation criteria were as follows: coatings without cracks were rated "A", coatings with slight cracks were rated "B", and coatings with obvious cracks were rated "C". It should be noted that the level of problems encountered in actual use is "C".

[0339] [Experiment 4]

[0340] A stone slab with a 0.5 mm thick coating formed from a flexible synthetic resin emulsion-based repair surface coating material was prepared as the test substrate. The coating was applied using a spray gun at a rate of 0.3 kg / m². 2 Various water-based coating materials were tested, and samples were prepared by placing the coated surface horizontally in a thermostat at 5°C and drying for 24 hours. The appearance of the coating film after immersing the sample in water at 23°C for 24 hours was observed. The evaluation criteria were as follows: coating film without swelling was rated "AA", coating film with only very slight swelling was rated "A", coating film with only slight swelling was rated "B", and coating film with obvious swelling was rated "C". It should be noted that the level of problems encountered in actual use is "C".

[0341] (Experimental Results)

[0342] The test results are shown in Table 1. In Test 1, Examples 1-28 (especially Examples 3-28) achieved good results, exhibiting excellent crack resistance. In Test 2, Examples 1-28 (especially Examples 11-16, 23-26, and 28) achieved good results, exhibiting excellent gloss. Examples 3-28 (especially Examples 4-16 and 18-28) also achieved good results in Test 3, demonstrating excellent crack resistance and weather resistance. In Test 4, Examples 1-28 (especially Examples 2-16 and 18-28) achieved good results, with early development of coating strength and excellent anti-swelling properties.

[0343] The results of Comparative Examples 1-3 in Experiment 1 were unsatisfactory; therefore, Experiment 3 was not performed in Comparative Examples 1-3. Comparative Example 4 does not contain pigments or other components and is not within the scope of this invention; therefore, Experiments 2 and 3 were not performed in Comparative Examples 4.

[0344] Table 1

[0345]

[0346] Table 2

[0347]

[0348] Table 3

[0349]

[0350] <Upper Coating Material 1>

[0351] A coloring pigment dispersion was prepared by mixing and stirring 27 parts by weight of water with 0.4 parts by weight of thickener 1, 0.1 parts by weight of defoamer 1, 2.5 parts by weight of pigment dispersant 1, and 70 parts by weight of coloring pigment 1.

[0352] Next, 100 parts by weight of the coloring pigment dispersion is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 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 defoamer 2 to produce the top coating material 1.

[0353] The elongation of the upper coating material 1 at -10°C is 17%.

[0354] <Upper Coating Material 2>

[0355] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 2, 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 defoamer 2 and stirred to produce the upper coating material 2.

[0356] The elongation of the upper coating material 2 at -10°C is 18%.

[0357] <Upper coating material 3>

[0358] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 3, 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 defoamer 2 and stirred to produce the upper coating material 3.

[0359] The elongation of the upper coating material 3 at -10°C is 18%.

[0360] <Upper coating material 4>

[0361] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 10, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 4.

[0362] The elongation of the upper coating material 4 at -10°C is 18%.

[0363] <Upper coating material 5>

[0364] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 11, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 5.

[0365] The elongation of the upper coating material 5 at -10°C is 18%.

[0366] <Upper coating material 6>

[0367] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 3, 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 defoamer 2 and 3 parts by weight of crosslinking agent 2 and stirred to produce the upper coating material 6.

[0368] The upper coating material 6 has an elongation of 20% at -10°C.

[0369] <Upper coating material 7>

[0370] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 4, 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 defoamer 2, and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 7.

[0371] The upper coating material 7 has an elongation of 20% at -10°C.

[0372] <Top Coating Material 8>

[0373] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 5, 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 defoamer 2, and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 8.

[0374] The elongation of the upper coating material 8 at -10°C is 14%.

[0375] <Upper coating material 9>

[0376] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 6, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 to produce the upper coating material 9.

[0377] The elongation of the upper coating material 9 at -10°C is 26%.

[0378] <Upper coating material 10>

[0379] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 12, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 to produce the upper coating material 10.

[0380] The elongation of the upper coating material 10 at -10°C is 23%.

[0381] <Upper coating material 11>

[0382] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 11.

[0383] The elongation of the upper coating material 11 at -10°C is 20%.

[0384] <Upper coating material 12>

[0385] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 9, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 to produce the upper coating material 12.

[0386] The elongation of the upper coating material 12 at -10°C is 18%.

[0387] <Upper coating material 13>

[0388] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 to produce the upper coating material 13.

[0389] The elongation of the upper coating material 13 at -10°C is 21%.

[0390] <Upper coating material 14>

[0391] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 8, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 to produce the upper coating material 14.

[0392] The elongation of the upper coating material 14 at -10°C is 20%.

[0393] <Upper coating material 15>

[0394] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 13, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 to produce the upper coating material 15.

[0395] The elongation of the upper coating material 15 at -10°C is 18%.

[0396] <Upper coating material 16>

[0397] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 14, 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 defoamer 2, and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 16.

[0398] The elongation of the upper coating material 16 at -10°C is 19%.

[0399] <Upper coating material 17>

[0400] The upper coating material 17 is prepared by mixing and stirring 100 parts by weight of the same coloring pigment dispersion as coating material 1 with 250 parts by weight (100 parts by weight in terms of solid content) of resin 17, 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 defoamer 2.

[0401] The elongation of the upper coating material 17 at -10°C is 18%.

[0402] <Upper coating material 18>

[0403] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed and stirred with 250 parts by weight (100 parts by weight in terms of solid content) of resin 18, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 to produce the upper coating material 18.

[0404] The elongation of the upper coating material 18 at -10°C is 18%.

[0405] <Upper coating material 19>

[0406] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 15, 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 defoamer 2 and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 19.

[0407] The elongation of the upper coating material 19 at -10°C is 32%.

[0408] <Upper coating material 20>

[0409] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 125 parts by weight (50 parts by weight in terms of solid content) of resin 8, 125 parts by weight (50 parts by weight in terms of solid content) of resin 16, 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 defoamer 2, and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 20.

[0410] The elongation of the upper coating material 20 at -10°C is 30%.

[0411] <Upper Coating Material 21>

[0412] The same 100 parts by weight of coloring pigment dispersion as the upper coating material 1 is mixed with 250 parts by weight (100 parts by weight in terms of solid content) of resin 16, 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 defoamer 2, and 1 part by weight of crosslinking agent 1 and stirred to produce the upper coating material 21.

[0413] The elongation of the upper coating material 21 at -10°C is 38%.

[0414] It should be noted that the elongation at -10°C of each top coating material is the value measured according to the method specified in "Elongation Test" of JIS A6909:2021. The specimen used for the elongation test is a mixture of the main materials of waterproof multilayer coating material E conforming to JIS A6909:2021, namely acrylic resin emulsion (Tg-28°C), titanium dioxide (average particle size 0.3 μm), and heavy calcium carbonate (average particle size 12 μm). The coating surface of the monomer film with an elongation of 38% at -10°C and a dry film thickness of 1 mm is coated with an top coating material with a dry film thickness of 80 μm.

[0415] (Experimental Methods)

[0416] The coating materials on each side were tested according to the following method.

[0417] [Experiment 5]

[0418] A mixture of main materials of a waterproof multilayer coating material E conforming to JIS A6909:2021 (acrylic resin emulsion (Tg -28℃), titanium dioxide (average particle size 0.3μm), and heavy calcium carbonate (average particle size 12μm)) was prepared as the test substrate. The elongation of the monomer coating at -10℃ was 38%. A stone slab with a textured surface (height difference approximately 1.5mm) was used as the test substrate. A spray gun was used to apply the coating at a rate of 0.15 kg / m² onto this test substrate. 2The first top layer of coating material was applied and allowed to dry for 2 hours. Then, a spray gun was used to apply the coating at a rate of 0.15 kg / m². 2 The second upper side was coated with the material and dried and cured for 168 hours to prepare the sample. In addition, the coating, drying and curing were all carried out under standard conditions (temperature 23°C, relative humidity 50%).

[0419] For the samples obtained by the above method, they were immersed in water for 18 hours, then left to stand at -20°C for 3 hours, followed by standing at 50°C for 3 hours. This thermal cycling test was considered one cycle. After a total of 10 cycles, the appearance of the coating was inspected, and the occurrence of defects (swelling, peeling, cracking, etc.) was evaluated. A four-level standard was used for evaluation (Excellent: A > B > C > D: Poor): a coating without defects was rated "A", and a coating with obvious defects was rated "D". It should be noted that in actual use, the grades of problems are "C" and "D".

[0420] [Experiment 6]

[0421] For samples obtained using the same method as in Test 5 above, the coating appearance was observed after 1000 hours of exposure using an accelerated weathering tester (xenon lamp weathering apparatus). Evaluation was conducted using a four-level standard (Excellent: A > B > C > D: Poor): a coating without defects was rated "A", and a coating with obvious defects was rated "D". It should be noted that in actual use, the grades of problems are "C" and "D".

[0422] (Experimental Results)

[0423] The test results are shown in Table 6. Examples 29–47 achieved good results in tests 5 and 6, demonstrating excellent crack resistance and weather resistance.

[0424] Table 4

[0425]

[0426] Table 5

[0427]

[0428] Note: Except for "Resin 16" in "Resin Composition" in Table 5 above, all others contain acrylic silicone resin. "Resin 16" does not contain silicone.

[0429]

Claims

1. A water-based coating material comprising an acrylic silicone resin emulsion (A) and a pigment (B), and having room temperature curing properties, characterized in that, The residual silica content in the acrylic silicone resin emulsion (A) is 1-40% by mass. The glass transition temperature of the acrylic silicone resin emulsion (A) is below 30°C. The monomers constituting the acrylic silicone resin emulsion (A) include two or more alkyl (meth)acrylates (s) having 4 or more carbon atoms, and the homopolymer of the alkyl (meth)acrylates (s) having 4 or more carbon atoms has a glass transition temperature of 0°C or below.

2. The aqueous coating material according to claim 1, characterized in that The alkyl (meth)acrylate (s) having 4 or more carbon atoms includes the alkyl (meth)acrylate (s1) having 5 or more branched alkyl groups.

3. The aqueous coating material according to claim 2, characterized in that The branched alkyl group includes methyl.

4. The aqueous coating material of claim 1, wherein Contains crosslinking agent (C). The acrylic silicone resin emulsion (A) has reactive functional groups. The crosslinking agent (C) has functional groups that can react with the reactive functional groups.

5. A method for forming a coating, comprising sequentially applying a first upper coating material and a second upper coating material to a surface to be coated to form an upper coating material coating, characterized in that, The first upper coating material is a coating material used to form a film with an elongation of 20% or more at -10°C. The second upper coating material is the water-based coating material according to any one of claims 1 to 4. The second upper coating material is a coating material used to form a film with an elongation at -10°C that is less than that of the first upper coating material at -10°C.

6. The film formation method according to claim 5, wherein The first upper coating material comprises a resin emulsion and a pigment. The monomers constituting the resin emulsion include two or more alkyl (meth)acrylates(s) having 4 or more carbon atoms, and the homopolymer of the alkyl (meth)acrylates(s) having 4 or more carbon atoms has a glass transition temperature below 0°C.

7. The film formation method according to claim 6, wherein The alkyl (meth)acrylate (s) having 4 or more carbon atoms includes the alkyl (meth)acrylate (s1) having 5 or more branched alkyl groups.

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

9. An upper coating material assembly, comprising a first upper coating material and a second upper coating material used in the film forming method of claim 5.

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