Aqueous coating composition, substrate with adhesive layer, and hard coat laminate

Abstract

To provide an aqueous coating composition capable of forming a coating film excellent in coating properties, transparency, surface smoothness and weather resistance without coating film unevenness or liquid sagging marks even when applied to a large-area object to be coated.SOLUTION: The aqueous coating composition contains: an emulsion particle (A) having a unit (a) derived from a vinyl monomer (a); an amine compound (B); inorganic particles (C); and water, wherein the amine compound (B) has a boiling point of 170°C or less under an external pressure of 1 atm, a vapor pressure ratio of the amine compound (B) to the water, P(B) / P(water), is 7.0 or less at 20°C, and the pH is 9.5 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aqueous coating composition, a substrate with an adhesive layer, and a hard coat laminate. [Background technology]

[0002] In recent years, there has been a demand for water-based paints in consideration of workplace hygiene and the burden on the global environment. In particular, when the surface area of ​​the object to be coated is large, the concentration of paint volatile components in the work environment increases due to the increased amount of paint used and the large surface area of ​​the liquid film immediately after coating. Therefore, attempts are being made to significantly reduce the burden on paint workers by using water-based paints.

[0003]

[0003] Conventionally, many aqueous coating compositions have been proposed, each comprising a binder resin including emulsion particles, a crosslinking agent, a pigment, an ultraviolet absorber, a solvent, and water. Such aqueous coating compositions can be dried at room temperature or under heat to form a film, and the coating films thus obtained are known to have barrier properties, contamination resistance, chemical resistance, flame retardancy, heat resistance, weather resistance, abrasion resistance, and wear resistance.

[0004] However, when paints containing such conventionally known aqueous coating compositions are used on substrates requiring transparency, especially for large-area applications, problems can arise during the drying process immediately after application, such as whitening, devitrification, surface roughness, and craze of the coating film due to aggregation and segregation of the components in the coating, resulting in a decrease in optical properties, and problems such as uneven film thickness due to variations in the drying speed of the liquid film and a decrease in coating film performance such as durability and heat resistance due to drip marks. Furthermore, particularly for applications requiring long-term outdoor use, high durability is required for the laminate of the substrate and the coating film, and it is necessary to firmly bond the substrate and the coating film so that they do not peel off over a long period of time. At the same time, there is a demand for recycling unnecessary resin substrates, such as coated products that do not meet quality standards and trimming off-cuts of coated substrates, during manufacturing. To recycle resin substrates, the coating film needs to be peeled off, but peeling is difficult when the coating film is firmly bonded.

[0005] Furthermore, since aggregation of the components in the paint occurs even during storage of the paint, there is also room for improvement in the storage stability of the paint.

[0006] As a technique for solving the above-mentioned problems, Patent Document 1 discloses a technique relating to an aqueous coating composition to which a hydroxyl group-containing organic solvent and an amine compound are added for the purpose of controlling the gloss of the coating film and improving the storage stability of the paint. Furthermore, Patent Document 2 discloses a technique relating to an aqueous coating composition to which water-dispersible acrylic polymer particles with an adjusted hydroxyl value and acid value and an amine compound are added in order to obtain excellent coating surface smoothness. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2012 / 133752 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-176618 Summary of the Invention [Problem to be solved by the invention]

[0008] The technology disclosed in Patent Document 1 adds an amine compound to prevent abnormal aggregation of paint components and a decrease in paint storage stability. However, the amine compound has a higher boiling point than the solvent, and the high-boiling amine compound remains in the paint film when the paint dries, resulting in a decrease in paint film durability. To address this issue, increasing the drying temperature to volatilize the high-boiling amine compound in the paint film causes deterioration of the coated object and the paint film, and is undesirable from a process perspective, including from an energy-saving perspective. Furthermore, depending on the properties of the high-boiling amine compound, the effect of inhibiting aggregation of paint components may not be fully exerted, resulting in failure to achieve the expected storage stability. Furthermore, when applying an aqueous coating composition to a large-area substrate requiring transparency, if the high-boiling amine compound's aggregation-inhibiting effect is insufficient, gloss and surface smoothness may not be achieved, resulting in quality variations within the coated surface.

[0009] Patent Document 2 discloses a paint containing polymer particles that require a neutralizing agent, but does not specify the specific properties of the amine compound that serves as the neutralizing agent. This poses the problem that, depending on the amine compound used, in an intermediate coating film for transparent materials, the transparency may decrease due to optical irregularities caused by the formation of voids inside the coating film, resulting in a product that is unsuitable for use as a transparent material.

[0010] The present invention has been made in consideration of the problems of the conventional art as described above, and aims to provide an aqueous coating composition that has excellent coatability without unevenness in the coating film or dripping marks even when applied to a large-area substrate, and can form a coating film that is excellent in transparency, surface smoothness, and weather resistance. The present invention also relates to a laminate, and aims to provide a laminate that has both releasability and durability, such that the coating film can be easily peeled off with only a short boiling water treatment during production, and that can maintain high adhesion of the coating film over long-term use. [Means for solving the problem]

[0011] As a result of intensive research conducted by the present inventors to solve the problems of the conventional techniques, they found that the above-mentioned problems can be solved by specifying, in an aqueous coating composition containing predetermined emulsion particles (A), an amine compound (B), inorganic particles (C), and water, the boiling point of the amine compound (B), the vapor pressure ratio of the amine compound (B) to water, and the pH of the aqueous coating composition within predetermined numerical ranges, and thus completed the present invention. That is, the present invention is as follows.

[0012] [1] Emulsion particles (A) having units (a) derived from a vinyl monomer (a); Amine compound (B), Inorganic particles (C), and water, the boiling point of the amine compound (B) is 170°C or less under an external pressure of 1 atmosphere, The vapor pressure ratio P of the amine compound (B) to water at 20°C (B) / P water is 7.0 or less, pH is 9.5 or higher, Aqueous coating compositions. [2] The glass transition temperature of the emulsion particles (A) is −30° C. or higher and 50° C. or lower. The aqueous coating composition according to [1] above. [3] the acid dissociation constant of the amine compound (B) is 7.5 or more; The aqueous coating composition according to [1] or [2] above. [4] The aqueous coating composition according to any one of [1] to [3] above, wherein the amine compound (B) has an octanol / water partition coefficient of -1.0 or more and 2.5 or less. [5] Further comprising a crosslinking agent (D), The aqueous coating composition according to any one of [1] to [4] above. [6] Further containing a biphenyltriazine skeleton ultraviolet absorber (E), The aqueous coating composition according to any one of [1] to [5] above. [7] A substrate; an adhesive layer disposed on the substrate; A substrate with an adhesive layer, The adhesive layer comprises the aqueous coating composition according to any one of [1] to [6] above. Substrate with adhesive layer. [8] A substrate with an adhesive layer according to [7] above, a hard coat layer disposed on the substrate with the adhesive layer; A hard coat laminate having [9] A substrate; An adhesive layer disposed on the substrate, and a functional layer disposed on the adhesive layer; A laminate having When the laminate was immersed in hot water at 98°C for 1 hour and then subjected to an adhesion test using the cross-cut method specified in JIS K5600-5-6, peeling of classification 3 or higher occurred, The laminate maintains adhesion of classification 2 or less when the laminate is immersed in water at 80°C for 8 hours and then in hot water at 98°C for 1 hour and then subjected to an adhesion test using the cross-cut method specified in JIS K5600-5-6.

[10] The adhesive layer contains a polymer derived from emulsion particles (A) having units (a) derived from a vinyl monomer (a). The laminate described in [9] above.

[11] The adhesive layer contains an amine compound (B). The laminate according to [9] or

[10] above.

[12] The boiling point of the amine compound (B) is −30° C. or higher and 180° C. or lower under an external pressure of 1 atmosphere. The laminate described in

[11] above.

[13] The adhesive layer contains inorganic particles (C). The laminate according to any one of [9] to

[12] above.

[14] The adhesive layer contains a crosslinking agent (D). The laminate according to any one of [9] to

[13] above.

[15] The adhesive layer contains an ultraviolet absorber (E'). The laminate according to any one of [9] to

[14] above.

[16] The functional layer disposed on the adhesive layer is a hard coat layer. The laminate according to any one of [9] to

[15] above. [Effects of the Invention]

[0013] According to the present invention, there is provided an aqueous coating composition which can form a coating film having excellent coating properties without unevenness or dripping marks even when applied to a large-area substrate, and which has excellent transparency, surface smoothness, and weather resistance. Furthermore, during production, the coating film can be easily peeled off with only a short boiling water treatment, and the coating film can maintain high adhesion even when used for a long period of time, providing a laminate that combines peelability and durability. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, an embodiment for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist of the present invention. In this specification, "(meth)acrylic" means "acrylic" and its corresponding "methacrylic". Furthermore, in this specification, unless otherwise specified, the symbol "to" means that the numerical values ​​at both ends thereof are included as the upper and lower limits.

[0015] [Aqueous Coating Composition] The aqueous coating composition of this embodiment contains emulsion particles (A) having units (a) derived from a vinyl monomer (a), an amine compound (B), inorganic particles (C), and water. The boiling point of the amine compound is 170°C or less at an external pressure of 1 atmosphere, and the vapor pressure ratio P (B) The pH of the aqueous coating composition of this embodiment is 9.5 or higher. The aqueous coating composition of the present embodiment has the above-described structure, and therefore exhibits excellent coatability, transparency, surface smoothness, and weather resistance even when applied to a large-area substrate.

[0016] The inventors speculate that the reason for this effect is as follows. That is, the amine compound (B) is a neutralizer for the emulsion particles (A), and during the drying process after the aqueous coating composition is applied to the substrate, the evaporation rate of the amine compound (B) is determined by its vapor pressure and boiling point. During the drying process at room temperature around 20 to 25°C, the higher the vapor pressure, the faster the evaporation rate of the amine compound (B) from the aqueous coating composition. Therefore, the emulsion particles (A) that have lost the neutralizer undergo abnormal aggregation, causing whitening of the coating film, surface roughness, and quality variations in large-area coating films. At this time, the vapor pressure of the amine compound (B) is expressed as P (B) , the vapor pressure of water is P water, and the ratio P (B) When the / P water is 7.0 or less, abnormal aggregation during the drying process can be sufficiently suppressed.

[0017] In the aqueous coating composition of this embodiment, the amine compound (B) preferably has an octanol / water partition coefficient of −1.0 or more and 2.5 or less, which allows the amine compound (B) to function as a neutralizer more effectively. This is because an octanol / water partition coefficient of 2.5 or less allows the amine compound (B) to dissolve in water, which is the solvent, and to function effectively as a neutralizing agent, and furthermore, absorption by the emulsion particles (A) and the occurrence of particle swelling due to the amine compound (B) is suppressed, thereby effectively preventing the promotion of abnormal aggregation. Furthermore, an octanol / water partition coefficient of -1.0 or more suppresses the interaction of the amine compound (B) with water due to solvation, allowing the amine compound (B) to volatilize well during the drying process, preventing the amine compound (B) from remaining in the coating film, and tending to obtain excellent coating film performance such as weather resistance.

[0018] Furthermore, in the aqueous coating composition of this embodiment, the amine compound (B) preferably has an acid dissociation constant of 7.5 or more. This allows it to function as a neutralizer for the emulsion particles (A). When the acid dissociation constant of the amine compound (B) is 7.5 or more, it exhibits sufficient neutralizing effects, preventing the pH from reaching a value near the isoelectric point of the emulsion particles (A) during the coating drying process, preventing thickening due to abnormal aggregation, and preventing the occurrence of coating unevenness and drip marks. However, the mechanism of action of this embodiment is not intended to be limited to the above.

[0019] (Emulsion particles (A)) The aqueous coating composition of the present embodiment contains emulsion particles (A). The emulsion particles (A) mainly serve to improve adhesion to the substrate, and must contain the vinyl monomer (a) as a constituent unit, i.e., the emulsion particles (A) have units (a) derived from the vinyl monomer (a).

[0020] The unit (a) may contain a unit (a-1) derived from an ultraviolet-absorbing vinyl monomer (a-1). By containing the unit (a-1), the aqueous coating composition of this embodiment tends to be able to improve the weather resistance of a substrate with an adhesive layer or a hard coat laminate, which will be described later.

[0021] The ultraviolet absorbing vinyl monomer (a-1) is a vinyl monomer having an ultraviolet absorbing group. The ultraviolet absorbing group is a functional group that has absorption in the ultraviolet region (wavelength of 400 nm or less), and the ultraviolet absorbing vinyl monomer (a-1) is not particularly limited as long as it is a vinyl monomer having such properties. Examples of the ultraviolet absorbing vinyl monomer (a-1) include, but are not limited to, (meth)acrylic monomers having an ultraviolet absorbing group in the molecule, and specific examples thereof include benzophenone-based monomers such as 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-diethoxy)benzophenone, and 2-hydroxy-4-(acryloxy-triethoxy)benzophenone. and benzotriazole-based compounds such as 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole (trade name "RUVA-93" manufactured by Otsuka Chemical Co., Ltd.), 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacrylyloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole, and 3-methacryloyl-2-hydroxypropyl-3-[3'-(2"-benzotriazolyl)-4-hydroxy-5-tert-butyl]phenylpropionate (trade name "CGL-104" manufactured by Nippon Ciba-Geigy Ltd.).

[0022] The content of the units (a-1) derived from the ultraviolet-absorbing vinyl monomer (a-1) is preferably 1 to 20 mass %, more preferably 1 to 10 mass %, based on the total mass of the units (a) derived from the vinyl monomer (a) constituting the emulsion particles (A), from the viewpoint of the weather resistance of the adhesive layer and the laminate described below.

[0023] In the emulsion particles (A), the units (a) derived from the vinyl monomer (a) preferably have units (a-2) derived from a hydroxyl group-containing vinyl monomer (a-2) that has a hydroxyl group and is a monomer other than the units (a-1) derived from the ultraviolet-absorbing vinyl monomer (a-1). Examples of the hydroxyl group-containing vinyl monomer (a-2) include, but are not limited to, hydroxyalkyl esters of (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; hydroxyethyl (meth)acrylamides such as N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide; di-2-hydroxyethyl (meth)acrylamide; Examples of the hydroxyalkyl ester include hydroxyalkyl esters of fumaric acid such as hydroxyethyl fumarate and mono-2-hydroxyethyl monobutyl fumarate; allyl alcohol, (poly)oxyethylene mono(meth)acrylates having 1 to 100 ethylene oxide groups; (poly)oxypropylene mono(meth)acrylates having 1 to 100 propylene oxide groups; and further, "Placcel FM, FA Monomer" (trade name of a caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.) and other hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids. These may be used alone or in combination of two or more.

[0024] Examples of the (poly)oxyethylene mono(meth)acrylate include, but are not limited to, ethylene glycol (meth)acrylate, ethylene glycol methoxy(meth)acrylate, diethylene glycol (meth)acrylate, diethylene glycol methoxy(meth)acrylate, tetraethylene glycol (meth)acrylate, and tetraethylene glycol methoxy(meth)acrylate.

[0025] The content of the units (a-2) derived from the hydroxyl group-containing vinyl monomer (a-2) is preferably 10% by mass to 40% by mass, more preferably 20% by mass to 30% by mass, based on the total mass of the units (a) derived from the vinyl monomer (a) constituting the emulsion particles (A). When the content of the units (a-2) is within this range, the reaction between the hydroxyl group-containing vinyl monomer (a-2) and other vinyl monomers tends to proceed favorably. Furthermore, since the hydrophilicity of the emulsion particles (A) is ensured, when a substrate with an adhesive layer or a hard coat laminate, described below, is formed using the aqueous coating composition of this embodiment, a decrease in transparency and surface roughness tend to be prevented.

[0026] In the emulsion particles (A), the units (a) may contain units derived from other vinyl monomers in addition to the units (a-1) and (a-2). Examples of other vinyl monomers include, but are not limited to, (meth)acrylic acid esters, (meth)acrylic acid alkyl esters, aromatic vinyl compounds, and vinyl cyanide compounds, as well as carboxyl group-containing vinyl monomers, epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, and vinyl monomers having secondary and / or tertiary amide groups.

[0027] Examples of the (meth)acrylic acid ester include, but are not limited to, (meth)acrylic acid alkyl esters having 1 to 50 carbon atoms in the alkyl moiety, and (poly)oxyethylene di(meth)acrylates having 1 to 100 ethylene oxide groups.

[0028] Examples of the (poly)oxyethylene di(meth)acrylate include, but are not limited to, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, diethylene glycol methoxy(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

[0029] Examples of the (meth)acrylic acid alkyl ester include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, and dodecyl (meth)acrylate.

[0030] The aromatic vinyl compound is not limited to the following, but examples thereof include styrene and 4-vinyltoluene.

[0031] The vinyl cyanide compound is not limited to the following, but examples thereof include acrylonitrile and methacrylonitrile.

[0032] Examples of the carboxyl group-containing vinyl monomer include, but are not limited to, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, and half esters of dibasic acids such as itaconic acid, maleic acid, and fumaric acid. When a carboxyl group-containing vinyl monomer is used, carboxyl groups can be introduced into the emulsion particles (A), imparting electrostatic repulsion between the particles, improving emulsion stability and tending to improve resistance to external dispersion-disrupting effects, such as aggregation during stirring. To further improve the electrostatic repulsion, the introduced carboxyl groups may be partially or completely neutralized with a base such as an amine.

[0033] Examples of the epoxy group-containing vinyl monomer include, but are not limited to, glycidyl group-containing vinyl monomers, etc. Examples of the glycidyl group-containing vinyl monomer include, but are not limited to, glycidyl (meth)acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, etc.

[0034] The carbonyl-containing vinyl monomer is not limited to the following, but examples thereof include diacetone acrylamide.

[0035] Examples of the vinyl monomer having a secondary and / or tertiary amide group include, but are not limited to, N-alkyl or N-alkylene substituted (meth)acrylamides, etc. Specific examples include N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-iso ... Examples of the copolymer include amide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, and N-methylol methacrylamide.

[0036] Furthermore, examples of other vinyl monomers other than those mentioned above include, but are not limited to, olefins such as ethylene, propylene, and isobutylene; dienes such as butadiene; haloolefins such as vinyl chloride, vinylidene chloride vinyl fluoride, tetrafluoroethylene, and chlorotrifluoroethylene; vinyl carboxylic acid esters such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, and vinyl laurate; isopropenyl carboxylic acid esters such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether; Examples of the vinyl monomer include vinyl ethers such as isobutyl vinyl ether and cyclohexyl vinyl ether, allyl esters such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether and allyl phenyl ether, and further include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl(meth)acrylate, perfluoropropyl(meth)acrylate, perfluoropropylmethyl(meth)acrylate, vinylpyrrolidone, trimethylolpropane tri(meth)acrylate, and allyl(meth)acrylate. These other vinyl monomers may be used alone or in combination of two or more.

[0037] The emulsion particles (A) may have a structure derived from an emulsifier. Examples of emulsifiers include, but are not limited to, acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, and polyoxyethylene distyrylphenyl ether sulfonic acid; anionic surfactants such as alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, and fatty acid soaps; cationic surfactants of the quaternary ammonium salt, pyridinium salt, and imidazolinium salt type such as alkyltrimethylammonium bromide, alkylpyridinium bromide, and imidazolinium laurate; nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block copolymer, and polyoxyethylene distyrylphenyl ether; and reactive emulsifiers having a radically polymerizable double bond.

[0038] Examples of the reactive emulsifier having a radically polymerizable double bond include, but are not limited to, Eleminol JS-2 (trade name, manufactured by Sanyo Chemical Industry Co., Ltd.), Latemul S-120, S-180A, or S-180 (trade name, manufactured by Kao Corporation), Aqualon HS-10, KH-1025, RN-10, RN-20, RN30, or RN50 (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Adeka Reasop SE1025, SR-1025, NE-20, NE-30, or NE-40 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), ammonium salt of p-styrenesulfonic acid, sodium salt of p-styrenesulfonic acid, potassium salt of p-styrenesulfonic acid, alkylsulfonic acid (meth)acrylates such as 2-sulfoethyl acrylate, methylpropanesulfonic acid (meth)acrylamide, ammonium salt of allylsulfonic acid, sodium salt of allylsulfonic acid, and potassium salt of allylsulfonic acid.

[0039] The emulsion particles (A) preferably contain a chain transfer agent, that is, the aqueous coating composition of the present embodiment preferably contains a chain transfer agent. Examples of chain transfer agents include, but are not limited to, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, and t-tetradecyl mercaptan; xanthogen disulfides such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide, and diisopropyl xanthogen disulfide; thiuram disulfides such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, and tetrabutyl thiuram disulfide; carbon tetrachloride, ethylene bromide, and the like. hydrocarbons such as pentaphenylethane; and unsaturated cyclic hydrocarbon compounds such as acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, terbinolene, α-terpinene, γ-terpinene, dipentene, α-methylstyrene dimer (preferably those containing 50 mass% or more of 2,4-diphenyl-4-methyl-1-pentene), 9,10-dihydroanthracene, 1,4-dihydronaphthalene, indene, and 1,4-cyclohexadiene; and unsaturated heterocyclic compounds such as xanthene and 2,5-dihydrofuran. These may be used alone or in combination of two or more.

[0040] The method for preparing the emulsion particles (A) used in the aqueous coating composition of this embodiment is not particularly limited, but examples thereof include a method in which a vinyl monomer is polymerized in the presence of water, an emulsifier, and a polymerization initiator.

[0041] Examples of the polymerization initiator include, but are not limited to, organic polymerization initiators such as hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide; peroxides such as benzoyl peroxide and lauroyl peroxide; and azo compounds such as 2,2′-azobis{2-methyl-N-[2-(1-hydroxybutyl)propionamide]}, 2,2′-azobis[(2-methylpropionamidine) dihydrochloride], 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropiondiamine] tetrahydrate, 2,2′-azobis(2,4-dimethylvaleronitrile), and azobisisobutyronitrile; and inorganic polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. Also usable are so-called redox polymerization initiators, which are polymerization initiators combined with reducing agents such as sodium bisulfite, ascorbic acid and salts thereof.

[0042] <Weight-average molecular weight of units (a) derived from vinyl monomer (a)> In the emulsion particles (A) used in the aqueous coating composition of this embodiment, the weight-average molecular weight of the unit (a) derived from the vinyl monomer (a), calculated from a chromatogram measured by gel permeation chromatography using the molecular weight of standard polystyrene as a reference, is preferably in the range of 10,000 to 1,000,000. This tends to result in excellent transparency and adhesion when a substrate with an adhesive layer, as described below, is formed using the aqueous coating composition of this embodiment. Furthermore, from the viewpoint of further improving adhesion, the weight-average molecular weight of the unit (a) is more preferably 500,000 or less, and even more preferably 250,000 or less. The weight average molecular weight of the unit (a) derived from the vinyl monomer (a) can be controlled within the above-mentioned range, for example, by adjusting the amount of vinyl monomer added in the polymerization step, the polymerization time, or by using the chain transfer agent described above.

[0043] <Average particle size of emulsion particles (A)> The average particle size of the emulsion particles (A) is determined from the particle size observed by dynamic light scattering. The average particle size of the emulsion particles (A) is not limited to the following, but is preferably 200 nm or less. By setting the average particle size of the emulsion particles (A) within the above range, the aqueous coating composition of this embodiment tends to be able to form an adhesive layer with even better adhesion due to an increased contact area with the substrate. Furthermore, from the viewpoint of improving the transparency of the substrate with an adhesive layer (described below), the average particle size of the emulsion particles (A) is more preferably 100 nm or less. From the viewpoint of improving the storage stability of the aqueous coating composition of this embodiment, it is preferably 10 nm or more, and more preferably 25 nm or more. Specifically, the average particle size of the emulsion particles (A) can be measured by the method described in the Examples described below. The average particle size of the emulsion particles (A) can be controlled within the above-mentioned range by adjusting the polymerization conditions and the like.

[0044] <Glass transition temperature of emulsion particles (A)> The glass transition temperature of the emulsion particles (A) can be measured using a differential scanning calorimeter. The glass transition temperature of the emulsion particles (A) is not limited to the following, but is preferably from -30°C to 50°C. By setting the glass transition temperature of the emulsion particles (A) within the above range, the aqueous coating composition of this embodiment can form a coating film with excellent adhesion to the substrate. Furthermore, from the viewpoint of the transparency of the substrate with an adhesive layer, which will be described later, the glass transition temperature of the emulsion particles (A) is more preferably from -20°C to 45°C, and even more preferably from -10°C to 40°C. The glass transition temperature of the emulsion particles (A) can be controlled within the above range by adjusting the type and amount of the monomer used, the polymerization temperature, and the polymerization time in the polymerization step.

[0045] <Content of emulsion particles (A)> The content of emulsion particles (A) relative to the total solid content in the aqueous coating composition of this embodiment is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, from the viewpoints of the transparency and adhesion of the substrate with an adhesive layer, which will be described later. Here, the total solid content in the aqueous coating composition refers to the total mass of components contained in the aqueous coating composition other than volatile components. The volatile components mainly include solvents and neutralizers.

[0046] (Amine compound (B)) The aqueous coating composition of the present embodiment contains an amine compound (B). The amine compound (B) is a neutralizer for the emulsion particles (A), and it is essential to select and add an appropriate amine compound (B). This allows the aqueous coating composition of this embodiment to form a coating film that is excellent in coating film properties such as transparency, surface smoothness, and weather resistance, even when applied to a large-area substrate. Examples of the amine compound (B) used in the aqueous coating composition include, but are not limited to, n-butylamine, isobutylamine, amylamine, cyclopentylamine, hexylamine, dipropylamine, diisopropylamine, dibutylamine, pyrrolidine, piperidine, morpholine, triethylamine, tripropylamine, triisopropylamine, 1-methylpiperidine, 1-methylpyrrolidine, N,N-dimethylpropylamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, and dimethylethanolamine.

[0047] <Boiling point of amine compound (B)> The amine compound (B) used in the aqueous coating composition of this embodiment has a boiling point of 170°C or less at an external pressure of 1 atmosphere. By making the boiling point of the amine compound (B) 170°C or less, it is possible to prevent the amine compound (B) from remaining in the coating film after the heat drying process, and a coating film with excellent weather resistance and heat resistance tends to be obtained. The boiling point of the amine compound (B) is preferably 150°C or less, and more preferably 130°C or less. The boiling point of the amine compound (B) is a value measured at an external pressure of 1 atmosphere, and can be measured, for example, by the initial boiling point measurement method of JIS K 2254 using an automatic distillation tester manufactured by Tanaka Chemical Instruments Co., Ltd. The boiling point of the amine compound (B) can be controlled within the above range by changing the chemical structure of the functional group or the like of the amine compound (B).

[0048] <Vapor pressure ratio of amine compound (B) to water> The amine compound (B) in the aqueous coating composition of the present embodiment has a vapor pressure ratio P (B) / P water is 7.0 or less. The amine compound (B) is a neutralizer for the emulsion particles (A), and during the drying process after application of the aqueous coating composition of this embodiment to the substrate, the evaporation rate of the amine compound (B) is determined by its vapor pressure and boiling point. During the drying process at room temperature around 20 to 25°C, the higher the vapor pressure, the faster the evaporation rate of the amine compound (B) from the aqueous coating composition. Therefore, the emulsion particles (A) that have lost the neutralizer tend to undergo abnormal aggregation, causing whitening of the coating film, surface roughness, and variations in the quality of large-area coating films. From the viewpoint of preventing such abnormal aggregation of the emulsion particles (A) and improving the quality of the coating film, the vapor pressure ratio P (B) / P water should be 7.0 or less, preferably 5.0 or less, and more preferably 4.0 or less. The vapor pressure ratio of the amine compound (B) to water can be calculated, for example, by measuring the vapor pressures of the amine compound (B) and water using an automatic distillation tester manufactured by Tanaka Chemical Instruments Co., Ltd. according to the Reid method of JIS K 2258-1. The vapor pressure ratio of the amine compound (B) to water can be controlled within the above range by changing the chemical structure of the functional group of the amine compound (B) and thereby changing the vapor pressure of the amine compound (B).

[0049] <Acid dissociation constant of amine compound (B)> The amine compound (B) in the aqueous coating composition of this embodiment preferably has an acid dissociation constant of 7.5 or more. When the acid dissociation constant of the amine compound (B) is 7.5 or more, a sufficient neutralization effect can be obtained, abnormal aggregation of the emulsion particles (A) can be suppressed, and a decrease in transparency and the occurrence of surface roughness can be effectively prevented when the amine compound (B) is applied to a large-area substrate. The acid dissociation constant is more preferably 8.0 or more, and even more preferably 8.5 or more. The acid dissociation constant of the amine compound (B) can be measured by neutralization titration, absorptiometry, capillary electrophoresis, or the like. The acid dissociation constant of the amine compound (B) can be controlled within the above-mentioned range by changing the chemical structure of the functional group or the like of the amine compound (B).

[0050] <Octanol / water partition coefficient of amine compound (B)> The amine compound (B) in the aqueous coating composition of this embodiment preferably has an octanol / water partition coefficient of -1.0 or more and 2.5 or less. An octanol / water partition coefficient of 2.5 or less prevents the amine compound (B) from being absorbed into the emulsion particles (A) and causing particle swelling, thereby preventing abnormal aggregation. Furthermore, an octanol / water partition coefficient of -1.0 or more suppresses the interaction of the amine compound (B) with water due to solvation, allowing the amine compound (B) to volatilize without problem during the drying process and preventing it from remaining in the coating film, which tends to result in a coating film with excellent durability. The octanol / water partition coefficient of the amine compound (B) is more preferably −0.8 or more and 2.0 or less, and further preferably −0.6 or more and 1.5 or less. The octanol / water partition coefficient of the amine compound (B) can be measured, for example, according to Japanese Industrial Standards Z7260-107 (2000) "Measurement of partition coefficient (1-octanol / water) - Shake flask method." The octanol / water partition coefficient of the amine compound (B) can be controlled within the above-mentioned range by changing the chemical structure of the functional group or the like of the amine compound (B).

[0051] The content of the amine compound (B) in the aqueous coating composition of this embodiment must be such that the pH of the aqueous coating composition is 9.5 or higher. The maximum content is preferably 10.0 mass% relative to the aqueous coating composition of this embodiment. By keeping the content at 10.0 mass% or less, the risk of residual amine compound (B) in a coating film formed using the aqueous coating composition of this embodiment can be effectively suppressed, and the amine odor in the coating environment can be prevented, which tends to effectively reduce the risk of health problems for workers. From the above-mentioned viewpoints, the content of the amine compound (B) in the aqueous coating composition of the present embodiment is preferably 0.3 to 10.0 mass %, more preferably 0.5 to 8.0 mass %, and even more preferably 1.0 to 5.0 mass %.

[0052] (Inorganic particles (C)) The aqueous coating composition of the present embodiment contains inorganic particles (C). When the aqueous coating composition of the present embodiment contains inorganic particles (C), the resulting hard coat laminate, which will be described later, tends to have excellent transparency and adhesion due to the interaction between the hard coat layer and an adhesive layer, which will be described later, containing the aqueous coating composition of the present embodiment.

[0053] Examples of inorganic particles (C) include, but are not limited to, oxides of silicon, aluminum, titanium, zirconium, zinc, cerium, tin, indium, gallium, germanium, antimony, molybdenum, niobium, magnesium, bismuth, cobalt, copper, etc. These may be used alone or in combination of two or more.

[0054] The inorganic particles (C) are preferably silica particles, such as dry silica or colloidal silica, from the viewpoint of adhesion to the hard coat layer in the hard coat laminate described below. Colloidal silica is also preferred because it can be used in the form of an aqueous dispersion.

[0055] <Shape of inorganic particles (C)> The shape of the inorganic particles (C) is not limited to the following, but examples thereof include spherical, angular, polyhedral, elliptical, flat, linear, beaded, and chain-like shapes, and may be one of these shapes or a mixture of two or more kinds. From the viewpoint of the transparency of the hard coat laminate described later, the inorganic particles (C) are preferably spherical and / or have a beaded or chain-like connection structure. Furthermore, in the hard coat laminate described later, from the viewpoint of the adhesion between the adhesive layer containing the aqueous coating composition of this embodiment and the hard coat layer, the inorganic particles (C) are more preferably beaded or chain-like connection structure. Here, "beaded" refers to a structure in which spherical primary particles are connected in a beaded shape, and "chain-like" refers to a structure in which spherical primary particles are connected in a chain shape. It is more preferable that the inorganic particles (C) are silica having a spherical and / or chained structure, and even more preferable that they are silica having a chained structure.

[0056] The primary particle diameter of the inorganic particles (C) is preferably 2 nm or more from the viewpoint of improving the storage stability of a substrate with an adhesive layer having an adhesive layer containing the coating composition of this embodiment and of a raw material composition for the adhesive layer constituting the hard coat laminate described later, and is preferably 100 nm or less, more preferably 50 nm or less, from the viewpoint of improving the transparency of the hard coat laminate as a whole described later. Methods for measuring the primary particle diameter of the inorganic particles (C) include, but are not limited to, the BET method, in which molecules or ions with a known area occupied by the surface of the inorganic particles are adsorbed and the specific surface area is determined from the amount of adsorption.

[0057] <Colloidal silica suitable for use as inorganic particles (C)> The inorganic particles (C) used in the aqueous coating composition of this embodiment are preferably acidic colloidal silica in which water is used as a dispersion medium. The colloidal silica is not particularly limited, but can be prepared by a sol-gel method, and commercially available products can also be used. For preparation by the sol-gel method, reference can be made to Werner Stober et al.; J. Colloid and Interface Sci., 26, 62-69 (1968), Rickey D. Badley et al.; Lang muir 6, 792-801 (1990), Journal of the Japan Society of Color Materials, 61[9] 488-493 (1988), etc. When a commercially available product is used, examples thereof include Snowtex-O, Snowtex-OS, Snowtex-OXS, Snowtex-O-40, Snowtex-OL, Snowtex-OYL, Snowtex-OUP, Snowtex-PS-SO, Snowtex-PS-MO, Snowtex-AK-XS, Snowtex-AK, Snowtex-AK-L, Snowtex-AK-YL, Snowtex-AK-PS-S (trade names, manufactured by Nissan Chemical Industries, Ltd.), Adelite AT-20Q (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crebosol 20H12, Crebosol 30CAL25 (trade names, manufactured by Clariant Japan Co., Ltd.), and the like. These colloidal silicas may be used alone or in combination of two or more.

[0058] Furthermore, basic colloidal silica can also be used as the colloidal silica. Examples of basic colloidal silica include, but are not limited to, silica stabilized by the addition of alkali metal ions, ammonium ions, and amines, and examples thereof include, but are not limited to, Snowtex-20, Snowtex-30, Snowtex-XS, Snowtex-50, Snowtex-30L, Snowtex-XL, Snowtex-YL, Snowtex-ZL, Snowtex-UP, Snowtex-ST-PS-S, Snowtex-ST-PS-M, Snowtex-C, Snowtex-CXS, Snowtex-CM, Snowtex-N, Snowtex-NXS, Snowtex-NS, Snowtex- Examples of such surfactants include Adelite AT-N-40 (trade name, manufactured by Nissan Chemical Industries, Ltd.), Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50 (trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Crebosol 30R9, Crebosol 30R50, Crebosol 50R50 (trade names, manufactured by Clariant Japan Co., Ltd.), Ludox HS-40, Ludox HS-30, Ludox LS, Ludox AS-30, Ludox SM-AS, Ludox AM, Ludox HSA, and Ludox SM (trade names, manufactured by DuPont).

[0059] Furthermore, examples of colloidal silica using an aqueous solvent as a dispersion medium include, but are not limited to, MA-ST-M (methanol dispersion type with a particle size of 20 to 25 nm), IPA-ST (isopropyl alcohol dispersion type with a particle size of 10 to 15 nm), EG-ST (ethylene glycol dispersion type with a particle size of 10 to 15 nm), EGST-ZL (ethylene glycol dispersion type with a particle size of 70 to 100 nm), NPC-ST (ethylene glycol monopropyl ether dispersion type with a particle size of 10 to 15 nm), and TOL-ST (toluene dispersion type with a particle size of 10 to 15 nm), all manufactured by Nissan Chemical Industries, Ltd.

[0060] Examples of dry silica particles include, but are not limited to, AEROSIL manufactured by Nippon Aerosil Co., Ltd. and Reolosil manufactured by Tokuyama Corporation.

[0061] The silica particles may contain an inorganic base (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.) or an organic base (tetramethylammonium, triethylamine, etc.) as a stabilizer.

[0062] <Content of inorganic particles (C) relative to total solid content of aqueous coating composition> From the viewpoint of the transparency and adhesion of the substrate with an adhesive layer and the hard coat laminate described below, the content of the inorganic particles (C) relative to the total solid content of the aqueous coating composition of the present embodiment is preferably 30 mass % to 60 mass %, more preferably 37.5 mass % to 47.5 mass %.

[0063] (Crosslinking agent (D)) The aqueous coating composition of the present embodiment preferably contains a crosslinking agent (D) from the viewpoint of improving the adhesion of the substrate with an adhesive layer, which will be described later.

[0064] The crosslinking agent (D) preferably contains an isocyanate compound from the viewpoint of reactivity with the emulsion particles (A) used in the aqueous coating composition of this embodiment.

[0065] The isocyanate compound refers to a compound having at least one isocyanate group per molecule, and may be a compound having two or more isocyanate groups per molecule. The isocyanate compound is not limited to the following, but examples thereof include aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanato) hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, and 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4- Aliphatic triisocyanates such as isocyanatomethyl octane, 2-isocyanatoethyl (2,6-diisocyanato) hexanoate; 1,3- or 1,4-bis(isocyanatomethyl cyclohexane), 1,3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl (3-isocyanatomethyl) cyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,5- or 2,6-diisocyanato Alicyclic diisocyanates such as 2,5- or 2,6-diisocyanate, methyl-2-isocyanate, propylnorbornane, and other alicyclic triisocyanates; m-xylylene diisocyanate, α,α,α'α'-tetramethyl-m-xylylene diisocyanate, and other aralkylene diisocyanates; m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate aromatic diisocyanates such as 4,4'-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, and diphenylether-4,4'-diisocyanate; and aromatic triisocyanates such as triphenylmethane triisocyanate and tris(isocyanatophenyl)thiophosphate.

[0066] Further examples of the isocyanate compound include diisocyanates or polyisocyanates having a uretdione structure obtained by cyclodimerization of isocyanate groups of the above-mentioned diisocyanates or triisocyanates; polyisocyanates having an isocyanurate structure obtained by cyclotrimerization of isocyanate groups of the above-mentioned diisocyanates or triisocyanates; polyisocyanates having a biuret structure obtained by reacting the above-mentioned diisocyanates or triisocyanates with water; polyisocyanates having an oxadiazinetrione structure obtained by reacting the above-mentioned diisocyanates or triisocyanates with carbon dioxide; polyisocyanates having an allophanate structure obtained by reacting the above-mentioned diisocyanates or triisocyanates with various alcohols; and polyisocyanates obtained by reacting the above-mentioned diisocyanates or triisocyanates with compounds containing active hydrogen, such as polyhydroxy compounds, polycarboxy compounds, and polyamine compounds. Further examples of the isocyanate compound include isocyanate compounds having an alkoxysilane moiety and / or a siloxane moiety in the molecule, such as 3-isocyanatepropyltriethoxysilane and / or hydrolysis condensates of 3-isocyanatepropyltriethoxysilane. These may be used alone or in combination of two or more.

[0067] From the viewpoint of the storage stability of the aqueous coating composition of this embodiment, the isocyanate compound is more preferably a blocked polyisocyanate compound in which an isocyanate group is reacted with a blocking agent. The blocked polyisocyanate compound is not particularly limited, and can be appropriately selected from compounds that function as a crosslinking agent. Examples of the blocked polyisocyanate compound include, but are not limited to, oxime-based compounds, alcohol-based compounds, acid amide-based compounds, acid imide-based compounds, phenol-based compounds, amine-based compounds, active methylene-based compounds, imidazole-based compounds, and pyrazole-based compounds. Examples of oxime compounds include, but are not limited to, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime. Examples of alcohol compounds include, but are not limited to, methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol. Examples of acid amide compounds include, but are not limited to, acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam. Examples of the acid imide compound include, but are not limited to, succinimide and maleimide. Examples of phenolic compounds include, but are not limited to, phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid esters. Examples of the amine compound include, but are not limited to, diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine. Examples of active methylene compounds include, but are not limited to, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Examples of imidazole compounds include, but are not limited to, imidazole and 2-methylimidazole. Examples of pyrazole compounds include, but are not limited to, pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

[0068] From the viewpoint of water dispersibility, the blocked polyisocyanate compound is preferably a compound obtained by reacting the polyisocyanate compound having two or more isocyanate groups per molecule with a hydroxyl-containing hydrophilic compound having a nonionic and / or ionic hydrophilic group at an isocyanate group / hydroxyl group equivalent ratio of 1.05 to 1000, and then reacting the resulting water-dispersible isocyanate compound with the blocking agent. Such a water-dispersible blocked polyisocyanate compound is not particularly limited, and commercially available products can also be used. For example, WT30-100 manufactured by Asahi Kasei Corporation and WM44-L70G manufactured by Asahi Kasei Corporation are preferably used as they have the above-mentioned characteristics.

[0069] (Biphenyltriazine-based ultraviolet absorber (E)) From the viewpoint of improving weather resistance, the aqueous coating composition of this embodiment preferably contains an ultraviolet absorber (E) having a biphenyltriazine skeleton. Examples of the ultraviolet absorber having a biphenyltriazine skeleton include, but are not limited to, 2,4,6-tri([1,1'-biphenyl]-4-yl)-1,3,5-triazine, 2,4,6-tri([1,1'-biphenyl]-3-yl)-1,3,5-triazine, and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine. (trade name "TINUVIN479" manufactured by BASF), TINUVIN1600 (trade name, manufactured by BASF), 2-(biphenyl-4-yl)-4-chloro-6-phenyl-1,3,5-triazine, 4,4'-bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl, 2-[3'-bromo[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine, and the like.

[0070] (UV absorbers other than those with biphenyltriazine skeleton) The aqueous coating composition of this embodiment may contain an ultraviolet absorber other than the biphenyltriazine-based ultraviolet absorber (E) from the viewpoint of improving weather resistance. Examples of such ultraviolet absorbers include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 benzophenone-based ultraviolet absorbers such as 2,2',4,4'-dihydroxy-4,4'-dimethoxybenzophenone (trade name "UVINUL3049" manufactured by BASF), 2,2',4,4'-tetrahydroxybenzophenone (trade name "UVINUL3050" manufactured by BASF), 4-dodecyloxy-2-hydroxybenzophenone, 5-benzoyl-2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, and 4,6-dibenzoylresortinol;2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenyl] benzotriazole), methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight 300) condensation product (trade name "TINUVIN1130" manufactured by BASF), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (trade name "TINUVIN384" manufactured by BASF), 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)propionate 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole (trade name "TINUVIN571" manufactured by BASF), 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, benzotriazole-based ultraviolet absorbers such as 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (trade name "TINUVIN900" manufactured by BASF), TINUVIN384-2, TINUVIN326, TINUVIN327, TINUVIN109, TINUVIN970, TINUVIN328, TINUVIN171, TINUVIN970, TINUVIN PS, TINUVIN P, TINUVIN99-2, and TINVIN928 (trade names, manufactured by BASF);triazine-based UV absorbers such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)-1,3,5-triazine (trade name "TINUVIN460" manufactured by BASF), TINUVIN400, TINUVIN405, and TINUVIN477; malonic acid ester-based UV absorbers such as HOSTAVIN PR25, HOSTAVIN B-CAP, and HOSTAVIN VSU (trade names, manufactured by Clariant); HOSTAVIN3206 LIQ and HOSTAVINVSU Examples of such ultraviolet absorbers include anilide ultraviolet absorbers such as HOSTAVIN 3212 LIQ (trade name, manufactured by Clariant) and salicylate ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanol phenyl salicylate.

[0071] <Content of biphenyltriazine-based ultraviolet absorber (E)> In the aqueous coating composition of the present embodiment, the content of the biphenyltriazine skeleton ultraviolet absorber (E) in the aqueous coating composition is preferably 0.3 mass % or more, more preferably 0.5 mass % or more, and even more preferably 0.7 mass % or more, from the viewpoint of weather resistance. On the other hand, from the viewpoint of storage stability of the aqueous coating composition of this embodiment, the content is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0072] (solvent) The aqueous coating composition of this embodiment may contain a solvent. In this embodiment, "aqueous" means that the most abundant component among the components contained in the solvent is water. From the viewpoint of maintaining sanitary conditions at the work site and reducing the burden on the global environment, it is preferable that 50 mass % or more of the solvent is water. Usable solvents other than water are not particularly limited, and general solvents can be used. Examples of solvents other than water include, but are not limited to, alcohols such as ethylene glycol, butyl cellosolve, isopropanol, n-butanol, 2-butanol, ethanol, methanol, denatured ethanol, 2-methoxy-1-propanol, 1-methoxy-2-propanol, diacetone alcohol, glycerin, monoalkyl monoglyceryl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol monophenyl ether, and tetraethylene glycol monophenyl ether; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, and heptane; esters such as ethyl acetate and n-butyl acetate; amides such as dimethylacetamide and dimethylformamide; halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride; dimethyl sulfoxide, nitrobenzene, and the like. These may be used alone or in combination of two or more.

[0073] The aqueous coating composition of the present embodiment may contain an aprotic organic solvent in the solvent. The compatibility of the emulsion particles (A) and the ultraviolet absorber (E) via the aprotic organic solvent makes it possible for the ultraviolet absorber (E) to be stably dispersed in the aqueous coating composition, and the storage stability tends to be excellent. The boiling point of the aprotic organic solvent contained in the solvent is preferably less than 100° C. This makes it possible to suppress deterioration of the substrate due to the organic solvent when forming a substrate with an adhesive layer, which will be described later, and as a result, tends to result in excellent transparency when forming a hard coat laminate, which will be described later. Examples of aprotic organic solvents include, but are not limited to, ethers such as tetrahydrofuran (THF), dimethoxyethane (DME), 2-methyltetrahydrofuran (2-MeTHF), tetrahydropyran, diethyl ether, t-butyl methyl ether, and diisopropyl ether; esters such as methyl acetate, ethyl acetate, and propyl acetate; ketones such as acetone; and acetonitrile.

[0074] <Aprotic organic solvent content> When the aqueous coating composition of the present embodiment contains the aprotic organic solvent as a solvent, the content of the aprotic organic solvent in the aqueous coating composition is preferably 0.1% by mass to 30% by mass. By ensuring that the content of the aprotic organic solvent in the aqueous coating composition of this embodiment is 30 mass % or less, when the aqueous coating composition is applied to the substrate in the production of a substrate with an adhesive layer, which will be described later, the surface of the substrate can be prevented from being dissolved by the aprotic organic solvent, and this tends to make it possible to provide excellent transparency to the substrate with an adhesive layer and the hard coat laminate, which will be described later.

[0075] (light stabilizer) The aqueous coating composition of the present embodiment may contain a light stabilizer from the viewpoint of improving weather resistance. Examples of light stabilizers include, but are not limited to, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethylpiperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3-(3,5-di-tert-butyl -4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethylpiperidine, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate (trade name "TINUVIN 292" manufactured by BASF), bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 249, TI hindered amine light stabilizers such as NUVIN 292 and TINUVIN 5100 (trade names, manufactured by BASF); 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2,2,6,6-tetramethyl-4-imino Examples of such light stabilizers include radically polymerizable hindered amine light stabilizers such as piperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, and 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate; and light-stable polymers such as U-DOUBLE E-133, U-DOUBLE E-135, U-DOUBLE S-2000, U-DOUBLE S-2834, U-DOUBLE S-2840, U-DOUBLE S-2818, and U-DOUBLE S-2860 (trade names, manufactured by Nippon Shokubai Co., Ltd.).

[0076] <Light stabilizer content> From the viewpoint of improving weather resistance, the light stabilizer is preferably contained in an amount of 1 part by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the total amount of all ultraviolet absorbers contained in the aqueous coating composition of this embodiment.

[0077] Other Components That May Be Included in the Aqueous Coating Composition In addition to the components described above, the aqueous coating composition of the present embodiment may contain emulsifiers, plasticizers, pigments, dyes, fillers, antioxidants, conductive materials, light stabilizers, release adjusters, softeners, surfactants, flame retardants, antioxidants, catalysts, and the like, depending on the application.

[0078] [Method for producing aqueous coating composition] The aqueous coating composition of this embodiment can be produced by mixing the emulsion particles (A), the amine compound (B), and the inorganic particles (C) using a solvent containing water. Specifically, the method may include a "diffusion step of the ultraviolet absorber into the emulsion" in which the ultraviolet absorber (E) dissolved in the aprotic organic solvent is dropped into an aqueous solution containing the emulsion particles (A) in a stirred state. This step allows the ultraviolet absorber (E) to be diffused into the emulsion particles (A), and as a result, an aqueous coating composition with excellent storage stability can be prepared.

[0079] [Physical Properties of Aqueous Coating Composition] (Average particle size of aqueous coating composition) The average particle size calculated by dynamic light scattering when the aqueous coating composition of this embodiment is diluted 50 times with ion-exchanged water is preferably 150 nm or less. When the average particle size is within this range, the components in the coating material tend to be less likely to spontaneously settle, and the coating material using the aqueous coating composition of this embodiment tends to have excellent storage stability. Furthermore, from the viewpoint of further improving storage stability and the transparency of the substrate with an adhesive layer, which will be described later, the average particle size is more preferably 100 nm or less. The average particle size measured by dynamic light scattering can be measured by the method described in the Examples section below.

[0080] (pH of aqueous coating composition) The aqueous coating composition of this embodiment has a pH of 9.5 or higher. The pH within the above range improves the dispersibility of the emulsion particles (A), and as a result, the storage stability of the paint using the aqueous coating composition of this embodiment tends to be improved. Furthermore, thickening due to abnormal aggregation can be suppressed during the room temperature drying process after application of the paint using the aqueous coating composition of this embodiment, and unevenness in the coating film and drip marks tend to be reduced. The pH of the aqueous coating composition of this embodiment is preferably 10.0 or higher, and more preferably 10.5 or higher. The pH of the aqueous coating composition can be measured, for example, with a pH meter (HM-25R type) manufactured by DKK-TOA Corp. The pH can be controlled within the above-mentioned range, for example, by adjusting the amount of the amine compound added.

[0081] (Solids concentration of aqueous coating composition) The solid content of the aqueous coating composition of this embodiment is preferably 10.0 to 25.0 mass% from the viewpoint of coatability, and more preferably 12.5.0 to 22.5 mass%, and even more preferably 15.0 to 20.0 mass%, from the viewpoint of storage stability of the aqueous coating composition of this embodiment.

[0082] [Substrate with adhesive layer] The substrate with an adhesive layer of this embodiment has a substrate and an adhesive layer disposed on the substrate. The adhesive layer comprises the aqueous coating composition of the present embodiment described above. The phrase "the adhesive layer comprises the aqueous coating composition of this embodiment" encompasses the adhesive layer being obtained from the aqueous coating composition of this embodiment. That is, the adhesive layer can be obtained, for example, by applying the aqueous coating composition of this embodiment to a substrate and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, or the like. Furthermore, the coating method includes, but is not limited to, spraying, flow coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, etc. The applied aqueous coating composition of the present embodiment can be formed into a coating film by heat treatment, preferably at room temperature to 250°C, more preferably at 50°C to 150°C, or by ultraviolet or infrared irradiation. Furthermore, this coating includes not only coating on already formed substrates, but also coating on flat plates before forming, such as pre-coated metals including rust-resistant steel plates.

[0083] The thickness of the adhesive layer constituting the substrate with an adhesive layer of this embodiment is preferably 1.0 μm or more, more preferably 3.0 μm or more, from the viewpoint of imparting sufficient weather resistance when forming the hard coat laminate described below, and is preferably 50.0 μm or less, more preferably 10.0 μm or less, from the viewpoint of transparency.

[0084] The substrate constituting the substrate with an adhesive layer of this embodiment is not particularly limited, but examples thereof include resin, metal, glass, and the like. The shape of the substrate is not limited to the following, but examples thereof include a plate shape, a shape including irregularities, a shape including a curved surface, a hollow shape, a porous shape, and combinations thereof. The type of the substrate is not limited to the following, but examples thereof include a sheet, a film, and a fiber. The substrate is preferably made of a resin from the viewpoint of imparting abrasion resistance and moldability. Resins used as the substrate include, but are not limited to, thermoplastic resins and thermosetting resins. Thermoplastic resins used as the substrate include, but are not limited to, polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, fluororesin, polycarbonate, polyester resin, and the like. Furthermore, examples of the thermosetting resin used as the substrate include, but are not limited to, phenolic resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicon resin, silicone rubber, SB rubber, natural rubber, and thermosetting elastomer.

[0085] (Transparency of substrate with adhesive layer) The substrate with an adhesive layer of this embodiment preferably has a haze value H1 of 20% or less, more preferably 15% or less. When the haze value H1 of the substrate with an adhesive layer is within the above range, the transparency of the hard coat laminate described below tends to be excellent. The haze value of the adhesive-backed substrate can be measured, for example, using a turbidity meter (NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd. according to the method specified in JIS K 7136, and can be controlled to 20% or less by adjusting the type and amount of the amine compound added, drying conditions, etc.

[0086] (Surface roughness of substrate with adhesive layer) In the present embodiment, the substrate with an adhesive layer has a surface roughness of preferably 200 nm or less, more preferably 100 nm or less, from the viewpoint of transparency. In the present embodiment, the substrate with an adhesive layer has a surface roughness of preferably 10 nm or more, more preferably 20 nm or more, from the viewpoint of adhesion. Here, the surface roughness is the arithmetic mean roughness Sa defined by ISO 25178 Surface Quality (Surface Roughness Measurement). The surface roughness of the adhesive-attached substrate can be measured, for example, by a laser microscope OLS5000 manufactured by Olympus Corporation, and can be controlled to 200 nm or less by adjusting the type and amount of the amine compound added, drying conditions, etc.

[0087] [Hard Coat Laminate] The hard coat laminate of this embodiment has the substrate with an adhesive layer of this embodiment described above, and a hard coat layer disposed on the substrate with an adhesive layer. The hard coat laminate of this embodiment can be obtained by overcoating a predetermined hard coat coating material onto the substrate with the adhesive layer. The hard coat paint is a paint intended to form a coating film that is primarily scratch-resistant on the surface of a substrate or the like. The components contained in the hard coat coating material are not limited to the following, but from the viewpoint of the transparency and adhesion of the hard coat laminate, it is preferable to contain a hydrolyzable silicon compound. In this specification, "containing a hydrolyzable silicon compound" means that the hard coat coating material contains a polymer having a structural unit derived from a hydrolyzable silicon compound. The hydrolyzable silicon compound is not particularly limited as long as it is a silicon compound having hydrolysis properties, or its hydrolysis product or condensation product.

[0088] Examples of the hydrolyzable silicon compound include, but are not limited to, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, cyclohex ... Methoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(triphenoxysilyl)ethane, 1,1-bis(triethoxysilyl)ethane, 1,2-bis(triethoxysilyl) 1,1-bis(triethoxysilyl)ethane, 1,1-bis(triethoxysilyl)propane, 1,2-bis(triethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(triethoxysilyl)butane, 1,5-bis(triethoxysilyl)pentane, 1,1-bis(trimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,1-bis(trimethoxysilyl)propane, 1,2-bis(trimethoxysilyl)propane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)ethane 1,5-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,3-bis(triphenoxysilyl)propane, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,7-bis(triethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, and the like.

[0089] Examples of the hydrolyzable silicon compound include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. Ethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane Examples thereof include trimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-trimethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and triacetoxysilane.

[0090] Examples of the hydrolyzable silicon compound include tris(trichloroacetoxy)silane, tris(trifluoroacetoxy)silane, tris-(trimethoxysilylpropyl)isocyanurate, tris-(triethoxysilylpropyl)isocyanurate, methyltriacetoxysilane, methyltris(trichloroacetoxy)silane, trichlorosilane, tribromosilane, methyltrifluorosilane, tris(methylethylketoxime)silane, phenyltris(methylethylketoxime)silane, bis(methylethyl)silane, and methyltris(methylethyl)silane. methylbis(methylethylketoxime)silane, methylbis(methylethylketoxime)silane, hexamethyldisilane, hexamethylcyclotrisilazane, bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, 2-[(triethoxysilyl)propyl]dibenzylresorcinol, 2-[(trimethoxysilyl)propyl]dibenzylresorcinol, 2,2,6,6-tetramethyl-4-[3-(triethoxysilyl)propoxy]piperidinol dimethylsilane, 2,2,6,6-tetramethyl-4-[3-(trimethoxysilyl)propoxy]piperidine, 2-hydroxy-4-[3-(triethoxysilyl)propoxy]benzophenone, 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone, tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(i-propoxy)silane, tetra(n-butoxy)silane, tetra(i-butoxy)silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane , tetraacetoxysilane, tetra(trichloroacetoxy)silane, tetra(trifluoroacetoxy)silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, tetra(methylethylketoxime)silane, partial hydrolysis condensates of tetramethoxysilane or tetraethoxysilane (for example, trade names "M Silicate 51," "Silicate 35," "Silicate 45," "Silicate 40," and "FR-3" manufactured by Tama Chemical Industries Co., Ltd.; trade names "MS51," "MS56," "MS57," and "MS56S" manufactured by Mitsubishi Chemical Corporation);Examples include trade names of Colcoat Co., Ltd.: "Methyl Silicate 51," "Methyl Silicate 53A," "Ethyl Silicate 40," "Ethyl Silicate 48," "EMS-485," "N-103X," "PX," "PS-169," "PS-162R," "PC-291," "PC-301," "PC-302R," "PC-309," and "EMSi48");

[0091] The method for overcoating the hard coat paint onto the substrate with an adhesive layer is not particularly limited, but examples include a method in which the hard coat paint is applied to the substrate with an adhesive layer and then formed into a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc. Furthermore, examples of the coating method include, but are not limited to, spraying, flow coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, etc. The applied hard coat paint can be formed into a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc., preferably at room temperature to 250°C, more preferably at 50°C to 150°C, to form a hard coat layer.

[0092] [Laminate] In this embodiment, a laminate can be provided that has a substrate, an adhesive layer disposed on the substrate, and a functional layer disposed on the substrate. The functional layer may have the form of the hard coat layer described above. It is preferable that the laminate of this embodiment exhibits peeling of Class 3 or higher when immersed in hot water at 98°C for 1 hour and then subjected to an adhesion test by the cross-cut method specified in JIS K5600-5-6, and maintains adhesion of Class 2 or lower when immersed in water at 80°C for 8 hours, then immersed in hot water at 98°C for 1 hour, and then subjected to an adhesion test by the cross-cut method specified in JIS K5600-5-6. The laminate of the present embodiment has the above-described structure, which allows the coating film to be easily peeled off with only a short boiling water treatment during production, and furthermore, when used over a long period of time, the coating film can maintain high adhesion, resulting in excellent peelability and durability.

[0093] The adhesive layer constituting the laminate preferably contains a polymer derived from emulsion particles (A) having units (a) derived from a vinyl monomer (a). The adhesive layer constituting the laminate preferably contains an amine compound (B), which preferably has a boiling point of −30° C. or higher and 180° C. or lower under an external pressure of 1 atmosphere. Furthermore, the adhesive layer constituting the laminate preferably contains inorganic particles (C). Furthermore, the adhesive layer constituting the laminate preferably contains a crosslinking agent (D). Furthermore, the adhesive layer constituting the laminate preferably contains an ultraviolet absorber (E'). The ultraviolet absorber (E') may be the above-mentioned ultraviolet absorber (E) having a biphenyltriazine skeleton, or other ultraviolet absorbers may also be used. The above-mentioned hard coat layer can be used as the functional layer disposed on the adhesive layer.

[0094] The inventors speculate that the reason why the laminate of this embodiment has the effect of easily peeling off the coating film with just a short boiling water treatment during production, and furthermore, being able to maintain high adhesion of the coating film over long-term use, resulting in excellent peelability and durability, is as follows. During manufacturing, if the adhesive layer in the laminate contains a compound that accelerates the decomposition of polycarbonate in hot water, such as an amine compound (B), localized decomposition of the polycarbonate occurs at the interface between the adhesive layer and the polycarbonate when treated with hot water at 90°C or higher, resulting in excellent peelability and easy removal of the coating film. On the other hand, polycarbonate decomposition does not occur in water below 80°C, and the compound that accelerates polycarbonate decomposition is removed from the adhesive layer, eliminating peeling even when treated with hot water above 90°C. In other words, over long periods of use in practical environments, the compound that accelerates polycarbonate decomposition is removed from the adhesive layer, preventing coating peeling due to polycarbonate decomposition and resulting in excellent durability.

[0095] (Hard coat laminate and surface treatment of laminate) From the viewpoint of weather resistance, the hard coat laminate and the laminate of this embodiment may have their surfaces silica-treated to form a silica layer. Methods for forming a silica layer include, but are not limited to, silica processing by PECVD, which involves vapor-depositing and curing silicone or silazane, and silica processing techniques that modify the surface to silica by irradiating it with 155 nm ultraviolet light. Surface processing by PECVD is particularly preferred, as it can produce a layer that is impermeable to oxygen and water vapor without deteriorating the surface. Examples of silicones or silazanes that can be used in PECVD include, but are not limited to, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, vinylmethyxylane, vinylmethoxysilane, dimethyldimethoxysilane, TEOS, tetramethyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethyldisilazane. These may be used alone or in combination of two or more.

[0096] The hard coat laminate and laminate of this embodiment may further have a specified other functional layer on at least one surface, in addition to on the above-mentioned silica layer, i.e., between the silica layer and the hard coat layer or functional layer, or between the adhesive layer and the hard coat layer or functional layer. Examples of the other functional layers include, but are not limited to, an anti-reflection layer, an anti-fouling layer, a polarizing layer, and an impact absorbing layer.

[0097] (Hard Coat Laminate and Applications of Laminate) The hard coat laminate of this embodiment and the above-described laminates have excellent transparency, adhesion, and weather resistance. Therefore, applications of the hard coat laminate of this embodiment include, but are not limited to, building materials, vehicle components, electronic devices, electrical products, etc. Examples of building material applications include, but are not limited to, window glass for construction machinery, window glass for buildings, houses, greenhouses, etc., roofs for garages and arcades, etc., lighting fixtures and traffic lights, wallpaper covering materials, signs, sanitary products such as bathtubs and washbasins, kitchen building materials, exterior wall materials, flooring materials, cork materials, tiles, cushion flooring, interior flooring materials such as linoleum, etc. Examples of vehicle components include, but are not limited to, parts used in automobiles, aircraft, and trains. Specific examples include glass for front, rear, front door, rear door, rear quarter, sunroof, etc., exterior components for front bumpers, rear bumpers, spoilers, door mirrors, front grilles, emblem covers, and bodies, interior components for center panels, door panels, instrument panels, and center consoles, lamp components for headlamps and rear lamps, lens components for in-vehicle cameras, lighting covers, decorative films, and various glass substitutes. Preferred examples of electronic devices and electrical products include, but are not limited to, mobile phones, personal digital assistants, personal computers, portable game consoles, office automation equipment, solar cells, flat panel displays, touch panels, optical discs such as DVDs and Blu-ray discs, optical components such as polarizing plates, optical filters, lenses, prisms, and optical fibers, and optical films such as anti-reflection films, alignment films, polarizing films, and retardation films. The hard coat laminate of this embodiment and the laminates described above can be applied to a variety of fields, including machine parts, agricultural materials, fishing materials, transport containers, packaging containers, play equipment, and miscellaneous goods, in addition to the above. [Example]

[0098] The present embodiment will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.

[0099] In the examples and comparative examples described below, various physical properties and characteristics were measured and evaluated by the following methods.

[0100] [Evaluation of physical properties and characteristics of Examples 1-1 to 11 and Comparative Examples 1-1 to 1-3] ((1) Weight average molecular weight of unit (a) derived from vinyl monomer (a) contained in emulsion particle (A)) Emulsion particles (A) obtained by the method described below were diluted with dimethylformamide to 0.5% by mass, and passed through a membrane filter with a pore size of 0.45 μm to extract units (a). The units (a) were then measured by gel permeation chromatography to obtain a chromatogram. From the chromatogram, the weight-average molecular weight of the units (a) contained in the emulsion particles (A) was calculated based on the molecular weight of standard polystyrene. The gel permeation chromatograph used was an "HLC-8420GPC" (manufactured by Tosoh Corporation). Four columns were used: a "TSKgel guardcolumn SuperAW-H," two "TSKgel SuperAWM-H," and a "TSKgel SuperH-RC" (all manufactured by Tosoh Corporation). The mobile phase was dimethylformamide, the measurement temperature was 40°C, the flow rate was 0.6 mL / min, and the detector was RI.

[0101] ((2) Average particle size of emulsion particles (A) and aqueous coating composition) The emulsion particles (A) and the aqueous coating composition obtained by the method described below were each diluted 50 times with ion-exchanged water, and then the cumulant average particle size was measured using a dynamic light scattering particle size distribution analyzer (product number: nanoSAQLA) manufactured by Otsuka Electronics Co., Ltd., and this was used as the average particle size of the emulsion particles (A) and the aqueous coating composition.

[0102] ((3) pH of the aqueous coating composition) The pH of the aqueous coating composition obtained by the method described below was measured with a pH meter (HM-25R type) manufactured by DKK-TOA Corporation.

[0103] ((4) Evaluation of the paintability of aqueous coating compositions) The aqueous coating composition prepared by the method described below was applied to a 1 m square polycarbonate substrate using the coating method described below, and after drying, the coating was visually observed and the coatability was evaluated according to the following criteria. A: No drip marks or uneven film thickness on the entire surface of the 1m square substrate B: There are drip marks and uneven film thickness on the bottom edge of the 1m square substrate. C: There are drip marks and uneven film thickness on the entire surface of the 1m square substrate.

[0104] (5) Evaluation of surface smoothness of substrate with adhesive layer obtained by applying aqueous coating composition) The aqueous coating composition prepared by the method described below was applied to a 1 m square polycarbonate substrate using the coating method described below to form an adhesive layer. After drying, the layer was visually observed and the surface smoothness of the substrate with the adhesive layer was evaluated according to the following criteria. A: 1m square base material with glossy finish on the entire surface B: 1m square substrate with part of it in frosted glass state C: 1m square substrate with frosted glass surface

[0105] (6) Sa evaluation of substrate with adhesive layer obtained by applying aqueous coating composition) An aqueous coating composition prepared by the method described below was applied to a 1 m square polycarbonate substrate using the coating method described below to form an adhesive layer. After drying, the substrate was cut into 16 25 cm square pieces to obtain measurement samples. The arithmetic mean roughness Sa was measured using an Olympus OLS5000 laser microscope (100x objective lens) according to the method specified in ISO 25178 Surface Texture (Area Roughness Measurement). Five images were randomly taken from each of the 16 25 cm square samples, and the average of the arithmetic mean roughness raw data obtained by analyzing the entire image area was used as the arithmetic mean roughness Sa.

[0106] (7) Evaluation of Transparency of Adhesive-Coated Substrate and Hard Coat Laminate The transparency of the substrate with an adhesive layer and the hard coat laminate was evaluated by the haze value measured by the method specified in JIS K7136 using a turbidity meter (product number: NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd. The haze value H1 was measured and evaluated using the above method for the substrate with the adhesive layer. The haze value H2 was measured and evaluated using the above method for the hard coat laminate.

[0107] ((8) Weather resistance evaluation) The weather resistance of the hard coat laminate was evaluated by irradiating ultraviolet light using a xenon arc (product name SX-75, manufactured by Suga Test Instruments Co., Ltd.) in accordance with the conditions of the ANSI / SAE Z26.1 standard at 2000MJ / m 2Δb was measured before and after irradiation and evaluated according to the following criteria. A: Δb<0.5 A: Δb = 0.5 to 2.0 B:Δb>2.0

[0108] ((9) Mass ratio (content) of each component) The mass ratio (content) of each component in the aqueous coating composition was determined from the ratio of the amount of each component charged when the aqueous coating composition was prepared.

[0109] [Preparation of materials for Examples 1-1 to 11 and Comparative Examples 1-1 to 1-3, and preparation of materials for evaluation] (Preparation of aqueous dispersion of emulsion particles (A)) The following emulsion particles (A-1) to (A-3) were prepared as emulsion particles used in the examples and comparative examples described below.

[0110] (Preparation of aqueous dispersion of emulsion particles (A-1)) The aqueous dispersion of emulsion particles (A-1) used in Examples 1-1 to 11 and Comparative Examples 1-1 to 3 described below was prepared as follows. Polymerization was carried out in a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer at 85°C using a monomer mixture prepared by dissolving 650.00 g of ion-exchanged water, 38.46 g of a 10% aqueous solution of dodecylbenzenesulfonic acid, 96.15 g of a 2% aqueous solution of ammonium persulfate, 1.92 g of Aqualon KH-1025 (a reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd., with a solids concentration of 25%), 1.92 g of Adeka Reasoap SR-1025 (a reactive emulsifier manufactured by ADEKA Corporation, with a solids concentration of 25%), and 9.62 g of the ultraviolet-absorbing vinyl monomer "RUVA-93" (trade name, manufactured by Otsuka Chemical Co., Ltd.) in a mixture of 122.12 g of butyl acrylate, 57.69 g of 2-hydroxyethyl methacrylate, 1.92 g of acrylic acid, and 1.92 g of 1-dodecanethiol, using a conventional emulsion polymerization method. After the polymerization, the mixture was filtered through a 100-mesh wire screen, and the solid content was adjusted to 20% by mass with ion-exchanged water to obtain an aqueous dispersion of emulsion particles (A-1). The resulting emulsion particles (A) had an average particle size of 45.1 nm and a weight average molecular weight of the unit (a) of 110,000.

[0111] (Preparation of aqueous dispersion of emulsion particles (A-2)) The aqueous dispersion of emulsion particles (A-2) used in Examples 1-1 to 11 and Comparative Examples 1-1 to 3 described below was prepared as follows. Polymerization was carried out in a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer using a monomer mixture dissolved in a mixture of 650.00 g of ion-exchanged water, 38.46 g of a 10% aqueous solution of dodecylbenzenesulfonic acid, 96.15 g of a 2% aqueous solution of ammonium persulfate, 1.92 g of Aqualon KH-1025 (a reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd., having a solids concentration of 25%), 1.92 g of Adeka Reasoap SR-1025 (a reactive emulsifier manufactured by ADEKA Corporation, having a solids concentration of 25%), 151.92 g of butyl acrylate, 27.88 g of 2-hydroxyethyl methacrylate, 1.92 g of acrylic acid, and 1.92 g of 1-dodecanethiol, using a general emulsion polymerization method at 85°C. After polymerization, the mixture was filtered through a 100-mesh wire net and the solid content was adjusted to 20% by mass with ion-exchanged water to obtain an aqueous dispersion of emulsion particles (A-2). The resulting emulsion particles (A) had an average particle size of 37.5 nm and a weight-average molecular weight of unit (a) of 140,000.

[0112] (Preparation of aqueous dispersion of emulsion particles (A-3)) The aqueous dispersion of emulsion particles (A-3) used in Examples 1-1 to 11 and Comparative Examples 1-1 to 3 described below was prepared as follows. Polymerization was carried out in a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer using a monomer mixture dissolved in a mixture of 650.00 g of ion-exchanged water, 38.46 g of a 10% aqueous solution of dodecylbenzenesulfonic acid, 96.15 g of a 2% aqueous solution of ammonium persulfate, 1.92 g of Aqualon KH-1025 (a reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd., with a solids concentration of 25%), 1.92 g of Adeka Reasoap SR-1025 (a reactive emulsifier manufactured by ADEKA Corporation, with a solids concentration of 25%), 111.54 g of methyl methacrylate, 40.38 g of butyl acrylate, 27.88 g of 2-hydroxyethyl methacrylate, 1.92 g of acrylic acid, and 1.92 g of 1-dodecanethiol, using a general emulsion polymerization method at 85°C. After polymerization, the mixture was filtered through a 100-mesh wire net and the solid content was adjusted to 20% by mass with ion-exchanged water to obtain an aqueous dispersion of emulsion particles (A-2). The resulting emulsion particles (A) had an average particle size of 54.7 nm and a weight-average molecular weight of unit (a) of 110,000.

[0113] [Preparation of hard coat paint] The hard coat coating materials used in Examples 1-1 to 11 and Comparative Examples 1-1 to 3 described below were prepared as follows. 62.4 g of ion-exchanged water, 3.4 g of ethanol, 3.0 g of BYK-349 (a surface conditioner manufactured by BYK Chemie) adjusted to a concentration of 5% as a surface conditioner, 1.4 g of 1 M acetic acid and 1.4 g of 1 M sodium acetate as pH adjusters, and 23.9 g of methyltrimethoxysilane and 4.4 g of tris-(trimethoxysilylpropyl)isocyanurate as hydrolyzable silicon compounds were mixed at room temperature for 6 hours to obtain a hard coat paint.

[0114] Preparation of Aqueous Coating Composition In the following Examples 1-1 to 11 and Comparative Examples 1-1 to 3, aqueous coating compositions were prepared.

[0115] (Example 1-1) An aqueous coating composition of Example 1 was obtained by mixing 6.63 g of ion-exchanged water, 27.38 g of an aqueous dispersion of emulsion particles (A-1), 2.50 g of 1-methylpiperidine as a neutralizing agent, and 63.50 g of water-dispersed colloidal silica "Snowtex PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15 mass%, primary particle diameter 15 nm) as metal oxide microparticles. The aqueous dispersion of emulsion particles was then mixed for 1 hour at room temperature. The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.5, and an average particle size of 80.6 nm. Next, the aqueous coating composition of Example 1-1 was applied to a 1 m square polycarbonate substrate using a flow coater, and the substrate was left to stand in a hanging state for 30 minutes at a temperature of 25°C and a humidity of 35%RH, and then dried for 1 hour at a temperature of 130°C to form an adhesive layer on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 1-1 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 1-1 in the same manner, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer. Table 1 shows the results of various evaluations performed on the aqueous coating composition of Example 1-1, the substrate with an adhesive layer, and the hard coat laminate.

[0116] (Example 1-2) An aqueous coating composition of Example 1-2 was obtained in the same manner as in Example 1-1, except that the amine compound (B) in Example 1-1 was changed to 2-amino-2-methyl-1-propanol. The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.0, and an average particle size of 79.8 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-2. Table 1 shows the results of various evaluations carried out on the aqueous coating composition, the substrate with an adhesive layer, and the hard coat laminate of Example 1-2.

[0117] (Examples 1-3) An aqueous coating composition of Example 1-3 was obtained in the same manner as in Example 1-1, except that the amine compound (B) in Example 1-1 was changed to N,N-dimethylpropylamine. The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.0, and an average particle size of 92.2 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-3. The aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1 to 3 were subjected to various evaluations, and the results are shown in Table 1.

[0118] (Examples 1-4) An aqueous coating composition of Example 1-4 was obtained in the same manner as in Example 1-1, except that the amine compound (B) in Example 1-1 was changed to morpholine. The aqueous coating composition had a solids concentration of 15.0%, a pH of 9.5, and an average particle size of 93.5 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-4. The aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1 to 4 were subjected to various evaluations, and the results are shown in Table 1.

[0119] (Examples 1-5) An aqueous coating composition of Example 1-5 was obtained in the same manner as in Example 1-1, except that the amine compound (B) in Example 1-1 was changed to hexylamine. The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.5, and an average particle size of 84.0 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-5. Table 1 shows the results of various evaluations carried out on the aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1 to 5.

[0120] (Examples 1 to 6) An aqueous coating composition of Example 1-6 was obtained in the same manner as in Example 1-1, except that the amine compound (B) in Example 1-1 was changed to monoisopropanolamine. The aqueous coating composition had a solids concentration of 15.0%, a pH of 11.0, and an average particle size of 78.0 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-6. The aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1 to 6 were subjected to various evaluations, and the results are shown in Table 1.

[0121] (Examples 1-7) The aqueous coating composition of Example 1-7 was obtained in the same manner as in Example 1-1, except that the metal oxide microparticles (C) in Example 1-1 were replaced with water-dispersed colloidal silica "Snowtex OUP" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass, primary particle diameter 12 nm). The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.6, and an average particle size of 83.0 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-7. Table 2 shows the results of various evaluations carried out on the aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1-7.

[0122] Examples 1-8 An aqueous coating composition of Example 1-8 was obtained in the same manner as in Example 1-1, except that the emulsion particles (A-1) of Example 1-1 were changed to emulsion particles (A-2). The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.6, and an average particle size of 90.4 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-8. Table 2 shows the results of various evaluations carried out on the aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1-8.

[0123] Examples 1-9 An aqueous coating composition of Example 1-9 was obtained in the same manner as in Example 1-1, except that the emulsion particles (A-1) in Example 1-1 were changed to emulsion particles (A-3). The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.5, and an average particle size of 88.8 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Example 1-9. Table 2 shows the results of various evaluations carried out on the aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1-9.

[0124] Examples 1-10 The aqueous dispersion of emulsion particles obtained by mixing 23.23 g of ion-exchanged water, 20.85 g of an aqueous dispersion of emulsion particles (A-1), 48.30 g of water-dispersed colloidal silica "Snowtex PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15 mass%, primary particle diameter 15 nm) as metal oxide microparticles, 5.12 g of WM44-L70G (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70 mass%, effective NCO 5.3 mass%) as a crosslinking agent, and 2.50 g of 1-methylpiperidine as a neutralizing agent was mixed, and the aqueous dispersion of emulsion particles was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 1-10. The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.4, and an average particle size of 81.0 nm. Next, the aqueous coating composition of Example 1-10 was applied to a 1 m square polycarbonate substrate using a flow coater, and the substrate was left to stand in a hanging state for 30 minutes at a temperature of 25°C and a humidity of 35% RH, and then dried at a temperature of 130°C for 1 hour to form an adhesive layer on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 1-10 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 1-10 in the same manner, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer. Table 2 shows the results of various evaluations carried out on the aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1 to 10.

[0125] (Examples 1-11) An aqueous dispersion of emulsion particles was obtained by mixing 21.46 g of ion-exchanged water, 153.13 g of an aqueous dispersion of emulsion particles (A-1), 354.17 g of water-dispersed colloidal silica "Snowtex PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 15% by mass) as metal oxide fine particles, 37.50 g of WM44-L70G (trade name, manufactured by Asahi Kasei Corporation, solids content 70% by mass, effective NCO 5.3% by mass) as a crosslinking agent, and 25.00 g of 1-methylpiperidine as a neutralizing agent. This aqueous dispersion was mixed with a mixture of 12.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids content 100%) as an ultraviolet absorber, 2.50 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids content 100%) as a light stabilizer, and 393.75 g of tetrahydrofuran as an aprotic organic solvent, and the mixture was mixed at room temperature for 1 hour to obtain an aqueous coating composition precursor. Distillation was then carried out until the ratio of aprotic organic solvents in the paint was less than 1.0% by mass, and ion-exchanged water was then added to adjust the solid content to 20%, thereby obtaining the aqueous coating composition of Example 1-11. The aqueous coating composition had a pH of 10.0 and an average particle size of 83.0 nm. Next, the aqueous coating composition of Example 1-11 was applied to a 1 m square polycarbonate substrate using a flow coater, and the substrate was left to stand in a suspended state for 30 minutes at a temperature of 25°C and a humidity of 35%RH, and then dried at a temperature of 130°C for 1 hour to form an adhesive layer on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 1-11 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 1-11 in the same manner, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer. Table 2 shows the results of various evaluations carried out on the aqueous coating compositions, substrates with adhesive layers, and hard coat laminates of Examples 1-11.

[0126] (Comparative Example 1-1) An aqueous coating composition of Comparative Example 1-1 was obtained in the same manner as in Example 1-1, except that the amine compound (B) in Example 1-1 was changed to benzylamine. The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.0, and an average particle size of 86.6 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Comparative Example 1-1. Table 3 shows the results of various evaluations performed on the aqueous coating composition of Comparative Example 1-1, the substrate with an adhesive layer, and the hard coat laminate. As a result, the weather resistance of the hard coat laminate was such that Δb was greater than 2.0.

[0127] (Comparative Example 1-2) An aqueous coating composition of Comparative Example 1-2 was obtained in the same manner as in Example 1-1, except that diethylamine was used as the amine compound (B). The aqueous coating composition had a solids concentration of 15.0%, a pH of 10.4, and an average particle size of 85.1 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Comparative Example 1-2. Table 3 shows the results of various evaluations performed on the aqueous coating composition of Comparative Example 1-2, the substrate with an adhesive layer, and the hard coat laminate. During the drying process, drip marks and uneven film thickness occurred all over the surface, resulting in a ground glass-like surface.A large amount of precipitate was also confirmed after one month of storage of the aqueous coating composition at 25°C.

[0128] (Comparative Examples 1-3) An aqueous coating composition of Comparative Example 1-3 was obtained in the same manner as in Example 1-1, except that the amine compound (B) in Example 1-1 was changed to N-methylmorpholine. The aqueous coating composition had a solids concentration of 15.0%, a pH of 9.0, and an average particle size of 112.0 nm. Next, the aqueous coating composition was treated in the same manner as in Example 1-1 to obtain a substrate with an adhesive layer and a hard coat laminate of Comparative Example 1-3. Table 3 shows the results of various evaluations performed on the aqueous coating compositions of Comparative Examples 1-3, the substrates with adhesive layers, and the hard coat laminates. Some drip marks and uneven film thickness were observed on the lower part of the adhesive layer surface, and the entire adhesive layer surface had a ground glass appearance. A large amount of precipitate was also observed after one month in the aqueous coating composition stored at 25°C.

[0129] Tables 1 to 3 show the various evaluation results for Examples 1-1 to 11 and Comparative Examples 1-1 to 1-3.

[0130] [Table 1]

[0131] [Table 2]

[0132] [Table 3]

[0133] [Evaluation of physical properties and characteristics of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-3] (Transparency Assessment) The transparency of the substrate with adhesive layer and the laminate was evaluated by measuring the haze value according to the method specified in JIS K7136 using a turbidity meter (product number: NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd., and evaluating it according to the following criteria: A:<1.0% B: 1.0-2.0% C:>2.0%

[0134] (Evaluation of Adhesion) Using the cross-cut method specified in JIS K5600-5-6, 25 squares were cut at 1 mm intervals using a cutter blade on the hard coat layer side of the laminate, and tape (Nichiban's tape conforming to cross-cut and cross-cut tests) was applied to the squares. When the tape was peeled off, the initial adhesion of the laminate was evaluated based on the number of squares that still had the coating film remaining, according to the following criteria. Category 0: No peeling at all Category 1: Only small peeling of the paint film at the intersection of the cuts. Category 2: Peeling along the cut lines at the intersections. Peeling area is 5% to less than 15%. Category 3: Partial or complete peeling along the cut line. Peeling area is 15% or more but less than 35%. Category 4: Peeling occurs along the entire cut line. Peeling area is 35% or more but less than 65%. Category 5: Peeling is greater than Category 4.

[0135] (Evaluation of peelability) Deionized water and a test piece of the laminate were placed in a separable flask equipped with a thermometer and heated. After holding at 98°C for 1 hour, the test piece was taken out, cooled to room temperature, and subjected to the above-mentioned adhesion test, which was evaluated according to the following criteria. Class 3 or higher was considered to be good releasability. A: Classification 5 B: Classification 4 C: Classification 3 D: Classification 2 or below

[0136] (Durability evaluation) Deionized water and a laminate test piece were placed in a separable flask equipped with a thermometer, heated, and maintained at 80°C for 8 hours, after which the test piece was removed. Deionized water and the removed test piece were placed in another separable flask, heated, and maintained at 98°C for 1 hour, after which the test piece was removed and cooled to room temperature. The above adhesion test was conducted and evaluated according to the following criteria. Class 2 or below was considered to have good durability. A: Classification 0 B: Classification 1 C: Classification 2 D: Classification 3 or higher

[0137] [Preparation of materials for Examples 2-1 to 2-6 and Comparative Examples 1-1 to 1-3, and preparation of materials for evaluation] Example 2-1 2.15 g of ion-exchanged water, 15.31 g of the aqueous dispersion of emulsion particles (A-1) prepared in the above (Preparation of aqueous dispersion of emulsion particles (A-1)), 35.42 g of water-dispersed colloidal silica "Snowtex PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass) as metal oxide fine particles, 3.75 g of WM44-L70G (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) as a crosslinking agent, and 1-methylpiperazine as a neutralizing agent were added. A water dispersion of emulsion particles obtained by mixing 2.50 g of lysine with 1.25 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.25 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 39.34 g of tetrahydrofuran as an aprotic organic solvent was mixed at room temperature for 1 hour to obtain an aqueous coating composition precursor. Distillation was then carried out until the ratio of the aprotic organic solvent in the coating was less than 1.0 mass%, and ion-exchanged water was added to adjust the solids concentration to 20%, yielding the aqueous coating composition of Example 2-1. The pH of the aqueous coating composition was 10.4. Next, the aqueous coating composition of Example 2-1 was applied to a 10 cm square polycarbonate substrate using a bar coater, and the substrate was left to stand for 30 minutes at a temperature of 25°C and a humidity of 35% RH, and then dried for 1 hour at a temperature of 130°C to form an adhesive layer on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 2-1 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 2-1 in the same manner, and then dried at 130° C. for 1.5 hours to obtain a laminate having a hard coat layer. Table 4 shows the results of various evaluations performed on the laminate of Example 2-1.

[0138] (Example 2-2) An aqueous coating composition of Example 2-2 was obtained in the same manner as in Example 2-1, except that the amine compound (B) in Example 2-1 was changed to 2-amino-2-methyl-1-propanol. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Example 2-2. The aqueous coating composition and laminate of Example 2-2 were subjected to various evaluations, and the results are shown in Table 4.

[0139] (Example 2-3) An aqueous coating composition of Example 2-3 was obtained in the same manner as in Example 2-1, except that the amine compound (B) in Example 2-1 was changed to 2-aminoethanol. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Example 2-3. Table 4 shows the results of various evaluations of the aqueous coating composition and laminate of Example 2-3.

[0140] (Examples 2-4) An aqueous coating composition of Example 2-4 was obtained in the same manner as in Example 2-1, except that the amine compound (B) in Example 2-1 was changed to ethylamine. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Example 2-4. The aqueous coating compositions and laminates of Examples 2-4 were subjected to various evaluations, and the results are shown in Table 4.

[0141] (Examples 2-5) An aqueous coating composition of Example 2-5 was obtained in the same manner as in Example 2-1, except that the amine compound (B) in Example 2-1 was changed to methylamine. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Example 2-5. The aqueous coating compositions and laminates of Examples 2-5 were subjected to various evaluations, and the results are shown in Table 4.

[0142] (Examples 2-6) An aqueous coating composition of Example 2-6 was obtained in the same manner as in Example 2-1, except that the metal oxide (C) in Example 1 was changed to Snowtex OUP. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Example 2-6. The aqueous coating compositions and laminates of Examples 2-6 were subjected to various evaluations, and the results are shown in Table 4.

[0143] (Comparative Example 2-1) An aqueous coating composition of Comparative Example 2-1 was obtained in the same manner as in Example 2-1, except that the amine compound (B) of Example 2-1 was omitted. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Comparative Example 2-1. Table 5 shows the results of various evaluations carried out on the aqueous coating composition and laminate of Comparative Example 2-1.

[0144] (Comparative Example 2-2) An aqueous coating composition of Comparative Example 2-1 was obtained in the same manner as in Example 2-1, except that the amine compound (B) in Example 2-1 was changed to ammonia. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Comparative Example 2-2. The aqueous coating composition and laminate of Comparative Example 2-2 were subjected to various evaluations, and the results are shown in Table 2.

[0145] (Comparative Example 2-3) An aqueous coating composition of Comparative Example 2-3 was obtained in the same manner as in Example 2-1, except that the amine compound (B) in Example 2-1 was changed to benzylamine. Next, the aqueous coating composition was treated in the same manner as in Example 2-1 to obtain a laminate of Comparative Example 2-3.

[0146] Tables 4 and 5 show the various evaluation results for Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-3.

[0147] [Table 4]

[0148] [Table 5]

[0149] [Evaluation results] From Tables 1 to 5, it can be seen that the aqueous coating compositions of the examples have excellent coatability without unevenness or dripping marks even when applied to large-area substrates, and can form coating films with excellent surface smoothness and weather resistance. Furthermore, the hard coat laminates of the examples exhibit high levels of transparency and weather resistance, and are therefore evaluated as being suitable for use as window materials for automobiles. [Industrial Applicability]

[0150] The aqueous coating composition, substrate with adhesive layer, and hard coat laminate provided by the present invention have industrial applicability as building materials, automobile parts, electronic devices, electrical products, and the like.

Claims

1. Emulsion particles (A) having units (a) derived from a vinyl monomer (a); an amine compound (B); inorganic particles (C), and water, the boiling point of the amine compound (B) is 170°C or less under an external pressure of 1 atmosphere, The vapor pressure ratio P of the amine compound (B) to water at 20°C (B) / P water is 7.0 or less, pH is 9.5 or higher; Aqueous coating compositions.

2. The glass transition temperature of the emulsion particles (A) is −30° C. or higher and 50° C. or lower. The aqueous coating composition of claim 1.

3. The acid dissociation constant of the amine compound (B) is 7.5 or more. The aqueous coating composition of claim 1.

4. the amine compound (B) has an octanol / water partition coefficient of −1.0 or more and 2.5 or less; The aqueous coating composition of claim 1.

5. Further comprising a crosslinking agent (D), The aqueous coating composition of claim 1.

6. Further containing a biphenyltriazine skeleton ultraviolet absorber (E), The aqueous coating composition of claim 1.

7. A substrate; an adhesive layer disposed on the substrate; A substrate with an adhesive layer, The adhesive layer comprises the aqueous coating composition of any one of claims 1 to 6. Substrate with adhesive layer.

8. A substrate with an adhesive layer according to claim 7; a hard coat layer disposed on the substrate with the adhesive layer; A hard coat laminate having

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