Aqueous coating composition, method for producing aqueous coating composition, substrate with adhesive layer, and hard coat laminate

Abstract

To provide an aqueous coating composition capable of forming a coating film with superior transparency, adhesion, and weather resistance while exhibiting superior coating stability.SOLUTION: An aqueous coating composition comprising emulsion particles (A), an ultraviolet absorber (B) having a biphenyl triazine skeleton, and a non-protonic organic solvent (C) having a boiling point of less than 100°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aqueous coating composition, a method for producing 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. Aqueous dispersions obtained by polymerizing specific components tend to exhibit barrier properties, contamination resistance, chemical resistance, flame retardancy, heat resistance, weather resistance, abrasion resistance, and abrasion resistance when dried at room temperature or under heat to form coating films. However, when such water-based paints are used in applications requiring transparency, problems such as loss of transparency and optical properties such as cloudiness, discoloration, whitening, and crazes can arise due to long-term exposure outdoors or to ultraviolet light. To prevent UV-induced deterioration of water-based paints, it is desirable to include an ultraviolet absorber in the water-based paint. However, many ultraviolet absorbers are insoluble in water, making their application to water-based paints problematic.

[0003] As a technique for improving the optical properties of water-based paints, for example, Patent Document 1 describes a method of incorporating an ultraviolet absorber into a polymer for the purpose of imparting weather resistance. Furthermore, for example, Patent Document 2 describes a method in which an ultraviolet absorber is dissolved in a film-forming auxiliary component and the resulting solution is contained in a curable resin composition. Furthermore, for example, Patent Document 3 describes a method for incorporating ultraviolet absorbing groups into an acrylic copolymer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-12505 [Patent Document 2] Japanese Patent Application Publication No. 7-173404 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-97631 Summary of the Invention [Problem to be solved by the invention]

[0005] The methods described in Patent Documents 1 and 2 are common methods for imparting weather resistance to water-based paints, but have the problem that the content of UV absorber in the paint film is low, making it difficult to impart high weather resistance. Also, it is difficult to apply UV absorbers with extremely hydrophobic skeletons to water-based paints, which limits the types of UV absorbers that can be used. Furthermore, the method described in Patent Document 3 also has the problem that there is still room for improvement in terms of weather resistance.

[0006] In view of the above-mentioned problems of the prior art, the present invention aims to provide an aqueous coating composition that has excellent coating stability and is capable of forming a coating film that is excellent in transparency, adhesion, and weather resistance. [Means for solving the problem]

[0007] As a result of extensive research into solving the problems of the prior art, the present inventors have discovered that the problems can be solved by an aqueous coating composition containing emulsion particles (A), a specified ultraviolet absorber (B), and a specified organic solvent (C), thereby completing the present invention. That is, the present invention is as follows.

[0008] [1] Emulsion particles (A); an ultraviolet absorber (B) having a biphenyltriazine skeleton; an aprotic organic solvent (C) having a boiling point of less than 100°C; An aqueous coating composition comprising: [2] The aqueous coating composition according to [1] above, wherein the solubility parameter (HSP value) of the organic solvent (C) is within the following range: △D:10.0~20.0 △P:1.0~10.0 △H:1.0~10.0 [3] The aqueous coating composition according to [1] or [2] above, wherein the ultraviolet transmittance at a wavelength of 315 nm when the aqueous coating composition is diluted 1000 times with ion-exchanged water is 20% or less. [4] The aqueous coating composition according to any one of [1] to [3], wherein the average particle size calculated by dynamic light scattering when the aqueous coating composition is diluted 50 times with ion-exchanged water is 150 nm or less. [5] The aqueous coating composition according to any one of [1] to [4] above, wherein the pH of the aqueous coating composition is 9.0 or higher. [6] The aqueous coating composition according to any one of [1] to [5] above, having a solid content concentration of 12.5% ​​by mass or more and 25% by mass or less. [7] The aqueous coating composition according to any one of [1] to [6] above, further comprising a light stabilizer (D). [8] The aqueous coating composition according to any one of [1] to [7] above, further comprising a crosslinking agent (E). [9] The aqueous coating composition according to any one of [1] to [8] above, further comprising metal oxide fine particles (F).

[10] A method for producing the aqueous coating composition according to any one of [1] to [9], The method comprises the steps of stirring an aqueous solution containing emulsion particles (A) and adding dropwise an ultraviolet absorber (B) dissolved in an organic solvent (C) to the stirred aqueous solution, A method for producing an aqueous coating composition.

[11] A substrate; an adhesive layer disposed on the substrate; A substrate with an adhesive layer, The adhesive layer contains the aqueous coating composition according to any one of [1] to [9]. Substrate with adhesive layer.

[12] A substrate with an adhesive layer according to

[11] above, a hard coat layer disposed on the substrate with the adhesive layer; A hard coat laminate having [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an aqueous coating composition that has excellent coating stability and is capable of forming a coating film that is excellent in transparency, adhesion and weather resistance. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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.

[0011] [Water-based paint composition] The aqueous coating composition of this embodiment contains emulsion particles (A), an ultraviolet absorber having a biphenyltriazine skeleton (B), and an aprotic organic solvent (C) having a boiling point of less than 100°C. The aqueous coating composition of this embodiment has the above-mentioned constitution, and therefore has excellent coating stability, and when a coating film is formed, it has excellent transparency, adhesion, and weather resistance.

[0012] The reason for this effect is thought to be as follows. That is, the aprotic organic solvent (C) promotes the diffusion of the ultraviolet absorber (B) into the emulsion particles (A), and the ultraviolet absorber (B) is incorporated and stabilized inside the emulsion particles (A), thereby improving the paint stability (storage stability). Furthermore, since the boiling point of the aprotic organic solvent (C) is less than 100°C, when a coating film is formed using the aqueous coating composition of this embodiment, the aprotic organic solvent (C) does not remain in the coating film, and therefore a coating film with excellent transparency, adhesion, and weather resistance can be formed. It is not intended that the mechanism of action of this embodiment be limited to the above.

[0013] (Emulsion particles (A)) The aqueous coating composition of this embodiment contains emulsion particles (A). The emulsion particles (A) mainly serve to improve adhesion to the substrate and preferably contain a vinyl monomer (a) as a constituent unit, i.e., the emulsion particles (A) preferably have units (a) derived from the vinyl monomer (a).

[0014] The unit (a) preferably has a unit (a-1) derived from an ultraviolet-absorbing vinyl monomer (a-1). The inclusion of the unit (a-1) improves the affinity between the emulsion particle (A) and the ultraviolet absorber (B), making it easier to incorporate the ultraviolet absorber (B) into the emulsion particle (A). This improves the paint stability of the aqueous coating composition of this embodiment, and tends to prevent a decrease in transparency when forming a substrate with an adhesive layer or a hard coat laminate, as described below.

[0015] 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 (meth)acrylic monomers having an ultraviolet-absorbing group in the molecule, and specific examples thereof include benzophenone compounds 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; Examples of benzotriazole compounds include 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 Ciba-Geigy Japan Ltd.).

[0016] The content of the unit (a-1) is preferably 1 to 20 mass %, more preferably 1 to 10 mass %, based on the total mass of the unit (a) constituting the emulsion particle (A), from the viewpoints of the adhesive layer constituting the adhesive-layer-attached substrate of the present embodiment described later and the weather resistance and adhesion of the hard coat laminate of the present embodiment described later.

[0017] In the emulsion particles (A), the units (a) preferably have units (a-2) derived from a hydroxyl group-containing vinyl monomer (a-2) that is a monomer other than the units (a-1) and has a hydroxyl group. 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.

[0018] 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.

[0019] The content of the unit (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 vinyl monomer (a) constituting the emulsion particle (A). By having the content of the unit (a-2) in this range, the reaction between the hydroxyl group-containing vinyl monomer (a-2) and other vinyl monomers tends to proceed favorably, and since the hydrophilicity of the emulsion particle (A) is ensured, when a substrate with an adhesive layer or a hard coat laminate, which will be described later, is formed using the aqueous coating composition of this embodiment, a decrease in transparency and adhesion tends to be prevented.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] The aromatic vinyl compound is not limited to the following, but examples thereof include styrene and 4-vinyltoluene.

[0025] The vinyl cyanide compound is not limited to the following, but examples thereof include acrylonitrile and methacrylonitrile.

[0026] 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.

[0027] 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.

[0028] The carbonyl-containing vinyl monomer is not limited to the following, but examples thereof include diacetone acrylamide.

[0029] 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-isopropylacrylamide, Examples of the copolymer include N-vinyl 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.

[0030] Furthermore, examples of vinyl monomers other than the above-mentioned vinyl monomers 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; and ethyl vinyl Examples of the vinyl monomer include vinyl ethers such as ether, 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, 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.

[0031] 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.

[0032] 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.

[0033] The emulsion particles (A) preferably contain a chain transfer agent, that is, the aqueous coating composition of this 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.

[0034] The method for preparing the emulsion particles (A) used in the aqueous coating composition of this embodiment is not particularly limited, but examples include a method in which a vinyl monomer is polymerized in the presence of water, an emulsifier, and a polymerization initiator.

[0035] Examples of the polymerization initiator include, but are not limited to, hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide; peroxides such as benzoyl peroxide and lauroyl peroxide; and organic polymerization initiators such as 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 that are used in combination with reducing agents such as sodium bisulfite, ascorbic acid and salts thereof.

[0036] <Weight average molecular weight of unit (a) derived from vinyl monomer> In the emulsion particles (A) used in the aqueous coating composition of this embodiment, the weight-average molecular weight of the vinyl monomer-derived unit (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) can be controlled within the above range by, for example, adjusting the amount of vinyl monomer added in the polymerization step, the polymerization time, or by using the chain transfer agent described above.

[0037] <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 the 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 coating 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 range by adjusting the amount of the emulsifier, polymerization conditions, and the like.

[0038] <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 50°C or lower. 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 that has excellent transparency and adhesion to the substrate. Furthermore, from the viewpoint of the transparency of the substrate with an adhesive layer of this embodiment, which will be described later, the glass transition temperature of the emulsion particles (A) is more preferably 25°C or lower. 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.

[0039] <Content of emulsion particles (A)> The content of emulsion particles (A) relative to the total solid content in the aqueous coating composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 22.5% by mass or more, from the viewpoint of the transparency and adhesion of the substrate with an adhesive layer of this embodiment described below. Here, the total solid content in the aqueous coating composition refers to the total mass of components other than volatile components contained in the aqueous coating composition. The volatile components in the aqueous coating composition mainly include the solvent and neutralizer described below.

[0040] (UV absorber (B) having a biphenyltriazine skeleton) The aqueous coating composition of this embodiment contains an ultraviolet absorber (B) having a biphenyltriazine skeleton from the viewpoint of improving the weather resistance of a coating film using the aqueous coating composition of this embodiment, a substrate with an adhesive layer of this embodiment described below, and a hard coat laminate. Examples of the ultraviolet absorber (B) 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, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, Examples of such azine include TINUVIN 479 (trade name, manufactured by BASF), TINUVIN 1600 (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, and 2-[3'-bromo[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine.

[0041] (UV absorbers other than those with biphenyltriazine skeleton) The aqueous coating composition of this embodiment may contain an ultraviolet absorber other than the ultraviolet absorber (B) having a biphenyltriazine skeleton, from the viewpoint of improving the weather resistance of the coating film using the aqueous coating composition of this embodiment, the substrate with the adhesive layer of this embodiment described later, and the hard coat laminate. 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 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.

[0042] <Content of ultraviolet absorber (B) having a biphenyltriazine skeleton> In the aqueous coating composition of this embodiment, from the viewpoint of the weather resistance of the coating film using the aqueous coating composition of this embodiment, the substrate with an adhesive layer of this embodiment, and the hard coat laminate described below, the content of the ultraviolet absorber (B) having a biphenyltriazine skeleton in the aqueous coating composition is preferably 0.3 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more. On the other hand, from the viewpoint of paint stability of the aqueous paint composition of this embodiment, it is preferably 3.0 mass % or less, more preferably 2.5 mass % or less, and even more preferably 2.0 mass % or less.

[0043] <UV absorber content> In the aqueous coating composition of this embodiment, from the viewpoint of the weather resistance of the coating film using the aqueous coating composition of this embodiment, the substrate with an adhesive layer of this embodiment, and the hard coat laminate described below, the total content of the ultraviolet absorber in the aqueous coating composition is preferably 0.3 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more. On the other hand, from the viewpoint of the storage stability of the aqueous coating composition of this embodiment, it is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, and even more preferably 2.0% by mass or less.

[0044] (solvent) The aqueous coating composition of this embodiment contains 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.

[0045] <Aprotic organic solvent (C) with a boiling point of less than 100°C> The aqueous coating composition of this embodiment contains an aprotic organic solvent (C) having a boiling point of less than 100° C. (hereinafter sometimes referred to as organic solvent (C)) in the solvent. The compatibility of the emulsion particles (A) and the ultraviolet absorber (B) via the aprotic organic solvent (C) allows the ultraviolet absorber (B) to be stably dispersed in the aqueous coating composition, which tends to result in excellent coating stability. Furthermore, since the boiling point of the aprotic organic solvent (C) contained in the aqueous coating composition of this embodiment is less than 100°C, deterioration of the substrate due to organic solvents can be suppressed when forming a substrate with an adhesive layer of this embodiment, as described below, and as a result, the hard coat laminate of this embodiment, as described below, tends to have excellent transparency when formed. Examples of the aprotic organic solvent (C) having a boiling point of less than 100°C 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.

[0046] [Solubility parameter of organic solvent (C)] From the viewpoint of improving the paint stability of the aqueous paint composition of this embodiment, the Hansen solubility parameter (HSP value) of the organic solvent (C) is preferably in the following range. △D:10.0~20.0 △P:1.0~10.0 △H:1.0~10.0 Furthermore, from the viewpoint of further improving the paint stability, the range below is more preferable. △D:15.0~18.0 △P:3.0~8.0 △H:3.0~8.0 Furthermore, from the viewpoint of further improving the paint stability, the following range is more preferable. △D:15.0~17.5 △P:3.0~7.0 △H:3.0~7.0 Organic solvents (C) having an HSP value within the above range tend to have a high affinity for the ultraviolet absorber (B) and to be able to swell the emulsion particles (A) to a moderate degree without completely dissolving them, which promotes the diffusion of the ultraviolet absorber (B) into the emulsion particles (A), resulting in the stabilization of the ultraviolet absorber (B) inside the emulsion particles (A), and thus tends to improve the paint stability of the aqueous coating composition of this embodiment. The HSP value can be obtained, for example, by using calculation software for a personal computer such as "HSPiP: Hansen Solubility Parameters in Practice." The HSP value of the organic solvent (C) is a value inherent to the material, and can be adjusted to fall within the above-mentioned range by selecting the material.

[0047] [Content of aprotic organic solvent (C) with a boiling point of less than 100°C] The content of the organic solvent (C) in the aqueous coating composition of this embodiment is preferably 30 mass % or less. By ensuring that the content of the aprotic organic solvent (C) 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 preparation of the substrate with an adhesive layer of this embodiment described below, the surface of the substrate can be prevented from being dissolved by the aprotic organic solvent, and this tends to result in excellent transparency of the substrate with an adhesive layer and the hard coat laminate described below. Furthermore, the content of the organic solvent (C) in the aqueous coating composition of this embodiment is preferably 0.1% by mass or more from the viewpoint of improving the adhesion of the substrate with the adhesive layer of this embodiment, which will be described later. By having the content of the organic solvent (C) in the aqueous coating composition of this embodiment be 0.1% by mass or more, an effect of improving adhesion tends to be obtained. From the above-mentioned viewpoints, the content of the organic solvent (C) in the aqueous coating composition of this embodiment is more preferably 0.1 to 30 mass %, and even more preferably 0.2 to 25 mass %.

[0048] (Light stabilizer (D)) From the viewpoint of improving weather resistance, the aqueous coating composition of this embodiment preferably contains a light stabilizer. Examples of the light stabilizer (D) 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, hindered amine light stabilizers such as TINUVIN 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 radical polymerizable hindered amine light stabilizers such as 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 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.).

[0049] <Light stabilizer (D) content> From the viewpoint of improving weather resistance, the light stabilizer (D) is preferably contained in an amount of 1 part by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the total amount of all ultraviolet absorbers contained in the aqueous coating composition of this embodiment.

[0050] (Crosslinking agent (E)) The aqueous coating composition of this embodiment preferably contains a crosslinking agent (E) from the viewpoint of improving the adhesion of the substrate with the adhesive layer of this embodiment, which will be described later.

[0051] The crosslinking agent (E) preferably contains an isocyanate compound from the viewpoint of reactivity with the emulsion particles (A). 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.

[0052] The isocyanate compound as the crosslinking agent (E) 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, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate; Aliphatic triisocyanates such as 4-isocyanatomethyloctane, 2-isocyanatoethyl (2,6-diisocyanato) hexanoate; 1,3- or 1,4-bis(isocyanatomethylcyclohexane), 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 methyl diisocyanate norbornane; alicyclic triisocyanates such as 2,5- or 2,6-diisocyanatomethyl-2-isocyanatopropylnorbornane; aralkylene diisocyanates such as m-xylylene diisocyanate and α,α,α'α'-tetramethyl-m-xylylene diisocyanate; m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate Examples of the aromatic diisocyanates include isocyanates, 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.

[0053] Further examples of the isocyanate compound include diisocyanates or polyisocyanates having a uretdione structure obtained by cyclodimerization of the isocyanate groups of the diisocyanates or triisocyanates; polyisocyanates having an isocyanurate structure obtained by cyclotrimerization of the isocyanate groups of the diisocyanates or triisocyanates; polyisocyanates having a biuret structure obtained by reacting the diisocyanates or triisocyanates with water; polyisocyanates having an oxadiazinetrione structure obtained by reacting the diisocyanates or triisocyanates with carbon dioxide; polyisocyanates having an allophanate structure obtained by reacting the diisocyanates or triisocyanates with various alcohols; and polyisocyanates obtained by reacting the 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.

[0054] From the viewpoint of paint stability of the aqueous paint composition of this embodiment, the isocyanate compound is more preferably a blocked polyisocyanate compound in which an isocyanate group has been 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.

[0055] As the blocked polyisocyanate compound, from the viewpoint of water dispersibility, a water-dispersible isocyanate compound obtained by reacting a polyisocyanate compound having two or more isocyanate groups in one molecule with a hydroxyl group-containing hydrophilic compound having a nonionic and / or ionic hydrophilic group at an equivalent ratio of isocyanate group / hydroxyl group in the range of 1.05 to 1000 is preferably reacted with the blocking agent. Such a water-dispersible blocked polyisocyanate compound is not particularly limited, and commercially available products can also be adopted. For example, WT30-100 manufactured by Asahi Kasei Corporation and WM44-L70G manufactured by Asahi Kasei Corporation are preferably used as those having the above-described characteristics.

[0056] <NCO / OH ratio> In the aqueous coating composition of the present embodiment, the content of the isocyanate compound as the crosslinking agent (E) with respect to the emulsion particles (A) polymerized from the monomers including the hydroxyl group-containing vinyl monomer (a-2) is preferably such that the ratio (NCO / OH ratio) of the number of moles of hydroxyl groups contained in the emulsion particles (A) to the number of moles of isocyanate groups contained in the isocyanate compound is 0.1 to 1.0, and more preferably 0.4 to 0.8. When the NCO / OH ratio is within the above range, when forming the substrate with an adhesive layer of the present embodiment described later, excellent adhesion can tend to be exhibited without impairing transparency.

[0057] (Metal oxide fine particles (F)) The aqueous coating composition of the present embodiment preferably contains metal oxide fine particles (F). Since the aqueous coating composition of the present embodiment contains metal oxide fine particles (F), when forming the hard coat laminate of the present embodiment by the interaction between the adhesive layer and the hard coat layer including the aqueous coating composition of the present embodiment described later, it tends to be excellent in transparency and adhesion.

[0058] Examples of the metal oxide fine particles (F) 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, and the like. These may be used alone or in combination of two or more.

[0059] The metal oxide fine particles (F) 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.

[0060] <Shape of metal oxide particles (F)> The shape of the metal oxide fine particles (F) 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 metal oxide fine particles (F) preferably have a spherical and / or 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 metal oxide fine particles (F) more preferably have a 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 metal oxide fine particles (F) are silica having a spherical and / or connected structure, and even more preferable that they are silica having a connected structure.

[0061] The primary particle diameter of the metal oxide microparticles (F) is preferably 2 nm or more from the viewpoint of improving the coating stability of a substrate having an adhesive layer containing the aqueous coating composition of this embodiment and of the raw material composition of the adhesive layer that constitutes 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 metal oxide microparticles (F) include, but are not limited to, the BET method, in which molecules or ions with a known area of ​​surface area are adsorbed onto the surface of metal oxide microparticles and the specific surface area is determined from the amount of adsorption.

[0062] <Colloidal silica suitable for use as metal oxide fine particles (F)> The metal oxide fine particles (F) 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.

[0063] 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).

[0064] 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.

[0065] Examples of dry silica particles include, but are not limited to, AEROSIL manufactured by Nippon Aerosil Co., Ltd. and Reolosil manufactured by Tokuyama Corporation.

[0066] 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.

[0067] <Mass ratio of metal oxide fine particles (F) to the total solid content of the 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 mass ratio of the metal oxide microparticles (F) to the total solid content of the aqueous coating composition of this embodiment is preferably 30 mass% to 60 mass%, more preferably 37.5 mass% to 47.5 mass%.

[0068] (Components that may be contained in the aqueous coating composition) The aqueous coating composition of the present embodiment may contain, depending on the application, an emulsifier, a plasticizer, a pigment, a dye, a filler, an antioxidant, a conductive material, a light stabilizer, a release adjuster, a softener, a surfactant, a flame retardant, an antioxidant, a catalyst, or a neutralizer. In particular, from the viewpoint of paint stability of the aqueous paint composition of this embodiment, it is preferable to contain a neutralizing agent. Examples of neutralizing agents include, but are not limited to, ammonia, amines such as triethylamine, dimethylethanolamine, and 1-methylpiperidine, and bases such as NaOH and KOH.

[0069] The boiling point of the neutralizer is preferably 50°C or higher. When the boiling point of the neutralizer is within the above range, deterioration in stability due to evaporation of the neutralizer during storage is suppressed, and coating stability (storage stability) tends to be improved. Furthermore, from the viewpoint of the transparency of the substrate with an adhesive layer, which will be described later, it is more preferable that the boiling point of the neutralizer is 100°C or higher.

[0070] [Method for producing aqueous coating composition] The aqueous coating composition of this embodiment can be produced by mixing the emulsion particles (A), an ultraviolet absorber (B) having a biphenyltriazine skeleton, and an aprotic organic solvent (C) having a boiling point of less than 100°C using a solvent containing water. Specifically, the method preferably includes a "diffusion step of the ultraviolet absorber into the emulsion" in which the ultraviolet absorber (B) dissolved in the aprotic organic solvent (C) is added dropwise to an aqueous solution containing the emulsion particles (A) in a stirred state. This step allows the ultraviolet absorber (B) to be diffused into the emulsion particles (A), resulting in the preparation of an aqueous coating composition with excellent coating stability.

[0071] In the method for producing an aqueous coating composition of this embodiment, it is also possible to reduce the content of the aprotic organic solvent (C) in the aqueous coating composition after the "step of diffusing an ultraviolet absorber into the emulsion." Methods for reducing the content of the aprotic organic solvent (C) include, but are not limited to, removal by distillation. When the step of reducing the content of the aprotic organic solvent (C) is carried out, it is preferable to reduce the content of the aprotic organic solvent (C) in the aqueous coating composition to 0.1% by mass or more but less than 1.0% by mass, from the viewpoint of reducing the environmental load and health hazards during application of the aqueous coating composition of this embodiment.

[0072] [Physical properties of aqueous coating composition] (UV transmittance of aqueous coating composition) The aqueous coating composition of this embodiment preferably has an ultraviolet transmittance at a wavelength of 315 nm when the aqueous coating composition is diluted 1000 times with ion-exchanged water of 20% or less, more preferably 10% or less, and even more preferably 5.0% or less. When the ultraviolet transmittance is within the above range, sufficient weather resistance tends to be imparted when forming the hard coat laminate of the present embodiment described later. The ultraviolet transmittance can be measured by the method described in the examples described later. The ultraviolet transmittance of the aqueous coating composition of this embodiment can be controlled within the above-mentioned range by adjusting the content of the ultraviolet absorber (B) having a biphenyltriazine skeleton and other ultraviolet absorbers.

[0073] (Average particle size of aqueous coating composition) The aqueous coating composition of this embodiment preferably has an average particle size of 150 nm or less, as calculated by dynamic light scattering when diluted 50 times with ion-exchanged water. Having an average particle size within this range makes it difficult for the components in the aqueous coating composition of this embodiment to spontaneously settle, and the coating tends to have excellent stability. Furthermore, from the viewpoint of further improving the coating stability and the transparency of the substrate with an adhesive layer of this embodiment, which will be described later, the aqueous coating composition of this embodiment preferably has an average particle size of 150 nm or less, and more preferably 100 nm or less. The average particle size by dynamic light scattering can be measured by the method described in the examples below. The average particle size of the aqueous coating composition of this embodiment can be controlled within the above numerical range by adjusting the average particle size of the emulsion particles (A) and the average particle size of the metal oxide fine particles (F) added as needed.

[0074] (pH of aqueous coating composition) The aqueous coating composition of this embodiment preferably has a pH of 9 or higher. A pH within the above range improves the dispersibility of the emulsion particles (A), and as a result, the paint stability of the aqueous paint composition of this embodiment tends to be improved. Furthermore, from the viewpoint of the transparency of the substrate with an adhesive layer of this embodiment, which will be described later, the pH of the aqueous paint composition of this embodiment is more preferably 9 to 11, and even more preferably 10 to 11. The pH of the aqueous coating composition is not limited to the following, but can be controlled within the above numerical range, for example, by adjusting the amount of the neutralizing agent added.

[0075] (Solid content concentration of aqueous coating composition) From the viewpoint of coatability, the solids concentration of the aqueous coating composition of this embodiment is preferably 12.5 to 25.0 mass %, and from the viewpoint of coating stability of the aqueous coating composition of this embodiment, the solids concentration is more preferably 15.0 to 23.0 mass %, and even more preferably 15.0 to 21.0 mass %.

[0076] [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 contains the aqueous coating composition of this embodiment. 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 this 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 can be applied not only to already formed substrates, but also to flat plates before forming, such as pre-coated metals including rust-resistant steel plates.

[0077] 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.

[0078] The substrate constituting the substrate with an adhesive layer of this embodiment is not limited to the following, but examples thereof include resin, metal, and glass. 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.

[0079] (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 of this embodiment, which will be described later, tends to be excellent. The haze value of the adhesive-attached substrate can be measured using a haze meter, which will be described later, and can be controlled to 20% or less by adjusting the ratio of each component in the aqueous coating composition.

[0080] (Surface roughness Ra of substrate with adhesive layer) In the present embodiment, the substrate with an adhesive layer has a surface roughness Ra 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 Ra of preferably 10 nm or more, more preferably 20 nm or more, from the viewpoint of adhesion. The surface roughness of the adhesive-attached substrate can be measured using a laser microscope or the like, and can be controlled to 200 nm or less by adjusting the particle diameter of the emulsion particles (A) and metal oxide fine particles (F) described above.

[0081] [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 is obtained by overcoating the substrate with the adhesive layer with the hard coat paint. A 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.

[0082] 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.

[0083] 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.

[0084] 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");

[0085] The method for overcoating the substrate with an adhesive layer with the hard coat paint 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.

[0086] (Surface treatment of hard coat laminate) From the viewpoint of weather resistance, the hard coat laminate of this embodiment may have its surface 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.

[0087] The hard coat laminate of this embodiment may further have a functional layer on at least one surface in addition to the silica layer described above. Note that the "at least one surface" may include a side surface of the hard coat laminate, or may be between the layers constituting the hard coat laminate. Examples of the functional layer include, but are not limited to, an anti-reflection layer, an anti-fouling layer, a polarizing layer, and an impact absorbing layer.

[0088] (Applications of hard coat laminates) The hard coat laminate of this embodiment has 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, and the like. 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, 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. In addition to the above, the hard coat laminate of this embodiment can be applied to various fields such as machine parts, agricultural materials, fishing materials, transport containers, packaging containers, play equipment, and miscellaneous goods. [Example]

[0089] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.

[0090] In the examples and comparative examples described below, various physical properties and characteristics were measured and evaluated by the following methods.

[0091] ((1) Weight-average molecular weight of unit (a) contained in emulsion particles (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.

[0092] ((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 diameter 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 diameter of the emulsion particles (A) and the aqueous coating composition.

[0093] ((3) pH of 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.

[0094] ((4) Ultraviolet transmittance of aqueous coating composition) The aqueous coating composition obtained by the method described below was diluted 1000 times with ion-exchanged water, and then the absorbance at a wavelength of 315 nm was measured using a UV-vis (product number: Lambda950) manufactured by PerkinElmer. The ultraviolet transmittance was calculated from the obtained absorbance using the following formula. UV transmittance=10 -(吸光度)

[0095] ((5) Evaluation of storage stability of aqueous coating composition The state of the aqueous coating composition prepared by the method described below was visually observed immediately after preparation and after leaving it to stand for one month in a 25°C environment, and the storage stability of the coating was evaluated according to the following criteria. A: No precipitates after 1 month of storage at 25°C B: A small amount of precipitate appears after 1 month of storage at 25°C C: A large amount of precipitate formed after 1 month of storage at 25°C D: Precipitation occurs immediately after mixing

[0096] (6) 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 haze 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.

[0097] (7) Evaluation of Adhesion of Substrate with Adhesive Layer and Hard Coat Laminate <Grid test> Using the cross-cut method specified in JIS K5600-5-6, 25 squares were cut at 1 mm intervals with a cutter blade on the coating film side of the substrate with adhesive layer and the hard coat laminate, and tape (Nichiban's tape conforming to cross-cut and cross-cut tests) was stuck on the squares. When the tape was peeled off, the number of squares with the coating film remaining was used to evaluate adhesion as follows: A: 25 squares B: 5 to 24 squares C: 5 squares or less

[0098] ((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 2 Δb was measured before and after irradiation and evaluated according to the following criteria. A:Δb<1.0 B: Δb = 1.0 to 2.0 C:Δb>2.0

[0099] ((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. Regarding the mass ratio of each component in the aqueous coating composition that had undergone the aprotic organic solvent (C) reduction step, the mass ratio was calculated based on the assumption that all non-volatile components remained in the coating liquid during the reduction step, taking into account the amount of solvent added for concentration adjustment after the reduction step.

[0100] ((10) NCO / OH molar ratio) The NCO / OH molar ratio was calculated from the amounts of the units (a-2) derived from the hydroxyl group-containing vinyl monomer and the blocked polyisocyanate compound used. Here, the number of moles of NCO was calculated from the charged amount and the available NCO %.

[0101] [Preparation of aqueous dispersion of emulsion particles (A)] The following emulsion particles (A-1) and (A-2) were prepared as used in the examples and comparative examples described below.

[0102] (Preparation of aqueous dispersion of emulsion particles (A-1)) The aqueous dispersion of emulsion particles (A-1) used in the examples and comparative examples 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.

[0103] (Preparation of aqueous dispersion of emulsion particles (A-2)) The aqueous dispersion of emulsion particles (A-2) used in the examples and comparative examples 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%), 150.96 g of butyl acrylate, 38.46 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 39.4 nm and a weight-average molecular weight of unit (a) of 140,000.

[0104] [Preparation of hard coat paint] The hard coat paints used in the examples and comparative examples 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.

[0105] Preparation of Aqueous Coating Composition In the following Examples and Comparative Examples, aqueous coating compositions were prepared.

[0106] Example 1 An aqueous dispersion of emulsion particles was obtained by mixing 11.50 g of ion-exchanged water, 67.50 g of an aqueous dispersion of emulsion particles (A-1), and 2.50 g of 1-methylpiperidine as a neutralizing agent, and a mixture was obtained by mixing 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber and 17.00 g of tetrahydrofuran as an aprotic organic solvent. The mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 1. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.5, an average particle size of 64.0 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.0%. Next, the aqueous coating composition of Example 1 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 µm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 1 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 1 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 1, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0107] Example 2 An aqueous dispersion of emulsion particles obtained by mixing 8.75 g of ion-exchanged water, 65.63 g of an aqueous dispersion of emulsion particles (A-1), and 2.50 g of 1-methylpiperidine as a neutralizer was mixed with a mixture obtained by mixing 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.38 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 21.25 g of tetrahydrofuran as an aprotic organic solvent. The mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 2. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.5, an average particle size of 71.2 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 2.9%. Next, the aqueous coating composition of Example 2 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 µm on the polycarbonate substrate. In this way, a substrate with an adhesive layer of Example 2 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 2 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 2, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0108] Example 3 A water dispersion of emulsion particles was obtained by mixing 32.15 g of ion-exchanged water, 44.63 g of an aqueous dispersion of emulsion particles (A-1), 6.32 g of WM44-L70G (trade name, manufactured by Asahi Kasei Corporation, solids concentration 70% by mass, effective NCO 5.3% by mass) as a crosslinker, and 2.50 g of 1-methylpiperidine as a neutralizer. A mixture was obtained by mixing 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.15 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 12.75 g of tetrahydrofuran as an aprotic organic solvent. The mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 3. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.4, an average particle size of 69.5 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.1%. Next, the aqueous coating composition of Example 3 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 µm on the polycarbonate substrate. In this way, a substrate with an adhesive layer of Example 3 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 3 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 3, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0109] Example 4 9.66 g of ion-exchanged water, 20.63 g of the aqueous dispersion of emulsion particles (A-1), 45.00 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 fine particles, 3.64 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 were added. The aqueous dispersion of emulsion particles obtained by mixing was mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 4. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 82.3 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.3%. Next, the aqueous coating composition of Example 4 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, a substrate with an adhesive layer of Example 4 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 4 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 4, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0110] Example 5 13.85 g of ion-exchanged water, 20.25 g of the aqueous dispersion of emulsion particles (A-1), 40.00 g of water-dispersed colloidal silica "Snowtex OUP" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass, primary particle diameter 12 nm) as metal oxide fine particles, 4.82 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 2.50 g of 1-methylpiperidine as a neutralizing agent were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 5. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.1, an average particle size of 84.0 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.2%. Next, the aqueous coating composition of Example 5 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, a substrate with an adhesive layer of Example 5 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 5 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 5, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0111] Example 6 8.76 g of ion-exchanged water, 19.88 g of the aqueous dispersion of emulsion particles (A-1), 47.50 g of water-dispersed colloidal silica "Snowtex PS-MO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15 mass%, primary particle diameter 25 nm) as metal oxide fine particles, 2.79 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 were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 6. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 99.1 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.2%. Next, the aqueous coating composition of Example 6 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 6 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 6 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 6, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0112] Example 7 16.80 g of ion-exchanged water, 21.68 g of the aqueous dispersion of emulsion particles (A-1), 45.00 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 fine particles, 5.36 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 were added. The aqueous dispersion of emulsion particles obtained by mixing was mixed with 0.15 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.02 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 8.50 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The mixed liquid was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 7. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 71.1 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 24.3%. Next, the aqueous coating composition of Example 7 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 7 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 7 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 7, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0113] Example 8 17.64 g of ion-exchanged water, 20.63 g of the aqueous dispersion of emulsion particles (A-1), 45.00 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 fine particles, 5.36 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 were added. The aqueous dispersion of emulsion particles obtained by mixing was mixed with 0.30 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 8.50 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 8. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 73.6 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 19.9%. Next, the aqueous coating composition of Example 8 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 8 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 8 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 8, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0114] Example 9 2.04 g of ion-exchanged water, 23.40 g of the aqueous dispersion of emulsion particles (A-1), 48.00 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 fine particles, 5.14 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 were added. The aqueous dispersion of emulsion particles obtained by mixing was mixed with 2.34 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.18 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 16.4 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 9. The aqueous coating composition had a solids concentration of 18.0% by mass, a pH of 10.1, an average particle size of 98.9 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 1.7%. Next, the aqueous coating composition of Example 9 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 9 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 9 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 9, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0115] Example 10 0.65 g of ion-exchanged water, 22.05 g of the aqueous dispersion of emulsion particles (A-1), 46.67 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 fine particles, 4.75 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 were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 2.63 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.13 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 20.63 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 10. The aqueous coating composition had a solids concentration of 17.5% by mass, a pH of 10.1, an average particle size of 120.7 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 1.5%. Next, the aqueous coating composition of Example 10 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 10 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 10 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 10, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 1.

[0116] Example 11 A water-based 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 mixture was mixed with 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. The mixture was mixed at room temperature for 1 hour to obtain an aqueous coating composition. 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 solids concentration to 20% by mass, thereby obtaining the aqueous paint composition of Example 11. The aqueous coating composition had a pH of 10.0, an average particle size of 83 nm, and an ultraviolet transmittance of 0.7% at a wavelength of 315 nm. Next, the aqueous coating composition of Example 11 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 11 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 11 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 4.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 11, the substrate with an adhesive layer, and the hard coat laminate.

[0117] Example 12 An aqueous dispersion of emulsion particles obtained by mixing 19.49 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., solid content 15% by mass) as metal oxide fine particles, 37.50 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 25.0 g of 1-methylpiperidine as a neutralizing agent, and A mixture of 2.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) and 13.14 g of Tinuvin 400 (trade name, manufactured by BASF Japan Ltd., solids concentration 85%) as ultraviolet absorbers, 1.24 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 393.75 g of tetrahydrofuran as an aprotic organic solvent was mixed at room temperature for 1 hour to obtain an aqueous coating composition. Distillation was then carried out until the aprotic organic solvent ratio in the coating was less than 1.0% by mass, and ion-exchanged water was added to adjust the solids concentration to 20% by mass, yielding the aqueous coating composition of Example 12. The aqueous coating composition had a pH of 10.1, an average particle size of 76.1 nm, and an ultraviolet transmittance of 5.0% at a wavelength of 315 nm. Next, the aqueous coating composition of Example 12 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 12 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 12 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 4.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 12, the substrate with an adhesive layer, and the hard coat laminate.

[0118] Example 13 An aqueous dispersion of emulsion particles obtained by mixing 21.03 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., solid content 15% by mass) as metal oxide fine particles, 37.50 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 25.0 g of 1-methylpiperidine as a neutralizing agent, and A mixture of 11.25 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) and 2.94 g of Tinuvin 400 (trade name, manufactured by BASF Japan Ltd., solids concentration 85%) as ultraviolet absorbers, 1.24 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 393.75 g of tetrahydrofuran as an aprotic organic solvent was mixed at room temperature for 1 hour to obtain an aqueous coating composition. Distillation was then carried out until the aprotic organic solvent ratio in the coating was less than 1.0% by mass, and ion-exchanged water was added to adjust the solids concentration to 20% by mass, yielding the aqueous coating composition of Example 13. The aqueous coating composition had a pH of 10.1, an average particle size of 89.4 nm, and an ultraviolet transmittance of 2.0% at a wavelength of 315 nm. Next, the aqueous coating composition of Example 13 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 13 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 13 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 4.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 13, the substrate with an adhesive layer, and the hard coat laminate.

[0119] Example 14 13.85 g of ion-exchanged water, 20.25 g of the aqueous dispersion of emulsion particles (A-1), 40.00 g of water-dispersed colloidal silica "Snowtex OUP" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass, primary particle diameter 12 nm) as metal oxide fine particles, 4.82 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 2.50 g of 1-methylpiperidine as a neutralizing agent were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of dimethoxyethane as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 14. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 87.3 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.3%. Next, the aqueous coating composition of Example 14 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 14 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 14 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 14, the substrate with an adhesive layer, and the hard coat laminate.

[0120] Example 15 13.85 g of ion-exchanged water, 20.25 g of the aqueous dispersion of emulsion particles (A-1), 40.00 g of water-dispersed colloidal silica "Snowtex OUP" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass, primary particle diameter 12 nm) as metal oxide fine particles, 4.82 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 2.50 g of 1-methylpiperidine as a neutralizing agent were mixed. The resulting aqueous dispersion of emulsion particles was mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of 2-methyltetrahydrofuran as an aprotic organic solvent to obtain a mixture, which was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 15. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 85.6 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.1%. Next, the aqueous coating composition of Example 15 was applied to a polycarbonate substrate using a bar coater and dried at 130 ° C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 15 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 15 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 15, the substrate with an adhesive layer, and the hard coat laminate.

[0121] Example 16 13.85 g of ion-exchanged water, 20.25 g of the aqueous dispersion of emulsion particles (A-1), 40.00 g of water-dispersed colloidal silica "Snowtex OUP" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass, primary particle diameter 12 nm) as metal oxide fine particles, 4.82 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 2.50 g of 1-methylpiperidine as a neutralizing agent were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of diethyl ether as an aprotic organic solvent to obtain a mixture, which was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 16. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 104.5 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.6%. Next, the aqueous coating composition of Example 16 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 16 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 16 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 16, the substrate with an adhesive layer, and the hard coat laminate.

[0122] Example 17 9.66 g of ion-exchanged water, 20.63 g of the aqueous dispersion of emulsion particles (A-1), 45.00 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 fine particles, 3.64 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 were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 1.50 g of Tinuvin 1600 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 17. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.1, an average particle size of 80.1 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.5%. Next, the aqueous coating composition of Example 17 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 17 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 17 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 17, the substrate with an adhesive layer, and the hard coat laminate.

[0123] Example 18 10.66 g of ion-exchanged water, 20.63 g of the aqueous dispersion of emulsion particles (A-1), 45.00 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 fine particles, 3.64 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 1.50 g of 1-methylpiperidine as a neutralizing agent were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 1.50 g of Tinuvin 1600 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 18. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 9.2, an average particle size of 143.6 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 4.2%. Next, the aqueous coating composition of Example 18 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 18 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 18 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. The aqueous coating composition of Example 18, the substrate with an adhesive layer, and the hard coat laminate were subjected to various evaluations, and the results are shown in Table 2.

[0124] Example 19 9.66 g of ion-exchanged water, 20.63 g of an aqueous dispersion of emulsion particles (A-2), 45.00 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 fine particles, 3.64 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 1.50 g of 1-methylpiperidine as a neutralizing agent were mixed. The aqueous dispersion of emulsion particles obtained by combining these was mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber, 0.08 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as a light stabilizer, and 17.00 g of tetrahydrofuran as an aprotic organic solvent to obtain a mixed liquid. The resulting mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 19. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.1, an average particle size of 101.2 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.7%. Next, the aqueous coating composition of Example 19 was applied to a polycarbonate substrate using a bar coater and dried at 130 ° C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 19 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 19 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 19, the substrate with an adhesive layer, and the hard coat laminate.

[0125] Example 20 An aqueous dispersion of emulsion particles was obtained by mixing 38.09 g of ion-exchanged water, 40.91 g of polyurethane dispersion "Superflex 170" (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solids content 33% by mass, shown as SF-170 in Table 2) as emulsion particles, and 2.50 g of 1-methylpiperidine as a neutralizing agent. This aqueous dispersion was mixed with a mixture obtained by mixing 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber and 17.00 g of tetrahydrofuran as an aprotic organic solvent, and the mixture was mixed at room temperature for 1 hour to obtain the aqueous coating composition of Example 20. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.7, an average particle size of 69.2 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 3.6%. Next, the aqueous coating composition of Example 20 was applied to a polycarbonate substrate using a bar coater and dried at 130 ° C for 1 hour to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 20 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Example 20 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 2 shows the results of various evaluations carried out on the aqueous coating composition of Example 20, the substrate with an adhesive layer, and the hard coat laminate.

[0126] Comparative Example 1 An aqueous dispersion of emulsion particles was prepared by mixing 11.50 g of ion-exchanged water, 67.50 g of an aqueous dispersion of emulsion particles (A-1), and 2.50 g of 1-methylpiperidine as a neutralizer. This mixture was then mixed with 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber and 17.00 g of ethanol. The mixture was then mixed at room temperature for 1 hour to obtain the aqueous coating composition of Comparative Example 1. However, the Tinuvin 479 did not dissolve in the ethanol, and the aqueous coating composition could not be obtained. The formulation results are shown in Table 3.

[0127] Comparative Example 2 An aqueous dispersion of emulsion particles was obtained by mixing 11.50 g of ion-exchanged water, 67.50 g of an aqueous dispersion of emulsion particles (A-1), and 2.50 g of 1-methylpiperidine as a neutralizing agent, and a mixture was obtained by mixing 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber and 17.00 g of dimethylformamide (referred to as DMF in Table 3, boiling point 153°C) as an aprotic organic solvent. The mixture was mixed at room temperature for 1 hour to obtain an aqueous coating composition of Comparative Example 2. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 180.0 nm, and an ultraviolet transmittance of 5.0% at a wavelength of 315 nm. Next, the aqueous coating composition of Comparative Example 2 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 µm on the polycarbonate substrate. In this way, a substrate with an adhesive layer of Comparative Example 2 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Comparative Example 2 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 3 shows the results of various evaluations carried out on the aqueous coating composition of Comparative Example 2, the substrate with an adhesive layer, and the hard coat laminate.

[0128] Comparative Example 3 An aqueous dispersion of emulsion particles was obtained by mixing 11.50 g of ion-exchanged water, 67.50 g of an aqueous dispersion of emulsion particles (A-1), and 2.50 g of 1-methylpiperidine as a neutralizing agent, and a mixture was obtained by mixing 1.50 g of Tinuvin 479 (trade name, manufactured by BASF Japan Ltd., solids concentration 100%) as an ultraviolet absorber and 17.00 g of 1,4-dioxane (boiling point 101°C) as an aprotic organic solvent. The mixture was mixed at room temperature for 1 hour to obtain an aqueous coating composition of Comparative Example 3. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.2, an average particle size of 152.0 nm, and an ultraviolet transmittance at a wavelength of 315 nm of 4.3%. Next, the aqueous coating composition of Comparative Example 3 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 µm on the polycarbonate substrate. In this way, a substrate with an adhesive layer of Comparative Example 3 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Comparative Example 3 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 3 shows the results of various evaluations carried out on the aqueous coating composition of Comparative Example 3, the substrate with an adhesive layer, and the hard coat laminate.

[0129] Comparative Example 4 An aqueous dispersion of emulsion particles was obtained by mixing 5.50 g of ion-exchanged water, 75.00 g of an aqueous dispersion of emulsion particles (A-1), and 2.50 g of 1-methylpiperidine as a neutralizing agent, and then 17.00 g of tetrahydrofuran was mixed as an aprotic organic solvent, followed by mixing at room temperature for 1 hour to obtain an aqueous coating composition of Comparative Example 4. The aqueous coating composition had a solids concentration of 15.0% by mass, a pH of 10.5, an average particle size of 61.1 nm, and an ultraviolet transmittance of 89.4% at a wavelength of 315 nm. Next, the aqueous coating composition of Comparative Example 4 was applied to a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer with a thickness of 5.0 µm on the polycarbonate substrate. In this way, a substrate with an adhesive layer of Comparative Example 4 was obtained. Furthermore, the hard coat coating liquid was applied to the substrate with the adhesive layer of Comparative Example 4 using a bar coater, and then dried at 130° C. for 1.5 hours to obtain a hard coat laminate having a hard coat layer with a thickness of 5.0 μm. Table 3 shows the results of various evaluations carried out on the aqueous coating composition of Comparative Example 4, the substrate with an adhesive layer, and the hard coat laminate.

[0130] The evaluation results of Examples 1 to 20 and Comparative Examples 1 to 4 are shown in Tables 1 to 3 below.

[0131] [Table 1]

[0132] [Table 2]

[0133] [Table 3]

[0134] [Evaluation results] It is clear from Tables 1 to 3 that the aqueous coating composition of this embodiment has excellent storage stability and can form a coating film that is excellent in transparency, adhesion, and weather resistance. Furthermore, as described above, the hard coat laminates of Examples 1 to 20 exhibit high levels of transparency, adhesion, and weather resistance, and were therefore evaluated as being suitable for use as window materials for automobiles. [Industrial Applicability]

[0135] 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); an ultraviolet absorber (B) having a biphenyltriazine skeleton; an aprotic organic solvent (C) having a boiling point of less than 100°C; An aqueous coating composition comprising:

2. 2. The aqueous coating composition according to claim 1, wherein the organic solvent (C) has a solubility parameter (HSP value) in the range below. △D: 10.0 to 20.0 △P: 1.0 to 10.0 △H: 1.0 to 10.0

3. The aqueous coating composition has an ultraviolet transmittance of 20% or less at a wavelength of 315 nm when diluted 1000 times with ion-exchanged water. The aqueous coating composition according to claim 1.

4. the aqueous coating composition has an average particle size of 150 nm or less as calculated by a dynamic light scattering method when diluted 50 times with ion-exchanged water; The aqueous coating composition according to claim 1.

5. The pH of the aqueous coating composition is 9.0 or more. The aqueous coating composition according to claim 1.

6. The solid content concentration is 12.5% ​​by mass or more and 25% by mass or less. The aqueous coating composition according to claim 1.

7. Further comprising a light stabilizer (D), The aqueous coating composition according to claim 1.

8. Further comprising a crosslinking agent (E), The aqueous coating composition according to claim 1.

9. Further containing metal oxide fine particles (F), The aqueous coating composition according to claim 1.

10. A method for producing the aqueous coating composition according to any one of claims 1 to 9, comprising: a step of stirring an aqueous solution containing emulsion particles (A) and adding dropwise an ultraviolet absorber (B) dissolved in an organic solvent (C) to the stirred aqueous solution, A method for producing an aqueous coating composition.

11. 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 claims 1 to 9. Substrate with adhesive layer.

12. A substrate with an adhesive layer according to claim 11; a hard coat layer disposed on the substrate with the adhesive layer; A hard coat laminate having

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