JP2015218267A - Aqueous resin composition, and laminate and article using the same - Google Patents

Abstract

The present invention has excellent adhesion to both a base material and a cured coating film of an active energy ray-curable composition, such as a polyester film, which is difficult to adhere, and Provided are a water-based resin composition that can maintain adhesion after a weathering acceleration test and serves as a highly transparent primer layer, and a laminate and article using the same. An organic solvent solution of an ultraviolet absorber (A) and a urethane resin (B) having an aromatic ring is mixed to obtain a mixture (C), and then the mixture (C) is dispersed in an aqueous medium (D). Then, an aqueous resin composition obtained by removing the organic solvent, wherein the ultraviolet absorber (A) is a benzotriazole ultraviolet absorber and a triazine ultraviolet absorber, and the ultraviolet absorber (A) Is contained in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the urethane resin (B). [Selection figure] None

Description

  The present invention provides an aqueous resin composition that can be used as a primer for improving the adhesion between a substrate and the coating film when forming a cured coating film of the active energy ray-curable composition on the surface of the substrate, The present invention relates to a laminate and an article using

  In recent years, application of aqueous urethane resin compositions to films and sheets for optical applications has been studied. Specific examples of the optical application include a liquid crystal display and a touch panel. The display device such as the liquid crystal display is usually configured by laminating a large number of optical films having various functions in order to display clear images. Examples of the optical film include an antireflection film, a retardation film, and a prism. A lens sheet etc. are mentioned.

  As a base material for these optical films, a polyester film, particularly a polyethylene terephthalate (PET) film is used because of its excellent optical properties, mechanical strength, and durability. For optical applications, the active energy ray-curable composition is applied to the surface of the polyester film and cured to form a hard coat layer or a layer in which the active energy ray-curable composition is cast. The polyester film may be a prism sheet, but the polyester film has a problem of low adhesion to the cured coating film of the active energy ray-curable composition due to its high crystallinity.

  As a method for improving the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition, an acrylic resin is used between the polyester film as the base material and the cured coating film of the active energy ray-curable composition. It has been proposed to provide a primer layer (see, for example, Patent Document 1). However, even when a primer layer made of an acrylic resin is provided, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition is not sufficient.

  Moreover, although the thing using urethane resin as a primer layer has sufficient adhesiveness with the cured coating film of an active energy ray curable composition, there existed a problem that the adhesiveness after a weather resistance accelerated test fell.

  Therefore, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition can be made sufficient, and it can be used as a primer capable of maintaining the adhesion after the weather resistance promotion test. Material was sought.

JP 2010-215843 A

  The problem to be solved by the present invention is excellent adhesion to both the base material and the cured coating film of the active energy ray-curable composition, even if the base material is difficult to adhere, such as a polyester film. It is to provide a water-based resin composition that becomes a primer layer having high transparency and that can maintain adhesion after the weather resistance acceleration test and has high transparency, and a laminate and an article using the same.

  As a result of diligent research to solve the above problems, the present inventors have mixed a specific ultraviolet absorber with an organic solvent solution of a urethane resin having an aromatic ring, and then dispersed it in an aqueous medium. By using the aqueous resin composition obtained by removing the solvent as a primer, it improves the adhesion between the base material and the active energy ray-cured coating film even for difficult-to-adhere base materials such as polyester films. It was found that a laminate having high transparency can be obtained while maintaining adhesion after the weather resistance promotion test, and the present invention was completed.

That is, the present invention mixes an organic solvent solution of the ultraviolet absorber (A) and the urethane resin (B) having an aromatic ring to obtain a mixture (C), and then the mixture (C) in the aqueous medium (D). An aqueous resin composition obtained by removing the organic solvent after being dispersed in
The said ultraviolet absorber (A) is a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber, and the said ultraviolet absorber (A) is 0.01-5 mass with respect to 100 mass parts of said urethane resins (B). The present invention relates to an aqueous resin composition characterized by containing a part. The present invention also relates to a laminate and an article using the aqueous resin composition.

  The water-based resin composition of the present invention is a primer that greatly improves the adhesion between the base material and the cured coating film of the active energy ray-curable composition, even if it is a difficult-to-adhere base material such as a polyester film. Since it can be used, it is suitable for the laminated body which used the polyester film as the base material and formed the cured coating film of the active energy ray-curable composition on the surface. Examples of such a laminate include optical films such as an antireflection film, a retardation film, and a prism lens sheet. Further, these optical films can be applied to image display devices such as liquid crystal displays.

  In the aqueous resin composition of the present invention, an organic solvent solution of the ultraviolet absorber (A) and the urethane resin (B) having an aromatic ring is mixed to obtain a mixture (C). It is an aqueous resin composition obtained by dispersing in D) and removing the organic solvent.

  The ultraviolet absorber (A) has high heat resistance, good compatibility with the resin, and can absorb ultraviolet rays in a wide range. Therefore, a benzotriazole ultraviolet absorber and a triazine ultraviolet absorber are used in combination. And use.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -1,4-dihydroxybenzene], 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (hydroxymethyl) phenol], 2, 2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1- Methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 3-tetramethylbutyl) phenol, and the like.

  Commercially available benzotriazole ultraviolet absorbers include, for example, “TINUVIN PS”, “TINUVIN99-2”, “TINUVIN384-2”, “TINUVIN900”, “TINUVIN928”, “TINUVIN1130” (all of which are BASF Japan shares) And “TINUVIN” is a registered trademark).

  Examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy -4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy -4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6 (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3 -Triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine and the like.

  Moreover, as a commercial item of a triazine type | system | group ultraviolet absorber, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN479 (all are BASF Japan KK-made, "TINUVIN" is a registered trademark) etc. are mentioned, for example.

  The blending ratio of the ultraviolet absorber (A) is 0.01 parts by mass or more, and the transparency of the coating film is 100 parts by mass with respect to 100 parts by mass of the urethane resin (B). From the point to ensure, it is preferable that it is 5 mass parts or less, and it is more preferable that it exists in the range of 0.1-2.5 mass parts.

  The urethane resin used in the present invention uses a urethane resin having an aromatic ring in order to improve compatibility with the ultraviolet absorber.

  The urethane resin (B) having an aromatic ring reacts a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group and a polyisocyanate (b2). It was obtained.

  By using the polyol (b1-1) as a raw material for the urethane resin (B), the urethane resin (B) has an aromatic ring. Moreover, the range of 1.5-8 mol / kg is preferable and, as for the aromatic ring density | concentration in the said polyol (b1-1), the range of 1.6-5 mol / kg is more preferable.

  Examples of the polyol (b1-1) include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, and bisphenol alkylene oxide adducts. These can be used alone or in combination of two or more.

  Among the polyols (b1-1), aromatic polyester polyols and aromatic polyether polyols are preferable because of excellent substrate adhesion. Therefore, as the polyol (b1-1), it is preferable to use one containing at least one of an aromatic polyester polyol and an aromatic polyether polyol.

  The aromatic polyester polyol is obtained by an esterification reaction of a polyvalent carboxylic acid and a polyhydric alcohol, and at least one of the polyvalent carboxylic acid and the polyol has an aromatic ring. Use.

  Examples of the polyvalent carboxylic acid having an aromatic ring include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and esterified products thereof. Examples of those having no aromatic ring include succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4- Examples include aliphatic dicarboxylic acids such as butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, and fumaric acid, or esterified products thereof. These polyvalent carboxylic acids or esterified products thereof can be used alone or in combination of two or more.

  Examples of the polyhydric alcohol having an aromatic ring include aromatic diols such as benzene dimethanol, toluene dimethanol, and xylene dimethanol. Examples of those having no aromatic ring include ethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butane diol, 1,6-hexane diol, 1,8-octane diol, diethylene glycol, Examples include aliphatic polyols such as triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol ethylene glycol. These polyhydric alcohols can be used alone or in combination of two or more.

  In the esterification reaction for producing the aromatic polyester polyol, it is preferable to use an esterification catalyst for the purpose of promoting the esterification reaction. Examples of the esterification catalyst include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, and dibutyltin. Such as diacetate, dibutyltin dilaurate, tin octoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium, etc. A metal compound etc. are mentioned.

  Examples of the aromatic polyether polyol include bisphenol A ethylene oxide addition diol, bisphenol A propylene oxide addition diol, bisphenol A butylene oxide addition diol, bisphenol F ethylene oxide addition diol, and bisphenol F propylene oxide addition diol. And propylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthoquinone, and the like.

  The polyol (b1-2) is a polyol having a hydrophilic group. Examples of the hydrophilic group include an anionic group, a cationic group, and a nonionic group. An anionic group is preferable, and among the anionic groups, a carboxyl group and a sulfonic acid group are preferable.

  Examples of the polyol having a carboxyl group as a hydrophilic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and the like. Among these, 2,2-dimethylolpropionic acid is preferable. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol and carboxylate which have the said carboxyl group react can also be used.

  Examples of the polyol having a sulfonic acid group as a hydrophilic group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (4-sulfophenoxy) isophthalic acid, or salts thereof. Examples thereof include polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and neopentyl glycol.

  Neutralization of a part or all of the anionic group with a basic compound is preferable because good water dispersibility can be imparted to the urethane resin (B).

  Examples of the basic compound include ammonia; organic amines such as triethylamine, morpholine, monoethanolamine, and diethylethanolamine; metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. Since the water dispersion stability of the aqueous resin composition of the present invention can be further improved, the amount of the basic compound used is 0 in terms of the molar ratio of the basic compound to the anionic group [basic compound / anionic group]. The range of 0.5-3 is preferable, and the range of 0.7-1.5 is more preferable.

  In the present invention, the polyol (b1) contains the polyol (b1-1) and the polyol (b1-2), but may contain other polyols (b1-3). Examples of the polyol (b1-3) include aliphatic polyester polyols, aliphatic polycarbonate polyols, aliphatic polyether polyols, and alkylene oxide adducts of hydrogenated bisphenol. Moreover, you may use the said polyhydric alcohol quoted as a raw material of the said aromatic polyester polyol as said polyol (b1-3). These polyols (b1-3) can be used alone or in combination of two or more.

  Moreover, since the adhesiveness with respect to a base material improves more, the ratio of the polyol (b1-1) which has an aromatic ring contained in a polyol (b1) has the preferable range of 40-98 mass%, and is 60-98 mass. % Range is more preferred.

  Examples of the polyisocyanate (b2) used as the raw material for the urethane resin (B) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, and tolylene diene. Examples include aromatic polyisocyanates such as isocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. These polyisocyanates (b2) can be used alone or in combination of two or more.

  Among the polyisocyanates (b2), those containing an aromatic polyisocyanate are preferable because adhesion to the substrate is further improved. In this case, the content of the aromatic polyisocyanate in the polyisocyanate (b2) is preferably in the range of 15 to 35% by mass.

  The urethane resin (B) is, for example, mixed with the polyol (b1) and the polyisocyanate (b2) in the absence of a solvent or in the presence of an organic solvent, and at a temperature of 40 to 120 ° C. for 3 to 20 hours. It can be produced by reacting. Moreover, when manufacturing the said urethane resin (B), you may use a chain extender as needed.

  The reaction between the polyol (b1) and the polyisocyanate (b2) is such that the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (b1) and the isocyanate group of the polyisocyanate (b2) is 0. It is preferable to carry out in the range of 0.5 to 3.5, and more preferably in the range of 0.9 to 2.5.

  Examples of the organic solvent that can be used in producing the urethane resin (B) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; acetonitrile And nitrile solvents such as amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.

  As the weight average molecular weight of the urethane resin (B) obtained by the above method, the adhesion between the base material and the cured coating film of the active energy ray-curable composition is further improved. The range of 000 is preferable, and the range of 3,000 to 100,000 is more preferable.

  Examples of the aqueous medium (D) used in the aqueous resin composition of the present invention include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; Examples include alkyl ether solvents; lactam solvents such as N-methyl-2-pyrrolidone. These water-miscible organic solvents can be used alone or in combination of two or more.

  The aqueous medium (D) is preferably water alone or a mixture of water and an organic solvent miscible with water, and more preferably water alone, in consideration of safety and environmental load reduction.

  The ratio of the aqueous medium (D) in the aqueous resin composition of the present invention is preferably in the range of 10 to 90% by mass, and more preferably in the range of 30 to 70% by mass.

  In the method for producing an aqueous resin composition of the present invention, first, a mixture (C) of an organic solvent solution of the ultraviolet absorber (A) and the urethane resin (B) is dispersed in the aqueous medium (D). Next, by removing the organic solvent, an aqueous resin composition in which the mixture (C) of the ultraviolet absorber (A) and the urethane resin (B) is dispersed in the aqueous medium (D) can be obtained. At this time, in order to reduce the load on the safety and the environment, for example, the organic solvent may be partially or wholly removed by distilling off under reduced pressure.

  Moreover, the said ultraviolet absorber (A) and the said urethane resin (B) in the said aqueous medium (D) are a part or all of the said ultraviolet absorber (A) existing in a urethane resin (B). The state which is carrying out is preferable. More specifically, it is preferable that the ultraviolet absorbent (A) is a core-shell type resin particle in which a core part is formed and the urethane resin (B) is a shell part.

  Moreover, the ratio of the total amount of the said ultraviolet absorber (A) and the said urethane resin (B) in the aqueous resin composition of this invention is 10-90 mass% from a viewpoint of the storage stability of an aqueous resin composition. The range is preferable, and the range of 20 to 70% by mass is more preferable.

  If necessary, the aqueous resin composition of the present invention includes a film-forming aid, a curing agent, a crosslinking agent, a plasticizer, an antistatic agent, a wax, a light stabilizer, a flow regulator, a dye, a leveling agent, and a rheology control. Additives such as additives, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments; other resins such as polyester resins, urethane resins and acrylic resins can be blended.

  Examples of the crosslinking agent include melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and isocyanate compounds. Examples of the melamine compound include alkylated methylol melamine resins. The alkylated methylol melamine resin is obtained, for example, by reacting a methylolated melamine resin with a lower alcohol (alcohol having 1 to 6 carbon atoms) such as methyl alcohol or butyl alcohol. Examples of the methylolated melamine resins include methylol melamine resins having amino groups obtained by condensing melamine and formaldehyde, methylol melamine resins having imino groups, trimethoxymethylol melamine resins, hexamethoxymethylol melamine resins, and the like. It is done. Among these, trimethoxymethylol melamine resin and hexamethoxymethylol melamine resin are preferable. Examples of the alkylated methylol melamine resin include an alkylated methylol melamine resin having an imino group and an alkylated methylol melamine resin having an amino group.

  The laminate of the present invention has a primer layer formed using the aqueous resin composition of the present invention described above, and a cured coating film formed using an active energy ray-curable composition on the surface of the primer layer It is what has.

  The active energy ray-curable composition preferably contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group. The type of the monomer having a polymerizable unsaturated group is preferably appropriately selected according to the properties required for the cured coating film of the active energy ray-curable composition.

  Examples of the resin having a polymerizable unsaturated group include urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, and resin having maleimide group. Etc. These resins having a polymerizable unsaturated group can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “(meth) acryloyl group” refers to one or both of acryloyl group and methacryloyl group.

  Examples of the urethane (meth) acrylate resin include a urethane bond and a (meth) acryloyl group obtained by urethanization reaction of an aliphatic polyisocyanate or an aromatic polyisocyanate with a (meth) acrylate having a hydroxyl group. Examples thereof include resins.

  Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, and 3-methyl-1. , 5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, Hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate Cyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the like. Examples of the aromatic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and the like.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1 , 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalate neopentyl glycol mono (meth) acrylate, etc. (Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate Mono- or di (meth) acrylates of trivalent alcohols such as relate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Mono- and di (meth) acrylates having a monofunctional hydroxyl group and tri- or more functional (meth) acryloyl such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, poly (Meth) acrylate compounds having an oxyalkylene chain such as propylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The unsaturated polyester resin is a curable resin obtained by polycondensation of an α, β-unsaturated dibasic acid or acid anhydride thereof, an aromatic saturated dibasic acid or acid anhydride thereof, and glycol. Examples of the α, β-unsaturated dibasic acid or acid anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acid or acid anhydride thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and the like. And the like. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  As the epoxy (meth) acrylate resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or the like. What is obtained is mentioned.

  As said polyester (meth) acrylate resin, what is obtained by making (meth) acrylic acid react with the hydroxyl group of polyester polyol is mentioned, for example.

  As said acrylic (meth) acrylate resin, after polymerizing (meth) acrylate monomers, such as glycidyl methacrylate and alkyl (meth) acrylate as needed, for example, after obtaining the acrylic resin which has an epoxy group And those obtained by reacting the epoxy group with (meth) acrylic acid.

  As the resin having a maleimide group, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like.

  Examples of the monomer having a polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (number average molecular weight in the range of 150 to 1000) (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (me ) Acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate Rate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, aliphatic alkyl (meth) acrylate such as isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropy Glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N -Octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) Carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-dimale And maleimide compounds such as midcyclohexane. These monomers having a polymerizable unsaturated group can be used alone or in combination of two or more.

  The said active energy ray-curable composition can be made into a cured coating film by irradiating an active energy ray after apply | coating to a base material etc. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When the active energy ray-curable composition is used as a cured coating by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator is added to the active energy ray-curable composition to improve curability. It is preferable to do. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when irradiating an active energy ray with electron beam, α ray, β ray or γ ray to make the active energy ray curable composition as a cured coating film, a photopolymerization initiator or a photosensitizer is used. Since it cures quickly even if it is not used, it is not necessary to add a photopolymerization initiator or a photosensitizer.

  Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2. -Hydroxy-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur such as sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. Compound etc. are mentioned.

  As a base material used for the laminated body of this invention, a metal base material, a plastic base material, a glass base material, a paper base material, a wood base material, a fiber base material etc. are mentioned, for example. Among these base materials, a plastic base material is preferable when the aqueous resin composition of the present invention is used as a primer in order to improve the adhesion between the cured coating film of the active energy ray-curable composition and the base material. It is.

  Materials for the plastic substrate include polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin , Polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), and the like.

  The aqueous resin composition of the present invention is very useful as a primer for a polyester substrate among the plastic substrates described above. Specific examples of the polyester include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

  Examples of the plastic substrate include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and office automation equipment. Moreover, the film base material which used the plastic as a raw material is also mentioned. When the film substrate is used as the substrate of the laminate of the present invention, it can be used for optical films such as antireflection films, retardation films, and prism lens sheets; and high-performance films such as food packaging such as aluminum vapor deposition films. it can.

  Further, when the laminate of the present invention is used as an optical film such as an antireflection film, a retardation film, or a prism lens sheet, various kinds of liquid crystal display (LCD), organic EL display (OLED), plasma display (PDP), etc. It can be used as a member of a screen display device.

  The aqueous resin composition of the present invention can form a coating film on the surface of the substrate by, for example, applying directly to the surface of the substrate, and then drying and curing. The method for drying and curing the aqueous resin composition of the present invention may be a method of curing for about 1 to 10 days at room temperature. However, since curing can proceed rapidly, 100 ° C. to A method of heating at a temperature of 150 ° C. for about 1 to 600 seconds is preferable. Moreover, when using the plastic base material which is easy to deform | transform and discolor at comparatively high temperature, it is preferable to heat at comparatively low temperature about 70 to 100 degreeC.

  Examples of the method for applying the aqueous resin composition of the present invention to the surface of the substrate include a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a flow coater, and a spin coater. Application methods using a coater, dipping, screen printing, spraying, brushing, applicator, bar coater and the like can be mentioned.

  Although the film thickness of the coating film formed using the aqueous resin composition of this invention can be suitably adjusted according to the use used, Usually, it is preferable that it is the range of 0.01-20 micrometers.

  The laminate of the present invention is further coated with the active energy ray-curable composition on the surface of the primer layer, which is a coating film of the aqueous resin composition of the present invention obtained as described above, to obtain an active energy ray. Can be obtained by forming a cured coating film of the active energy ray-curable composition. In addition, the application | coating method of the said active energy ray curable composition can use the same method as the application | coating method of said aqueous resin composition of this invention.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

(Synthesis Example 1: Synthesis of aromatic polyester polyol)
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 27.6 parts by mass of isophthalic acid, 27.6 parts by mass of terephthalic acid, 11.7 parts by mass of ethylene glycol, 19. 9 parts by mass and 0.03 part by mass of dibutyltin oxide were charged, and a polycondensation reaction was carried out at 230 ° C. for 24 hours until the acid value became 1 or less at 180 to 230 ° C., and an aromatic polyester polyol [acid value 0.6, hydroxyl group Value 50.0, aromatic cyclic concentration 4.41 mol / Kg].

(Production Example 1: Synthesis of urethane resin having aromatic ring)
In a reaction vessel, 100 parts by mass of the aromatic polyester polyol of Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 33.07 parts by mass of methyl ethyl ketone was added, stirred and mixed uniformly. Next, 6.1 parts by mass of 2,2′-dimethylolpropionic acid was added, and then 23.1 parts by mass of isophorone diisocyanate was added and reacted at 80 ° C. for 12 hours to carry out a urethanization step. After confirming that the isocyanate value was 0.1% or less, 3 parts by mass of n-butanol was added, and further reacted for 2 hours, then cooled to 50 ° C., and the non-volatile content of the urethane resin having an aromatic ring was 80. A 0 wt% solution was obtained.

(Example 1: Preparation of aqueous resin composition (1))
To 125 parts by mass of a non-volatile content 80.0% by mass solution of the urethane resin having an aromatic ring obtained in Production Example 1 (100 parts by mass as a urethane resin having an aromatic ring), a benzotriazole-based ultraviolet absorber (BASF Japan Ltd.) 0.5 parts by weight of “TINUVIN 928” manufactured by TINUVIN 928) and 0.5 parts by weight of triazine-based UV absorber (“TINUVIN 479” manufactured by BASF Japan Ltd.) were added and stirred to mix uniformly. Next, 3 parts by mass of a 25% aqueous ammonia solution was added, and 342 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (1) having a nonvolatile content of 23.0% by mass.

(Example 2: Preparation of aqueous resin composition (2))
To 125 parts by mass of a non-volatile content 80.0% by mass solution of the urethane resin having an aromatic ring obtained in Production Example 1 (100 parts by mass as a urethane resin having an aromatic ring), a benzotriazole-based ultraviolet absorber (BASF Japan Ltd.) 2.5 parts by mass of “TINUVIN928” manufactured by TINUVIN 92.5 and 2.5 parts by mass of triazine-based ultraviolet absorber (“TINUVIN479” manufactured by BASF Japan Ltd.) were added and stirred and mixed uniformly. Next, 3 parts by mass of a 25% aqueous ammonia solution was added, and 342 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (2) having a nonvolatile content of 23.5% by mass.

  Table 1 shows the compositions of the aqueous resin compositions (1) and (2) obtained in Examples 1 and 2. In addition, the urethane resin in a table | surface represents the amount of non volatile matters (amount of resin only).

(Preparation Example 1: Preparation of UV-curable composition (UV-1))
An ultraviolet curable composition was obtained by mixing 50 parts by mass of urethane acrylate resin (“Unidic 17-824-9” manufactured by DIC Corporation) and 12.5 parts by mass of methyl ethyl ketone.

(Example 3: Production of laminate (1))
A primer (P-1) was obtained by mixing 100 parts by mass of the aqueous resin composition (1) obtained in Example 1 and 283 parts by mass of ion-exchanged water. Subsequently, the primer (P-) obtained as described above was formed on the surface of a film substrate (thickness: 125 μm) made of polyethylene terephthalate (hereinafter abbreviated as “PET”) so that the film thickness after drying was about 1 μm. The primer layer was formed on the surface of the substrate by applying 1) and heating at 150 ° C. for 5 minutes.

On the surface of the primer layer, the ultraviolet curable composition (UV-1) obtained in Preparation Example 1 was applied so as to have a film thickness of 15 μm, heated at 80 ° C. for 10 minutes, and then applied to the coated surface. By using a high-pressure mercury lamp as a light source and irradiating ultraviolet rays at an irradiation amount of 0.5 J / cm ² , the surface of the substrate has a primer layer, and the cured coating film of the ultraviolet curable composition on the surface of the primer layer A laminate (1) having (hereinafter abbreviated as “UV coating film”) was obtained.

(Example 4: Production of laminate (2))
Except having prepared and used the primer (P-2) using the aqueous resin composition (2) obtained in Example 2 instead of the aqueous resin composition (1) used in Example 3, it implemented. In the same manner as in Example 3, a laminate (2) was obtained.

  The following evaluation was performed using the aqueous resin compositions and laminates obtained in the above Examples and Comparative Examples.

[Method for evaluating storage stability]
The aqueous composite resin compositions immediately after production and the comparative aqueous composite resin compositions obtained in the examples and comparative examples were stored in an environment of 40 ° C. for 30 days. The appearance of the aqueous composite resin composition after 30 days was visually observed and evaluated based on the following criteria.
(Double-circle): The aggregate was not seen at all and there was no change compared with the thing immediately after manufacture.
○: Some precipitates were confirmed, but at a practically usable level, and the precipitates could be redispersed by stirring again.
(Triangle | delta): The deposit was a little, and even if it stirred again, a part of deposit remained, and it could not fully re-disperse.
X: About 50% by mass or more of the total amount of the resin was precipitated, and could not be redispersed even by stirring again.

[Preparation of test plate]
A primer layer is applied to the surface of the base material by applying a primer on the surface of a base material made of polyethylene terephthalate having a thickness of 125 μm so that the film thickness when dried is about 1 μm and heating at 150 ° C. for 5 minutes. A test plate made of laminated members was prepared.

[Evaluation method of film-forming property]
The surface of the primer layer of the test plate was visually evaluated according to the following evaluation criteria.
○: When the surface of the primer layer was visually observed, it was transparent.
(Triangle | delta): When the surface of the primer layer was observed visually, although it was transparent, the crack was able to be confirmed.
X: When the surface of the primer layer was visually observed, cracks to the extent that whitening occurred appeared, and a part of the primer layer was easily peeled from the polyethylene terephthalate substrate.

[Measurement of haze value]
The haze value of the test plate produced by the above method was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.). Measured by a method based on JIS test method (JIS K7136: 2000). The haze value (H) was calculated from the following formula.
H (%) = Td / Tt × 100
H: Haze (cloudiness value) (%)
Td: diffuse transmissivity (%)
Tt: Total light transmittance (%)

[Evaluation method of adhesion (initial) between substrate and primer layer]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed to the surface of the primer layer of the test plate produced by the above method.

Next, the surface of the primer layer when the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the primer layer and the pressure-sensitive adhesive tape was peeled off from the surface of the primer layer was visually evaluated according to the following evaluation criteria.
(Double-circle): The primer layer did not peel at all from the base-material surface which comprises a test board.
○: A part of the primer layer was peeled off from the surface of the base material constituting the test plate, but the peeled range was less than 20% with respect to the total area of the film constituting the test plate.
(Triangle | delta): The primer layer of the range of 20% or more and less than 50% with respect to the area of the primer layer which comprises a test board peeled from the base-material surface which comprises a test board.
X: The primer layer of the range of 50% or more with respect to the whole area of the primer layer which comprises a test board peeled from the base-material surface which comprises a test board.

[Evaluation method of adhesion (initial) between primer layer and UV coating]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed to the surface of the UV coating film constituting the laminates obtained in Examples and Comparative Examples.

Next, the surface of the UV coating film is visually evaluated according to the following evaluation criteria when the pressure-sensitive adhesive tape is pulled in a direction perpendicular to the UV coating film and the pressure-sensitive adhesive tape is peeled off from the surface of the UV coating film. did.
(Double-circle): UV coating film did not peel from the base-material surface which comprises a laminated body at all.
○: A part of the UV coating film was peeled off from the surface of the base material constituting the laminate, but the peeled range was less than 20% with respect to the total area of the UV coating film constituting the laminate. .
(Triangle | delta): The UV coating film of the range of 20% or more and less than 50% with respect to the area of the UV coating film which comprises a laminated body peeled from the base-material surface which comprises a laminated body.
X: The UV coating film in the range of 50% or more with respect to the total area of the UV coating film constituting the laminate was peeled off from the substrate surface constituting the laminate.

[Adhesion between primer layer and UV coating (after weather resistance acceleration test)]
The obtained laminate was subjected to a dew panel light control weather meter (manufactured by Suga Test Instruments Co., Ltd.) and subjected to a weather resistance promotion test for one week. It carried out by the method based on the JIS test method (JIS K5600-7-7: 2008). Thereafter, the laminate was taken out, and the adhesion between the primer layer and the UV coating film was evaluated in the same manner as in [Adhesion between the primer layer and UV coating film (initial)].

  Table 2 shows the substrates, primers, and ultraviolet curable compositions used in the laminates (1) to (6) obtained in Examples 7 to 12 and the evaluation results.

(Comparative Example 1: Preparation of aqueous resin composition (C1))
125 mass parts of a non-volatile content 80.0 mass% urethane resin having an aromatic ring obtained in Production Example 1 (100 mass parts as a urethane resin having an aromatic ring) is added 4.0 mass parts of a 25 mass% ammonia aqueous solution. In addition, 452 parts by mass of ion exchange water was slowly added to effect water solubilization. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (C1) having a nonvolatile content of 22.5% by mass.

(Comparative Example 2: Preparation of aqueous resin composition (C2))
To 125 parts by mass of a non-volatile content 80.0% by mass solution of the urethane resin having an aromatic ring obtained in Production Example 1 (100 parts by mass as a urethane resin having an aromatic ring), a benzotriazole-based ultraviolet absorber (BASF Japan Ltd.) 10 parts by mass of “TINUVIN 928” manufactured by TINUVIN 928) and 10 parts by mass of triazine-based ultraviolet absorber (“TINUVIN 479” manufactured by BASF Japan Ltd.) were added and stirred and mixed uniformly. Next, 4.0 parts by mass of a 25% aqueous ammonia solution was added, and 452 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (C2) having a nonvolatile content of 23.5% by mass.

(Comparative Preparation Example 1: Preparation of primer (P′-1))
A primer (P′-1) was obtained by mixing 100 parts by mass of the aqueous resin composition (C1) obtained in Comparative Example 1 and 275 parts by mass of ion-exchanged water.

(Comparative Preparation Example 2: Preparation of primer (P′-2))
To 100 parts by mass of the aqueous resin composition (C1) obtained in Comparative Example 1, 0.56 parts by mass of a benzotriazole-based ultraviolet absorber (“TINUVIN928” manufactured by BASF Japan Ltd.) and a triazine-based ultraviolet absorber (BASF Japan) A primer (P′-2) was obtained by mixing 0.56 parts by mass of “TINUVIN479” manufactured by Co., Ltd. and 292.6 parts by mass of ion-exchanged water.

(Comparative Preparation Example 3: Preparation of primer (P′-3))
To 100 parts by mass of the aqueous resin composition (C1) obtained in Comparative Example 1, 2.8 (20% active ingredient) parts by mass of an ultraviolet absorber for water-based paint (“TINUVIN99-DW” manufactured by BASF Japan Ltd.), A primer (P′-3) was obtained by mixing 0.56 parts by mass of a triazine-based ultraviolet absorber (“TINUVIN479” manufactured by BASF Japan Ltd.) and 290.3 parts by mass of ion-exchanged water.

(Comparative Preparation Example 4: Preparation of primer (P′-4))
To 100 parts by mass of the aqueous resin composition (C1) obtained in Comparative Example 1, 2.8 (20% active ingredient) parts by mass of an ultraviolet absorbent for water-based paint (“TINUVIN479-DW” manufactured by BASF Japan Ltd.) Part, a benzotriazole ultraviolet absorber (“TINUVIN928” manufactured by BASF Japan Ltd.) is mixed with 0.56 parts by mass and 290.3 parts by mass of ion-exchanged water to obtain a primer (P′-4). It was.

(Comparative Preparation Example 5: Preparation of primer (P′-5))
To 100 parts by mass of the aqueous resin composition (C1) obtained in Comparative Example 1, 2.8 (20% active ingredient) parts by mass of an ultraviolet absorber for water-based paint (“TINUVIN99-DW” manufactured by BASF Japan Ltd.) By mixing 2.8 parts by mass (20% active ingredient) of UV absorbent for water-based paint (“TINUVIN479-DW” manufactured by BASF Japan Ltd.) and 288.1 parts by mass of ion-exchanged water, a primer (P′-7) was obtained.

(Comparative Preparation Example 6: Preparation of primer (P′-6))
A primer (P′-6) was obtained by mixing 100 parts by mass of the aqueous resin composition (C2) obtained in Comparative Example 2 and 291.6 parts by mass of ion-exchanged water.

(Comparative Example 3: Production of laminate (R1))
The primer (P′-1) obtained in Comparative Preparation Example 1 was applied to the surface of a PET film substrate (thickness: 125 μm) so that the film thickness after drying was about 1 μm. A primer layer was formed on the surface of the substrate by heating for a minute.

Next, the ultraviolet curable composition (UV-1) obtained in Preparation Example 1 was applied to the surface of the primer layer so as to have a film thickness of 15 μm, heated at 80 ° C. for 10 minutes, and then applied. A laminate having a primer layer on the surface of the base material and a UV coating on the surface of the primer layer by irradiating the surface with ultraviolet light at a dose of 0.5 J / cm ² using a high pressure mercury lamp as a light source (R1) was obtained.

(Comparative Examples 4 to 8: Production of laminates (R2) to (R6))
Comparative Example except that the primers (P′-2) to (P′-6) obtained in Comparative Preparation Examples 2 to 6 were used in place of the primer (P′-1) used in Comparative Example 3. 3 was performed, and laminates (R2) to (R6) were obtained.

  Table 3 shows the base materials, primers and ultraviolet curable compositions used in the laminates (R1) to (R6) obtained in Comparative Examples 3 to 8, and the evaluation results. In Comparative Examples 4 and 8, since the film forming property was poor and a coating film could not be formed, the evaluation items for adhesion and haze value were not evaluated.

  From the evaluation results shown in Table 2, the primer layer formed using the aqueous resin composition of the present invention has excellent adhesion to the substrate, and adhesion to the cured coating film of the active energy ray-curable composition. It was confirmed that it was excellent.

  Moreover, it was confirmed that the primer layer formed using the aqueous resin composition of the present invention has high adhesion even after the weather resistance promotion test.

  On the other hand, Comparative Example 3 is an example using a primer that does not contain an ultraviolet absorber. It was confirmed that the adhesion after the weather resistance promotion test was insufficient as compared with the primer layer formed using the aqueous resin composition of the present invention.

  Comparative Example 4 is an example in which an ultraviolet absorber was added after the urethane resin was dispersed in water. As compared with the primer layer formed using the aqueous resin composition of the present invention, it was confirmed that the film forming property was remarkably poor and a coating film could not be formed.

  Comparative Examples 5 to 7 are examples in which an ultraviolet absorbent for water-based paint was added after the urethane resin was dispersed in water. Compared to the primer layer formed using the aqueous resin composition of the present invention, the adhesion (initial) between the primer layer and the UV coating and the adhesion after the weather resistance promotion test are both insufficient, and the laminate It was confirmed that the transparency of was low.

  The comparative example 8 is a thing of the example whose compounding ratio of the ultraviolet absorber with respect to 100 mass parts of urethane resins is outside the range of 0.01-5 mass parts. As compared with the primer layer formed using the aqueous resin composition of the present invention, it was confirmed that the film forming property was poor and a coating film could not be formed.

Claims (8)

An organic solvent solution of the ultraviolet absorber (A) and the urethane resin (B) having an aromatic ring is mixed to obtain a mixture (C), and then the mixture (C) is dispersed in the aqueous medium (D), and then the organic An aqueous resin composition obtained by removing the solvent,
The said ultraviolet absorber (A) is a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber, and the said ultraviolet absorber (A) is 0.01-5 mass with respect to 100 mass parts of said urethane resins (B). An aqueous resin composition characterized by containing a part.   The urethane resin (B) is obtained by reacting a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group with a polyisocyanate (b2). The aqueous resin composition according to claim 1, which is obtained.   The aqueous resin composition according to claim 2, wherein the polyol (b1-1) having an aromatic ring is a polyol containing at least one of an aromatic polyester polyol and an aromatic polyether polyol.   The aqueous resin composition according to claim 2, wherein the concentration of the aromatic ring in the polyol (b1) is in the range of 1.5 to 8 mol / kg.   The aqueous resin composition according to claim 2, wherein the polyisocyanate (b2) contains an aromatic polyisocyanate.   It has the primer layer formed using the aqueous resin composition of any one of Claims 1-5 in the surface of a base material, and uses the active energy ray-curable composition on the surface of the said primer layer. A laminate having a cured coating film formed in the above manner.   The laminate according to claim 6, wherein the active energy ray-curable resin composition contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group.   An article comprising the laminate according to claim 6 or 7.