JP2017014307A - Aqueous resin composition, laminate and article using the same - Google Patents

Abstract

[PROBLEMS] To provide a high refractive index performance at a level that can be used for optical applications, and adhesion between a base material and a cured coating film of an active energy ray-curable composition, even for a hard-to-adhere base material such as a polyester film. Provided is an aqueous resin composition that can be used as a primer for greatly improving the properties. An aqueous resin composition in which a vinyl ester resin and a urethane resin having an aromatic ring are dispersed in an aqueous medium, wherein the vinyl ester resin is selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin. It is obtained by reacting one or more selected epoxy resins with a compound having an acid group and a polymerizable unsaturated group, and part or all of the vinyl ester resin is contained in the urethane resin particles. An aqueous resin composition that is inherently formed with resin particles, has an aromatic ring concentration in the resin particles of 3.5 mol / kg or more, and an unsaturated group concentration in the resin particles of 1 mol / kg or more. Is used. [Selection figure] None

Description

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

  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, a urethane resin composition is used between the polyester film as the substrate and the cured coating film of the active energy ray-curable composition. It has been proposed to provide a primer layer made of a material (for example, interference fringes may occur due to a difference in refractive index from the PET base material.

  Therefore, it has a high refractive index performance of a level that can be used for optical applications, and even a hard-to-adhere base material such as a polyester film is formed between the base material and the cured coating film of the active energy ray-curable composition. There has been a demand for a material that can be used as a primer that greatly improves the adhesion.

WO2015 / 019899

  The problem to be solved by the present invention is that it has a high refractive index performance of a level that can be used for optical applications, and even a hard-to-adhere base material such as a polyester film and the active energy ray curability. An object of the present invention is to provide an aqueous resin composition that can be used as a primer that greatly improves the adhesion of the composition to a cured coating film, and a laminate and article using the same.

  As a result of diligent research to solve the above problems, the present inventors have obtained a vinyl ester resin obtained by reacting a specific epoxy resin with a compound having an acid group and a polymerizable unsaturated group, and an aromatic ring. By using an aqueous resin composition in which a specific urethane resin is dispersed in an aqueous medium as a primer, it has a high refractive index performance at a level that can be used for optical applications, and is difficult to adhere to like a polyester film. Even if it was a base material, it discovered that the adhesiveness of the base material and the cured coating film of an active energy ray curable composition was improved significantly, and completed this invention.

That is, the present invention is an aqueous resin composition in which a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring are dispersed in an aqueous medium (C),
The vinyl ester resin (A) is one or more epoxy resins (a1) selected from the group consisting of novolak type epoxy resins and bisphenol type epoxy resins, a compound (a2) having an acid group and a polymerizable unsaturated group, It was obtained by reacting
A part or all of the vinyl ester resin (A) resides in the urethane resin (B) particles to form resin particles (D),
The aromatic ring concentration in the resin particles (D) is 3.5 mol / kg or more,
The present invention relates to an aqueous resin composition, a laminate and an article using the same, wherein the unsaturated group concentration in the resin particles (D) is 1 mol / kg or more.

  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. Moreover, these optical films are applicable to image display apparatuses, such as a liquid crystal display and a touch panel.

  The aqueous resin composition of the present invention is an aqueous resin composition in which a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring are dispersed in an aqueous medium (C).

  The vinyl ester resin (A) includes at least one epoxy resin (a1) selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin, a compound (a2) having an acid group and a polymerizable unsaturated group, The one obtained by reacting is used.

  The equivalent of the polymerizable unsaturated group of the vinyl ester resin (A) is 200 to 2,000 g / eq. The range of is preferable.

  As the epoxy resin (a1), one or more selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin can be used.

  Examples of the novolac type epoxy resin include a cresol novolac type epoxy resin and a phenol novolac type epoxy resin. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin. Among these, a novolak type epoxy resin having a large number of epoxy groups capable of reacting with the acid group of the compound (a2) is preferable. Moreover, these epoxy resins (a1) can be used alone or in combination of two or more.

  The epoxy resin (a1) has an epoxy equivalent of 150 to 2,000 g / eq. The range of 150-1500 g / eq. The range of is more preferable.

  The compound (a2) has an acid group and a polymerizable unsaturated group. A polymerizable unsaturated group can be introduced into the vinyl ester resin (A) by reacting the acid group of the compound (a2) with the epoxy group of the epoxy resin (a1). At this time, it is preferable to react 80-100 mol% in the total amount of the epoxy group which the said epoxy resin (a1) has with the acid group of the said compound (a2), and all the said epoxy groups are said compound (a2). It is preferable to react with the acid group.

  Examples of the compound (a2) include acrylic acid, methacrylic acid, itaconic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2,2,2, -trisacryloyloxymethylethylphthalic acid, and the like. Is mentioned. Among these compounds, an acryloyl group that easily undergoes a polymerization reaction with a polymerizable unsaturated group of a resin or monomer in the active energy ray-curable composition described later can be introduced into the vinyl ester resin (A). Acrylic acid is preferred. These compounds (a2) can be used alone or in combination of two or more.

  The reaction temperature between the epoxy resin (a1) and the compound (a2) is preferably in the range of 60 to 150 ° C, more preferably in the range of 70 to 120 ° C.

  Moreover, when making the said epoxy resin (a1) and the said compound (a2) react, in order to prevent the thermal polymerization of the polymerizable unsaturated group which the said compound (a2) has, it is preferable to use a polymerization inhibitor. . The addition amount of the polymerization inhibitor is preferably in the range of 500 to 5,000 ppm with respect to the total mass of the epoxy resin (a1) and the compound (a2).

  Examples of the polymerization inhibitor include 2,6-bis (tert-butyl) -4-methylphenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), p-tert-butylcatechol, nitrobenzene, nitrobenzoic acid, o-Dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrophenol, trinitrobenzene and the like can be mentioned. These polymerization inhibitors can be used alone or in combination of two or more.

  Furthermore, when making the said epoxy resin (a1) and the said compound (a2) react, a reaction catalyst can be used. The amount of the reaction catalyst used is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin (a1).

  Examples of the reaction catalyst include amine catalysts, imidazole catalysts, phosphorus catalysts, boron catalysts, and phosphorus-boron catalysts. Specifically, alkyl-substituted guanidine such as ethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine; 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea 3-substituted phenyl-1,1-dimethylurea such as 3- (4-chlorophenyl) -1,1-dimethylurea; 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline Imidazolines such as 2-aminopyridine; amine imides such as N, N-dimethyl-N- (2-hydroxy-3-allyloxypropyl) amine-N′-lactoimide; ethylphosphine, propylphosphine, butyl Phosphine, phenylphosphine, trimethylphos Organophosphorus catalysts such as fin, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine-triphenylborane complex, tetraphenylphosphonium tetraphenylborate, 1,8-diazabicyclo [5.4 0.0] undecene-7,1,4-diazabicyclo [2.2.2] octane and other diazabicycloundecene catalysts. These reaction catalysts can be used alone or in combination of two or more.

  The weight average molecular weight of the vinyl ester resin (A) obtained by the above method is preferably in the range of 500 to 10,000 and more preferably in the range of 1,000 to 6,000 because the dispersion stability of the resin particles is improved. More preferred.

  The vinyl ester resin (A) is partly or wholly contained in the urethane resin (B) particles to be described later and forms composite resin particles (D) than the urethane resin (B). It is preferably hydrophobic. Hydrophobic refers to a property that is difficult to dissolve in water.

  The urethane resin (B) having an aromatic ring includes a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group, a polyisocyanate (b2), What was obtained by making it react with a chain extender as needed can be used.

  By using the polyol (b1-1) having the aromatic ring as a raw material of the urethane resin (B), the urethane resin (B) has an aromatic ring. In addition, the aromatic ring concentration in the urethane resin (B) is preferably in the range of 4 to 6.5 mol / kg because a coating film having excellent film forming property and a coating film having high refractive index performance can be formed. A range of ˜6 mol / kg is more preferred. In the present invention, the aromatic ring concentration refers to the number of moles of aromatic rings contained in 1 kg of resin solid content.

  Examples of the polyol (b1-1) having an aromatic ring include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, and alkylene oxide adducts of bisphenol. Among these, an aromatic polyester polyol is preferable because a coating film having high refractive index performance can be formed and the adhesion to the substrate can be improved. These polyols (b1-1) can be used alone or in combination of two or more.

  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.

  Among the polyhydric alcohols, those having an aromatic ring include, for example, 1,3-benzenedimethanol, 1,4-benzenedimethanol, toluenedimethanol having 1 mol of aromatic ring skeleton in 1 mol of a compound, Xylene dimethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 1,8-naphthalene diethanol having 2 mol of aromatic ring skeleton in 1 mol of compound 2,9-naphthalene diethanol, 2,7-naphthalene diethanol, 1,5-naphthalene diethanol, 9,9-bis [4- (2-hydroxyethoxy) having 4 mol of aromatic ring skeleton in 1 mol of the compound And aromatic diols such as phenyl] fluorene. 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.

  As said aromatic polyester polyol, since the base-material adhesiveness can be improved further, the thing of the range of the number average molecular weights 500-4,000 is preferable.

  Examples of the polyol (b1-2) having a hydrophilic group include a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group other than the polyol (b1-1) described above. Can be used. Among these, it is preferable to use a polyol having an anionic group or a polyol having a cationic group, and it is more preferable to use a polyol having an anionic group.

  Examples of the polyol having an anionic group include a polyol having a carboxyl group and a polyol having a sulfonic acid group.

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

  The anionic groups are preferably partially or wholly neutralized with a basic compound or the like in order to exhibit good water dispersibility.

  Examples of basic compounds that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine, sodium hydroxide, Examples thereof include metal hydroxides containing potassium hydroxide and lithium hydroxide. From the viewpoint of improving the water dispersion stability of the urethane resin composition, the basic compound is used in a range where the basic group / anionic group of the basic compound is 0.5 to 2 (molar ratio). Is preferable, and it is more preferable to use in the range of 0.8 to 1.2 (molar ratio).

  Examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specific examples include N-methyl-diethanolamine, a polyol obtained by reacting a compound having two epoxies in one molecule and a secondary amine.

  It is preferable that a part or all of the cationic group is neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid and adipic acid.

  Further, the tertiary amino group as the cationic group is preferably partly or entirely quaternized. Examples of the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like. Of these, dimethyl sulfate is preferred.

  Examples of the polyol having a nonionic group include a polyol having a polyoxyethylene structure.

  The polyol (b1-2) having a hydrophilic group is preferably used in the range of 1 to 20% by mass in the total amount of the polyol (b1) used for the production of the urethane resin (B).

  In addition to the polyol (b1-1) and the polyol (b1-2), other polyols can be used as necessary as the polyol (b1).

  Examples of the other polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Examples include 1,4-cyclohexanediol, 1,6-hexanediol, and cyclohexanedimethanol.

  Examples of the polyisocyanate (b2) that can react with the polyol (b1) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, triene diisocyanate, Aromatic polyisocyanates such as naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate; Fats such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate Cyclic structure Such as polyisocyanates with. These polyisocyanates (b2) can be used alone or in combination of two or more.

  Moreover, when manufacturing the said urethane resin (B), as a chain extender used as needed, a polyamine, a hydrazine compound, the compound which has another active hydrogen atom is mentioned, for example.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. Among these, ethylenediamine is preferable.

  Examples of the hydrazine compound include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide. Examples include propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane, and the like.

  Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, Water etc. are mentioned.

  For example, when a polyamine is used as the chain extender, the equivalent ratio [amino group / isocyanate group] of the amino group and isocyanate group of the polyamine is preferably 1.2 or less, more preferably in the range of 0.3 to 1. preferable.

  The urethane resin (B) is produced, for example, by reacting the polyol, the polyisocyanate, and, if necessary, the chain extender by a known method in the absence of a solvent or in the presence of an organic solvent. it can.

  The reaction between the polyol and the polyisocyanate is in consideration of safety by paying sufficient attention to sudden heat generation, foaming, etc., and preferably at a reaction temperature of 50 to 120 ° C., more preferably 80 to 100 ° C. The polyisocyanate can be mixed by batch feeding or sequentially supplied by a method such as dropping one of them to the other and reacted for about 1 to 15 hours.

  In the reaction between the polyol (b1) and the polyisocyanate (b2), 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 5-2, and it is more preferable to carry out in the range of 0.8-1.2.

  When manufacturing the said urethane resin, an organic solvent can also be used as a solvent. Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone. An aromatic solvent such as toluene; These organic solvents can be used alone or in combination of two or more.

  The organic solvent is preferably removed by distillation or the like after the production of the urethane resin.

  The weight average molecular weight of the urethane resin is preferably in the range of 3,000 to 200,000, more preferably in the range of 5,000 to 100,000, and 15,000 to 80, because of excellent adhesion to the substrate. A range of 1,000 is more preferred.

  In the present invention, the weight average molecular weight is a value in terms of polyethylene measured by gel permeation chromatography (GPC).

  Examples of the aqueous medium (C) 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 (C) 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 aqueous medium (C) is preferably contained in the range of 10 to 60% by mass and more preferably in the range of 20 to 50% by mass in the total amount of the aqueous resin composition of the present invention.

  The aqueous resin composition of the present invention is obtained by dispersing the vinyl ester resin (A) and the urethane resin (B) in the aqueous medium (C). At this time, the vinyl ester resin (A) and the urethane resin (B) are part of the vinyl ester resin (A) in the aqueous medium (C), and the urethane resin (B) particles. What formed the resin particle (D) contained in the inside is used. More specifically, the vinyl ester resin (A) is a core-shell type resin particle (D) in which a core layer is formed and the urethane resin (B) is a shell layer.

  In addition, as said resin particle (D), it is preferable that the said vinyl ester resin (A) is completely covered with the said urethane resin (B), but it is not essential and the range which does not impair the effect of this invention Then, a part of the vinyl ester resin (A) may exist outside the resin particles (D).

  Moreover, although the said vinyl ester resin (A) and the said urethane resin (B) may form the covalent bond, it is preferable not to form the bond.

  For the resin particles (D), the vinyl ester resin (A) and the urethane resin (B) are manufactured in advance, and then the vinyl resin (A) and the urethane resin are added to the urethane resin (B). It can manufacture by mixing the basic compound which neutralizes the anionic group which (B) has, and the said aqueous medium (C).

  When an organic solvent is contained in the aqueous resin composition obtained by the above method, the organic solvent may be removed by distillation or the like in order to reduce safety and environmental burden. Thereby, the aqueous resin composition in which the resin particles (D) are dispersed in the aqueous medium (C) can be obtained.

  The aromatic ring concentration in the resin particles (D) is preferably 3.5 mol / kg or more because it can form a coating film having excellent film-forming properties and a coating film having high refractive index performance, and is preferably 4 to 5.5 mol. / Kg is more preferable, and 4 to 5 mol / kg is more preferable.

  The unsaturated group concentration in the resin particles (D) is preferably 1 mol / kg or more and more preferably in the range of 1 to 3 mol / kg because the adhesiveness with the active energy ray-curable composition can be further improved. More preferably, the range of 1.5-3 mol / kg is still more preferable.

  The acid value in the resin particles (D) is preferably 5 mgKOH / g or more from the viewpoint of ensuring storage stability as an aqueous dispersion.

  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 film forming aid include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, butyl cellosolve, polypropylene glycol monomethyl ether, and butyl cellosolve. Among these, it is preferable to use N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone because of excellent compatibility with the aqueous resin composition of the present invention.

  As the curing agent, it is preferable to use a water-soluble or water-dispersible one. Examples thereof include aliphatic amines, amines having a cyclic structure, aliphatic aromatic amines, polyamines such as polyoxyalkylene polyamines, and the like.

  Examples of the crosslinking agent include melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, and the like. 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 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, number average molecular weight in the range of 150 to 1,000 Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) 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) Aliphatic alkyl (meth) acrylates such as acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 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, methoxy dip Pyrene 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-ethylcarbonate, 2-maleimidoethyl-propylcarbonate, N-ethyl- (2-maleimide) Ethyl) carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-dimer And maleimide compounds such as reimidecyclohexane. 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 an image display device.

  Examples of the article of the present invention include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and OA equipment.

  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 polyester polyol (1))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 1,400 parts by mass, 2,6- 173 parts by weight of dimethyl naphthalenedicarboxylate, 94 parts by weight of terephthalic acid, 21 parts by weight of orthophthalic acid, and 0.5 parts by weight of dibutyltin oxide were charged at 230 ° C. for 15 hours until the acid value became 0.5 or less. This gave polyester polyol (1) (hydroxyl value: 117 mgKOH / g, acid value: 0.2 mgKOH / g, aromatic ring concentration: 9.22 mol / kg).

(Synthesis Example 2: Synthesis of polyester polyol (2))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 420 parts by mass of ethylene glycol, 660 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, 300 parts by mass of terephthalic acid, 120 of orthophthalic acid The polyester polyol (2) (hydroxyl value: 111 mgKOH / g, acid value) was charged at 230 ° C. for 15 hours until 0.5 parts by mass of dibutyltin oxide and 0.5 parts by mass of dibutyltin oxide were added. : 0.1 mg KOH / g, aromatic ring concentration: 7.09 mol / kg).

(Synthesis Example 3: Synthesis of polyester polyol (3))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 160 parts by mass of ethylene glycol, 360 parts by mass of 1,4-butanediol, 440 parts by mass of terephthalic acid, and 440 parts by mass of isophthalic acid In addition, 0.5 parts by mass of dibutyltin oxide was added, and a polycondensation reaction was performed at 230 ° C. for 15 hours until the acid value became 0.5 or less. Polyester polyol (3) (hydroxyl value: 106 mgKOH / g, acid value: 0) 0.3 mg KOH / g, aromatic ring concentration: 4.38 mol / kg).

  Table 1 shows the compositions of polyester polyols (1) to (3) synthesized in Synthesis Examples 1 to 3.

(Production Example 1: Production of vinyl ester resin (I-1) solution)
In a reaction vessel, cresol novolac type epoxy resin (“EPICLON N-673” manufactured by DIC Corporation, solid content epoxy equivalent: 209 g / eq., Nonvolatile content: 100% by mass) 1040 parts by mass, acrylic acid 369.3 parts by mass, methoquinone 2.2 parts by mass and 5.2 parts by mass of triphenylphosphine were added and reacted at a reaction temperature of 115 ° C. until the acid value was 1.5 or less. Subsequently, after cooling to 80 ° C. or less, 472.2 parts by mass of methyl ethyl ketone was charged and mixed uniformly to obtain a 75% by mass solution of a vinyl ester resin (I-1) with a nonvolatile content. The vinyl ester resin (I-1) had an aromatic ring concentration per solid content of 3.51 mol / kg and an unsaturated group concentration of 3.62 mol / kg.

(Production Example 2: Production of vinyl ester resin (I-2) solution)
In a reaction vessel, phenol novolac type epoxy resin (“EPICLON N-740” manufactured by DIC Corporation, solid content epoxy equivalent: 180 g / eq., Nonvolatile content: 100% by mass) 1040 parts by mass, acrylic acid 428.8 parts by mass, methoquinone 2.2 parts by mass and 5.2 parts by mass of triphenylphosphine were added and reacted at a reaction temperature of 115 ° C. until the acid value was 1.5 or less. Next, after cooling to 80 ° C. or lower, 492.1 parts by mass of methyl ethyl ketone was charged and mixed uniformly to obtain a 75% by mass solution of vinyl ester resin (I-2) with a nonvolatile content. The vinyl ester resin (I-2) had an aromatic ring concentration per solid content of 3.91 mol / kg and an unsaturated group concentration of 4.03 mol / kg.

(Production Example 3: Production of vinyl ester resin (I-3) solution)
In a reaction vessel, bisphenol A type epoxy resin (“EPICLON 850S” manufactured by DIC Corporation, solid content epoxy equivalent: 188 g / eq., Nonvolatile content: 100% by mass) 1040 parts by mass, acrylic acid 410.6 parts by mass, methoquinone 2. 2 parts by mass and 5.2 parts by mass of triphenylphosphine were added and reacted at a reaction temperature of 115 ° C. until the acid value was 1.5 or less. Subsequently, after cooling to 80 ° C. or lower, 486 parts by mass of methyl ethyl ketone was charged and mixed uniformly to obtain a 75% by mass solution of a vinyl ester resin (I-3) with a nonvolatile content. The vinyl ester resin (I-3) had an aromatic ring concentration per solid content of 3.79 mol / kg and an unsaturated group concentration of 3.91 mol / kg.

(Production Example 4: Production of vinyl ester resin (I-4) solution)
In a reaction vessel, cresol novolac type epoxy resin (“EPICLON N-673” manufactured by DIC Corporation, solid content epoxy equivalent: 209 g / eq., Nonvolatile content: 100% by mass) 1040 parts by mass, acrylic acid 221.6 parts by mass, methacrylic acid 176.5 parts by mass of acid, 2.2 parts by mass of methoquinone, and 5.2 parts by mass of triphenylphosphine were added and reacted at a reaction temperature of 115 ° C. until the acid value was 1.5 or less. Subsequently, after cooling to 80 ° C. or less, 481.8 parts by mass of methyl ethyl ketone was charged and mixed uniformly to obtain a 75% by mass nonvolatile solution of vinyl ester resin (I-4). The vinyl ester resin (I-4) had an aromatic ring concentration per solid content of 3.44 mol / kg and an unsaturated group concentration of 3.55 mol / kg.

(Production Example 5: Production of vinyl ester resin (I-5) solution)
In a reaction vessel, 1040 parts by mass of sorbitol polyglycidyl ether (“DENACOL EX-614B” manufactured by Nagase Chemtech Co., Ltd., solid content epoxy equivalent: 171 g / eq., Nonvolatile content: 100% by mass), 451.4 parts by mass of acrylic acid, Metoquinone 2.2 parts by mass and triphenylphosphine 5.2 parts by mass were added and reacted at a reaction temperature of 115 ° C. until the acid value was 1.5 or less. Subsequently, after cooling to 80 ° C. or less, 499.6 parts by mass of methyl ethyl ketone was charged and mixed uniformly to obtain a 75% by mass solution of a vinyl ester resin (I-5) with a nonvolatile content. The vinyl ester resin (I-5) had an aromatic ring concentration per solid content of 0 mol / kg and an unsaturated group concentration of 4.18 mol / kg.

(Production Example 6: Production of vinyl ester resin (I-6) solution)
1889.0 parts by mass of a non-volatile content 75% by mass solution of vinyl ester resin (I-1) obtained by the same method as in Production Example 1 and sodium polyoxyethylene alkyl ether sulfate (“LATEMUL E-118B manufactured by Kao Corporation) ”, Nonvolatile content: 26% by mass) and 544.9 parts by mass, and uniformly mixed. 2288.6 parts by mass of ion-exchanged water was added to this over 1 hour. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain a 50 mass% solution of vinyl ester resin (I-6) in a nonvolatile content. The vinyl ester resin (I-6) had an aromatic ring concentration per solid content of 3.19 mol / kg and an unsaturated group concentration of 3.29 mol / kg.

  Table 2 shows the compositions of the vinyl ester resins (I-1) to (I-6) produced in Production Examples 1 to 6.

(Production Example 7: Production of urethane resin (II-1) solution)
In a reaction vessel, 571.3 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 553.9 parts by mass of methyl ethyl ketone was added, stirred and homogeneous Mixed. Next, 50.0 parts by mass of 2,2-dimethylolpropionic acid was added, then 215.5 parts by mass of isophorone diisocyanate and 0.4 parts by mass of stannous octylate were added, and the mixture was reacted at 80 ° C. for 12 hours. . It confirmed that the mass ratio (isocyanate value) of the isocyanate group with respect to the total mass of the raw material used for manufacture of the said urethane resin became 0.1 mass% or less, added 3.5 mass parts of n-butanol, and also 2 After making it react for time, the non-volatile content 60 mass% solution of urethane resin (II-1) was obtained by cooling to 50 degreeC. The aromatic ring concentration per solid content of this urethane resin (II-1) was 6.29 mol / kg, the unsaturated group concentration was 0 mol / kg, and the acid value was 25.0 mgKOH / g.

(Production Example 8: Production of urethane resin (II-2) solution)
In a reaction vessel, 615.7 parts by mass of the polyester polyol (-2) obtained in Synthesis Example 2 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 553.9 parts by mass of methyl ethyl ketone was added and stirred. Mix evenly. Next, 50 parts by mass of 2,2-dimethylolpropionic acid was added, and then 171.1 parts by mass of toluene diisocyanate was added, followed by reaction at 80 ° C. for 12 hours. It confirmed that the mass ratio (isocyanate value) of the isocyanate group with respect to the total mass of the raw material used for manufacture of the said urethane resin became 0.1 mass% or less, added 3.5 mass parts of n-butanol, and also 2 After making it react for time, the non-volatile content 60 mass% solution of urethane resin (II-2) was obtained by cooling to 50 degreeC. The aromatic ring concentration per solid content of this urethane resin (II-2) was 5.22 mol / kg, the unsaturated group concentration was 0 mol / kg, and the acid value was 25 mgKOH / g.

(Production Example 9: Production of urethane resin (II-3) solution)
In a reaction vessel, 522 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 557.8 parts by mass of methyl ethyl ketone was added, stirred and mixed uniformly. did. Next, 50 parts by mass of 2,2-dimethylolpropionic acid was added, then 220.4 parts by mass of isophorone diisocyanate and 0.4 parts by mass of stannous octylate were added, and the mixture was reacted at 80 ° C. for 7 hours. Subsequently, 0.5 parts by mass of methoquinone and 17.1 parts by mass of 2-hydroxyethyl acrylate were added and reacted at 80 ° C. for 8 hours. Next, 0.8 parts by mass of triphenylphosphine and 26.5 parts by mass of glycidyl methacrylate were added and reacted for another 15 hours, and then cooled to 50 ° C., whereby the nonvolatile content of the urethane resin (II-3) was 60 parts by mass. % Solution was obtained. The aromatic ring concentration per solid content of this urethane resin (II-3) was 5.75 mol / kg, the unsaturated group concentration was 0.4 mol / kg, and the acid value was 12.5 mgKOH / g.

(Production Example 10: Production of urethane resin (II-4) solution)
In a reaction vessel, 491.7 parts by mass of the polyester polyol (3) obtained in Synthesis Example 3 was dehydrated at 100 ° C. under reduced pressure, then cooled to 80 ° C., and then 9,9-bis [4- (2-hydroxy). Ethoxy) phenyl] fluorene (70.4 parts by mass) and methyl ethyl ketone (554.3 parts by mass) were added, and the mixture was stirred and mixed uniformly. Next, 50 parts by mass of 2,2-dimethylolpropionic acid was added, and then 226.8 parts by mass of isophorone diisocyanate and 0.4 parts by mass of stannous octylate were added and reacted at 80 ° C. for 12 hours. It confirmed that the mass ratio (isocyanate value) of the isocyanate group with respect to the total mass of the raw material used for manufacture of the said urethane resin became 0.1 mass% or less, added 4.5 mass parts of n-butanol, and also 2 After making it react for time, the non-volatile content 60 mass% solution of urethane resin (II-4) was obtained by cooling to 50 degreeC. The aromatic ring concentration per solid content of this urethane resin (II-4) was 4.16 mol / kg, the unsaturated group concentration was 0 mol / kg, and the acid value was 24.9 mgKOH / g.

(Production Example 11: Production of urethane resin (II-5) solution)
In a reaction vessel, 583.2 parts by mass of the polyester polyol (3) obtained in Synthesis Example 3 was dehydrated at 100 ° C. under reduced pressure. After cooling to 80 ° C., 554.8 parts by mass of methyl ethyl ketone was added, and the mixture was stirred uniformly. Mixed. Next, 50 parts by mass of 2,2-dimethylolpropionic acid was added, and then 205.7 parts by mass of isophorone diisocyanate and 0.4 parts by mass of stannous octylate were added and reacted at 80 ° C. for 12 hours. It confirmed that the mass ratio (isocyanate value) of the isocyanate group with respect to the total mass of the raw material used for manufacture of the said urethane resin became 0.1 mass% or less, added 4.1 mass parts of n-butanol, and also 2 After making it react for time, the non-volatile content 60 mass% solution of urethane resin (II-5) was obtained by cooling to 50 degreeC. The aromatic ring concentration per solid content of the urethane resin (II-5) was 3.05 mol / kg, the unsaturated group concentration was 0 mol / kg, and the acid value was 24.9 mgKOH / g.

  Table 2 shows the compositions of the urethane resins (II-1) to (II-5) produced in Production Examples 7 to 11.

(Example 1: Preparation of aqueous resin composition (III-1))
A non-volatile content 75% by mass solution of the vinyl ester resin (I-1) obtained in Production Example 1 is added to 1394.7 parts by mass of a non-volatile content 60% by mass solution of the urethane resin (II-1) obtained in Production Example 7. 1115.8 parts by mass and 39.6 parts by mass of triethylamine were added, and 3536 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to obtain an aqueous resin composition (III-1) having a nonvolatile content of 45% by mass. This aqueous resin composition (III-1) had an aromatic ring concentration per solid content of 4.90 mol / kg, an unsaturated group concentration of 1.81 mol / kg, and an acid value of 12.5 mgKOH / g. It was.

(Example 2: Preparation of aqueous resin composition (III-2))
A non-volatile content 75% by mass solution of the vinyl ester resin (I-1) obtained in Production Example 1 is added to 1394.7 parts by mass of a non-volatile content 60% by mass solution of the urethane resin (II-1) obtained in Production Example 7. 2603.5 parts by mass and 39.6 parts by mass of triethylamine were added, and 4679 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III-2) having a nonvolatile content of 50% by mass. This aqueous resin composition (III-2) had an aromatic ring concentration per solid content of 4.48 mol / kg, an unsaturated group concentration of 2.53 mol / kg, and an acid value of 7.5 mgKOH / g. It was.

(Example 3: Preparation of aqueous resin composition (III-3))
A non-volatile content 75% by mass solution of the vinyl ester resin (I-1) obtained in Production Example 1 is added to 1394.7 parts by mass of a non-volatile content 60% by mass solution of the urethane resin (II-1) obtained in Production Example 7. 4463.1 parts by mass and 39.6 parts by mass of triethylamine were added, and 6057 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III-3) having a nonvolatile content of 50% by mass. This aqueous resin composition (III-3) had an aromatic ring concentration per solid content of 4.15 mol / kg, an unsaturated group concentration of 2.90 mol / kg, and an acid value of 5.0 mgKOH / g. It was.

(Example 4: Preparation of aqueous resin composition (III-4))
Non-volatile content 75% by mass solution of vinyl ester resin (I-1) obtained in Production Example 1 to 1394.7 parts by mass of non-volatile content 60% by mass of urethane resin (II-2) obtained in Production Example 8. 1115.8 parts by mass and 39.6 parts by mass of triethylamine were added, and 3536 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III-4) having a nonvolatile content of 45% by mass. This aqueous resin composition (III-4) had an aromatic ring concentration per solid content of 4.86 mol / kg, an unsaturated group concentration of 1.81 mol / kg, and an acid value of 12.5 mgKOH / g. It was.

(Example 5: Preparation of aqueous resin composition (III-5))
Non-volatile content 75% by mass solution of vinyl ester resin (I-1) obtained in Production Example 1 to 1394.7 parts by mass of non-volatile content 60% by mass of urethane resin (II-2) obtained in Production Example 8. 478.2 parts by mass and 39.6 parts by mass of triethylamine were added, and 3521 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III-5) having a nonvolatile content of 30% by mass. This aqueous resin composition (III-5) had an aromatic ring concentration per solid of 5.39 mol / kg, an unsaturated group concentration of 1.09 mol / kg, and an acid value of 17.5 mg KOH / g. It was.

(Example 6: Preparation of aqueous resin composition (III-6))
Non-volatile content 75% by mass solution of vinyl ester resin (I-2) obtained in Production Example 2 to 1394.7 parts by mass of non-volatile content 60% by mass of urethane resin (II-2) obtained in Production Example 8. 1115.8 parts by mass and 39.6 parts by mass of triethylamine were added, and 3123 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to obtain an aqueous resin composition (III-6) having a nonvolatile content of 45% by mass. This aqueous resin composition (III-6) had an aromatic ring concentration per solid content of 5.06 mol / kg, an unsaturated group concentration of 2.02 mol / kg, and an acid value of 12.5 mgKOH / g. It was.

(Example 7: Preparation of aqueous resin composition (III-7))
Non-volatile content 75 mass% solution of vinyl ester resin (I-3) obtained in Production Example 3 to 1394.7 parts by mass of non-volatile content 60 mass% of urethane resin (II-2) obtained in Production Example 8 743.9 parts by mass and 39.6 parts by mass of triethylamine were added, and 2803 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III-7) having a nonvolatile content of 45% by mass. This aqueous resin composition (III-7) had an aromatic ring concentration per solid content of 5.24 mol / kg, an unsaturated group concentration of 1.56 mol / kg, and an acid value of 15.0 mgKOH / g. It was.

(Example 8: Preparation of aqueous resin composition (III-8))
Non-volatile content 75 mass% solution of vinyl ester resin (I-3) obtained in Production Example 3 to 1394.7 parts by mass of non-volatile content 60 mass% of urethane resin (II-2) obtained in Production Example 8 1115.8 parts by mass and 39.6 parts by mass of triethylamine were added, and 3029 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III-8) having a nonvolatile content of 45% by mass. This aqueous resin composition (III-8) had an aromatic ring concentration per solid content of 4.82 mol / kg, an unsaturated group concentration of 1.78 mol / kg, and an acid value of 12.5 mgKOH / g. It was.

(Example 9: Preparation of aqueous resin composition (III-9))
A non-volatile content 75% by mass solution of the vinyl ester resin (I-1) obtained in Production Example 1 was added to 1395.4 parts by mass of the non-volatile content 60% by mass of the urethane resin (II-3) obtained in Production Example 9. 2604.8 parts by mass and 19.8 parts by mass of triethylamine were added, and 4188 parts by mass of ion-exchanged water was slowly added. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to obtain an aqueous resin composition (III-9) having a nonvolatile content of 50% by mass. This aqueous resin composition (III-9) had an aromatic ring concentration per solid content of 4.18 mol / kg, an unsaturated group concentration of 2.65 mol / kg, and an acid value of 7.5 mgKOH / g. It was.

(Example 10: Preparation of aqueous resin composition (III-10))
A non-volatile content 75% by mass solution of the vinyl ester resin (I-1) obtained in Production Example 1 is added to 1398.2 parts by mass of the non-volatile content 60% by mass of the urethane resin (II-4) obtained in Production Example 10. 1118.6 parts by mass and 39.6 parts by mass of triethylamine were added, and 3658 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III-10) having a nonvolatile content of 45% by mass. This aqueous resin composition (III-10) had an aromatic ring concentration per solid content of 3.56 mol / kg, an unsaturated group concentration of 1.81 mol / kg, and an acid value of 12.5 mgKOH / g. It was.

(Comparative Example 1: Preparation of aqueous resin composition (III'-1))
Non-volatile content 75% by mass solution of vinyl ester resin (I-1) obtained in Production Example 1 to 1394.7 parts by mass of non-volatile content 60% by mass of urethane resin (II-2) obtained in Production Example 8. 6322.8 parts by mass and 39.6 parts by mass of triethylamine were added, and 7740 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to obtain an aqueous resin composition (III′-1) having a nonvolatile content of 50% by mass. The aqueous resin composition (III′-1) has an aromatic ring concentration per solid content of 3.91 mol / kg, an unsaturated group concentration of 3.08 mol / kg, and an acid value of 3.8 mgKOH / g. It was.

(Comparative Example 2: Preparation of aqueous resin composition (III'-2))
Non-volatile content 75% by mass solution of vinyl ester resin (I-1) obtained in Production Example 1 to 1394.7 parts by mass of non-volatile content 60% by mass of urethane resin (II-2) obtained in Production Example 8. 278.9 parts by mass and 39.6 parts by mass of triethylamine were added, and 4098 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III′-2) having a nonvolatile content of 27% by mass. This aqueous resin composition (III′-2) has an aromatic ring concentration per solid content of 5.66 mol / kg, an unsaturated group concentration of 0.72 mol / kg, and an acid value of 20.0 mgKOH / g. there were.

(Comparative Example 3: Preparation of aqueous resin composition (III'-3))
Non-volatile content 75 mass% solution of vinyl ester resin (I-5) obtained in Production Example 5 to 1394.7 parts by mass of non-volatile content 60 mass% solution of urethane resin (II-2) obtained in Production Example 8 478.2 parts by mass and 39.6 parts by mass of triethylamine were added, and 4379 parts by mass of ion-exchanged water was slowly added. However, the state after water solubilization contained an extremely large amount of aggregates. Therefore, preparation of the aqueous resin composition (III′-3) was impossible.

(Comparative Example 4: Preparation of aqueous resin composition (III'-4))
In addition to 39.6 parts by mass of triethylamine, 3996 parts by mass of ion-exchanged water was slowly added to 1394.7 parts by mass of the non-volatile content 60% by mass solution of the urethane resin (II-2) obtained in Production Example 8. Next, 1673.7 parts by mass of a non-volatile content 75% by mass solution of the vinyl ester resin (I-6) obtained in Production Example 6 was added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition having a nonvolatile content of 50% by mass. This aqueous resin composition (III′-4) has an aromatic ring concentration per solid content of 4.70 mol / kg, an unsaturated group concentration of 1.65 mol / kg, and an acid value of 10.0 mgKOH / g. there were.

(Comparative Example 5: Preparation of aqueous resin composition (III'-5))
39.6 parts by mass of triethylamine was added to 1395.4 parts by mass of a non-volatile content 60% by mass solution of the urethane resin (II-3) obtained in Production Example 9, and 2205 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III′-5) having a nonvolatile content of 35% by mass. This aqueous resin composition (III′-5) has an aromatic ring concentration per solid content of 5.75 mol / kg, an unsaturated group concentration of 0.4 mol / kg, and an acid value of 12.5 mgKOH / g. there were.

(Comparative Example 6: Preparation of aqueous resin composition (III′-6))
A non-volatile content 75% by mass solution of the vinyl ester resin (I-1) obtained in Production Example 1 is added to 1398.2 parts by mass of the non-volatile content 60% by mass of the urethane resin (II-5) obtained in Production Example 11. 1677.9 parts by mass and 19.8 parts by mass of triethylamine were added, and 3240 parts by mass of ion-exchanged water was slowly added. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (III′-6) having a nonvolatile content of 50% by mass. The aqueous resin composition (III′-6) has an aromatic ring concentration per solid content of 3.32 mol / kg, an unsaturated group concentration of 2.17 mol / kg, and an acid value of 10.0 mgKOH / g. there were.

  Compositions of aqueous resin compositions (III-1) to (III-10) prepared in Examples 1 to 10 and aqueous resin compositions (III′-1) to (III ′) prepared in Comparative Examples 1 to 6 The composition of -6) is shown in Table 4.

(Preparation Example 1: Preparation of photocurable resin composition)
Mixing 70 parts by mass of epoxy acrylate resin ("UNIDIC V-5500" manufactured by DIC Corporation), 30 parts by mass of tripropylene glycol diacrylate and 3 parts by mass of a photopolymerization initiator ("Irgacure 184" manufactured by BASF Japan Ltd.) Thus, a photocurable resin composition was obtained.

(Example 11: Production of laminate (1))
100 parts by mass of the aqueous resin composition (III-1) obtained in Example 1 and a carbodiimide curing agent (“CARBO DILITE SV-02” manufactured by Nisshinbo Chemical Co., Ltd., nonvolatile content: 40% by weight, carbodiimide group equivalent: 430 g / eq.) 5 parts by mass and 51.7 parts by mass of ion-exchanged water were mixed and stirred to obtain a blended solution. Next, on the surface of a film substrate made of polyethylene terephthalate (hereinafter abbreviated as “PET”) having a film thickness of 125 μm, the blended liquid obtained above was applied so that the film thickness when dried was about 1 μm. By heating at 150 ° C. for 5 minutes, a primer layer (P-1) was formed on the substrate surface.

The photocurable resin composition obtained in Preparation Example 1 was applied to the surface of the primer layer (P-1) with an application thickness of 50 μm, and the application surface was irradiated with an irradiation intensity of 0. By irradiating with ultraviolet rays at 5 J / cm ² , the surface of the base material has a primer layer, and the surface of the primer layer has a cured coating film of a photocurable resin composition (hereinafter referred to as “photocured coating film”). A laminate (1) having abbreviated) was obtained.

(Example 12: Production of laminate (2))
Instead of the carbodiimide curing agent used in Example 11 (“CARBO DILITE SV-02” manufactured by Nisshinbo Chemical Co., Ltd.), sorbitol polyglycidyl ether (“DENACOL EX-614B” manufactured by Nagase Chemtech Co., Ltd., solid content epoxy equivalent: 171 g / Eq., Non-volatile content: 100 mass%) 3 mass parts, melamine curing agent (DIC Corporation "BECKAMINE APM", non-volatile content: 80 mass%) 5 mass parts, and ion-exchanged water 65.3 mass parts Mixing and stirring were performed to obtain a mixed solution. Other than that was performed like Example 11, the primer layer (P-2) was formed, and the laminated body (2) was obtained.

(Example 13: Production of laminate (3))
Instead of the aqueous resin composition (III-1) used in Example 12, the aqueous resin composition (III-2) was used, and sorbitol polyglycidyl ether (“DENACOL EX-614B” manufactured by Nagase Chemtech Co., Ltd.) 3 5 parts by mass, 5 parts by mass of a melamine curing agent (“BECKAMINE APM” manufactured by DIC Corporation), and 82 parts by mass of ion-exchanged water were mixed and stirred to obtain a blended solution. Other than that was performed like Example 11, the primer layer (P-3) was formed, and the laminated body (3) was obtained.

(Example 14: Production of laminate (4))
The primer layer (P) was prepared in the same manner as in Examples 11 and 13, except that the aqueous resin composition (III-3) was used instead of the aqueous resin composition (III-2) used in Example 13. -4) was formed to obtain a laminate (4).

(Example 15: Production of laminate (5))
A primer layer (P) was prepared in the same manner as in Examples 11 and 13, except that the aqueous resin composition (III-4) was used instead of the aqueous resin composition (III-2) used in Example 13. −5) was formed to obtain a laminate (5).

(Example 16: Production of laminate (6))
100 parts by mass of the aqueous resin composition (III-4) obtained in Example 4 and 50 parts by mass of ion-exchanged water were mixed and stirred to obtain a blended solution. Other than that was performed like Example 11, the primer layer (P-6) was formed, and the laminated body (6) was obtained.

(Example 17: Production of laminate (7))
Instead of the aqueous resin composition (III-1) used in Example 12, the aqueous resin composition (III-5) was used, and sorbitol polyglycidyl ether (“DENACOL EX-614B” manufactured by Nagase Chemtech Co., Ltd.) 3 Mass parts, 5 parts by mass of a melamine curing agent (“BECKAMINE APM” manufactured by DIC Corporation) and 15.3 parts by mass of ion-exchanged water were mixed and stirred to obtain a blended solution. Other than that was performed like Example 11, the primer layer (P-7) was formed, and the laminated body (7) was obtained.

(Example 18: Production of laminate (8))
A primer layer (P) was prepared in the same manner as in Examples 11 and 12, except that the aqueous resin composition (III-6) was used instead of the aqueous resin composition (III-1) used in Example 12. −8) was formed to obtain a laminate (8).

(Example 19: Production of laminate (9))
A primer layer (P) was prepared in the same manner as in Examples 11 and 12, except that the aqueous resin composition (III-7) was used instead of the aqueous resin composition (III-1) used in Example 12. -9) was formed to obtain a laminate (9).

(Example 20: Production of laminate (10))
A primer layer (P) was prepared in the same manner as in Examples 11 and 12, except that the aqueous resin composition (III-8) was used instead of the aqueous resin composition (III-1) used in Example 12. −10) was formed to obtain a laminate (10).

(Example 21: Production of laminate (11))
A primer layer (P) was prepared in the same manner as in Examples 11 and 13, except that the aqueous resin composition (III-9) was used instead of the aqueous resin composition (III-2) used in Example 13. -11) was formed to obtain a laminate (11).

(Example 22: Production of laminate (12))
A primer layer (P) was prepared in the same manner as in Examples 11 and 12, except that the aqueous resin composition (III-10) was used instead of the aqueous resin composition (III-1) used in Example 12. -12) was formed to obtain a laminate (12).

(Comparative Example 7: Production of laminate (R1))
100 parts by mass of the aqueous resin composition (III′-1) obtained in Comparative Example 1, 3 parts by mass of sorbitol polyglycidyl ether (“DENACOL EX-614B” manufactured by Nagase Chemtech Co., Ltd.), melamine curing agent (DIC Corporation) "BECKAMINE APM" manufactured by 5 parts by mass and 82 parts by mass of ion-exchanged water were mixed and stirred to obtain a blended solution. Other than that was performed like Example 11, the primer layer (P'-1) was formed, and the laminated body (R1) was obtained.

(Comparative Example 8: Production of laminate (R2))
Instead of the aqueous resin composition (III′-1) used in Comparative Example 7, the aqueous resin composition (III′-2) was used, and sorbitol polyglycidyl ether (“DENACOL EX-614B” manufactured by Nagase Chemtech Co., Ltd.) was used. ) 3 parts by mass, 5 parts by mass of a melamine curing agent (“BECKAMINE APM” manufactured by DIC Corporation) and 5.3 parts by mass of ion-exchanged water were mixed and stirred to obtain a blended solution. Other than that was performed like Example 11, the primer layer (P'-2) was created, and the laminated body (R2) was obtained.

(Comparative Example 9: Production of laminate (R3))
A primer layer was prepared in the same manner as in Example 11 and Comparative Example 7 except that the aqueous resin composition (III′-4) was used instead of the aqueous resin composition (III′-1) used in Comparative Example 7. (P′-3) was created to obtain a laminate (R3).

(Comparative Example 10: Production of laminate (R4))
In place of the aqueous resin composition (III′-1) used in Comparative Example 7, the aqueous resin composition (III′-5) was used, and sorbitol polyglycidyl ether (“DENACOL EX-614B” manufactured by Nagase Chemtech Co., Ltd.) was used. ) 3 parts by mass, 5 parts by mass of a melamine curing agent (“BECKAMINE APM” manufactured by DIC Corporation) and 32 parts by mass of ion-exchanged water were mixed and stirred to obtain a blended solution. Other than that was performed like Example 11 and the comparative example 7, the primer layer (P'-4) was created, and the laminated body (R4) was obtained.

(Comparative Example 11: Production of laminate (R5))
A primer layer was prepared in the same manner as in Example 11 and Comparative Example 7, except that the aqueous resin composition (III′-6) was used instead of the aqueous resin composition (III′-1) used in Comparative Example 7. (P′-5) was prepared to obtain a laminate (R5).

  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 resin compositions immediately after production and the comparative aqueous resin compositions obtained in 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.

[Evaluation method of film-forming property]
The primer layer is applied to the surface of the base material by applying the primer to the surface of the 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. Formed.
(Double-circle); When the surface of the primer layer was visually observed, it was transparent and no crack was generated even when the film was bent at 90 °.
○: When the surface of the primer layer was visually observed, it was transparent, but some cracks were generated when the film was bent at 90 °.
Δ: When the surface of the primer layer was visually observed, cracks were confirmed although it was transparent.
X: When the surface of the primer layer was visually observed, cracks to the extent that whitening occurred occurred, and a part of the primer layer was easily peeled off from the polyethylene terephthalate substrate.

[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.

[Adhesion 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.

A: The substrate surface constituting the test plate did not peel at all or only a part of the primer layer was peeled off, but the peeled range was less than 10% with respect to the total area of the film constituting the test plate. there were.
○: 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 10% or more and less than 25% with respect to the total area of the film constituting the test plate.
(Triangle | delta): The primer layer of the range of 25% 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.

[Adhesion between primer layer and photocured coating film (initial)]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed to the surface of the photocured coating film constituting the laminates obtained in Examples and Comparative Examples.
Next, the surface state of the photocured coating film when the pressure sensitive adhesive tape was pulled in a direction perpendicular to the photocured coating film and the pressure sensitive adhesive tape was peeled off from the surface of the photocured coating film was determined according to the following evaluation criteria Visually evaluated.

(Double-circle): The photocuring coating film did not peel at all from the base-material surface which comprises a laminated body.
○: A small part of the photocured coating film was peeled off from the surface of the substrate constituting the laminate, but the peeled range was less than 25% with respect to the total area of the photocured coating film constituting the laminate. there were.
(Triangle | delta): The photocurable coating film of the range of 25% or more and less than 50% with respect to the area of the photocurable coating film which comprises a laminated body peeled from the base-material surface which comprises a laminated body.
X: The photocurable coating film of the range of 50% or more with respect to the total area of the photocurable coating film which comprises a laminated body peeled from the base-material surface which comprises a laminated body.

[Adhesion between primer layer and photocured coating (after durability test)]
The obtained laminate was put into a high-temperature humidity chamber having a temperature of 60 ° C. and a relative humidity of 90% for 50 hours. Then, the said laminated body was taken out and the adhesiveness of a primer layer and a photocuring coating film was evaluated by the method similar to said [Adhesion of a primer layer and a photocuring coating film (initial)].

[Refractive index measurement]
The primer layer is applied to the surface of the base material by applying the primer to the surface of the base material made of polyethylene terephthalate having a thickness of 125 μm so that the film thickness when dried is about 5 μm and heating at 150 ° C. for 5 minutes. Formed. Next, the refractive index of this resin laminate was measured using a model 2010 manufactured by METRICON Corporation. In addition, it was set as "-" which cannot be measured about the thing which cannot be measured by film forming defect.

  Table 5 shows the evaluation results of the laminates (1) to (12) obtained in Examples 11 to 22.

  Table 6 shows the evaluation results of the laminates (R1) to (R5) obtained in Comparative Examples 7 to 11.

  From the evaluation results shown in Table 5, the primer layer formed using the aqueous resin composition of the present invention has high refractive index performance and excellent adhesion to the substrate, and is an active energy ray curable composition. It was confirmed that the adhesion with the cured film was also excellent.

  On the other hand, the evaluation results shown in Table 6 are examples of laminates formed using the aqueous resin compositions of Comparative Examples 1-6. It was confirmed that the adhesion of the active energy ray-curable composition to the cured coating film was extremely insufficient.

Claims (8)

An aqueous resin composition in which a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring are dispersed in an aqueous medium (C),
The vinyl ester resin (A) is one or more epoxy resins (a1) selected from the group consisting of novolak type epoxy resins and bisphenol type epoxy resins, a compound (a2) having an acid group and a polymerizable unsaturated group, It was obtained by reacting
A part or all of the vinyl ester resin (A) resides in the urethane resin (B) particles to form resin particles (D),
The aromatic ring concentration in the resin particles (D) is 3.5 mol / kg or more,
The aqueous resin composition, wherein an unsaturated group concentration in the resin particles (D) is 1 mol / kg or more.   The aqueous resin composition according to claim 1, wherein an acid value of the resin particles (D) is 5 mgKOH / g or more.   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 1, wherein the concentration of the aromatic ring in the urethane resin (B) is in the range of 4 to 6.5 mol / kg.   The aqueous resin composition according to claim 1, wherein the compound (a2) is acrylic acid or methacrylic acid.   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.