JPWO2018123795A1 - Aqueous resin composition, laminate using the same, optical film, and image display device - Google Patents

Abstract

The present invention is an aqueous solution that can be used as a primer that greatly improves the adhesion between the substrate and the cured coating film of the active energy ray-curable composition, even if it is a difficult-to-adhere substrate such as a polyester film. It is an object to provide a resin composition. In the present invention, an aqueous resin composition comprising a composite resin containing a vinyl ester resin and a urethane resin having an aromatic ring, an aqueous resin, and an aqueous medium, wherein the vinyl ester resin is a novolac epoxy resin and A reaction product of at least one epoxy resin selected from the group consisting of bisphenol-type epoxy resins and a compound having an acid group and a polymerizable unsaturated group, wherein the urethane resin is a polyol having an aromatic ring and a hydrophilic group An aqueous resin composition is used, which is a reaction product of a polyol containing a polyol having a polyisocyanate.

Description

  The present invention is an aqueous resin that can be used as a primer for improving the adhesion between a substrate and the cured coating when a cured coating of an active energy ray-curable composition is formed on one or both sides of the substrate. The present invention relates to a composition, a laminate using the composition, and an optical film.

  Aqueous resin compositions, in particular aqueous urethane resin compositions, generally have good adhesion to substrates and can form flexible coatings, so they can be used in various applications including coating agents and adhesives. in use. Among these, in recent years, application 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. In optical applications, a hard coat layer is formed by coating and curing an active energy ray-curable composition on the surface of a polyester film, or a layer in which an active energy ray-curable composition is cast is used. There are cases where the polyester film is provided as a prism sheet, but the polyester film has a problem of low adhesion due to the high crystallinity of the cured film of the active energy ray-curable composition.

  So far, as a method of improving the adhesion between the polyester film and the cured coating film of the active energy ray curable composition, 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 an acrylic resin (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.

  Therefore, there has been a demand for a material that can be used for the primer layer that has sufficient adhesion between the polyester film and the cured coating film of the active energy ray-curable composition.

JP 2010-215843 A

  The problem to be solved by 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 hard-to-adhere base material such as a polyester film. It is providing the water-based resin composition which can be used as, a laminated body using the same, an optical film, and an image display apparatus.

  As a result of diligent research to solve the above problems, the present inventors have found that a water-resistant resin composition containing a specific composite resin and a water-based resin is used as a primer to form a difficult-to-adhere base material such as a polyester film. However, it has been found that the adhesion between the substrate and the cured coating film of the active energy ray curable composition is greatly improved, and the present invention has been completed.

That is, the present invention is an aqueous resin containing a composite resin (A) containing a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring, an aqueous resin (B), and an aqueous medium (C). A composition, wherein the vinyl ester resin (a1) is at least one epoxy resin (a1-1) selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin, an acid group and a polymerizable unsaturated group It is a reaction product with the compound (a1-2) having a group,
The urethane resin (a2) is a reaction product of a polyol (a2-1) containing a polyol having an aromatic ring and a polyol having a hydrophilic group and a polyisocyanate (a2-2). The present invention relates to a resin composition, a laminate using the resin composition, an optical film, and an image display device.

  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.

  The aqueous resin composition of the present invention contains a composite resin (A) containing a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring, an aqueous resin (B), and an aqueous medium (C). To do.

  The composite resin (A) contains a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring.

  The vinyl ester resin (a1) is, for example, a compound having at least one epoxy resin (a1-1) selected from the group consisting of a novolak type epoxy resin and a bisphenol type epoxy resin, and an acid group and a polymerizable unsaturated group A reaction product with (a1-2) is included.

  Although the said epoxy resin (a1-1) contains 1 or more types chosen from the group which consists of a novolak-type epoxy resin and a bisphenol-type epoxy resin, specifically, the following 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. These epoxy resins (a1) can be used alone or in combination of two or more.

  Among the epoxy resins (a1-1), it is preferable to use a novolac type epoxy resin having a large number of epoxy groups capable of reacting with the acid group of the compound (a1-2).

  Moreover, the epoxy equivalent of the said epoxy resin (a1-1) is 150-2,000 g / eq. The range of 160 to 1,000 g / eq. The range of is more preferable.

  Furthermore, it is preferable to react 80-100 mol% in the total amount of the epoxy group which the said epoxy resin (a1-1) has with the acid group of the said compound (a1-2), and all the said epoxy groups are said compounds. It is more preferable to react with the acid group of (a1-2).

  The compound (a1-2) has an acid group and a polymerizable unsaturated group. Introducing a polymerizable unsaturated group into the vinyl ester resin (a1) by reacting the acid group of the compound (a1-2) with the epoxy group of the epoxy resin (a1-1); it can.

  Since the polymerizable unsaturated group of the compound (a1-2) does not participate in the reaction with the epoxy resin, as a result, the vinyl ester resin (a1) is converted into the compound (a1-2). It has a polymerizable unsaturated group derived from it. The polymerizable unsaturated group of the vinyl ester resin (a1) is covalently bonded by a polymerization reaction with the polymerizable unsaturated group of the resin or monomer contained in the active energy ray-curable composition described later. The adhesion with the primer layer formed and formed of the aqueous resin composition of the present invention becomes strong.

  Examples of the compound (a1-2) having an acid group and a polymerizable unsaturated group include acrylic acid, methacrylic acid, itaconic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2,2 2,2-trisacryloyloxymethylethylphthalic acid and the like. 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 (a1). Acrylic acid is preferred. These compounds (a1-2) can be used alone or in combination of two or more, but it is preferable to use 50% by mass or more of acrylic acid in the total amount of the compound (a1-2). .

  The reaction temperature of the epoxy resin (a1-1) and the compound (a1-2) is preferably in the range of 60 to 150 ° C, more preferably in the range of 80 to 120 ° C.

  Moreover, when the said epoxy resin (a1-1) and the said compound (a1-2) are made to react, in order to prevent the thermal polymerization of the polymerizable unsaturated group which the said compound (a1-2) has, superposition | polymerization prohibition is carried out. It is preferable to use an agent. 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 (a1-1) and the compound (a1-2).

  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 (a1-1) and the said compound (a1-2) 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 (a1-1).

  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 (a1) 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.
In the present specification, the weight average molecular weight and the number average molecular weight can be obtained as polystyrene converted values measured by gel permeation chromatography.

  The equivalent of the polymerizable unsaturated group contained in the vinyl ester resin (a1) is 250 to 2,000 g / eq. The range of is preferable.

  The urethane resin (a2) having an aromatic ring includes a reaction product of a polyol (a2-1) containing a polyol having an aromatic ring and a polyol having a hydrophilic group, and a polyisocyanate (a2-2).

  By using the polyol having the aromatic ring as a raw material of the urethane resin (a2), the urethane resin (a2) has an aromatic ring. The aromatic ring concentration in the polyol having an aromatic ring is preferably in the range of 1.5 to 8 mol / kg, more preferably in the range of 1.6 to 5 mol / kg. Furthermore, the ratio of the polyol having the aromatic ring contained in the polyol (a2-1) is preferably in the range of 40 to 98% by mass and more preferably in the range of 60 to 98% by mass because the adhesion to the substrate is further improved. A range is more preferred.

  Examples of the polyol having an aromatic ring include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, and bisphenol alkylene oxide adducts. Among these, an aromatic polyester polyol and an alkylene oxide adduct of bisphenol are preferable because of excellent substrate adhesion and blocking resistance. In addition, the alkylene oxide adduct of bisphenol A is preferably an alkylene oxide adduct of bisphenol A. In addition, the polyol which has these aromatic rings can be used individually, or can also use 2 or more types together.

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

  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.

  The content of the polyhydric alcohol having an aromatic ring is preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and still more preferably 10% by mass or less in the polyhydric alcohol. Especially preferably, it is 5 mass% or less, and a minimum is 0 mass%.

  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. Diacetate, dibutyltin dilaurate, tin octoate, 2-ethylhexanetin, acetylacetonate zinc, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium, etc. A metal compound etc. are mentioned.

  The alkylene oxide adduct of bisphenol A is obtained by adding alkylene oxide to the phenolic hydroxyl group of bisphenol A. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Moreover, the range of 1-8 is preferable and, as for the average addition mole number of the alkylene oxide with respect to 1 mol of bisphenol A, the range of 1-4 is more preferable.

  The weight average molecular weight of the polyol having an aromatic ring is preferably 500 to 10,000, more preferably 1,000 to 6,000.

  Examples of the polyol having a hydrophilic group include a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group. Among these, a polyol having an anionic group is preferable.

  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 polyol having a carboxyl group and the polyol having a sulfonic acid group are preferably used in the range where the acid value of the urethane resin (a2) is 2 to 70 mgKOH / g, and in the range of 10 to 50 mgKOH / g. More preferably it is used. In addition, the acid value as used in the field of this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a polyol which has the carboxyl group and sulfonic acid group which were used for manufacture of the said urethane resin (a2).

  In addition, it is preferable that part or all of the anionic group is neutralized with a basic compound or the like because good water dispersibility can be imparted to the urethane resin (a2).

  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.

  Moreover, as said polyol (a2-1), other polyol can be used as needed besides the above-mentioned polyol.

  Examples of the other polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 1,4-butanediol. , 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol and the like (for example, less than 500, preferably 400 The following polyols are mentioned. These other polyols can be used alone or in combination of two or more.

  Examples of the polyisocyanate (a2-2) that can react with the polyol (a2-1) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, and phenylene diisocyanate. Aromatic polyisocyanates such as tolylene diisocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. . These polyisocyanates (a2-2) can be used alone or in combination of two or more.

  Among the polyisocyanates (a2-2), it is preferable to include an aromatic polyisocyanate because adhesion to the substrate is further improved. In this case, the content of the aromatic polyisocyanate in the polyisocyanate (a2-2) is preferably in the range of 15 to 35% by mass.

  The urethane resin (a2) is, for example, mixed with the polyol (a2-1) and the polyisocyanate (a2-2) in the absence of a solvent or in the presence of an organic solvent, and at a temperature of 40 to 120 ° C., It can manufacture by making it react for 3 to 20 hours. Moreover, when manufacturing the said urethane resin (a2), you may use a chain extender as needed.

  Reaction of the said polyol (a2-1) and the said polyisocyanate (a2-2) is equivalent ratio of the hydroxyl group which the said polyol (a2-1) has, and the isocyanate group which the said polyisocyanate (a2-2) has [ Isocyanate group / hydroxyl group] is preferably 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 (a2) 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.

  The urethane resin (a2) obtained by the above method has a weight average molecular weight of 3,000 to 200,000 because adhesion between the substrate and the cured coating film of the active energy ray-curable composition is further improved. Is preferable, and the range of 3,000 to 100,000 is more preferable.

  The composite resin (A) includes the vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring, and the vinyl ester resin (a1) and the urethane resin (a2) are contained in an aqueous medium. It is preferable to be dispersed in At this time, it is preferable that a part or all of the vinyl ester resin (a1) forms resin particles inherent in the urethane resin (a2) particles in the aqueous medium. More specifically, it is preferable that the vinyl ester resin (a1) is a core-shell type resin particle in which a core part is formed and the urethane resin (a2) is a shell part.

  For the composite resin (A), the vinyl ester resin (a1) and the urethane resin (a2) are manufactured in advance, and then the vinyl resin (a1) and the urethane resin are added to the urethane resin (a2). It can manufacture by mixing the basic compound and the aqueous medium which neutralize the anionic group which (a2) has.

  Since the mass ratio [(a1) / (a2)] of the vinyl ester resin (a1) and the urethane resin (a2) improves the adhesion with the cured coating film of the active energy ray-curable composition. The range of 60/40 to 10/90 is preferable, and the range of 55/45 to 20/80 is more preferable.

  The content of the composite resin (A) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90% by mass in the nonvolatile content of the aqueous resin composition. It is above, Preferably it is 99.9 mass% or less.

  As said aqueous resin (B), a urethane resin (b1), a polyester resin, an acrylic resin etc. are mentioned, for example. Among these, the urethane resin (b1) is preferable because a coating film having excellent adhesion to a hardly-adherent substrate can be formed. Moreover, these water-based resins can be used alone or in combination of two or more.

  As said urethane resin (b1), the thing similar to above-described urethane resin (a2) can be used.

  The mass ratio [(A) / (B)] of the composite resin (A) and the aqueous resin (B) is 99/1 from the viewpoint of blending stability and adhesion to the hard coat agent described below. A range of ˜80 / 20 is preferred.

  Examples of the aqueous medium (C) 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 organic solvents miscible with water 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 can be obtained by dispersing the composite resin (A) and the aqueous resin (B) in the aqueous medium (C).

  Further, the aqueous resin composition of the present invention can further contain a water-insoluble additive.

  The water-insoluble additive is preferably used by being previously dispersed in the aqueous dispersion of the aqueous resin (B).

  Examples of the water-insoluble additive include an antioxidant and an ultraviolet absorber. These water-insoluble additives can be used alone or in combination of two or more.

  Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants. Among these, a phenolic antioxidant is capable of forming a coating film having excellent adhesion to a difficult-to-adhere substrate, and can form a coating film excellent in heat resistance, heat discoloration, and auto-oxidation suppression. Phosphorous antioxidants are preferred. These antioxidants can be used alone or in combination of two or more.

  If the molecular weight is too small, the antioxidant tends to migrate to the coating surface and the adhesion to the substrate is lowered. On the other hand, if the molecular weight is too large, the compatibility with the aqueous resin (B) is deteriorated. To a weight average molecular weight of 500 to 1,000 is preferable.

  Moreover, since the said antioxidant is easy to block the coating-film surface when melting | fusing point is low, on the other hand, since compatibility with the said aqueous resin (B) will worsen when melting | fusing point is high, melting | fusing point is 80-180 degreeC. Are preferred.

  The content of the additive is preferably 0.001 parts by mass or more, 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, preferably 100 parts by mass of the composite resin (A). Is 1 part by mass or less, more preferably 0.5 part by mass or less, and still more preferably 0.3 part by mass or less.

  In the aqueous resin composition of the present invention, if necessary, in addition to the water-insoluble additive, a film-forming aid, a curing agent, a crosslinking agent, a plasticizer, an antistatic agent, a wax, a light stabilizer, Additives such as flow modifiers, dyes, leveling agents, rheology control agents, photocatalytic compounds, inorganic pigments, organic pigments, extender pigments and the like can be blended.

  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 on one or both sides of a substrate, and a cured coating formed using an active energy ray-curable composition on the surface of the primer layer. It has a film.

  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 base material among the above plastic base materials. 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 polyester polyol (1))
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 performed at 230 ° C. for 24 hours until the acid value became 1 or less at 180 to 230 ° C., and polyester polyol (1) [acid value 0.6, Hydroxyl value 50.0, aromatic ring concentration 4.41 mol / Kg].

(Synthesis Example 2: Synthesis of polyester polyol (2))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, nitrogen gas inlet tube, and stirrer, 35.4 parts by mass of isophthalic acid, 17.8 parts by mass of sebacic acid, 7.8 parts by mass of adipic acid, ethylene glycol 6 2 parts by mass, 22.9 parts by mass of neopentyl glycol, 11.7 parts by mass of 1,6-hexanediol and 0.03 parts by mass of dibutyltin oxide were added until the acid value became 1 or less at 180 to 230 ° C. A polycondensation reaction was carried out at 24 ° C. for 24 hours to obtain a polyester polyol (2) [acid value 0.6, hydroxyl value 42.5, aromatic ring concentration 2.51 mol / Kg].

(Synthesis Example 3: Synthesis of vinyl ester resin (I))
46.7 parts by mass of cresol novolac type epoxy resin (“EPICLON N-673-80M” manufactured by DIC Corporation, solid content epoxy equivalent = 209 g / eq, non-volatile content = 80% by mass, solvent: methyl ethyl ketone) in a reaction vessel, acrylic 13.3 parts by mass of acid, 0.08 parts by mass of methoquinone, and 13.3 parts by mass of methyl ethyl ketone were charged and stirred to be mixed uniformly. Next, 0.37 parts by mass of triphenylphosphine was added and reacted at a reaction temperature of 80 ° C. until the acid value became 1.5 or less to obtain a vinyl ester resin (I).

(Synthesis Example 4: Synthesis of Urethane Resin (II-1))
In a reaction vessel, 75.7 parts by mass of the polyester polyol (1) of Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 67.89 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 20.3 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 became 0.1% or less, add 0.3 parts by mass of n-butanol, and further react for 2 hours. A urethane resin (II-1) having a ring was obtained.

(Synthesis Example 5: Synthesis of urethane resin (II-2))
In a reaction vessel, 69 parts by mass of the polyester polyol (2) of Synthesis Example 2 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 93.3 parts by mass of methyl ethyl ketone was added, stirred and mixed uniformly. Next, 3.0 parts by mass of 1,4-butanediol and 6.1 parts by mass of 2,2-dimethylolpropionic acid were added, and then 19.4 parts by mass of tolylene diisocyanate was added and the mixture was heated at 80 ° C. for 12 hours. The urethanization process was implemented by making it react. After confirming that the isocyanate value was 0.1% or less, add 0.3 parts by mass of n-butanol, and further react for 2 hours, then cooled to 50 ° C., and an aromatic ring having a nonvolatile content of 51% by mass Urethane resin (II-2) having

(Synthesis Example 6: Synthesis of urethane resin (II-3))
To the reaction vessel, 76.1 parts by mass of polytetramethylene ether glycol (average molecular weight 2000) and 43.1 parts by mass of methyl ethyl ketone were added, and stirred and mixed uniformly. Next, 6.0 parts by mass of 2,2-dimethylolpropionic acid was added, and then 18.7 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, add 0.3 parts by mass of n-butanol, and further react for 2 hours, then cooled to 50 ° C., and urethane having a nonvolatile content of 70% by mass Resin (II-3) was obtained.

(Production Example 1: Preparation of composite resin composition (A-1))
To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 136.1 parts by mass of the vinyl ester resin (I) obtained in Synthesis Example 3 and 5.5 parts by mass of triethylamine are added, and ion exchange is performed. 938.5 parts by mass of water was slowly added to effect water solubilization. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain a composite resin composition (A-1) having a nonvolatile content of 40% by mass.

(Production Example 2: Preparation of aqueous resin (B-1) aqueous dispersion)
1.28 parts by mass of a phenolic antioxidant (1) (molecular weight: 640, melting point: 160 ° C.) and a phosphorus-based antioxidant to the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4 1.28 parts by mass of the mixture was added and stirred and mixed uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 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 prepare an aqueous dispersion of aqueous resin (B-1) having a nonvolatile content of 23% by mass.

(Production Example 3: Preparation of aqueous resin (B-2) aqueous dispersion)
To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 2.56 parts by mass of the phenol-based antioxidant (1) and 2.56 parts by mass of the phosphorus-based antioxidant are added and stirred. Mix evenly. Next, 4.8 parts by mass of triethylamine was added, and 548 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 prepare an aqueous dispersion of an aqueous resin (B-2) having a nonvolatile content of 23.5% by mass.

(Production Example 4: Preparation of aqueous resin (B-3) aqueous dispersion)
1.22 parts by mass of a phenolic antioxidant and 1.22 parts by mass of a phosphorus antioxidant are added to the urethane resin (II-2) having an aromatic ring obtained in Synthesis Example 5, and the mixture is stirred and mixed uniformly. did. Next, 4.6 parts by mass of triethylamine was added, and 390 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 prepare an aqueous resin (B-3) aqueous dispersion having a nonvolatile content of 22.9% by mass.

(Production Example 5: Preparation of aqueous resin (B-4) aqueous dispersion)
To the urethane resin (II-3) obtained in Synthesis Example 6, 1.26 parts by mass of a phenol-based antioxidant and 1.26 parts by mass of a phosphorus-based antioxidant were added and stirred and mixed uniformly. Next, 4.8 parts by mass of triethylamine was added, and 410 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Next, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to prepare an aqueous dispersion of an aqueous resin (B-4) having a nonvolatile content of 23.3 mass%.

(Production Example 6: Preparation of aqueous resin (B-5) aqueous dispersion)
To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 1.28 parts by mass of a phenolic oxidant and 1.28 parts by mass of an ultraviolet absorber were added, and the mixture was stirred and mixed uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 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 prepare an aqueous resin (B-5) aqueous dispersion having a nonvolatile content of 23% by mass.

(Production Example 7: Preparation of aqueous resin (B-6) aqueous dispersion)
To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 2.56 parts by mass of a phenol-based oxidizing agent was added and stirred to mix uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-6) aqueous dispersion having a nonvolatile content of 23% by mass.

(Production Example 8: Preparation of aqueous resin (B-7) aqueous dispersion)
To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 2.56 parts by mass of a phosphorus-based oxidizing agent was added, and stirred and mixed uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 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 prepare an aqueous dispersion of an aqueous resin (B-7) having a nonvolatile content of 23% by mass.

(Production Example 9: Preparation of aqueous resin (B-8) aqueous dispersion)
To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 2.56 parts by mass of an ultraviolet absorber was added and stirred and mixed uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 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 prepare an aqueous resin (B-8) aqueous dispersion having a nonvolatile content of 23% by mass.

(Production Example 10: Preparation of aqueous resin (B-9) aqueous dispersion)
To the urethane resin (II-1) obtained in Synthesis Example 4, 2.56 parts by mass of the phenol-based antioxidant (2) (molecular weight: 1180, melting point: 120 ° C.) was added and stirred to mix uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous dispersion of an aqueous resin (B-9) having a nonvolatile content of 23% by mass.

(Production Example 11: Preparation of aqueous resin (B-10) aqueous dispersion)
To the urethane resin (II-1) obtained in Synthesis Example 4, 2.56 parts by mass of the phenol-based antioxidant (3) (molecular weight: 350, melting point: 120 ° C.) was added and stirred to mix uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 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 prepare an aqueous resin (B-10) aqueous dispersion having a nonvolatile content of 23% by mass.

(Production Example 12: Preparation of aqueous resin (B-11) aqueous dispersion)
To the urethane resin (II-1) obtained in Synthesis Example 4, 2.56 parts by mass of a phenolic antioxidant (4) (molecular weight: 780, melting point: 240 ° C.) was added, and the mixture was stirred and mixed uniformly. Next, 4.8 parts by mass of triethylamine was added, and 510 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 prepare an aqueous dispersion of an aqueous resin (B-11) having a nonvolatile content of 23% by mass.

(Production Example 13: Preparation of water-based resin (B-12) aqueous dispersion)
To the urethane resin (II-1) obtained in Synthesis Example 4, 2.56 parts by mass of a phenolic antioxidant (5) (molecular weight: 530, melting point: 50 ° C.) was added and stirred to mix uniformly. Next, 4.8 parts by mass of triethylamine was added, and 410 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Next, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to prepare an aqueous resin (B-12) aqueous dispersion having a nonvolatile content of 23% by mass.

(Production Example 14: Preparation of aqueous resin (B-13) aqueous dispersion)
To urethane resin (II-1) obtained in Synthesis Example 4, 4.8 parts by mass of triethylamine was added, and 405 parts by mass of ion-exchanged water was slowly added to effect water solubilization. Next, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to prepare an aqueous resin (B-13) aqueous dispersion having a nonvolatile content of 23% by mass.

  Table 1 shows the urethane resins, antioxidants, and ultraviolet absorbers used in Production Examples 2-14.

(Example 1: Preparation of aqueous resin composition (1))
100 parts by mass of the composite resin composition (A-1) obtained in Production Example 1, 2 parts by mass of the aqueous dispersion (B-1) obtained in Production Example 2, and 302.6 parts by mass of ion-exchanged water, Was mixed to obtain an aqueous resin composition (1) having a nonvolatile content of 10% by mass.

(Examples 2 to 15: Preparation of aqueous resin compositions (2) to (15))
A water-based resin composition was carried out in the same manner as in Example 1 except that the water-based resin (B-1) aqueous dispersion used in Example 1 was replaced by the water-based resin aqueous dispersion obtained in Production Examples 3 to 13. Products (2) to (15) were obtained.

  Table 2 shows the composite resins and aqueous resins used in Examples 1-15.

(Preparation Example 1: Preparation of photocurable resin composition (UV-1))
Photocuring by mixing 70 parts by mass of UNIDIC V-5500 (manufactured by DIC Corporation, epoxy acrylate resin), 30 parts by mass of tripropylene glycol diacrylate, and 3 parts by mass of Irgacure 184 (manufactured by BASF, photopolymerization initiator) Resin composition (UV-1) was obtained.

(Example 15: Production of laminate (1))
The aqueous resin composition obtained in Example 1 so that the film thickness after drying is about 1 μm on the surface of a film substrate (thickness: 125 μm) made of polyethylene terephthalate (hereinafter abbreviated as “PET”). (1) was applied and heated at 150 ° C. for 5 minutes to form a primer layer (P-1) on the surface of the substrate.

Next, the photocurable resin composition (UV-1) obtained in Preparation Example 1 was applied to the surface of the primer layer with a coating thickness of 15 μm, and the irradiation intensity was 0.5 J / cm using a high-pressure mercury lamp as a light source. By irradiating with ultraviolet rays at ² , the surface of the substrate has a primer layer, and a cured coating film of an ultraviolet curable composition (hereinafter abbreviated as “UV coating film”) is formed on the surface of the primer layer. A laminate (1) having was obtained.

(Examples 16 to 30: Production of laminates (2) to (15))
In place of the aqueous resin composition (1) used in Example 15, the primer layers (P-2) to (P) using the aqueous resin compositions (2) to (15) obtained in Examples 2 to 15 were used. Except that it was set to -15), it carried out similarly to Example 13 and obtained laminated body (2)-(12).

  Using the aqueous resin compositions and laminates obtained in the above Examples and Comparative Examples, the following adhesion was evaluated.

[Evaluation method of adhesion (initial) between substrate and primer layer]
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. Subsequently, a 1 mm grid peel test was performed using the test plate. Specifically, 100 grids were created at 1 mm intervals on the surface of the primer layer of the test plate, and a 24 mm wide adhesive tape made by Nichiban Co., Ltd. was applied thereon.

  Next, the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the primer layer, and evaluation was performed based on the number of cells remaining on the surface of the primer layer when the pressure-sensitive adhesive tape was peeled off from the surface of the primer layer.

[Evaluation method of adhesion (initial) between primer layer and UV coating]
A 1 mm cross-cut peel test was performed using the laminates obtained in the examples and comparative examples. On the surface of the UV coating film constituting the laminate obtained in Examples and Comparative Examples, 100 grids were created at 1 mm intervals, and a 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed thereon.

  Next, the adhesive tape was pulled in a direction perpendicular to the UV coating film, and evaluation was performed based on the number of cells remaining on the surface of the UV coating film when the adhesive tape was peeled off from the surface of the UV coating film. did.

[Evaluation method of adhesion between substrate and primer layer (after UV irradiation cycle test)]
The obtained laminate was irradiated with ultraviolet rays a predetermined number of times at an irradiation intensity of 0.5 J / cm ² using a high-pressure mercury lamp as a light source, and then the laminate was taken out, and the adhesion between the base material and the primer layer was determined as [ Evaluation was made in the same manner as in [Adhesion between substrate and primer layer (initial)]. In addition, the UV irradiation cycle test referred to in the present invention is a method for evaluating adhesiveness under more severe conditions by intentionally degrading the coating film by applying UV irradiation to the primer layer a predetermined number of times in advance, This is used to evaluate the adhesion between the substrate and the primer layer and the adhesion between the primer layer and the UV coating film.

[Evaluation method of adhesion between primer layer and UV coating (after UV irradiation cycle test)]
The obtained laminate is irradiated with ultraviolet rays a predetermined number of times at an irradiation intensity of 0.5 J / cm ² using a high-pressure mercury lamp as a light source, and then the photocurable resin composition obtained in Preparation Example 1 is formed on the surface of the primer layer. An object (UV-1) is applied with a coating thickness of 15 μm, and a high pressure mercury lamp is used as a light source to irradiate ultraviolet rays again with an irradiation intensity of 0.5 J / cm ² , thereby having a primer layer on the surface of the substrate. Then, a laminate having a UV coating film on the surface of the primer layer was obtained.
Next, the laminate was taken out, and the adhesion between the primer layer and the UV coating film was evaluated in the same manner as [Adhesion between the primer layer and UV coating film (initial)].

[Method for evaluating film appearance (measurement of haze value)]
The haze value of the laminate obtained above was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.). It measured by the method based on the JIS test method (JIS K7136: 2000). The haze value (H) was calculated from the following formula. Further, the haze value of only the PET substrate was also measured, and the haze value was 2.05%.
H (%) = Td / Tt × 100
H: Haze (cloudiness value) (%)
Td: diffuse transmissivity (%)
Tt: Total light transmittance (%)

  Table 3 shows the base materials and primers used in the laminates (1) to (15) obtained in Examples 16 to 30, and the evaluation results.

(Comparative Example 1: Preparation of aqueous resin composition (C1))
By mixing 100 parts by mass of the composite resin composition (A-1) obtained in Production Example 1 and 300 parts by mass of ion-exchanged water, an aqueous resin composition (C1) having a nonvolatile content of 10% by mass was obtained.

(Comparative Example 2: Preparation of aqueous resin composition (C2))
An aqueous resin composition (C2) having a nonvolatile content of 10% by mass was obtained by mixing 100 parts by mass of the aqueous dispersion (B-1) obtained in Production Example 2 and 130 parts by mass of ion-exchanged water.

(Comparative Example 3: Preparation of aqueous resin composition (C3))
An aqueous resin composition (C3) having a nonvolatile content of 10% by mass was obtained by mixing 100 parts by mass of the aqueous dispersion (B-3) obtained in Production Example 4 and 130 parts by mass of ion-exchanged water.

(Comparative Example 4: Creation of laminate (R1))
The aqueous resin composition (C1) obtained in Comparative 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, and the temperature was 150 ° C. for 5 minutes. By heating, a primer layer (P′-1) was formed on the surface of the substrate.

Next, the photocurable resin composition (UV-1) obtained in Preparation Example 1 was applied to the surface of the primer layer with a coating thickness of 15 μm, and the irradiation intensity was 0.5 J / cm using a high-pressure mercury lamp as a light source. By irradiating with ultraviolet rays at ² , a laminate (R1) having a primer layer on the surface of the substrate and a UV coating on the surface of the primer layer was obtained.

(Comparative Examples 2-3: Production of laminates (R2)-(R3))
In place of the aqueous resin composition (C1) used in Comparative Example 1, the primer layers (P′-2) to (P) using the aqueous resin compositions (C2) to (C3) obtained in Comparative Examples 2-3. Except having set to P'-3), it carried out similarly to the comparative example 1, and obtained the laminated body (R2)-(R3).

  Table 4 shows the base materials and primers used in the laminates (R1) to (R3) obtained in Comparative Examples 1 to 3, and the evaluation results.

  Examples 15 to 28 shown in Table 3 are examples using the aqueous resin composition of the present invention. From the evaluation results of Examples 15 to 28, the primer layer formed using the aqueous resin composition of the present invention has excellent adhesion to the substrate and also excellent adhesion to the UV coating film. It could be confirmed.

  On the other hand, Comparative Example 2 is an example using the aqueous resin composition containing the composite resin obtained in Comparative Example 1, and is an example not using the aqueous resin (B) of the present invention. The primer layer formed using the aqueous resin composition of Comparative Example 1 has an adhesion property between the base material and the primer layer before the UV irradiation cycle test (initial), and an adhesion property between the primer layer and the UV coating film. However, the adhesion after the UV irradiation cycle test was confirmed to be extremely insufficient.

  Comparative Example 3 is an example using the aqueous resin (B-1) obtained in Production Example 2, and is an example in which the composite resin (A) of the present invention is not used. The primer layer of Comparative Example 3 is excellent in adhesion between the base material and the primer layer before the UV irradiation cycle test (initial stage) and between the base material and the primer layer after the UV irradiation cycle test. It was confirmed that the adhesion between the layer and the UV coating was extremely insufficient.

  Comparative Example 4 is an example using the aqueous resin (B-3) obtained in Production Example 4, and is an example not using the composite resin (A) of the present invention. As in Comparative Example 3, the primer layer of Comparative Example 4 was adhered to the substrate before the UV irradiation cycle test (initial) and the primer layer, and the adhesion between the substrate and the primer layer after the UV irradiation cycle test. It was confirmed that the adhesion between the primer layer and the UV coating film was extremely insufficient.

(Examples 2 to 15: Preparation of aqueous resin compositions (2) to (15))
A water-based resin composition was carried out in the same manner as in Example 1 except that the water-based resin (B-1) aqueous dispersion used in Example 1 was replaced by the water-based resin aqueous dispersion obtained in Production Examples 3 to 13. Products (2) to (15) were obtained. However, Example 4 is a reference example.

Claims (12)

An aqueous resin composition containing a composite resin (A) containing a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring, an aqueous resin (B), and an aqueous medium (C),
The vinyl ester resin (a1) is one or more epoxy resins (a1-1) selected from the group consisting of novolak-type epoxy resins and bisphenol-type epoxy resins, and compounds having an acid group and a polymerizable unsaturated group (a1) -2), and
The urethane resin (a2) is a reaction product of a polyol (a2-1) containing a polyol having an aromatic ring and a polyol having a hydrophilic group and a polyisocyanate (a2-2). Resin composition.   The aqueous resin composition according to claim 1, wherein the aqueous resin (B) is a urethane resin (b1).   Furthermore, the water-based resin composition of Claim 1 or 2 containing a water-insoluble additive.   The aqueous resin composition according to claim 3, wherein the water-insoluble additive is at least one additive selected from the group consisting of an antioxidant and an ultraviolet absorber.   The aqueous resin composition according to claim 4, wherein the antioxidant is at least one antioxidant selected from the group consisting of phenolic antioxidants and phosphorus antioxidants.   The mass ratio [(A) / (B)] of the composite resin (A) and the aqueous resin (B) is in a range of 99/1 to 80/20, according to any one of claims 1 to 5. An aqueous resin composition.   The water-based resin composition according to any one of claims 1 to 6, wherein the antioxidant has a weight average molecular weight in the range of 500 to 1,000.   The aqueous resin composition according to any one of claims 1 to 7, wherein a melting point of the antioxidant is in a range of 80 to 180 ° C.   It has the primer layer formed using the aqueous resin composition of any one of Claims 1-8 in the single side | surface or both surfaces of a base material, The active energy ray curable composition is on the surface of the said primer layer. The laminated body characterized by having the cured coating film of this.   The laminate according to claim 9, 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 optical film comprising the laminate according to claim 9.   An image display device comprising the optical film according to claim 11.