KR102209385B1 - Water-based resin composition, laminate using same, optical film, and image display device - Google Patents

Abstract

The present invention provides a water-based resin composition that can be used as a primer that significantly improves the adhesion between the substrate and the cured coating film of the active energy ray-curable composition, even if it is a substrate of poorly adhesive such as a polyester film. Make it a task. In the present invention, as a composite resin containing a vinyl ester resin and a urethane resin having an aromatic ring, an aqueous resin, and an aqueous medium, the vinyl ester resin is a novolak type epoxy resin and a bisphenol type epoxy. A reaction product of at least one epoxy resin selected from the group consisting of resins and a compound having an acid group and a polymerizable unsaturated group, wherein the urethane resin is a polyol containing a polyol having an aromatic ring and a polyol having a hydrophilic group, and a polyisocyanate An aqueous resin composition characterized in that it is a reactant with is used.

Description

Water-based resin composition, laminate using same, optical film, and image display device

The present invention is a water-based resin composition that can be used as a primer to improve adhesion between the substrate and the cured coating film when forming a cured coating film of an active energy ray-curable composition on one or both sides of a substrate, and a laminate using the same And to an optical film.

Aqueous resin compositions, particularly aqueous urethane resin compositions, generally have good adhesion to a substrate and can form a flexible coating film, and are therefore used for various applications including coating agents and adhesives. Among them, in recent years, application to a film or sheet for optical applications has been studied. As said optical use, a liquid crystal display, a touch panel, etc. are specifically mentioned. A display device such as a liquid crystal display is usually formed by stacking a plurality of optical films having various functions in order to display a clear image, and examples of such optical films include an antireflection film, a retardation film, and a prism lens sheet. I can.

As a base material for these optical films, polyester films, especially polyethylene terephthalate (PET) films, are used because they are excellent in optical properties, mechanical strength, and durability. In addition, in optical applications, a hard coating layer is formed by coating and curing an active energy ray-curable composition on the surface of a polyester film, or a layer molded with an active energy ray-curable composition is provided. Although the ester film may be used as a prism sheet, the polyester film has a problem in that the adhesion of the active energy ray-curable composition to the cured coating film is low due to high crystallinity.

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

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

Japanese Unexamined Patent Publication No. 2010-215843

The problem to be solved by the present invention is a water-based resin composition that can be used as a primer that significantly improves adhesion between the substrate and the cured coating film of the active energy ray-curable composition, even if it is a substrate with poor adhesion such as a polyester film, It is to provide a laminate, an optical film and an image display device using the same.

As a result of intensive research in order to solve the above problems, the present inventors have used a water-based resin composition containing a specific composite resin and a water-based resin as a primer, so that even if it is a non-adhesive substrate such as a polyester film, the substrate and active energy It found that the adhesiveness of the pre-cured composition with the cured coating film was significantly improved, and the present invention was completed.

That is, the present invention is an aqueous resin composition comprising 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 a compound (a1-2) having at least one epoxy resin (a1-1) selected from the group consisting of a novolac-type epoxy resin and a bisphenol-type epoxy resin, and an acid group and a polymerizable unsaturated group. ) And is a reactant,

An aqueous resin composition characterized in that the urethane resin (a2) is a reaction product of a polyol having an aromatic ring and a polyol containing a polyol having a hydrophilic group (a2-1) and a polyisocyanate (a2-2), and a laminate using the same It relates to a sieve, an optical film, and an image display device.

The aqueous resin composition of the present invention can be used as a primer that significantly improves adhesion between the substrate and the cured coating film of the active energy ray-curable composition, even if it is a non-adhesive substrate such as a polyester film. It is suitable for a laminate in which a cured coating film of an active energy ray-curable composition is formed on its surface. As such a laminate, optical films, such as an antireflection film, a retardation film, and a prism lens sheet, are mentioned, for example. In addition, these optical films are applicable to image display devices including 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).

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, one or more epoxy resins (a1-1) selected from the group consisting of novolac-type epoxy resins and bisphenol-type epoxy resins, and a compound having an acid group and a polymerizable unsaturated group ( a1-2) and reactants.

The epoxy resin (a1-1) contains one or more selected from the group consisting of novolac-type epoxy resins and bisphenol-type epoxy resins, but specifically, the following can be used.

Examples of the novolac-type epoxy resin include cresol novolak-type epoxy resins and phenol novolac-type epoxy resins. Further, 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, tetrabromo bisphenol A type epoxy resin, and the like. . These epoxy resins (a1) may be used alone or in combination of two or more.

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

In addition, the epoxy equivalent of the epoxy resin (a1-1) is preferably in the range of 150 to 2,000 g/eq., and more preferably in the range of 160 to 1,000 g/eq.

Further, it is preferable to react 80 to 100 mol% of the total amount of the epoxy groups contained in the epoxy resin (a1-1) with the acid groups of the compound (a1-2), and all of the epoxy groups are reacted with the compound ( 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. A polymerizable unsaturated group can be introduced into the vinyl ester resin (a1) by reacting the acid group in the compound (a1-2) with the epoxy group in the epoxy resin (a1-1).

Since the polymerizable unsaturated group of the compound (a1-2) is not involved in the reaction in the reaction with the epoxy resin, as a result, the vinyl ester resin (a1) is the compound (a1-2) It has a derived polymerizable unsaturated group. The polymerizable unsaturated group of this vinyl ester resin (a1) is polymerized with the polymerizable unsaturated group of the resin or monomer contained in the active energy ray-curable composition described later, thereby forming a covalent bond, and consisting of the aqueous resin composition of the present invention. The adhesion with the primer layer becomes strong.

As the compound (a1-2) having an acid group and a polymerizable unsaturated group, for example, acrylic acid, methacrylic acid, itaconic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2,2,2,-trisacryloyloxymethylethylphthalic acid, and the like. Among these compounds, acrylic acid capable of introducing into the vinyl ester resin (a1) a polymerizable unsaturated group possessed by a resin or monomer in an active energy ray-curable composition to be described later and an acryloyl group that is easy to undergo polymerization reaction is preferable. In addition, although these compounds (a1-2) may be used alone or in combination of two or more, 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 between the epoxy resin (a1-1) and the compound (a1-2) is preferably in the range of 60 to 150°C, and more preferably in the range of 80 to 120°C.

In addition, when reacting the epoxy resin (a1-1) and the compound (a1-2), a polymerization inhibitor is used to prevent thermal polymerization of the polymerizable unsaturated group of the compound (a1-2). It is desirable. 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).

As the polymerization inhibitor, for example, 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. These polymerization inhibitors may be used alone or in combination of two or more.

Further, when reacting the epoxy resin (a1-1) with the compound (a1-2), a reaction catalyst may 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 an amine catalyst, an imidazole catalyst, a phosphorus catalyst, a boron catalyst, and a phosphorus-boron catalyst. Specifically, alkyl substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, and diphenylguanidine; 3-substituted phenyl such as 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 3-phenyl-1,1-dimethyl urea, and 3-(4-chlorophenyl)-1,1-dimethyl urea -1,1-dimethyl urea; Imidazolines such as 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, and 2-heptadecylimidazoline; Monoaminopyridine such as 2-aminopyridine; Amine imides such as N,N-dimethyl-N-(2-hydroxy-3-aryloxypropyl)amine-N'-lactoimide; Ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine -Organic phosphorus catalysts such as triphenylborane complex and tetraphenylphosphonium tetraphenylborate; Diazabicycloundecene catalysts, such as 1,8-diazabicyclo[5.4.0]undecene-7,1,4-diazabicyclo[2.2.2]octane, etc. are mentioned. These reaction catalysts may be used alone or in combination of two or more.

As the weight average molecular weight of the vinyl ester resin (a1) obtained by the above method, since dispersion stability of the resin particles is improved, the range of 500 to 10,000 is preferable, and the range of 1,000 to 6,000 is more preferable.

In this specification, the weight average molecular weight and the number average molecular weight can be obtained as polystyrene conversion values measured by a gel permeation chromatography method.

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

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

By using the polyol having an aromatic ring as a raw material for the urethane resin (a2), the urethane resin (a2) has an aromatic ring. In addition, the aromatic ring concentration in the polyol having an aromatic ring is preferably in the range of 1.5 to 8 mol/kg, and more preferably in the range of 1.6 to 5 mol/kg. In addition, since the proportion of the polyol having the aromatic ring contained in the polyol (a2-1) further improves the adhesion to the substrate, the range of 40 to 98 mass% is preferable, and the range of 60 to 98 mass% is more desirable.

As the polyol having an aromatic ring, an aromatic polyester polyol, an aromatic polycarbonate polyol, an aromatic polyether polyol, an alkylene oxide adduct of bisphenol, etc. are mentioned, for example. Among these, an aromatic polyester polyol and an alkylene oxide adduct of bisphenol are preferable because they are excellent in adhesion to a base material and blocking resistance. In addition, in the alkylene oxide adduct of bisphenol, the alkylene oxide adduct of bisphenol A is preferable. In addition, polyols having these aromatic rings may be used alone or in combination of two or more.

The aromatic polyester polyol is a reaction product obtained by esterifying a polyhydric carboxylic acid and a polyhydric alcohol, but among the polyhydric carboxylic acids and polyhydric alcohols, at least one having an aromatic ring is used.

Among the polyhydric carboxylic acids, examples of what has an aromatic ring include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, or esterified products thereof. In addition, as those having no aromatic ring, for example, succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2 Aliphatic dicarboxylic acids such as ,4-butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, and fumaric acid, or esterified products thereof. These polyhydric carboxylic acids or esterified products thereof may be used alone or in combination of two or more.

Among the polyhydric alcohols, aromatic diols such as benzene dimethanol, toluene dimethanol, and xylene dimethanol are exemplified as those having an aromatic ring. In addition, as a thing which does not have an aromatic ring, for example, ethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol And aliphatic polyols such as triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol ethylene glycol. These polyhydric alcohols may be used alone or in combination of two or more.

The content rate 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 in the polyhydric alcohol. Hereinafter, it is particularly preferably 5% by mass or less, and the lower limit is 0% by mass.

In the esterification reaction when producing the aromatic polyester polyol, it is preferable to use an esterification catalyst for the purpose of accelerating 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 oxyacetylacetonato, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, tin octanoate, 2-ethylhexane tin, acetylacetonatozinc And metal compounds such as zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium.

The alkylene oxide adduct of bisphenol A is obtained by adding an alkylene oxide to the phenolic hydroxyl group of bisphenol A. As said alkylene oxide, ethylene oxide, propylene oxide, etc. are mentioned. In addition, the average number of added moles of alkylene oxide to 1 mole of bisphenol A is preferably in the range of 1 to 8, and more preferably in the range of 1 to 4.

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, and 2,2-dimethylolvaleric acid. Among these, 2,2-dimethylolpropionic acid is preferable. Further, a polyester polyol having a carboxyl group obtained by reacting the polyol having a carboxyl group with a polyhydric carboxylic acid 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, and ethylene glycol, And 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 or the polyol having a sulfonic acid group is preferably used in a range in which the urethane resin (a2) has an acid value of 2 to 70 mgKOH/g, and 10 to 50 mgKOH/g. It is more preferable to use it. In addition, the acid value referred to in the present invention is a theoretical value calculated based on the amount of acid group-containing compound such as a polyol having a carboxyl group or a sulfonic acid group used in the production of the urethane resin (a2).

In addition, it is preferable that the anionic groups are partially or all of them neutralized with a basic compound or the like, since 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; And 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 preferably in the range of 0.5 to 3 in terms of the molar ratio of the basic compound and the anionic group [basic compound/anionic group], The range of 0.7 to 1.5 is more preferable.

Further, as the polyol (a2-1), in addition to the polyol described above, other polyols may be used as necessary.

Examples of the above other polyols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4 -Relatively low molecular weight such as butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, etc. Less, preferably 400 or less) of polyols. These other polyols may be used alone or in combination of two or more.

Examples of the polyisocyanate (a2-2) capable of reacting with the polyol (a2-1) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carboximide modified Aromatic polyisocyanates such as diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; Cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. are mentioned. These polyisocyanates (a2-2) may be used alone or in combination of two or more.

Among the polyisocyanates (a2-2), since the adhesion to the substrate is further improved, it is preferable to contain an aromatic polyisocyanate. The content of the aromatic polyisocyanate in the polyisocyanate (a2-2) at this time 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 no solvent or in the presence of an organic solvent, and at a temperature of 40 to 120°C, 3 It can be produced by reacting for -20 hours. Further, in the production of the urethane resin (a2), a chain stretching agent may be used if necessary.

The reaction between the polyol (a2-1) and the polyisocyanate (a2-2) is an equivalent ratio of the hydroxyl group of the polyol (a2-1) and the isocyanate group of the polyisocyanate (a2-2) [isocyanate group/ Hydroxy group] is preferably performed in the range of 0.5 to 3.5, and more preferably performed in the range of 0.9 to 2.5.

Examples of the organic solvent that can be used when producing the urethane resin (a2) include ketone solvents such as acetone and methyl ethyl ketone; Ether solvents such as tetrahydrofuran and dioxane; Acetate ester solvents such as ethyl acetate and butyl acetate; Nitrile solvents such as acetonitrile; And amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

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

The composite resin (A) contains 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 dispersed in an aqueous medium. It is desirable to do it. At this time, in the aqueous medium, it is preferable that a part or all of the vinyl ester resin (a1) forms resin particles contained in the urethane resin (a2) particles. More specifically, it is preferable that the vinyl ester resin (a1) forms a core portion, and the urethane resin (a2) is a core-shell type resin particle having a shell portion.

The composite resin (A) is prepared by preparing the vinyl ester resin (a1) and the urethane resin (a2) in advance, and then, to the urethane resin (a2), the vinyl ester resin (a1), and the urethane It can be produced by mixing an aqueous medium and a basic compound that neutralizes the anionic group contained in the resin (a2).

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

The content rate 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, particularly preferably 90% by mass of the nonvolatile content of the aqueous resin composition. It is mass% or more, preferably 99.9 mass% or less.

As said aqueous resin (B), a urethane resin (b1), polyester resin, acrylic resin, etc. are mentioned, for example. Among these, a urethane resin (b1) is preferable because a coating film having excellent adhesion to a base material of non-adhesion can be formed. In addition, these aqueous resins may be used alone or in combination of two or more.

As the urethane resin (b1), the same as the urethane resin (a2) described above can be used.

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

Examples of the aqueous medium (C) include water, an organic solvent 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; Alkyl ether solvent of polyalkylene glycol; And lactam solvents such as N-methyl-2-pyrrolidone. These organic solvents to be mixed with water may be used alone or in combination of two or more.

Further, the aqueous medium (C) is preferably only water, or a mixture of water and an organic solvent miscible with water, and more preferably only water in consideration of safety and reduction of the load on the environment.

The aqueous medium (C) is preferably contained in the range of 10 to 60 mass%, and more preferably contained in the range of 20 to 50 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 may further contain a water-insoluble additive.

It is preferable to use the water-insoluble additive by dispersing it in an aqueous dispersion of the aqueous resin (B) in advance.

Examples of the water-insoluble additives include antioxidants and ultraviolet absorbers. These water-insoluble additives may be used alone or in combination of two or more.

Examples of the antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, amine antioxidants, and the like. Among these, phenolic antioxidants and phosphorus antioxidants are preferred because a coating film having excellent adhesion to a non-adhesive substrate can be formed, and a coating film excellent in heat resistance, heat discoloration resistance, and automatic oxidation inhibition can be formed. . In addition, these antioxidants may be used alone or in combination of two or more.

When the molecular weight of the antioxidant is too small, it is easy to migrate to the surface of the coating film, and the adhesion to the substrate decreases. On the other hand, when the molecular weight is too large, the compatibility with the aqueous resin (B) is poor. It is preferable that the molecular weight is in the range of 500 to 1,000.

Further, when the melting point of the antioxidant is low, it is easy to block the surface of the coating film. On the other hand, when the melting point is high, the compatibility with the aqueous resin (B) is poor, so the melting point is preferably in the range of 80 to 180°C.

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 1 part by mass or less, more preferably, based on 100 parts by mass of the composite resin (A). It is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less.

In the aqueous resin composition of the present invention, if necessary, in addition to the above water-insoluble additives, film forming aids, curing agents, crosslinking agents, plasticizers, antistatic agents, waxes, light stabilizers, flow regulators, dyes, leveling agents, rheology control agents, photocatalysts Additives such as sexual compounds, inorganic pigments, organic pigments, and extender pigments can be blended.

As said crosslinking agent, a melamine compound, an epoxy compound, an oxazoline compound, a carboxydiimide compound, an isocyanate compound, etc. are mentioned, for example. As said melamine compound, an alkylated methylol melamine resin is mentioned, for example. The alkylated methylol melamine resin is obtained by, for example, reacting a methylolated melamine resin with a lower alcohol such as methyl alcohol or butyl alcohol (alcohol having 1 to 6 carbon atoms). Examples of the methylolated melamine resin include, for example, a methylolmelamine resin having an amino group obtained by condensing melamine and formaldehyde, a methylolmelamine resin having an imino group, a trimethoxymethylolmelamine resin, and a hexamethoxymethylolmelamine Resin, etc. are mentioned. Among these, trimethoxymethylolmelamine resin and hexamethoxymethylolmelamine resin are preferable. Moreover, as said alkylated methylol melamine resin, the alkylated methylol melamine resin which has an imino group, the alkylated methylol melamine resin which has an amino group, etc. is mentioned.

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 film formed using an active energy ray-curable composition on the surface of the primer layer.

The active energy ray-curable composition preferably contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group, and the types of the resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group are the active energy It is preferable to select appropriately in accordance with the properties required for the cured coating film of the linear curable composition.

As the resin having a polymerizable unsaturated group, a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, an acrylic (meth) acrylate resin, and a maleimide group Resin etc. which have been mentioned. These resins having a polymerizable unsaturated group may 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. Say.

As the urethane (meth)acrylate resin, for example, a resin having a urethane bond and a (meth)acryloyl group obtained by urethanizing an aliphatic polyisocyanate or an aromatic polyisocyanate and a (meth)acrylate having a hydroxyl group, etc. Can be mentioned.

As the aliphatic polyisocyanate, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentanedi Isocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylenedi Isocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and cyclohexyl diisocyanate. have. In addition, examples of the aromatic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, triazine diisocyanate, and p-phenylene diisocyanate. .

As the (meth)acrylate having a hydroxyl group, for example, 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, hydroxypivalic acid neo Mono (meth) acrylates of dihydric alcohols such as pentyl glycol mono (meth) acrylate; Trimethylolpropanedi(meth)acrylate, ethoxylated trimethylolpropane (meth)acrylate, propoxylated trimethylolpropanedi(meth)acrylate, glycerindi(meth)acrylate, bis(2-(meth)acrylate Mono or di(meth)acrylates of trihydric alcohols such as royloxyethyl)hydroxyethyl isocyanurate, or mono and di(meth) having hydroxyl groups in which some of these alcoholic hydroxyl groups are modified with ε-caprolactone ) Acrylate; Compounds having a monofunctional hydroxyl group and a trifunctional or higher (meth)acryloyl group such as pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. Or, a polyfunctional (meth)acrylate having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; (Meth)acrylates having oxyalkylene chains such as dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol mono(meth)acrylate compound; (Meth)acrylate compounds having block-structured oxyalkylene chains such as polyethylene glycol-polypropylene glycol mono(meth)acrylate and polyoxybutylene-polyoxypropylene mono(meth)acrylate; (Meth)acrylate compounds having an oxyalkylene chain having a random structure such as poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate and poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. I can.

The unsaturated polyester resin is a curable resin obtained by polycondensation of an α,β-unsaturated dibasic acid or an acid anhydride thereof, an aromatic saturated dibasic acid or an acid anhydride thereof, and a glycol. Examples of the α,β-unsaturated dibasic acid or its acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydro phthalic anhydride, endomethylene tetrahydro phthalic anhydride, halogenated phthalic anhydride and these esters. 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 these esters. 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, tetra Ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di-(4-hydroxypropoxydiphenyl)propane, and the like. In addition, oxides such as ethylene oxide and propylene oxide can be used similarly.

As the epoxy (meth)acrylate resin, obtained by reacting (meth)acrylic acid with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type epoxy resin. Can be mentioned.

Examples of the polyester (meth)acrylate resin include those obtained by reacting (meth)acrylic acid with the hydroxyl group of a polyester polyol.

As the acrylic (meth)acrylate resin, for example, glycidyl methacrylate and (meth)acrylate monomers such as alkyl (meth)acrylate were polymerized to obtain an acrylic resin having an epoxy group if necessary. After that, what is obtained by making (meth)acrylic acid react with the epoxy group is mentioned.

As the resin having a maleimide group, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethyl maleimide and isophorone diisocyanate, and a bifunctional maleimide ester obtained by esterifying maleimide acetic acid and polytetramethylene glycol Compounds, tetrafunctional maleimide ester compounds obtained by esterifying a tetraethylene oxide adduct of maleimidecaproic acid and pentaerythritol, and polyfunctional maleimide ester compounds obtained by esterifying maleimide acetic acid and a polyhydric alcohol compound. .

As the monomer having a polymerizable unsaturated group, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, a number average molecular weight of 150 to 1000 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 1000 Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Hexanedioldi(meth)acrylate, hydroxypivalic acid ester neopentylglycoldi(meth)acrylate, bisphenol Adi(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropanedi(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) acrylic Aliphatic alkyl (meth)acrylates such as acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate , Glycerol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, aryl (meth)acrylate, 2-butoxyethyl(meth)acrylate, 2-(diethylamino)ethyl(meth)acrylate, 2-(dimethylamino)ethyl(meth)acrylate, γ-(meth)acryloxypropyltrimethoxysilane , 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, nonylphenoxypolyp Lophylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydipropylene glycol (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, dicyclopentanyl ( Meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, methoxylated cyclodecatrien (meth)acrylate, phenyl (meth)acrylate; Maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearyl Maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethylcarbonate, 2-maleimideethyl-propylcarbonate, N-ethyl-(2-maleimideethyl)carbamate, N, Maleimide compounds such as N-hexamethylenebismaleimide, polypropylene glycol-bis(3-maleimidepropyl)ether, bis(2-maleimideethyl)carbonate, and 1,4-dimaleimidecyclohexane, etc. have. These monomers having a polymerizable unsaturated group may be used alone or in combination of two or more.

The active energy ray-curable composition can be applied to a substrate or the like and then irradiated with an active energy ray to form a cured coating film. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. When irradiating ultraviolet rays as an active energy ray to use the active energy ray-curable composition as a cured coating film, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve curability. Further, if necessary, a photosensitizer may be further added to improve curability. On the other hand, when the active energy ray-curable composition is used as a cured coating film by irradiating electron beam, α ray, β ray, or γ ray as an active energy ray, it is rapidly cured without using a photopolymerization initiator or a photosensitizer. It is not necessary to add an initiator or photosensitizer.

As the photoinitiator, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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-trimethyl) Benzoyl)-phenylphosphine oxide, etc. are mentioned.

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

Examples of the substrate used for the laminate of the present invention include metal substrates, plastic substrates, glass substrates, paper substrates, wood substrates, and fibrous substrates. Among these substrates, in order to improve the adhesion between the cured coating film of the active energy ray-curable composition and the substrate, when using the aqueous resin composition of the present invention as a primer, a plastic substrate is suitable.

As the material of the plastic substrate, 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 polyester substrates among the plastic substrates described above. As a specific example of the said polyester, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc. are mentioned.

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

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

The aqueous resin composition of the present invention can be applied directly to the surface of the substrate, for example, and then dried and cured to form a coating film on the surface of the substrate. As a method of drying and curing the aqueous resin composition of the present invention, a method of curing for about 1 to 10 days at room temperature may be used. However, since curing can be accelerated, at a temperature of 100 to 150° C., 1 to 600 seconds A method of heating to an extent is preferable. Further, in the case of using a plastic substrate that is easily deformed or discolored at a relatively high temperature, it is preferable to heat at a relatively low temperature of about 70°C to 100°C.

As a method of applying the water-based resin composition of the present invention to the surface of the substrate, for example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, A coating method using a spin coater, dipping, screen printing, spraying, brush application, applicator, bar coater or the like can be mentioned.

The film thickness of the coating film formed using the aqueous resin composition of the present invention can be appropriately adjusted depending on the intended use, but is usually preferably in the range of 0.01 to 20 µm.

In the layered product of the present invention, the active energy ray-curable composition is further applied to the surface of the primer layer, which is a coating film of the water-based resin composition of the present invention obtained as described above, and irradiated with an active energy ray. It can be obtained by forming a cured coating film of an energy ray-curable composition. In addition, as the method for applying the active energy ray-curable composition, the same method as the method for applying the aqueous resin composition of the present invention can be used.

[Example]

Hereinafter, the present invention will be described in detail by examples and comparative examples.

(Synthesis Example 1: Synthesis of polyester polyol (1))

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 of diethylene glycol, and 0.03 parts by mass of dibutyltin oxide while introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. After adding part, polycondensation reaction was performed at 230°C for 24 hours at 180 to 230°C until the acid value became 1 or less, and polyester polyol (1) [acid value 0.6, hydroxyl value 50.0, aromatic ring concentration 4.41 mol/kg] was prepared. Got it.

(Synthesis Example 2: Synthesis of polyester polyol (2))

35.4 parts by mass of isophthalic acid, 17.8 parts by mass of sebacic acid, 7.8 parts by mass of adipic acid, 6.2 parts by mass of ethylene glycol, 22.9 parts by mass of neopentyl glycol while introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer Parts, 11.7 parts by mass of 1,6-hexanediol and 0.03 parts by mass of dibutyltin oxide were added, polycondensation reaction was performed at 230°C for 24 hours at 180 to 230°C until the acid value became 1 or less, and polyester polyol (2 ) [Acid value 0.6, hydroxyl value 42.5, aromatic ring concentration 2.51 mol/kg] was obtained.

(Synthesis Example 3: Synthesis of vinyl ester resin (I))

46.7 parts by mass of cresol novolak type epoxy resin ("EPICLON N-673-80M" manufactured by DIC Corporation, solid content epoxy equivalent = 209 g/eq, non-volatile content = 80 mass%, solvent: methyl ethyl ketone) in a reaction vessel, 13.3 parts by mass of acrylic acid, 0.08 parts by mass of metoquinone, and 13.3 parts by mass of methyl ethyl ketone were added, stirred and mixed uniformly. Then, 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, thereby obtaining a vinyl ester resin (I).

(Synthesis Example 4: Synthesis of urethane resin (II-1))

To the 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 perform a urethanization step. After confirming that the isocyanate value became 0.1% or less, 0.3 parts by mass of n-butanol was added and reacted for an additional 2 hours, then cooled to 50° C. and a urethane resin (II-1) having an aromatic ring having a nonvolatile content of 60% by mass ).

(Synthesis Example 5: Synthesis of urethane resin (II-2))

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, followed by reaction at 80° C. for 12 hours to perform a urethanization process. . Urethane resin (II-2) having an aromatic ring having a nonvolatile content of 51% by mass after confirming that the isocyanate value became 0.1% or less, adding 0.3 parts by mass of n-butanol, and reacting for an additional 2 hours Got it.

(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, 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, followed by reacting at 80° C. for 12 hours to perform a urethanization step. After confirming that the isocyanate value became 0.1% or less, 0.3 parts by mass of n-butanol was added and reacted for further 2 hours, it was cooled to 50° C. to obtain a urethane resin (II-3) having a non-volatile content of 70% by mass.

(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 were added, and 938.5 parts by mass of ion-exchanged water was slowly added. Solubilization was carried out. Then, under reduced pressure, methyl ethyl ketone was removed 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)

To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 1.28 parts by mass of a phenolic antioxidant (1) (molecular weight; 640, melting point; 160°C) and 1.28 parts by mass of a phosphorus antioxidant were added, followed by stirring. 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous dispersion of an aqueous resin (B-1) having a nonvolatile content of 23% by mass was prepared.

(Production Example 3: Preparation of aqueous resin (B-2) aqueous dispersion)

2.56 parts by mass of a phenolic antioxidant (1) and 2.56 parts by mass of a phosphorus antioxidant were added to the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, followed by stirring and mixing uniformly. Next, 4.8 parts by mass of triethylamine was added, and 548 parts by mass of ion-exchanged water was slowly added to perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed 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)

To the urethane resin (II-2) having an aromatic ring obtained in Synthesis Example 5, 1.22 parts by mass of a phenolic antioxidant and 1.22 parts by mass of a phosphorus antioxidant were added, stirred, and mixed uniformly. Next, 4.6 parts by mass of triethylamine was added, and 390 parts by mass of ion-exchanged water was slowly added to perform water solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C. to prepare an aqueous dispersion of an aqueous resin (B-3) 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 phenolic antioxidant and 1.26 parts by mass of a phosphorus antioxidant were added, 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50°C to prepare an aqueous dispersion of an aqueous resin (B-4) having a nonvolatile content of 23.3% by 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 oxidizing agent and 1.28 parts by mass of an ultraviolet absorber were added, 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50°C to prepare an aqueous dispersion of an aqueous resin (B-5) 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 phenolic oxidizing agent was added, 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous dispersion of an aqueous resin (B-6) having a nonvolatile content of 23% by mass was prepared.

(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 oxidizing agent was added, 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed 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, 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C. to prepare an aqueous dispersion of an aqueous resin (B-8) 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 a phenolic antioxidant (2) (molecular weight: 1180, melting point: 120°C) was added, 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous dispersion of an aqueous resin (B-9) having a nonvolatile content of 23% by mass was prepared.

(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 a phenolic antioxidant (3) (molecular weight: 350, melting point: 120°C) was added, 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 perform aqueous solution. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous dispersion of an aqueous resin (B-10) having a non-volatile content of 23% by mass was prepared.

(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, 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 perform aqueous solution. Then, 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 aqueous 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, 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 perform aqueous solution. Then, methyl ethyl ketone was removed under reduced pressure at 30 to 50°C to prepare an aqueous dispersion of an aqueous resin (B-12) having a nonvolatile content of 23% by mass.

(Production Example 14: Preparation of aqueous resin (B-13) aqueous dispersion)

To the 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 perform water solubility. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50° C., and an aqueous dispersion of an aqueous resin (B-13) having a nonvolatile content of 23% by mass was prepared.

Table 1 shows the urethane resin, antioxidant, and ultraviolet absorber used in Production Examples 2 to 14.

[Table 1]

(Example 1: Preparation of aqueous resin composition (1))

A non-volatile content of 10 mass% aqueous by mixing 100 parts by mass of the composite resin composition (A-1) obtained in Production Example 1, 2 parts by mass of the aqueous resin (B-1) aqueous dispersion obtained in Production Example 2, and 302.6 parts by mass of ion-exchanged water The resin composition (1) was obtained.

(Examples 2 to 15: Preparation of aqueous resin compositions (2) to (15))

In place of the aqueous resin (B-1) aqueous dispersion used in Example 1, except for using the aqueous resin aqueous dispersion obtained in Production Examples 3 to 13, it was carried out in the same manner as in Example 1, and the aqueous resin compositions (2) to (15). ).

The composite resin and the aqueous resin used in Examples 1 to 15 are shown in Table 2.

[Table 2]

(Preparation Example 1: Preparation of photocurable resin composition (UV-1))

Photocurable resin 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) A composition (UV-1) was obtained.

(Example 15: Preparation of laminate (1))

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

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

(Examples 16 to 30: Preparation of laminates (2) to (15))

In place of the aqueous resin composition (1) used in Example 15, the aqueous resin compositions (2) to (15) obtained in Examples 2 to 15 were used to form primer layers (P-2) to (P-15). Except, it carried out similarly to Example 13, and obtained the laminated bodies (2)-(12).

The following adhesion evaluation was performed using the aqueous resin composition and laminate obtained in the above-described Examples and Comparative Examples.

[Evaluation method of adhesion (initial) between base material and primer layer]

A member in which a primer layer is laminated on the surface of the substrate by applying a primer to the surface of a substrate made of polyethylene terephthalate having a film thickness of 125 μm so that the film thickness upon drying becomes about 1 μm and heating at 150° C. for 5 minutes A test plate consisting of was prepared. Then, a 1 mm base wood peeling test was performed using the test plate. Specifically, 100 base woods were formed 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 Corporation was affixed thereon.

Then, the adhesive tape was stretched in a direction perpendicular to the primer layer, and evaluated based on the number of grids remaining on the surface of the primer layer when the adhesive tape was peeled off from the surface of the primer layer.

[Evaluation method of adhesion (initial) between primer layer and UV coating film]

Using the laminates obtained in Examples and Comparative Examples, a 1 mm base wood peel test was performed. On the surface of the UV coating film constituting the laminate obtained in Examples and Comparative Examples, 100 base woods were formed at 1 mm intervals, and a 24 mm wide adhesive tape made by Nichiban Corporation was affixed thereon.

Then, the adhesive tape was stretched in a direction perpendicular to the UV coating film, and the adhesive tape was evaluated based on the number of grids remaining on the surface of the UV coating film when the adhesive tape was peeled off from the surface of the UV coating film.

[Evaluation method of adhesion between substrate and primer layer (after UV irradiation cycle test)]

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

[Evaluation method of adhesion between primer layer and UV coating film (after UV irradiation cycle test)]

The obtained laminate was irradiated with ultraviolet rays at an irradiation intensity of 0.5 J/cm 2 for a predetermined number of times using a high-pressure mercury lamp as a light source, and then the photocurable resin composition (UV-1) obtained in Preparation Example 1 was applied to the surface of the primer layer. A laminate having a primer layer on the surface of the substrate and a UV coating film on the surface of the primer layer by applying it to a coating thickness of µm, using a high-pressure mercury lamp as a light source, and irradiating ultraviolet rays again at an irradiation intensity of 0.5 J/cm 2 Got it.

Then, the laminate was taken out, and the adhesion between the primer layer and the UV coating film was evaluated in the same manner as in the above [adherence between the primer layer and the UV coating film (initial)].

[Evaluation method of film appearance (measurement of haze value)]

The haze value of the laminated plate obtained above was measured using a haze meter (manufactured by Sugashi Kenki Co., Ltd.). It measured by the method conforming to the JIS test method (JIS K7136:2000). The haze value (H) was calculated from the following calculation formula. In addition, the haze value of only the PET substrate was also measured, and the haze value was 2.05%.

H(%)=Td/Tt×100

H; Haze (Mallus tooth) (%)

Td; Diffuse transmittance (%)

Tt; Total light transmittance (%)

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

[Table 3]

(Comparative Example 1: Preparation of aqueous resin composition (C1))

An aqueous resin composition (C1) having a nonvolatile content of 10% by mass was obtained 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.

(Comparative Example 2: Preparation of aqueous resin composition (C2))

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

(Comparative Example 3: Preparation of aqueous resin composition (C3))

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

(Comparative Example 4: Preparation 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 heated at 150° C. for 5 minutes, A primer layer (P'-1) was formed on the surface.

Then, on the surface of the primer layer, the photocurable resin composition (UV-1) obtained in Preparation Example 1 was applied with a coating thickness of 15 µm, and a high-pressure mercury lamp was used as a light source, and an ultraviolet ray at an irradiation intensity of 0.5 J/cm 2 By irradiation, a layered product (R1) having a primer layer on the surface of the substrate and a UV coating film on the surface of the primer layer was obtained.

(Comparative Examples 2 to 3: Preparation of laminates (R2) to (R3))

In place of the aqueous resin composition (C1) used in Comparative Example 1, the aqueous resin compositions (C2) to (C3) obtained in Comparative Examples 2 to 3 were used as primer layers (P'-2) to (P'-3). Except what was done, it carried out similarly to Comparative Example 1, and obtained the laminated bodies (R2)-(R3).

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

[Table 4]

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, it was confirmed that the primer layer formed by using the aqueous resin composition of the present invention was excellent in adhesion to the substrate and also excellent in adhesion to the UV coating film.

On the other hand, Comparative Example 2 is an example in which the aqueous resin composition containing the composite resin obtained in Comparative Example 1 is used, and the aqueous resin (B) of the present invention is not used. The primer layer formed using the aqueous resin composition of Comparative Example 1 was excellent in adhesion between the base material and the primer layer before the UV irradiation cycle test (initial), and the adhesion between the primer layer and the UV coating film, but the UV irradiation cycle test It was confirmed that the adhesion afterward was remarkably insufficient.

In addition, 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 (initial) the UV irradiation cycle test, and the adhesion between the base material and the primer layer after the UV irradiation cycle test, but the primer layer and the UV coating film It was confirmed that the adhesion was remarkably insufficient.

In addition, Comparative Example 4 is an example using the aqueous resin (B-3) obtained in Production Example 4, and is an example in which the composite resin (A) of the present invention is not used. The primer layer of Comparative Example 4, as in Comparative Example 3, was excellent in adhesion between the base material and the primer layer before (initial) the UV irradiation cycle test, and the adhesion 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 film was remarkably insufficient.

Claims (12)

As 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), a basic compound, and an aqueous medium (C),
The vinyl ester resin (a1) is a compound (a1-2) 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. Is a reactant with
The urethane resin (a2) is a reaction product of a polyol having an aromatic ring and a polyol containing a polyol having an anionic group (a2-1) and a polyisocyanate (a2-2),
The composite resin (A) is prepared by preparing the vinyl ester resin (a1) and the urethane resin (a2) in advance, and then, to the urethane resin (a2), the vinyl ester resin (a1), and the urethane A resin prepared by mixing a basic compound that neutralizes the anionic group of the resin (a2) and an aqueous medium (C), and a part or all of the vinyl ester resin (a1) is contained in the urethane resin (a2) particles Forming particles,
The aqueous resin (B) is a urethane resin (b1),
An aqueous resin composition, wherein the urethane resin (b1) has an aromatic ring. delete The method of claim 1,
An aqueous resin composition further containing a water-insoluble additive. The method of claim 3,
The aqueous resin composition wherein the water-insoluble additive is at least one additive selected from the group consisting of antioxidants and ultraviolet absorbers. The method of claim 4,
The aqueous resin composition wherein the antioxidant is at least one antioxidant selected from the group consisting of a phenolic antioxidant and a phosphorus antioxidant. The method according to any one of claims 1, 3 to 5,
The aqueous resin composition in which the mass ratio [(A)/(B)] of the composite resin (A) and the aqueous resin (B) is in the range of 99/1 to 80/20. The method of claim 4,
The aqueous resin composition in which the weight average molecular weight of the antioxidant is in the range of 500 to 1,000. The method of claim 4,
An aqueous resin composition having a melting point of the antioxidant in the range of 80 to 180°C. A primer layer formed by using the aqueous resin composition according to any one of claims 1, 3 to 5 on one or both sides of a substrate, and an active energy ray on the surface of the primer layer A laminate comprising a cured coating film of a curable composition. The method of claim 9,
The layered product, 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.