TW201833216A - Aqueous resin composition, laminate using same, optical film, and image display device - Google Patents

Abstract

The present invention addresses the problem of providing an aqueous resin composition that can be used as a primer that greatly improves adhesion between a substrate and a cured coating of an active energy ray-curable composition, even if the substrate is a poorly-adhesive one such as polyester film. The present invention is an aqueous resin composition containing: a composite resin containing a vinylester resin and a urethane resin having an aromatic ring; an aqueous resin; and an aqueous vehicle. The aqueous resin composition is characterized in that: the vinylester resin is a reaction product of at least one epoxy resin 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; and the urethane resin is a reaction product of polyols containing a polyol having an aromatic ring and a polyol having a hydrophilic group, and a polyisocyanate.

Description

   Water-based resin composition, laminated body using the same, optical film, and image display device   

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

Water-based resin compositions, especially water-based urethane resin compositions, generally have good adhesion to substrates. From the viewpoint of forming a soft coating film, they are used as coating agents and adhesives. In various uses. Among them, in recent years, it has been discussed in applications to films and sheets for optical applications. Specific examples of the optical application include a liquid crystal display and a touch panel. A display device such as a liquid crystal display is generally constituted by laminating a plurality of optical films having various functions in order to display vivid images. Examples of such optical films include an anti-reflection film, a retardation film, and a lens. Wait.

From the viewpoint of excellent optical characteristics, mechanical strength, and durability, a polyester film, particularly a polyethylene terephthalate (PET) film can be used as a substrate for such an optical film. In optical applications, an active energy ray-curable composition is applied to a surface of a polyester film and cured to form a hard coat layer, and a layer in which the active energy ray-curable composition is cast is provided to In the case of a polyester film as a fluorene lens, the polyester film has high crystallinity and has a problem of low adhesion to a cured coating film of an active energy ray-curable composition.

So far, as a method for improving the adhesion between a polyester film and an active energy ray-curable composition, a method has been proposed in which a polyester film as a substrate and an active energy ray-curable composition are cured. In between, a primer layer including an acrylic resin is provided (for example, refer to Patent Document 1). However, even if a primer layer containing an acrylic resin is provided, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition is insufficient.

Therefore, there is a need for a material that can be used for a primer layer, which can sufficiently adhere a polyester film and a cured coating film of an active energy ray-curable composition.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2010-215843

The problem to be solved by the present invention is to provide an aqueous resin composition that can be used as a primer. Even if it is difficult to adhere to a substrate such as a polyester film, it can greatly improve the hardening composition of the substrate and active energy rays. Adhesion of hardened coatings of materials; and laminated bodies, optical films, and image display devices using the same.

In order to solve the above-mentioned problems, the inventors of the present case conducted detailed studies, and found that by using an aqueous resin composition containing a specific composite resin and an aqueous resin as a primer, even a substrate that is difficult to adhere, such as a polyester film, can be significantly improved. The present invention improved the adhesion between the substrate and the cured coating film of the active energy ray-curable composition.

That is, the present invention relates to an aqueous resin composition, which is a composite resin (A), a water-based resin (B) including a vinyl ester resin (a1) and a urethane resin (a2) having an aromatic ring, And an aqueous resin composition of an aqueous medium (C), wherein the vinyl ester resin (a1) is one or more epoxy resins selected from the group consisting of a novolac epoxy resin and a bisphenol epoxy resin. Resin (a1-1) reacted with compound (a1-2) having an acid group and a polymerizable unsaturated group, and the urethane resin (a2) is a polyol (a2-1) and a polyisocyanate (a2) -2) The reactant, the polyol (a2-1) contains a polyol having an aromatic ring and a polyol having a hydrophilic group; and a laminate, an optical film, and an image display device using the same.

The water-based resin composition of the present invention can be used as a primer. Even if it is a substrate such as a polyester film that is difficult to adhere, it can greatly improve the adhesion of the substrate to the hardened coating film of the active energy ray-curable composition Therefore, it is suitable for a laminated body formed by using a polyester film as a substrate and forming a cured coating film of an 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 lens. These optical films can be applied to image display devices including liquid crystal displays.

    [Form of Implementing Invention]    

The aqueous resin composition of the present invention includes: 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) .

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

The vinyl ester resin (a1) includes, for example, one or more epoxy resins (a1-1) selected from the group consisting of novolac epoxy resins and bisphenol epoxy resins, and has an acid group and polymerizability. Reactant of unsaturated compound (a1-2).

This 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 epoxy resin include a cresol novolac epoxy resin, a phenol novolac epoxy resin, and the like. Examples of the bisphenol epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, and tetrabromobis epoxy resin. Phenol A type epoxy resin, etc. These epoxy resins (a1) may be used alone or in combination of two or more.

Among the epoxy resins (a1-1), novolak-type epoxy resins having a plurality of epoxy groups are preferably used, and the epoxy groups can react with an acid group of the compound (a1-2).

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.

Furthermore, it is preferred that 80 to 100 mole% of the total epoxy groups in the epoxy resin (a1-1) is reacted with the acid group of the compound (a1-2), and more preferably The epoxy groups are all reacted with the acid group of the compound (a1-2).

This compound (a1-2) has an acid group and a polymerizable unsaturated group. By reacting the acid group of the compound (a1-2) with the epoxy group of the epoxy resin (a1-1), a polymerizable unsaturated group can be introduced into the vinyl ester resin (a1).

Because the polymerizable unsaturated group of the compound (a1-2) has nothing to do with its reaction in the reaction with the epoxy resin, as a result, the vinyl ester resin (a1) has a compound derived from the compound (a1-2). Polymerizable unsaturated group. The polymerizable unsaturated group of the 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 polymer. Bond, and it is firmly adhered to the primer layer containing the water-based resin composition of this invention.

Examples of the compound (a1-2) having an acid group and a polymerizable unsaturated group include acrylic acid, methacrylic acid, itaconic acid, 2-propenyloxyethyl succinate, and 2-methyl group. Acrylic fluorenyloxyethyl succinate, 2,2,2, -p-acrylic fluorenyloxymethyl ethyl phthalate, and the like. Among these compounds, acrylic acid is preferred, and a vinyl fluorenyl group which can easily polymerize with a polymerizable unsaturated group of a resin or a monomer in an active energy ray-curable composition described later can be introduced into the vinyl ester. Resin (a1). These compounds (a1-2) may be used singly or in combination of two or more, but it is preferred 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, and more preferably in the range of 80 to 120 ° C.

When the epoxy resin (a1-1) is reacted with the compound (a1-2), in order to prevent thermal polymerization of the polymerizable unsaturated group of the compound (a1-2), it is preferable to use polymerization inhibition. Agent. The addition amount of the polymerization inhibitor is preferably in the range of 500 to 5,000 ppm based on the total mass of the epoxy resin (a1-1) and the compound (a1-2).

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

When the epoxy resin (a1-1) is reacted with the compound (a1-2), 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 based on 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. Specific examples include alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, and diphenylguanidine; and 3- (3,4-dichlorophenyl) -1,1-dimethylformate. 3-substituted phenyl-1,1-dimethyl, such as methyl urea, 3-phenyl-1,1-dimethyl urea, 3- (4-chlorophenyl) -1,1-dimethyl urea Urea; imidazolines such as 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline; monoaminopyridines such as 2-aminopyridine; N, N-dimethyl-N- (2-hydroxy-3-allyloxypropyl) amine-N'-lactamimine and other aminated ammonium imines; ethylphosphine, propylphosphine, butylphosphine , Phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine-triphenylborane complex, tetra Organophosphorus catalysts such as phenylphosphonium tetraphenylborate; 1,8-diazabicyclo [5.4.0] undecene-7,1,4-diazabicyclo [2.2.2] octane And other diazabicycloundecene catalysts. These reaction catalysts may be used alone or in combination of two or more.

The weight average molecular weight of the vinyl ester resin (a1) obtained by this method is preferably in the range of 500 to 10,000, and more preferably in the range of 1,000 to 6,000, from the viewpoint of improving the dispersion stability of the resin particles.

In this specification, a weight average molecular weight and a number average molecular weight can be calculated | required as a polystyrene conversion value measured by the gel permeation chromatography method.

The equivalent weight of the polymerizable unsaturated group of 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 (a2-1) and a polyisocyanate (a2-2); the polyol (a2-1) includes a polyol having an aromatic ring and Polyol having a hydrophilic group.

By using the polyol having an aromatic ring as a raw material of the urethane resin (a2), the urethane resin (a2) becomes a person having 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, and more preferably in the range of 1.6 to 5 mol / kg. The proportion of the polyol having an aromatic ring contained in the polyol (a2-1) is preferably in the range of 40 to 98% by mass from the viewpoint of further improving the adhesion to the substrate. A more preferable range is 60 to 98% by mass.

Examples of the polyol having an aromatic ring include an aromatic polyester polyol, an aromatic polycarbonate polyol, an aromatic polyether polyol, and an alkylene oxide adduct of bisphenol. Among these, aromatic polyester polyols and alkylene oxide adducts of bisphenol are preferred from the viewpoint of excellent substrate adhesion and blocking resistance. The alkylene oxide adduct of bisphenol is preferably an alkylene oxide adduct of bisphenol A. These polyols having an aromatic ring may be used alone or in combination of two or more kinds.

The aromatic polyester polyol is a reactant obtained by esterifying a polycarboxylic acid and a polyhydric alcohol, but among the polycarboxylic acid and the polyhydric alcohol, at least one having an aromatic ring is used.

Among the polycarboxylic acids, those having an aromatic ring include, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, or esters 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, and chlorobridged acid. Aliphatic dicarboxylic acids such as 1,1,2,4-butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, or their esterified products. These polycarboxylic acids or their esterified products may be used alone or in combination of two or more.

Examples of the polyhydric alcohol having an aromatic ring include aromatic diols such as xylylene glycol, toluene dimethanol, and xylene dimethanol. Examples of those having no aromatic ring include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and diethylene glycol. Aliphatic polyols such as diols, triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, neopentyl glycol, and the like. These polyols may 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, even more preferably 30% by mass or less, and even more preferably 10% by mass or less, Particularly preferred is 5 mass% or less, and the lower limit is 0 mass%.

In the esterification reaction in the production of the aromatic polyester polyol, an esterification catalyst is preferably used 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 acetone titanium oxide, and dibutyl Tin oxide, dibutyltin diacetate, dibutyltin dilaurate, tin octoate, 2-ethylhexanetin, zinc acetoacetone, 4 zirconium chloride, 4 zirconium chloride tetrahydrofuran complex, 4 chloride Thorium, terbium chloride tetrahydrofuran complex, germanium oxide, metal compounds such as tetraethoxy germanium, and the like.

This alkylene oxide adduct of bisphenol A is a phenolic hydroxyl addition alkylene oxide of bisphenol A. Examples of the alkylene oxide include ethylene oxide and propylene oxide. The average addition mole number of the alkylene oxide relative 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, and 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 polyhydric alcohol having an anionic group is preferred.

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. In addition, a polyester polyol having "a carboxyl group obtained by reacting a polyol having a carboxyl group with a polycarboxylic acid" can also be used.

Examples of the polyol having a sulfonic acid group include 5-sulfonic acid isophthalic acid, sulfonic acid terephthalic acid, 4-sulfonic acid phthalic acid, and 5- (4-sulfonic acid). Diphenoxy) isophthalic acid and other dicarboxylic acids or salts thereof, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, new Polyester polyols and the like obtained by the reaction of low molecular polyols such as pentanediol.

The polyol having a carboxyl group and the polyol having a sulfonic acid group are preferably used in a range of 2 to 70 mgKOH / g of the urethane resin (a2), and more preferably in a range of 10 to 70 mgKOH / g. Use within the range of 50mgKOH / g. In addition, the acid value referred to in the present invention is a theory calculated based on the amount of acid group-containing compounds, such as polyols having a carboxyl group or a sulfonic acid group, used in the production of the urethane resin (a2). value.

From the viewpoint of imparting good water dispersibility to the urethane resin (a2), it is preferred to neutralize a part or all of the anionic group with a basic compound or the like.

Examples of the basic compound include ammonia; triethylamine, Organic amines, such as phospholine, monoethanolamine, and diethylethanolamine; metal hydroxides, such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. From the viewpoint of further improving the water dispersion stability of the aqueous resin composition of the present invention, the amount of the basic compound to be used is based on the molar ratio of the basic compound to the anionic group [basic compound / anionic group] It is preferably in the range of 0.5 to 3, and more preferably in the range of 0.7 to 1.5.

The polyol (a2-1) can be used in addition to the above-mentioned polyols as required.

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 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol And lower molecular weight (e.g., less than 500, preferably 400 or less). These other polyols may be used alone or in combination of two or more kinds.

Examples of the polyisocyanate (a2-2) that can react with the polyol (a2-1) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbon. Aromatic polyisocyanates such as diimine modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, methylidene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate Aliphatic polyisocyanates such as methylene, diamine diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate; cyclohexane diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, and the like. These polyisocyanates (a2-2) may be used alone or in combination of two or more kinds.

Among the polyisocyanates (a2-2), an aromatic polyisocyanate is preferably contained from the viewpoint of further improving the adhesion to the substrate. 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.

For example, the polyol (a2-1) can be mixed with the polyisocyanate (a2-2) in the absence of a solvent or an organic solvent, and the reaction can be performed at a temperature of 40 to 120 ° C for 3 to 20 hours. Thus, the urethane resin (a2) can be produced. When producing the urethane resin (a2), a chain extender can also be used as required.

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

Examples of the organic solvent that can be used in the production of the urethane resin (a2) include ketone solvents such as acetone and methyl ethyl ketone; tetrahydrofuran and dihydrogen. Ether solvents such as dioxane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; and amidine 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 3,000 from the viewpoint of further improving the adhesion between the substrate and the cured coating film of the active energy ray-curable composition. A range of ~ 200,000, more preferably a range of 3,000 ~ 100,000.

The composite resin (A) includes the vinyl ester resin (a1) and the urethane resin (a2) having an aromatic ring. The vinyl ester resin (a1) and the urethane resin (a2) are compared with each other. It is preferably dispersed in an aqueous medium. At this time, in the aqueous medium, it is preferable that resin particles forming part or all of the vinyl ester resin (a1) are present inside 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) forms a core / shell type resin particle of a shell portion.

The composite resin (A) can be produced by manufacturing the vinyl ester resin (a1) and the urethane resin (a2) in advance, and then mixing the urethane resin (a2) with the A vinyl ester resin (a1), a basic compound which neutralizes the anionic group which this urethane resin (a2) has, and an aqueous medium.

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

In the non-volatile component of the aqueous resin composition, the content ratio of the composite resin (A) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass. % Or more, preferably 99.9% by mass or less.

Examples of the aqueous resin (B) include a urethane resin (b1), a polyester resin, and an acrylic resin. Among these, a urethane resin (b1) is preferable from the viewpoint that a coating film having excellent adhesion to a substrate that is difficult to adhere can be formed. These water-based resins may be used alone or in combination of two or more.

As this urethane resin (b1), the same thing as the said urethane resin (a2) can be used.

The mass ratio [(A) / (B)] of the composite resin (A) to the water-based resin (B) is preferable from the viewpoints of blending stability and adhesion with the hard coating agent described below. The range is from 99/1 to 80/20.

Examples of the aqueous medium (C) include water, water-miscible organic solvents, 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; and polyethylene glycol, diethylene glycol, and propylene glycol. Alkyl glycols; Alkyl ether solvents of polyalkylene glycols; L-amine solvents such as N-methyl-2-pyrrolidone and the like. These water-miscible organic solvents may be used alone or in combination of two or more.

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

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

The composite resin (A) and the aqueous resin (B) are dispersed in the aqueous medium (C) to obtain the aqueous resin composition of the present invention.

The water-based resin composition of the present invention may further contain a water-insoluble additive.

The water-insoluble additive is preferably previously dispersed in an aqueous dispersion of the aqueous resin (B) for use.

Examples of the water-insoluble additive include antioxidants and ultraviolet absorbers. These water-insoluble additives may 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, it is preferable from the viewpoint that a coating film having excellent adhesion to a substrate that is difficult to adhere can be formed, and from the viewpoint of forming a coating film that is excellent in heat resistance, heat discoloration, and automatic suppression of oxidation. It is a phenol-based antioxidant and a phosphorus-based antioxidant. These antioxidants may be used alone or in combination of two or more.

If the molecular weight is too small, the antioxidant tends to move to the surface of the coating film, resulting in a decrease in adhesion to the substrate. On the other hand, if the molecular weight is too large, the compatibility with the water-based resin (B) becomes poor. From a viewpoint, the weight average molecular weight is preferably in the range of 500 to 1,000.

In addition, if the anti-oxidant has a low melting point, the surface of the coating film tends to agglomerate. On the other hand, if the anti-oxidant has a high melting point, the compatibility with the water-based resin (B) becomes poor. 180 ° C range.

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

In addition to the water-insoluble additive, the water-based resin composition of the present invention may be blended with a film auxiliary agent, a hardener, a cross-linking agent, a plasticizer, an antistatic agent, a paraffin, a light stabilizer, and a flow control according to demand. Additives, dyes, levelling agents, rheology control agents, photocatalyst compounds, inorganic pigments, organic pigments, extender pigments, etc.

Examples of the crosslinking agent include melamine compounds, epoxides, An oxazoline compound, a carbodiimide compound, an isocyanate compound, and the like. Examples of the melamine compound include an alkylated methylol melamine resin. The alkylated methylol melamine resin is, for example, a product obtained by reacting a methylolated melamine resin with a lower alcohol (alcohol having 1 to 6 carbon atoms) such as methanol and butanol. Examples of the methylolated melamine resin include a methylol melamine resin having an amine group obtained by condensing melamine and formaldehyde, a methylol melamine resin having an imine group, a trimethoxymethylol melamine resin, Hexamethoxymethylol melamine resin and the like. Among these, a trimethoxymethylol melamine resin and a hexamethoxymethylol melamine resin are preferable. Examples of the alkylated methylol melamine resin include an alkylated methylol melamine resin having an imine group, and an alkylated methylol melamine resin having an amine group.

The laminated body of the present invention has a primer layer formed on one or both sides of a substrate using the aqueous resin composition, and has an active energy ray-curable composition formed on the surface of the primer layer. Hardened coating.

The active energy ray-curable composition preferably includes a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group; such a resin having a polymerizable unsaturated group and a polymerizable unsaturated group. The type of the monomer is preferably appropriately selected in accordance with the characteristics required for the cured coating film of the active energy ray-curable composition.

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

In the present invention, "(meth) acrylate" means one or both of acrylate and methacrylate; "(meth) acrylfluorenyl" means acrylfluorenyl and methacrylfluorenyl- Either or both.

Examples of the urethane (meth) acrylate resin include those obtained by subjecting an aliphatic polyisocyanate or an aromatic polyisocyanate to a urethane reaction with a (meth) acrylate having a hydroxyl group. Resins such as urethane bonds and (meth) acrylfluorene groups.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, and diisocyanate. Octamethylene acid, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecyl diisocyanate Methyl ester, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Ester, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated methylphenyl diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, Cyclohexyl isocyanate and the like. Examples of the aromatic polyisocyanate include methylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and tolylamine diisocyanate. Isocyanate, p-phenylene diisocyanate, etc.

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 Esters, mono (meth) acrylates of dihydric alcohols such as hydroxytrimethylacetate neopentyl glycol mono (meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated tris Methylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acrylfluorenyloxy) Mono- or di (meth) acrylates of trihydric alcohols such as ethyl) hydroxyethyl isocyanurate, or some of these alcoholic hydroxyl groups are modified with ε-caprolactone Mono and di (meth) acrylates with hydroxyl groups; neopentyl tetraol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (methyl) Mono) hydroxy groups such as acrylate and trifunctional The above (meth) acrylfluorenyl compound, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylic acid (Meth) acrylates having an oxyalkylene chain, such as esters, diethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, and polyethylene glycol mono (meth) acrylates Compound; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate, etc. ) Acrylate compounds; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, etc. (Meth) acrylate compounds having an oxyalkylene chain.

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

Examples of the epoxy (meth) acrylate resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and the like. The epoxy resin and (meth) acrylic acid reaction.

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

Examples of the acrylic (meth) acrylate resin include polymerization of (meth) acrylate monomers such as glycidyl methacrylate and (meth) acrylic acid alkyl esters according to demand to obtain a ring having a ring. After the acrylic resin having an oxygen group, the epoxy group is reacted with (meth) acrylic acid.

Examples of the resin having a maleimide group include bifunctional maleimide group obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate. Formate compounds, difunctional maleimide imide esterified by esterification of maleimide imineacetic acid and polytetramethylene glycol, tetramethyl ester of maleimide iminohexanoic acid and neopentaerythritol A tetrafunctional maleimide imide obtained by esterification of an ethylene oxide adduct, a polyfunctional maleimide imide obtained by esterifying maleimide imineacetic acid and a polyol compound, and the like.

Examples of the monomer having a polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylic acid with a number average molecular weight ranging from 150 to 1000 Ester, polypropylene glycol di (meth) acrylate having a number average molecular weight ranging from 150 to 1000, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, hydroxytrimethylacetate neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentaerythritol tetra (meth) acrylate, neopentyl Alcohol tri (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dicyclopentene (meth) acrylate, (meth) Acrylic Methyl ester, propyl (meth) acrylate, butyl (meth) acrylate, third butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, ( (Meth) acrylic acid such as decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate, etc. Aliphatic alkyl ester, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, propylene oxide (meth) acrylate, ( Allyl methacrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamine) (meth) acrylate Methyl) ethyl ester, γ- (meth) acryloxypropyltrimethoxysilane, (meth) acrylate 2-methoxyethyl ester, methoxydiethylene glycol (meth) acrylate, Methoxy dipropylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, (meth) acrylate phenoxy Ethyl ester, phenoxy dipropylene glycol (meth) acrylate, phenoxy poly Propylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, poly Styryl ethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentene (meth) acrylate, Isoamyl (meth) acrylate, methoxylated cyclodecadiene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N- Ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-deca Dimethylmaleimide, N-octadecylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethyl Carbonate, 2-maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) carbamate, N, N-hexamethylenebis Maleimide, polypropylene glycol-bis (3-maleimidepropyl) ether, bis (2-maleimideethyl) carbonate, 1,4-dimaleimide Cyclohexane acyl maleic imide compound. These monomers having a polymerizable unsaturated group may be used alone or in combination of two or more kinds.

This 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 rays include free radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. In a case where ultraviolet rays are irradiated as an active energy ray so that the active energy ray-curable composition becomes a cured coating film, a photopolymerization initiator is preferably added to the active energy ray-curable composition to improve hardenability. Moreover, if necessary, a photosensitizer can be further added, and hardenability can also be improved. On the other hand, when an electron beam, an alpha beam, a beta beam, or a gamma beam is irradiated as an active energy ray so that the active energy ray-curable composition becomes a hardened coating film, the photopolymerization initiator and photosensitizer are not used. It can harden quickly, so there is no need to add photopolymerization initiator and photosensitizer.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethyl (Oxy) -phenyl] -2-hydroxy-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethyl) Benzylfluorenyl) -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, sodium diethyldithiophosphate, and s-benzylthiourea p-toluenesulfonic acid. Sulfide and the like such as s-benzylthiuronium-p-toluenesulfonate.

Examples of the substrate used in the laminated body of the present invention include a metal substrate, a plastic substrate, a glass substrate, a paper substrate, a wood substrate, and a fibrous substrate. Among such substrates, in order to improve the adhesion between the hardened coating film of the active energy ray-curable composition and the substrate, when the water-based resin composition of the present invention is used as a primer, a plastic substrate is preferred. material.

Examples of the material of the plastic substrate include polyester, acrylic resin (such as polymethyl acrylate), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), ABS resin, and polycarbonate. Composite resin, polystyrene, polyurethane, epoxy resin, polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), cellulose triacetate ( TAC) and so on.

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

Examples of the plastic substrate include plastic molded products such as mobile phones, home appliances, automotive interior and exterior materials, and OA equipment. In addition, a film substrate using plastic as a material can also be cited. When a film substrate is used as the substrate of the laminated body of the present invention, it can be used for optical films such as antireflection film, retardation film, and lens, and high-performance films such as food packaging such as aluminum vapor-deposited film.

In addition, when the laminated body of the present invention is used as an optical film such as an anti-reflection film, a retardation film, or a lens, it can be used as a liquid crystal display (LCD), an organic EL display (OLED), or a plasma display (PDP). The various components of the screen display device are used.

For example, the aqueous resin composition of the present invention can be directly coated on the surface of the substrate, and then dried and hardened, thereby forming 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 at room temperature for about 1 to 10 days may be used, but for rapid curing, a temperature of 100 ° C to 150 ° C is preferred. Method of heating for about 1 to 600 seconds. In the case of using a plastic substrate that is easily deformed or discolored at a higher temperature, it is preferable to heat it at a relatively low temperature of about 70 ° C to 100 ° C.

Examples of the method for applying the aqueous resin composition of the present invention to the surface of the substrate include the use of a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, Coating methods such as curtain coater, anastomotic coater, shower coater, air-stream coater, spin coater, dipping, screen printing, spraying, brush coating, applicator, and bar coater.

The film thickness of the coating film formed using the aqueous resin composition of the present invention can be appropriately adjusted according to the application to be used, but it is usually preferably in the range of 0.01 to 20 μm.

The active energy ray-curable composition is further coated on the coating film of the aqueous resin composition of the present invention obtained above, that is, the surface of the primer layer, and the active energy ray is irradiated to form the active energy ray-curable composition. The hardened coating film can be used to obtain the laminated body of the present invention. The method for applying the active energy ray-curable composition may be the same as the method for applying the aqueous resin composition of the present invention.

    [Example]    

Hereinafter, the present invention will be specifically described using examples and comparative examples.

(Synthesis Example 1: Synthesis of Polyester Polyol (1))

While introducing nitrogen into a reaction vessel equipped with a thermometer, a nitrogen introduction 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, and 19.9 parts by mass of two Polyethylene glycol and 0.03 parts by mass of dibutyltin oxide were subjected to polycondensation at 230 ° C for 24 hours until the acid value became 1 or less at 180 to 230 ° C to obtain a polyester polyol (1) [acid value 0.6 , Hydroxyl value 50.0, aromatic ring concentration 4.41mol / Kg].

(Synthesis Example 2: Synthesis of Polyester Polyol (2))

While introducing nitrogen into a reaction vessel equipped with a thermometer, a nitrogen introduction tube, and a 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, 6.2 parts by mass of ethylene glycol, and neopentyl were added. 22.9 parts by mass of diol, 11.7 parts by mass of 1,6-hexanediol, and 0.03 parts by mass of dibutyltin oxide, and the polycondensation reaction was performed at 230 ° C for 24 hours at 180 to 230 ° C until the acid value became 1 or less. The polyester polyol (2) was obtained [acid value 0.6, hydroxyl value 42.5, and aromatic ring concentration 2.51 mol / Kg].

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

46.7 parts by mass of a cresol novolac epoxy resin ("EPICLON N-673-80M" manufactured by DIC Corporation) was added to the reaction container, epoxy equivalent of solid content = 209 g / eq, non-volatile content = 80% by mass, Solvent: methyl ethyl ketone), 13.3 parts by mass of acrylic acid, 0.08 parts by mass of hydroquinone monomethyl ether, and 13.3 parts by mass of methyl ethyl ketone, and they were stirred to uniformly mix them. Next, 0.37 parts by mass of triphenylphosphine was added, and the reaction was performed 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 container, 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 and stirred to make it uniform. mixing. Next, 6.1 parts by mass of 2,2-dimethylolpropionic acid was added, followed by 20.3 parts by mass of isophorone diisocyanate, and the mixture was reacted at 80 ° C. for 12 hours to perform a urethane step. After confirming that the isocyanate value was 0.1% or less, 0.3 parts by mass of n-butanol was added, and the mixture was allowed to react for 2 hours, and then cooled to 50 ° C to obtain a urethane resin having an aromatic ring having a nonvolatile content of 60% by mass ( II-1).

(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 and stirred to make it Mix well. 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 methylphenyl diisocyanate were added, and the mixture was heated at 80 ° C. It was reacted for 12 hours to perform a urethane step. After confirming that the isocyanate value was 0.1% or less, 0.3 parts by mass of n-butanol was added, and after reacting for 2 hours, it was cooled to 50 ° C to obtain 51% by mass of a non-volatile component urethane resin having an aromatic ring (II -2).

(Synthesis Example 6: Synthesis of Urethane Resin (II-3))

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 to the reaction vessel and stirred to uniformly mix them. Next, 6.0 parts by mass of 2,2-dimethylolpropionic acid was added, followed by 18.7 parts by mass of isophorone diisocyanate, and the mixture was reacted at 80 ° C. for 12 hours to perform a urethane step. After confirming that the isocyanate value was 0.1% or less, 0.3 parts by mass of n-butanol was added, and the mixture was allowed to react for 2 hours, and then cooled to 50 ° C to obtain a urethane resin (II-3 having a nonvolatile 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, 938.5 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to obtain a composite resin composition (A-1) having a nonvolatile content of 40% by mass.

(Manufacturing Example 2: Preparation of aqueous resin (B-1) water dispersion)

To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4 were added 1.28 parts by mass of a phenolic antioxidant (1) (molecular weight: 640, melting point: 160 ° C) and 1.28 parts by mass of The phosphorus-based antioxidant is stirred to uniformly mix it. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-1) aqueous dispersion having a non-volatile content of 23% by mass.

(Production Example 3: Preparation of Water Resin (B-2) Water Dispersion)

To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4 were added 2.56 parts by mass of a phenol-based antioxidant (1) and 2.56 parts by mass of a phosphorus-based antioxidant, and the mixture was stirred so that It mixes evenly. Next, 4.8 parts by mass of triethylamine was added, and 548 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-2) aqueous dispersion having a non-volatile content of 23.5% by mass.

(Production Example 4: Preparation of aqueous resin (B-3) water dispersion)

To the urethane resin (II-2) having an aromatic ring obtained in Synthesis Example 5 were added 1.22 parts by mass of a phenol-based antioxidant and 1.22 parts by mass of a phosphorus-based antioxidant, and stirred to uniformly mix them. . Next, 4.6 parts by mass of triethylamine was added, and 390 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure 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) water 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 to uniformly mix them. Next, 4.8 parts by mass of triethylamine was added, and 410 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-4) aqueous dispersion having a non-volatile content of 23.3% by mass.

(Production Example 6: Preparation of aqueous resin (B-5) water dispersion)

To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4, 1.28 parts by mass of a phenol-based oxidizing agent and 1.28 parts by mass of an ultraviolet absorber were added and stirred to uniformly mix them. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-5) aqueous dispersion having a non-volatile content of 23% by mass.

(Manufacturing Example 7: Preparation of aqueous resin (B-6) water dispersion)

To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4 was added 2.56 parts by mass of a phenol-based oxidant, and the mixture was stirred to uniformly mix them. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to dissolve in water. 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 non-volatile content of 23% by mass.

(Manufacturing Example 8: Preparation of water-based resin (B-7) water dispersion)

To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4 was added 2.56 parts by mass of a phosphorus-based oxidant, and the mixture was stirred to uniformly mix them. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-7) aqueous dispersion having a non-volatile content of 23% by mass.

(Production Example 9: Preparation of water-based resin (B-8) water dispersion)

To the urethane resin (II-1) having an aromatic ring obtained in Synthesis Example 4 was added 2.56 parts by mass of an ultraviolet absorber, and the mixture was stirred so as to be uniformly mixed. Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-8) aqueous dispersion having a non-volatile content of 23% by mass.

(Production Example 10: Preparation of aqueous resin (B-9) water dispersion)

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

(Production Example 11: Preparation of aqueous resin (B-10) water dispersion)

To the urethane resin (II-1) obtained in Synthesis Example 4 was added 2.56 parts by mass of a phenol-based antioxidant (3) (molecular weight: 350, melting point: 120 ° C), and the mixture was stirred to uniformly mix them. . Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-10) aqueous dispersion having a non-volatile content of 23% by mass.

(Production Example 12: Preparation of aqueous resin (B-11) water dispersion)

To the urethane resin (II-1) obtained in Synthesis Example 4 was added 2.56 parts by mass of a phenol-based antioxidant (4) (molecular weight: 780, melting point: 240 ° C), and the mixture was stirred to uniformly mix them. . Next, 4.8 parts by mass of triethylamine was added, and 510 parts by mass of ion-exchanged water was slowly added to dissolve in water. Next, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to prepare an aqueous resin (B-11) aqueous dispersion having a non-volatile content of 23% by mass.

(Production Example 13: Preparation of an aqueous resin (B-12) aqueous dispersion)

To the urethane resin (II-1) obtained in Synthesis Example 4 was added 2.56 parts by mass of a phenol-based antioxidant (5) (molecular weight: 530, melting point: 50 ° C), and the mixture was stirred to uniformly mix them. . Next, 4.8 parts by mass of triethylamine was added, and 410 parts by mass of ion-exchanged water was slowly added to dissolve in water. 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 non-volatile content of 23% by mass.

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

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

Table 1 shows the urethane resin, antioxidant, and ultraviolet absorber used in Production Examples 2 to 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 and 2 parts by mass of the aqueous resin (B-1) aqueous dispersion obtained in Production Example 2 were mixed with 302.6 parts by mass of ion-exchanged water Thus, an aqueous resin composition (1) having a non-volatile content of 10% by mass was obtained.

(Examples 2 to 15: Preparation of water-based resin composition (2) to (15))

The aqueous resin dispersion obtained in Production Examples 3 to 13 was used in place of the aqueous resin (B-1) aqueous dispersion used in Example 1, except that the same procedure was performed as in Example 1 to obtain an aqueous resin. Compositions (2) to (15).

The composite resins and water-based resins used in Examples 1 to 15 are shown in Table 2.

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

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) By mixing them, a photocurable resin composition (UV-1) was obtained.

(Example 15: Production of laminated body (1))

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

Next, on the surface of the primer layer, the photocurable resin composition (UV-1) obtained in Preparation Example 1 was applied with a coating film thickness of 15 μm, a high-pressure mercury lamp was used as a light source, and the irradiation intensity was 0.5 J / cm. ^By irradiating ultraviolet rays at ^{2 times} , a laminated body having a primer layer on the surface of the substrate and a cured coating film (hereinafter abbreviated as "UV coating film") of a UV-curable composition on the surface of the primer layer is obtained. (1).

(Examples 16 to 30: Production of laminated bodies (2) to (15))

The aqueous resin compositions (2) to (15) obtained in Examples 2 to 15 were used as the primer layers (P-2) to (P-15), instead of the aqueous resin composition used in Example 15 ( 1) Except for the above, the same procedures as in Example 13 were performed to obtain laminated bodies (2) to (12).

The following adhesiveness evaluation was performed using the aqueous resin composition and laminated body obtained by the said Example and the comparative example.

[Evaluation Method of Adhesion (Initial) of Base Material and Primer Layer]

A primer was coated on the surface of a base material containing polyethylene terephthalate having a film thickness of 125 μm so that the film thickness during drying was about 1 μm, and heated at 150 ° C. for 5 minutes to prepare a test plate. A component comprising a primer layer laminated on the surface of the substrate. Next, a 1-mm checkerboard peeling test was performed using this test plate. Specifically, on the surface of the primer layer of this test board, 100 checkerboards were produced at 1 mm intervals, and an adhesive tape with a width of 24 mm manufactured by NICHIBAN Co., Ltd. was attached thereon.

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

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

Using the laminates obtained in the examples and comparative examples, a 1 mm checkerboard peeling test was performed. On the surface of the UV coating film constituting the laminates obtained in the examples and comparative examples, 100 checkerboards were produced at 1 mm intervals, and an adhesive tape with a width of 24 mm manufactured by NICHIBAN Co., Ltd. was affixed thereto.

Next, the adhesive tape was peeled off 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 from the surface of the UV coating film.

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

The high-pressure mercury lamp was used as a light source, and the obtained laminated body was irradiated with ultraviolet rays at a predetermined number of times under an irradiation intensity of 0.5 J / cm ² , and then the laminated body was taken out to make the adhesiveness between the substrate and the primer layer (initial )] The same method was used to evaluate the adhesion between the substrate and the primer layer. In addition, the UV irradiation cycle test referred to in the present invention refers to a method in which a predetermined number of UV irradiations are performed on a primer layer in advance to intentionally degrade a coating film to evaluate adhesion under more severe conditions. This method was 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 film (after UV irradiation cycle test)]

With respect to the obtained laminated body, a high-pressure mercury lamp was used as a light source, and ultraviolet rays were irradiated at a predetermined number of times at an irradiation intensity of 0.5 J / cm ^2. Then, the surface of the primer layer was coated with a coating film thickness of 15 μm in Preparation Example 1. The obtained photocurable resin composition (UV-1) uses a high-pressure mercury lamp as a light source and irradiates ultraviolet rays again at an irradiation intensity of 0.5 J / cm ² to obtain a primer layer on the surface of the substrate. A laminated body having a UV coating film on the surface of the layer.

Next, the laminated body was taken out, and the adhesiveness between the primer layer and the UV coating film was evaluated in the same manner as in this [Adhesion between the primer layer and the UV coating film (initial stage)].

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

The haze value of the laminated board obtained in the above was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.). The measurement was carried out by a method in accordance with the JIS test method (JIS K7136: 2000). The haze value (H) was calculated by the following formula. Also, only the haze value of the PET substrate was measured, and the haze value was 2.05%.

H (%) = Td / Tt × 100

H: Haze (haze value) (%)

Td: Diffusion transmittance (%)

Tt: total light transmittance (%)

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

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

100 parts by mass of the composite resin composition (A-1) obtained in Production Example 1 was mixed with 300 parts by mass of ion-exchanged water, thereby obtaining an aqueous resin composition (C1) having a nonvolatile content of 10% by mass.

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

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 were mixed to obtain an aqueous resin composition (C2) having a nonvolatile content of 10% by mass.

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

100 parts by mass of the aqueous resin (B-3) aqueous dispersion obtained in Production Example 4 was mixed with 130 parts by mass of ion-exchanged water, thereby obtaining an aqueous resin composition (C3) having a nonvolatile content of 10% by mass.

(Comparative Example 4: Preparation of multilayer body (R1))

The aqueous resin composition (C1) obtained in Comparative Example 1 was applied on 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. This forms a primer layer (P'-1) on the surface of the substrate.

Next, on the surface of the primer layer, the photocurable resin composition (UV-1) obtained in Preparation Example 1 was applied with a coating film thickness of 15 μm, a high-pressure mercury lamp was used as a light source, and the irradiation intensity was 0.5 J / cm ^2. Ultraviolet rays were radiated downward to obtain a laminate (R1) having a primer layer on the surface of the substrate and a UV coating film on the surface of the primer layer.

(Comparative Examples 2 to 3: Production of Laminates (R2) to (R3))

The water-based resin compositions (C2) to (C3) obtained in Comparative Examples 2 to 3 were used as primer layers (P'-2) to (P'-3) instead of the water-based resin composition used in Comparative Example 1. (C1), except that it carried out similarly to the comparative example 1, and obtained laminated body (R2)-(R3).

Table 4 shows the substrates 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, it was confirmed that 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.

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

In addition, Comparative Example 3 is an example using the water-based 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. It was confirmed that the primer layer of Comparative Example 3 had excellent adhesion between the substrate and the primer layer before (initial) the UV irradiation cycle test, and excellent adhesion between the substrate and the primer layer after the UV irradiation cycle test. However, the adhesion between the primer layer and the UV coating film is obviously insufficient.

In addition, Comparative Example 4 is an example using the water-based resin (B-3) obtained in Production Example 4, and it is an example not using the composite resin (A) of the present invention. It can be confirmed that the primer layer of Comparative Example 4 is the same as that of Comparative Example 3, the adhesion between the substrate and the primer layer before (initial) the UV irradiation cycle test, and the substrate and the primer after the UV irradiation cycle test. The adhesion of the paint layer is excellent, but the adhesion of the primer layer and the UV coating film is obviously insufficient.

Claims (12)

    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). An aqueous resin composition, wherein the vinyl ester resin (a1) is one or more epoxy resins (a1-1) selected from the group consisting of a novolac epoxy resin and a bisphenol epoxy resin, and The reactant of the compound (a1-2) having an acid group and a polymerizable unsaturated group; the urethane resin (a2) is a reactant of the polyol (a2-1) and the polyisocyanate (a2-2), The polyol (a2-1) contains a polyol having an aromatic ring and a polyol having a hydrophilic group.         The water-based resin composition according to claim 1, wherein the water-based resin (B) is a urethane resin (b1).         The water-based resin composition according to claim 1 or 2, further comprising a water-insoluble additive.         The water-based resin composition according to claim 3, wherein the water-insoluble additive is one or more additives selected from the group consisting of an antioxidant and an ultraviolet absorber.         The aqueous resin composition according to claim 4, wherein the antioxidant is one or more antioxidants selected from the group consisting of a phenol-based antioxidant and a phosphorus-based antioxidant.         The water-based resin composition according to any one of claims 1 to 5, wherein the mass ratio [(A) / (B)] of the composite resin (A) to the water-based resin (B) is 99/1 to 80/20. range.         The water-based resin composition according to any one of claims 1 to 6, wherein the weight average molecular weight of the antioxidant is in a range of 500 to 1,000.         The water-based resin composition according to any one of claims 1 to 7, wherein the melting point of the antioxidant is in a range of 80 to 180 ° C.         A laminated body characterized in that a primer layer formed using the water-based resin composition according to any one of claims 1 to 8 is provided on one or both sides of a substrate, and the surface of the primer layer has A cured coating film of an active energy ray-curable composition.         The laminated body according to claim 9, wherein the active energy ray-curable resin composition includes a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group.         An optical film characterized by having a multilayer body as claimed in claim 9 or 10.         An image display device, comprising: an optical film as claimed in claim 11.