TWI663053B - Laminates and optical films - Google Patents

Abstract

The present invention provides a laminated body, which is characterized in that an aqueous resin composition containing an aqueous resin (A) having a carboxyl group, an aqueous resin (B) having a sulfonic acid group, and silicon dioxide (C) is used on a surface of a substrate. The formed undercoat layer has a hardened coating film formed on the surface thereof using an active energy ray-curable composition. The laminated body of the present invention uses an aqueous resin composition that is excellent in storage stability and transparency of the coating film as an undercoat layer for improving the adhesion of the cured coating film of the substrate and the active energy ray-curable composition. Even if it is a substrate that is difficult to adhere to, such as a polyester film, it can also be used as an optical film, as it can be used as an optical film by forming a cured coating film of an active energy ray-curable composition on the surface.

Description

Laminates and optical films

The present invention relates to a laminated body and an optical film. When the laminated system forms a hardened coating film of an active energy ray-curable composition on the surface of a substrate, it serves as an undercoat layer for improving the adhesion between the substrate and the hardened coating film. Those using a water-based resin composition containing silica.

In recent years, display devices such as liquid crystal displays are generally composed of a plurality of optical films laminated with various functions in order to display a clear image. Specific examples of the optical film and sheet include, for example, an anti-reflection film, a retardation film, and a reticle.

For the substrate of the optical film, a polyester film is used. In particular, a polyethylene terephthalate (PET) film is used because of excellent optical characteristics, mechanical strength, and durability. Further, in optical applications, a polyester film is coated with an active energy ray-curable composition to harden it to form a hard coat layer, or a polyester layer is formed by casting a layer having the active energy ray-curable composition, thereby curing the polyester. The film is made into a cymbal sheet, but the polyester film has a problem of low adhesiveness with a cured coating film of an active energy ray-curable composition because of high crystallinity.

Therefore, as a method for improving the adhesion between the polyester film and the hardened coating film of the active energy ray-curable composition, it is proposed to use a polyester film as a substrate and the hardened coating film of the active energy ray-curable composition. An undercoat layer including an acrylic resin or a urethane resin is provided between the units (for example, refer to Patent Document 1). At this time, due to the smoothness of the surface of the coating film and the viscosity of the resin used in the primer, there is a problem that blocking occurs when the film is wound or when the film is rolled back. As one of the solutions to such a problem, a method is used for coating a base coating material containing inorganic fine particles such as colloidal silica to form a fine uneven structure on the surface of the coating film to prevent agglomeration (for example, refer to Patent Documents) 2). However, a primer coated with inorganic fine particles may cause agglomeration or precipitation in many cases, resulting in a significant reduction in yield.

Therefore, it is required to have a sufficient adhesion of the cured coating film of the polyester film and the active energy ray-curable composition, and it can also be used as a base coating material that does not caking the coated film after application. Laminated body of optical film.

[Prior technical literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent Application Publication No. 2014-048348

The problem to be solved by the present invention is to provide a laminated body and an optical film using an aqueous resin composition, which is used as a substrate and an active energy ray-hardenable composition that can improve a difficult-to-bond substrate such as polyester. Adhesive primer for hard coating.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found that when an aqueous resin composition containing an aqueous resin having a carboxyl group, an aqueous resin having a sulfonic acid group, and a silica is used as an undercoat layer, For a substrate that is difficult to adhere to, such as polyester, a laminated body that can significantly improve the adhesion of the substrate and the cured coating film of the active energy ray-curable composition can be obtained, and the present invention has been completed.

That is, the present invention relates to a laminated body and an optical film. The features of the laminated body are: the use of an aqueous resin (A) containing a carboxyl group, an aqueous resin (B) containing a sulfonic acid group, and An undercoat layer formed of an aqueous resin composition of silicon oxide (C) has a hardened coating film formed on the surface of the undercoat layer using an active energy ray-curable composition.

The laminated system of the present invention uses an aqueous resin composition having excellent storage stability and excellent transparency of the coating film as a primer for improving the adhesion between the substrate and the cured coating film of the active energy ray-curable composition. The substrate of the polyester film that is difficult to adhere to can also be used as a laminated body that forms a cured coating film of an active energy ray-curable composition on the surface, and is suitable for use as an optical film. Examples of such an optical film include an antireflection film, a retardation film, and a reticle. In addition, these optical films can be applied to image display devices such as liquid crystal displays.

[Form of Implementing Invention]

The laminated system of the present invention has an undercoat layer formed on the surface of a substrate using an aqueous resin composition containing a water-based resin (A) having a carboxyl group, a water-based resin (B) having a sulfonic acid group, and silicon dioxide (C). The surface of the undercoat layer has a cured coating film formed using an active energy ray-curable composition.

The water-based resin (A) having a carboxyl group is a resin that becomes the main agent of the water-based resin composition used as a primer in the present invention, and examples thereof include water-based urethane resins having carboxyl groups and water-based acrylic acid having carboxyl groups Resin, etc.

As for the aqueous urethane resin having a carboxyl group, examples thereof include those obtained by reacting a polyhydric alcohol with a polyisocyanate and a necessary chain extender, and using a carboxyl group in a part of the polyol. It is possible to introduce a carboxyl group into a urethane resin.

Examples of the polyol include polyester polyol, polycarbonate polyol, polyether polyol, and polyolefin polyol. In addition, as the polyol having a carboxyl group used as a raw material of the urethane resin having a carboxyl group, for example, 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutyric acid , 2,2'-dimethylolbutyric acid and 2,2'-dimethylolvaleric acid. Among these, 2,2'-dimethylolpropionic acid is preferable from the viewpoint that the adhesiveness of the base material of the aqueous resin composition used in the present invention can improve the physical properties of the coating film. These polyols can be used alone or in combination of two or more.

Examples of the polyester polyol include polyesters obtained by esterifying a low molecular weight polyol and a polycarboxylic acid, and polyesters obtained by ring-opening polymerization of a cyclic ester compound such as ε-caprolactone. And such copolymerized polyesters.

The low-molecular-weight polyol is preferably one having a molecular weight in the range of 50 to 300. Specific examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and Aliphatic polyols such as ethylene glycol, neopentyl glycol, and 1,3-butanediol; alicyclic structure polyols such as cyclohexanedimethanol; bisphenols such as bisphenol A and bisphenol F Polyols having aromatic rings, such as compounds and these alkylene oxide adducts.

Moreover, examples of the polycarboxylic acid that can be used in the production of the polyester polyol include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid, and anhydride or ester-forming derivatives thereof.

Examples of the polycarbonate polyol that can be used in the polyol include those obtained by reacting a carbonate with a polyol, or those obtained by reacting phosgene with bisphenol A and the like.

Examples of the carbonate include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, and diphenyl carbonate.

Examples of the above-mentioned polyols that can react with carbonate include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3 -Methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, etc. Low molecular weight diols; polyester polyols such as polyethylene glycol, polypropylene glycol and polyhexamethylene adipate.

In addition, as the polyether polyol that can be used in the polyol, for example, one or two or more compounds having two or more active hydrogen atoms are used as initiators, and the alkylene oxide is additionally polymerized. Are waiting.

Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3 butanediol, 1,4-butanediol, and hexamethylene dioxane. Alcohols, bisphenol A, glycerol, trimethylolethane and trimethylolpropane.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

In addition, examples of the polyolefin polyol that can be used in the polyol include polyethylene polyol, polypropylene polyol, polyisobutylene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenation. (Hydrogenated) polyisoprene polyol and the like.

In addition to the above-mentioned polyols, other polyols may be used in combination in addition to the above-mentioned polyols. Examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, and 1,4-butane. Alcohols, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, and cyclohexanedimethanol Polyol.

Examples of the polyol polyisocyanate used as the raw material of the urethane resin include, for example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbodiimide modification. Diphenyl Aromatic polyisocyanates such as methane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, xylylene Aliphatic polyisocyanates such as diisocyanate, tetramethylxylylene diisocyanate, etc .; polyisocyanates having an alicyclic structure, such as cyclohexane diisocyanate, dicyclohexyl methane diisocyanate and isophorone diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

From the viewpoint of further improving the coating film physical properties of the aqueous resin composition used in the present invention, among the above-mentioned polyisocyanates, an aromatic polyisocyanate or a polyisocyanate having an alicyclic structure is preferred, and in particular, it can be further improved. From the viewpoint of light resistance of the coating film of the aqueous resin composition used in the present invention, a polyisocyanate having an alicyclic structure is more preferable.

The urethane resin is, for example, an aqueous urethane resin that is produced by reacting the polyol with the polyisocyanate in the absence of a solvent or an organic solvent, and then, in the urethane resin, When a hydrophilic group is present, it is produced by mixing part or all of the hydrophilic group with an aqueous medium if necessary to make it aqueous, and mixing it with a chain elongating agent as necessary to make it react.

The reaction system of the above-mentioned polyol and polyisocyanate is, for example, that the equivalent ratio [isocyanate group / hydroxyl] of the isocyanate group of the polyisocyanate with respect to the hydroxyl group of the polyol is preferably performed in the range of 0.8 to 2.5. It is more preferable to perform in the range of 0.9 to 1.5.

In addition, the organic solvents that can be used in the production of the urethane resin include ketone solvents such as acetone, methyl ethyl ketone, and the like; Ether solvents such as alkane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amine solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

Examples of the chain extender include ethylenediamine, 1,3-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,6-hexanediamine, and 1,4-cyclohexane Diamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5-bis (amine Methyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, Diamine compounds such as o-toluenediamine, m-toluenediamine and p-toluenediamine; triamine compounds such as diethylenetriamine; polyamines having four or more amino groups such as triethylenetetramine and tetraethylenepentamine Compounds etc. These chain elongating agents may be used alone or in combination of two or more kinds.

Since the urethane resin obtained by using the above-mentioned chain elongating agent has a urea bond in the molecule, it is preferable to form a coating film having excellent abrasion resistance. On the other hand, the above-mentioned urethane resin tends to decrease alcohol resistance due to the influence of urea bonds. Therefore, when forming a coating film having excellent solvent resistance, the above-mentioned urethane resin is Specifically, the urethane resin obtained by using a chain elongating agent or the urethane resin obtained by limiting the amount of the urethane resin used in the above-mentioned urethane resin is used. The urea bond ratio is preferably 10% by mass or less.

The weight-average molecular weight of the urethane resin obtained by the above-mentioned method is in the range of 3,000 to 200,000 from the viewpoint of further improving the adhesion of the cured coating film of the substrate and the active energy ray-curable composition. Better, more preferably in the range of 5,000 to 100,000, and even more preferably in the range of 10,000 to 80,000.

As the water-based acrylic resin having a carboxyl group, for example, a polymer obtained by polymerizing a mixture of (meth) acrylic monomers containing (meth) acrylic acid as an essential component by a conventional method may be mentioned.

Among the (meth) acrylic monomers, examples of the (meth) acrylic monomer other than (meth) acrylic acid include alkyl (meth) acrylate and the like.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylate. Base) tert-butyl acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid Nonyl ester, dodecyl (meth) acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentyl (meth) acrylate, phenyl (meth) acrylate, ( Benzyl meth) acrylate and the like. Among them, an alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms is preferred. The "(meth) acrylic acid" refers to one or both of acrylic acid and (meth) acrylic acid.

Moreover, in the above-mentioned water-based acrylic resin having a carboxyl group, the (meth) acrylic acid for introducing a carboxyl group is 0.5 to 30% by mass based on the total amount of the (meth) acrylic monomers used as a raw material of the acrylic resin. Use within the range.

In addition to the (meth) acrylic monomers that can be used in the production of the above-mentioned acrylic resins, in addition to the above, examples include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Ester, glycerol mono (meth) acrylate, dicyclopentyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2,2,2-trifluoro (meth) acrylate B Ester, 2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, ( Β- (perfluorooctyl) ethyl methacrylate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamine Amine, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N-monoalkyl (methyl) Acrylamide, N, N-dialkyl (meth) acrylamide, styrene or α-methylstyrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl acetic acid , Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, (meth) acrylonitrile, vinyl toluene, vinyl benzene Methyl ether, α-halostyrene, vinylnaphthalene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinyl pyrrolidine Ketone, (meth) acrylic acid, β-carboxyethyl (meth) acrylate, 2- (meth) acryloylpropanoic acid, butyl Acid, itaconic acid half esters, maleic acid half ester, [beta] (meth) Bing Xixi oxyethyl hydrogen succinate, butadiene, isoprene, and the like. In addition, examples of the vinyl monomer having a carboxyl group include ARONIX M-5300 (manufactured by Toa Synthesis Co., Ltd .; ω-carboxyl-polycaprolactone monoacrylate) and the like.

The weight average molecular weight of the acrylic resin having a carboxyl group is more preferably in the range of 3,000 to 200,000, and from 5,000 to 100,000, from the viewpoint of further improving the adhesion between the substrate and the hardened coating of the active energy ray-curable composition. The range is better, and the range is more preferably 8,000 to 80,000.

The water-based resin (B) having a sulfonic acid group is used for the purpose of preventing the agglomeration and sedimentation of silica (C) described later in the water-based resin composition used as a primer in the present invention, and improving storage stability. As for the aqueous resin (B) having a sulfonic acid group, examples thereof include an aqueous polyester resin having a sulfonic acid group, and an aqueous urethane resin having a sulfonic acid group.

As for the above-mentioned water-based polyester resin having a sulfonic acid group, for example, one obtained by reacting a polyhydric alcohol with a polycarboxylic acid, and by using a polyhydric alcohol having a sulfonic acid group in the above-mentioned polyol and polycarboxylic acid portion, Polysulfonic acid with sulfonic acid group can introduce sulfonic acid group into polyester resin. Moreover, the above-mentioned sulfonic acid group may form a salt.

In addition, the amount of the sulfonic acid group-containing polyol or polycarboxylic acid used in the production of the above-mentioned polyester resin is based on the ability to impart good water dispersibility to the above-mentioned polyester resin. The total amount of the above-mentioned polyol and the above-mentioned polycarboxylic acid is preferably used in a range of 3 to 30% by mass.

Examples of the polyol used in the production of the polyester resin include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 2-methyl-1,3. -Propylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl- Aliphatic polyols such as 2-butyl propylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol; polyhydric alcohols having an alicyclic structure, such as 1,4-cyclohexanedimethanol, and the like. In addition, as the polyol, for example, a polyol having three or more hydroxyl groups, such as glycerol, trimethylolethane, trimethylolpropane, and neopentyl tetraol, can be used.

As for the polyol having a sulfonic acid group, for example, a polyol having a sulfonic acid group obtained by sulfonating a polyol having an unsaturated group such as 2-butene-1,4-diol and the like .

Examples of the polycarboxylic acid include aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and biphenyl dicarboxylic acid; oxalic acid, succinic acid, succinic anhydride, and adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and dimerization Saturated or unsaturated aliphatic polycarboxylic acids such as acids; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5- Polycarboxylic acids having an alicyclic structure, such as norbornene dicarboxylic acid and its anhydride, tetrahydrophthalic acid and its anhydride, and the like. Among these, from the viewpoint of imparting more excellent water resistance and solvent resistance, aromatic polycarboxylic acids are preferred, and terephthalic acid and isophthalic acid are more preferred.

In addition to the polycarboxylic acids that can be used in the production of the above polyester resins, in addition to the above, examples include trimellitic acid, pyromelic acid, diphenyl ketone tetracarboxylic acid, trimellitic anhydride, and coke. Melamine anhydride, diphenyl ketone tetracarboxylic anhydride, 1,3,5-trimellitic acid, ethylene glycol bis (trimellitic anhydride), glycerol (trimellitic anhydride), 1, 2, 3, 4- Those having three or more carboxyl groups such as butanetetracarboxylic acid.

Examples of the polycarboxylic acid having a sulfonic acid group include 4-sulfonic acid isophthalic acid, 5-sulfonic acid isophthalic acid, sulfonic acid terephthalic acid, and 4-sulfonic acid naphthalene-2,7 -Dicarboxylic acids, dialkyl esters, etc., and those in which the sulfonic acid group of these compounds becomes a metal salt can also be cited. Among them, long-term storage stability can be maintained, and more excellent water resistance and resistance can be imparted. In terms of solvent, 5-sodium sulfonic acid isophthalate and 5-sodium sulfonic acid isophthalate are more preferred.

The weight average molecular weight of the above-mentioned polyester resin having a sulfonic acid group can impart water resistance to the coating film from the viewpoint of imparting more excellent storage stability, viscosity suitable for coating operations, and film-forming properties to the aqueous resin composition used in the present invention. In terms of resistance and solvent resistance, those having a weight average molecular weight of 5,000 to 30,000 are more preferred, and those having a weight average molecular weight of 5,000 to 15,000 are more preferred.

In the above-mentioned aqueous urethane resin having a sulfonic acid group, for example, a polyol having a sulfonic acid group or a metal salt of a sulfonic acid group may be used instead of the raw material of the aqueous urethane resin having a carboxyl group. Those using polyols with carboxyl groups.

Examples of the polyhydric alcohol having a sulfonic acid group include, for example, a polyester polyol using a polycarboxylic acid having a sulfonic acid group or a metal salt of a sulfonic acid group as a raw material, and by using 2-butene-1,4- Polyols having unsaturated groups, such as diols, are obtained by sulfonating polyols having sulfonic acid groups.

The sulfonic acid group concentration in the sulfonic acid group-containing aqueous resin (B) can further improve the dispersibility of the following silicon dioxide (C) in the aqueous resin composition used as a primer in the present invention, and To further improve the storage stability of the above-mentioned aqueous resin composition, a range of 0.5 to 2 mol / kg is preferable, and a range of 0.8 to 1.5 mol / kg is more preferable. Moreover, the sulfonic acid group concentration in the present invention is calculated from the amount of raw materials used.

In terms of the above silicon dioxide (C), from the viewpoint of further improving the transparency of the coating film of the aqueous resin composition used as a primer in the present invention, those having a nanometer size are preferred, and colloidal dioxide is used. Silicon good. The specific average particle diameter of the silicon dioxide (C) is preferably in a range of 5 to 100 nm, more preferably in a range of 10 to 50 nm, and even more preferably in a range of 10 to 20 nm. The average particle size is determined from the results measured by a dynamic light scattering method.

The content of the above-mentioned silicon dioxide (C) can further improve the transparency of the coating film of the aqueous resin composition used as a primer in the present invention, and can further prevent agglomeration. 100 parts by mass of the resin (A) is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.2 to 5 parts by mass, and even more preferably in the range of 0.4 to 3 parts by mass.

In addition, the content of the above-mentioned sulfonic acid group-containing water-based resin (B) can further improve the storage stability of the water-based resin composition used as a primer in the present invention, relative to the above-mentioned silica (C) 100. The mass part is preferably in the range of 20 to 400 parts by mass, more preferably in the range of 50 to 300 parts by mass, and even more preferably in the range of 100 to 250 parts by mass.

The water-based resin composition used in the present invention can be blended with film assistants, hardeners, crosslinking agents, plasticizers, antistatic agents, waxes, light stabilizers, flow regulators, dyes, and leveling agents as required. Additives, rheology control agents, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments; other resins such as polyester resins, urethane resins, acrylic resins, etc.

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

The laminated system of the present invention has an undercoat layer formed using the aqueous resin composition used in the present invention described above, and has a hardened coating film formed on the surface of the undercoat layer using an active energy ray-curable composition.

As for the active energy ray-curable composition, it is preferable to include a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group, and the resin having a polymerizable unsaturated group and the polymerizable unsaturated group. The type of the monomer is preferably selected appropriately 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 urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, and polyester (meth) Acrylate 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, and "(meth) acrylfluorenyl" means one of acrylfluorenyl and methacrylfluorenyl Or both.

Examples of the urethane (meth) acrylate resin include, for example, an aliphatic polyisocyanate or an aromatic polyisocyanate and a (meth) acrylate having a hydroxyl group obtained by a urethane reaction. A urethane bond and a methacryl group-based resin.

Examples of the aliphatic polyisocyanate include, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and decamethylene Diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane Diisocyanates, hydrogenated toluene diisocyanates, hydrogenated xylylene diisocyanates, hydrogenated tetramethylxylylene diisocyanates, cyclohexyl diisocyanates, and the like. Examples of the aromatic polyisocyanate include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, benzylamine diisocyanate, and Terephthalic acid, 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 (methyl) Mono (meth) acrylates of dihydric alcohols such as acrylate, neopentyl glycol mono (meth) acrylate, hydroxytrimethylacetic acid neopentyl glycol mono (meth) acrylate, etc .; trimethylolpropane Di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, and Mono or di (meth) acrylates of triols such as bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups starts with ε-caprolactone modified mono or di (meth) acrylates with hydroxyl groups; neopentaerythritol tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, dixin A compound having a monofunctional hydroxyl group and a trifunctional or more methacrylfluorenyl group, such as pentaerythritol penta (meth) acrylate, or a polyfunctional hydroxyl group modified with ε-caprolactone (Meth) acrylates; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) (Meth) acrylate compounds having an oxyalkylene chain such as acrylates; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate (Meth) acrylate compounds having an oxyalkylene chain block structure; poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) ) Mono (meth) acrylate and other random structure (meth) acrylate compounds having an oxyalkylene chain.

The unsaturated polyester resin is an α, β-unsaturated dibasic acid or an anhydride thereof, an aromatic saturated dibasic acid or an anhydride thereof, and a curable resin obtained by polycondensation of ethylene glycol. Examples of the α, β-unsaturated dibasic acid or anhydride thereof include maleic acid, maleic anhydride, fumaric acid, and Iraq Conic acid, citraconic acid, chloromaleic acid and esters thereof. Examples of the aromatic saturated dibasic acid or its anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, methylenetetrahydrophthalic anhydride, and halogenation. Phthalic anhydride and esters of these. Examples of the aliphatic or cycloaliphatic saturated dibasic acid include, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof Wait. Examples of the diol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 2-methylpropane-1,3-diethylene glycol. Alcohol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, and 2, In addition to 2-di- (4-hydroxypropoxydiphenyl) propane and the like, oxides such as ethylene oxide and propylene oxide can be similarly used.

Examples of the epoxy (meth) acrylate resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin. It is obtained by reacting (meth) acrylic acid in epoxy group of epoxy resin.

As for the polyester (meth) acrylic resin, for example, one obtained by reacting (meth) acrylic acid in a hydroxyl group of a polyester polyol.

Examples of the acrylic (meth) acrylate resin include, for example, polymerization of propylene methacrylate and methacrylate monomers such as alkyl (meth) acrylate as necessary to obtain an epoxy group. An acrylic resin is obtained by reacting (meth) acrylic acid with the epoxy group.

Examples of the above-mentioned resin having a maleimidine group include, for example, N-hydroxyethylmaleimide and isophorone diisocyanate via an amine group. Bifunctional maleimide imide compound obtained from formication, bifunctional maleimide imide compound obtained by esterification of maleimide imine acetic acid and polybutylene glycol, horse 4-functional maleimide imide compound, maleimide imide acetic acid and polyhydric alcohol compound obtained by esterification of tetraethylene oxide adduct of lyme iminohexanoic acid and neopentyl tetraol. The obtained multifunctional maleimide imide 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 in the range of 150 to 1000 Ester, polypropylene glycol di (meth) acrylate having a number average molecular weight ranging from 150 to 1,000, 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) Methyl enoate, propyl (meth) acrylate, butyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate Aliphatic (A) such as decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate Base) acrylic Acid alkyl ester, glyceryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, propylene oxide (meth) acrylate, (formaldehyde) Allyl) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate Esters, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, benzene Oxydipropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene Glycol-polybutylene glycol (meth) acrylate, polystyrene ethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate Ester, dicyclopentenyl (meth) acrylate, (meth) propyl Norbornyl enoate, methoxylated cyclodecadiene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethyl horse Lyme, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecyl Maleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethyl carbonate , 2-maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) carbamate, N, N-hexamethylenebismaleimide Amines, polypropylene glycol-bis (3-maleimide imidopropyl) ether, bis (2-maleimide iminoethyl) carbonate, and 1,4-dimaleimide imide cyclohexane醯 imine compounds and so on. These single systems having a polymerizable unsaturated group may be used alone, or two or more of them may be used in combination.

The active energy ray-curable composition can form a cured coating film after being coated with a substrate or the like and irradiated with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron rays, alpha rays, beta rays, and gamma rays. When ultraviolet rays are used as active energy rays to irradiate the active energy ray-curable composition as a hardened coating film, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve the hardenability. Moreover, if necessary, a photosensitizer may be further added to improve the hardenability. On the other hand, when an electron beam, an alpha ray, a beta ray, or a gamma ray is irradiated as the active energy ray and the active energy ray-curable composition is used as a hardened coating film, a photopolymerization initiator or a photosensitizer may not be used It hardens quickly, so there is no need to add a photopolymerization initiator or photosensitizer.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1- [4- (2-hydroxyethyl (Oxy) -phenyl] -2-hydroxy-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-N-morpholinylpropane 1-one, 2-benzyl-2-dimethylamino-1- (4-N-morpholinylphenyl) -butanone, bis (2,6-dimethoxybenzyl)- 2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzylfluorenyl) -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-benzylisothioureanium-p-toluene. Sulfur compounds such as sulfonates.

Examples of the substrate used in the laminated body of the present invention include, for example, metal substrates, plastic substrates, glass substrates, paper substrates, and wood Substrate and fiber substrate. Among these substrates, since the adhesion between the cured coating film of the active energy ray-curable composition and the substrate can be improved, the water-based resin composition used in the present invention is used as a primer when used. A plastic substrate is preferred.

As for the material of the above plastic substrate, for example, polyester, acrylic resin (such as polymethyl methacrylate), 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.), triethyl醯 cellulose (TAC) and so on.

The water-based resin composition used in the present invention is extremely 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.

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

Furthermore, when the laminated body of the present invention is used as an optical film such as an anti-reflection film, a retardation film, and a cymbal, it can be used for various screen displays such as a liquid crystal display (LCD), an organic EL display (OLED), and a plasma display (PDP). Use of device components.

The aqueous resin composition used in 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. The method of drying and hardening the aqueous resin composition used in the present invention can be a method of curing at room temperature for about 1 to 10 days, and because the hardening can be performed quickly, it is heated at a temperature of 100 ° C to 150 ° C. A method of about 1 to 600 seconds is preferred. Moreover, when used in plastic substrates that are easily deformed or discolored at higher temperatures, it is better to heat at a lower temperature of 70 ° C to 100 ° C.

Examples of the method for applying the aqueous resin composition used in the present invention to the surface of the substrate include using a gravure coater, a roll coater, a notch wheel coater, a knife coater, and an air knife coater. Coating methods for machines, curtain coaters, kiss coaters, shower coaters, flow coaters, spin coaters, dipping, screen printing, spray coating, brush coating, applicators, bar coaters and the like.

The thickness of the coating film formed by using the water-based resin composition used in the present invention can be appropriately adjusted depending on the intended use, but generally it is preferably in the range of 0.01 to 20 μm.

The laminated body of the present invention can be obtained by applying the above-mentioned active energy ray-curable composition and irradiating active energy on the surface of the undercoat layer of the coating film of the aqueous resin composition used in the present invention obtained as described above. The radiation is obtained by forming a cured coating film of the active energy ray-curable composition. Moreover, the coating method of the said active-energy-ray-curable composition can use the same method as the coating method of the aqueous resin composition used for the said invention.

[Example]

Hereinafter, the present invention will be specifically described using 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 dibutyltin while introducing nitrogen into a reaction vessel having a thermometer, a nitrogen introduction tube, and a stirrer Polyester polyol (1) was obtained by carrying out polycondensation reaction with 0.03 mass part of oxides so that an acid value might become 1 or less at 180-230 degreeC.

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

While introducing nitrogen gas into a reaction vessel having a thermometer, a nitrogen introduction tube, and a stirrer, 35.4 parts by mass of 1,6-hexanediol, 17.8 parts by mass of ε-caprolactone, and 5-sodium sulfonic acid isophthalic acid were introduced. Polyester polyol (2) was obtained by performing a polycondensation reaction with 10.7 parts by mass of methyl ester, 6.2 parts by mass of ethylene glycol, and 0.03 parts by mass of dibutyltin oxide at 180 to 230 ° C so that the acid value becomes 1 or less.

(Synthesis example 3: Synthesis of polyester resin (1))

23.9 parts by mass of isophthalic acid, 44.8 parts by mass of terephthalic acid, 27.9 parts by mass of ethylene glycol, 23.9 parts by mass of diethylene glycol, and dibutyltin while introducing nitrogen into a reaction vessel having a thermometer, a nitrogen introduction tube, and a stirrer 0.03 parts by mass of the oxide was heated to 240 ° C over 4 hours, and then the reaction was continued at 240 ° C to collect about 13 parts by mass of the distillate. Next, 10.7 parts by mass of dimethyl 5-sodium sulfonate isophthalate and 0.03 parts by mass of tetraisopropyl titanate were fed, and a polycondensation reaction was performed at 220 to 280 ° C. under a reduced pressure of 0.07 to 1.3 kPa for 1 hour. To obtain a polyester resin (1).

(Synthesis example 4: Synthesis of polyester resin (2))

23.9 parts by mass of isophthalic acid, 44.8 parts by mass of terephthalic acid, 27.9 parts by mass of ethylene glycol, 23.9 parts by mass of diethylene glycol, and dibutyltin while introducing nitrogen into a reaction vessel having a thermometer, a nitrogen introduction tube, and a stirrer 0.03 parts by mass of the oxide was heated to 240 ° C over 4 hours, and then the reaction was continued at 240 ° C to collect about 13 parts by mass of the distillate. Next, 26.5 parts by mass of trimellitic acid and 0.03 parts by mass of tetraisopropyl titanate were fed, and a polycondensation reaction was performed at 220 to 280 ° C and a reduced pressure of 0.07 to 1.3 kPa for 1 hour to obtain a polyester resin (2) .

(Production Example 1: Synthesis of an aqueous urethane resin having a carboxyl group)

In a reaction vessel, 100 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1 was dehydrated at 100 ° C under reduced pressure, and then cooled to 80 ° C. Then, 33.7 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, and then 23.1 parts by mass of isophorone diisocyanate was added, and the mixture was reacted at 80 ° C. for 12 hours to perform a urethane reaction. After confirming that the isocyanate value became 0.1% or less, 3 parts by mass of n-butanol was added, and the mixture was further reacted for 2 hours, and then cooled to 50 ° C. to obtain a non-volatile 80% by mass urethane resin having a carboxyl group.

Next, 3.7 parts by mass of triethylamine was added to 139.8 parts by mass of the urethane resin obtained above, and 391.5 parts by mass of ion-exchanged water was slowly added. Next, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain a non-volatile 22.5 mass% carboxyl-based aqueous urethane resin (neutralizer).

(Production Example 2: Synthesis of water-based acrylic resin having a carboxyl group)

In 29.0 parts by mass of ethyl acrylate, 37.0 parts by mass of methyl methacrylate, and 3.16 parts by mass of acrylic acid, 60.0 parts by mass of methyl ethyl ketone, 8.0 parts by mass of N-methyl-2-pyrrolidone, and azo were prepared. A mixture of 4.0 parts by mass of isobutyronitrile. Next, 25% by mass of the mixture was added to a reaction vessel, and the temperature was raised to 80 ° C. Then, the remaining 75% by mass of the mixture was added dropwise over 3 hours while stirring under a nitrogen atmosphere. At this time, the temperature in the reaction system was maintained at 80 ° C. After the dropwise addition was completed, 2.0 parts by mass of azoisobutyronitrile was added, and the mixture was further reacted at 80 ° C. for 5 hours, thereby obtaining an acrylic resin having a carboxyl group with a nonvolatile content of 52.5 mass%.

Next, 3.0 parts by mass of triethylamine was added to 100 parts by mass of the acrylic resin obtained above, and 200.5 parts by mass of ion-exchanged water was slowly added. Next, methyl ethyl ketone was removed at 30 ° C. to 50 ° C. under a reduced pressure to obtain a non-volatile matter 22.5% by mass of an aqueous acrylic resin (neutralizer) having a carboxyl group.

(Production Example 3: Synthesis of water-soluble polyester resin having sulfonic acid group)

In a reaction container, 100 parts by mass of the polyester resin (1) obtained in Synthesis Example 3 was dehydrated at 100 ° C under reduced pressure, and then cooled to 80 ° C. Then, 33.7 parts by mass of methyl ethyl ketone was added and stirred to uniformly mix. . Next, 391.5 parts by mass of ion-exchanged water was slowly added. Then, methyl ethyl ketone was removed at 30 ° C. to 50 ° C. under reduced pressure to obtain a nonvolatile matter 25.0% by mass of a water-based polyester resin having a sulfonic acid group. The concentration of the sulfonic acid group in the aqueous polyester resin having a sulfonic acid group was 1.19 mol / kg.

(Production Example 4: Synthesis of an aqueous urethane resin having a sulfonic acid group)

In a reaction container, 100 parts by mass of the polyester polyol (2) obtained in Synthesis Example 2 was dehydrated at 100 ° C under reduced pressure, and then cooled to 80 ° C. Then, 33.7 parts by mass of methyl ethyl ketone was added and stirred to make it uniform. mixing. Next, 6.1 parts by mass of 2-butyl-2-ethyl-1,3-propanediol was added, followed by 23.1 parts by mass of isophorone diisocyanate, and the mixture was reacted at 80 ° C. for 12 hours to perform a carbamate step. . After confirming that the isocyanate value was 0.1% or less, 3 parts by mass of n-butanol was added, and the mixture was further reacted for 2 hours, and then cooled to 50 ° C to obtain a non-volatile 80% by mass urethane resin.

Next, 391.5 parts by mass of ion-exchanged water was slowly added to 139.8 parts by mass of the urethane resin obtained above. Then, methyl ethyl ketone was removed at 30 ° C. to 50 ° C. under reduced pressure to obtain a non-volatile matter 25.0% by mass of an aqueous urethane resin having a sulfonic acid group. The concentration of the sulfonic acid group in the aqueous urethane resin having a sulfonic acid group was 1.04 mol / kg.

(Manufacturing example 5: Synthesis of water-based polyester resin)

In a reaction container, 100 parts by mass of the polyester resin (2) obtained in Synthesis Example 4 was dehydrated at 100 ° C under reduced pressure, and then cooled to 80 ° C. Then, 33.7 parts by mass of methyl ethyl ketone was added and stirred to uniformly mix. . Next, 3.7 parts by mass of triethylamine was added, and 391.5 parts by mass of ion-exchanged water was slowly added. Then, by removing methyl ethyl ketone at 30 ° C. to 50 ° C. under reduced pressure, a non-volatile matter 25.0% by mass of an aqueous polyester resin was prepared.

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

By mixing 444 parts by mass of a nonvolatile matter of a carboxyl group-containing aqueous urethane resin obtained in Production Example 1 with 444 parts by mass (100 parts by mass of a carboxyl-based aqueous urethane resin), Example 3 25% by mass of a non-volatile matter of a water-based polyester resin having a sulfonic acid group, 2.24 parts by mass (0.56 parts by mass of a water-based polyester resin having a sulfonic acid group), and colloidal silica (Nissan Chemical Industries, Ltd. "Snowtex OL" manufactured by Co., Ltd .; nonvolatile matter 20% by mass dispersion) 2.2 parts by mass (0.44 parts by mass in terms of silicon dioxide) to obtain an aqueous resin composition (1).

(Preparation example 2: Preparation of water-based resin composition (2))

By mixing 444 parts by mass of a nonvolatile matter of a carboxyl group-containing aqueous urethane resin obtained in Production Example 1 with 444 parts by mass (100 parts by mass of a carboxyl-based aqueous urethane resin), Non-volatile matter 25% by mass solution of sulfonic acid-based water-based polyester resin obtained in Example 3. 4.44 parts by mass (1.11 parts by mass of water-based polyester resin with sulfonic acid group) and colloidal silica (Nissan Chemical "Snowtex OL" manufactured by Industrial Co., Ltd .; 20% by mass non-volatile dispersion) 4.45 parts by mass (0.89 parts by mass in terms of silicon dioxide) to obtain an aqueous resin composition (2).

(Preparation example 3: Preparation of water-based resin composition (3))

444 parts by mass of a non-volatile matter 22.5 mass% solution of a carboxyl-containing aqueous urethane resin composition obtained in Production Example 1 (100 mass parts for a carboxyl-based aqueous urethane resin) 2. 8.88 parts by mass of a nonvolatile matter 25% by mass solution of the sulfonic acid-based water-based polyester resin composition obtained in Production Example 3 (2.22 parts by mass of the sulfonic acid-based water-based polyester resin) and colloidal dioxide 8.9 parts by mass of silicon ("Snowtex OL" manufactured by Nissan Chemical Industry Co., Ltd .; nonvolatile matter 20% by mass dispersion) (1.78 parts by mass in terms of silicon dioxide) to obtain an aqueous resin composition (3).

(Preparation example 4: Preparation of aqueous resin composition (4))

444 parts by mass of a non-volatile matter 22.5 mass% solution of a carboxyl-containing aqueous urethane resin composition obtained in Production Example 1 (100 mass parts for a carboxyl-based aqueous urethane resin) 2. 11.1 parts by mass of a nonvolatile matter 25% by mass solution of a sulfonic acid-based aqueous polyester resin composition obtained in Production Example 3 (2.78 parts by mass for a sulfonic acid-based aqueous polyester resin) and colloidal dioxide 11.1 parts by mass of silicon ("Snowtex OL" manufactured by Nissan Chemical Industry Co., Ltd .; nonvolatile matter 20% by mass dispersion) (2.22 parts by mass in terms of silicon dioxide) to obtain an aqueous resin composition (4).

(Preparation example 5: Preparation of water-based resin composition (4))

A water-based urethane resin having a sulfonic acid group obtained in Production Example 4 was used in place of the water-based polyester resin composition having a sulfonic acid group used in Preparation Example 1 except that the water-based polyester resin composition having a sulfonic acid group used in Preparation Example 1 was obtained. Aqueous resin composition (5).

(Preparation example 6: Preparation of water-based resin composition (6))

A water-based acrylic resin having a carboxyl group obtained in Production Example 2 was used in place of the water-based urethane resin composition having a carboxyl group used in Preparation Example 1, and a water-based resin composition was obtained in the same manner as in Preparation Example 1. 6).

(Comparative preparation example 1: preparation of water-based resin composition (C1))

444 parts by mass of a nonvolatile matter of a carboxyl group-containing aqueous urethane resin obtained in Production Example 1 (444 parts by mass of a carboxyl-based aqueous urethane resin) and colloid Silicon dioxide ("Snowtex OL" manufactured by Nissan Chemical Industries, Ltd .; no 20% by mass of volatile matter dispersion liquid) 2.2 parts by mass (0.44 parts by mass in terms of silicon dioxide) to obtain an aqueous resin composition (C1).

(Comparative preparation example 2: preparation of water-based resin composition (C2))

444 parts by mass of a nonvolatile matter of a carboxyl group-containing aqueous urethane resin obtained in Production Example 1 (444 parts by mass of a carboxyl-based aqueous urethane resin) and colloid Silicon dioxide ("Snowtex OL" manufactured by Nissan Chemical Industries, Ltd .; nonvolatile 20% by mass dispersion) 4.45 parts by mass (0.89 parts by mass in terms of silicon dioxide) to obtain an aqueous resin composition (C2) .

(Comparative preparation example 3: preparation of water-based resin composition (C3))

444 parts by mass of a nonvolatile matter of a carboxyl group-containing aqueous urethane resin obtained in Production Example 1 (444 parts by mass of a carboxyl-based aqueous urethane resin) and colloid 11.2 parts by mass of silicon dioxide ("Snowtex OL" manufactured by Nissan Chemical Industry Co., Ltd .; nonvolatile matter 20% by mass dispersion) (2.22 parts by mass in terms of silicon dioxide) to obtain an aqueous resin composition (C3) .

(Comparative preparation example 4: preparation of water-based resin composition (C4))

An aqueous resin composition (C4) was obtained in the same manner as in Preparation Example 1 except that the aqueous polyester resin obtained in Production Example 5 was used instead of the aqueous polyester resin having a sulfonic acid group used in Preparation Example 1.

(Comparative Preparation Example 5: Preparation of Aqueous Resin Composition (C5))

A water-based acrylic resin having a carboxyl group obtained in Production Example 2 was used in place of the water-based urethane resin having a carboxyl group used in Comparative Preparation Example 2, and the same procedure as in Comparative Preparation Example 2 was performed to obtain an aqueous resin composition C5).

The compositions of the aqueous resin compositions (1) to (6) obtained in Preparation Examples 1 to 6 and the aqueous resin compositions (C1) to (C5) obtained in Comparative Preparation Examples 1 to 5 are shown in Table 1. In addition, the composition (blending amount) in Table 1 is represented by the amount of non-volatile matter.

(Preparation example 7: Preparation of ultraviolet curable composition (UV-1))

By mixing 50 parts by mass of a urethane acrylate resin ("Unidic 17-824-9" manufactured by Dickson Corporation) and 12.5 parts by mass of methyl ethyl ketone, an ultraviolet curable composition (UV- 1).

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

By mixing 100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1 and 275 parts by mass of ion-exchanged water, a primer (P-1) was obtained. Next, the surface of the film substrate (thickness: 125 μm) made of polyethylene terephthalate (hereinafter referred to as “PET”) was coated so that the film thickness after drying was about 1 μm (P). -1) An undercoat layer is formed on the surface of the substrate by heating at 150 ° C for 5 minutes.

The UV curable composition (UV-1) obtained in Preparation Example 7 was applied so that the film thickness was 15 μm on the surface of the undercoat layer. After heating at 80 ° C. for 10 minutes, a high-pressure mercury lamp was applied to the coated surface. As a light source, ultraviolet rays were irradiated with an irradiation amount of 0.5 J / cm ² to obtain a hardened coating film (hereinafter referred to as "UV coating film") having an undercoat layer on the surface of the substrate and an ultraviolet curable composition on the surface of the undercoat layer. ) Laminated body (1).

(Examples 2 to 6: Production of laminated bodies (2) to (6))

In addition to using the aqueous resin compositions (2) to (6) obtained in Preparation Examples 2 to 6, instead of the aqueous resin composition (1) used in Example 1, the undercoats (P-2) to (P-6) were prepared. Except), it carried out similarly to Example 1, and obtained laminated bodies (2) to (6).

(Comparative Example 1: Production of multilayer body (R1))

100 parts by mass of the aqueous resin composition (C1) obtained in Comparative Preparation Example 1 and 275 parts by mass of ion-exchanged water were mixed to obtain a primer (P'-1). Next, the surface of the PET film substrate (thickness: 125 μm) was coated with the above-mentioned primer (P'-1) so that the film thickness after drying was about 1 μm, and heated at 150 ° C for 5 minutes. An undercoat layer is formed on the surface of the substrate.

The UV curable composition (UV-1) obtained in Preparation Example 7 was applied so that the film thickness was 15 μm on the surface of the undercoat layer. After heating at 80 ° C. for 10 minutes, a high-pressure mercury lamp was applied to the coated surface. As a light source, an ultraviolet ray was irradiated with an irradiation amount of 0.5 J / cm ² to obtain a multilayer body (R1) having an undercoat layer on the surface of the substrate and a UV coating film on the surface of the undercoat layer.

(Comparative Examples 2 to 5: Production of laminated bodies (R2) to (R5))

In addition to using the aqueous resin compositions (C2) to (C5) obtained in Comparative Preparation Examples 2 to 5 in place of the aqueous resin composition (C1) used in Comparative Example 1, the undercoats (P'-2) to (P Except for '-5), it carried out similarly to the comparative example 1, and obtained laminated body (R2)-(R5).

The following evaluations were performed using the water-based resin compositions and laminates obtained in the above examples and comparative examples.

(Assessment method for preservation stability)

The water-based resin composition obtained immediately after the preparation of the preparation example and the comparative preparation example was stored in a room temperature environment for 7 days. The appearance of the water-based resin composition was observed with the naked eye, and the storage stability was evaluated based on the following criteria.

：: No aggregate was observed, and there was no change compared to the substance immediately after production.

○: Although some precipitates were confirmed, it was a practically usable grade, and the precipitates could be redispersed by stirring again.

(Triangle | delta): The amount of precipitate was a little, and even if it stirred again, a part of the precipitate remained, and it was not able to fully re-disperse.

×: About 50% by mass or more of the total amount of the resin precipitated, and it could not be dispersed again even after stirring again.

[Evaluation method of substrate adhesion]

A 24 mm wide adhesive tape manufactured by Nichiban Co., Ltd. was adhered to the surface of the UV coating film of the laminated body obtained as described above. Next, the adhesive tape was stretched in a vertical direction to the undercoat layer, and the surface state of the undercoat layer when the adhesive tape was peeled from the surface of the undercoat layer was visually evaluated according to the following evaluation criteria. The measurement was performed in accordance with a JIS test method (JIS K5600: 1999).

：: The UV coating film was not peeled off from the substrate surface at all.

○: Less than 10% of the total area of the UV coating film is peeled from the substrate surface.

Δ: 10% or more and less than 50% of the total area of the UV coating film is peeled from the substrate surface.

×: 50% or more of the total area of the UV coating film was peeled from the substrate surface.

[Measurement of haze value (film appearance)]

The haze value of the laminated board obtained above was measured with a haze meter (manufactured by Suga Testing Machine Co., Ltd.). The measurement was performed in accordance with a JIS test method (JIS K7136: 2000). The haze value (H) is calculated by the following calculation formula. Moreover, the haze value of only the PET substrate was also measured, and the haze value was 2.05%.

H (%) = Td / Tt × 100

H: Haze (haze value) (%)

Td: Diffusion transmittance (%)

Tt: total light transmittance (%)

：: Compared to the haze value of the PET base material alone, the increase rate of the haze value was less than 10%, and no aggregate was observed.

○: Compared with the haze value of the PET base material alone, the increase rate was 10% or more and less than 20%, and no aggregate was observed.

(Triangle | delta): Compared with the haze value of a PET base material only, an increase rate is 20% or more and less than 50%, and agglomerate was slightly observed.

×: Compared with the haze value of the PET base material alone, the increase rate was 50% or more, and many aggregates were observed.

The evaluation results are shown in Table 2.

From the evaluation results of Examples 1 to 6 shown in Table 2, it can be confirmed that the aqueous resin composition used in the laminated body of the present invention is excellent in storage stability, and that the coating film obtained by using the aqueous resin composition is excellent in transparency. . Moreover, it was confirmed that the laminated body of this invention is excellent in the adhesiveness with a base material.

On the other hand, Comparative Examples 1 to 5 are examples in which an aqueous resin composition containing no aqueous resin having a sulfonic acid group is used. It can be confirmed that compared with the aqueous resin composition used in the laminated body of the present invention, the storage stability is significantly inferior, and the transparency of the coating film obtained by using the aqueous resin composition is also low. Furthermore, it was also confirmed that the adhesion between the laminate and the substrate obtained in Comparative Examples 1 to 5 was insufficient.

Claims (6)

A laminated body characterized in that it has a base formed on the surface of a substrate using an aqueous resin composition containing an aqueous resin (A) having a carboxyl group, an aqueous resin (B) having a sulfonic acid group, and a silicon dioxide (C). A coating layer, the surface of the undercoat layer has a hardened coating film formed using an active energy ray-curable composition, and the water-based resin (A) having a carboxyl group is a water-based urethane resin. The laminated body according to claim 1, wherein the water-based resin (B) having a sulfonic acid group is a polyester resin having a sulfonic acid group or a urethane resin having a sulfonic acid group. The laminated body according to claim 1, wherein the concentration of the sulfonic acid group in the aqueous resin (B) having a sulfonic acid group is in a range of 0.5 to 2 mol / kg. For example, the laminated body of claim 1, wherein the content of the silicon dioxide (C) is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing aqueous resin (A). For example, the layered product of claim 1, wherein the content of the sulfonic acid-based water-based resin (B) is in the range of 20 to 400 parts by mass relative to 100 parts by mass of the silicon dioxide (C). An optical film characterized by including a laminated body according to any one of claims 1 to 5.