Hardening components, hardened substances, laminates

Abstract

To provide an active energy ray-curable resin composition which enables formation of a cured coating film having excellent adhesion, and excellent adhesion and moisture resistance necessary for an undercoat layer and a top coat layer, a cured product of the composition, and a laminate having a cured coating film formed from the cured product on the surface of a base material.SOLUTION: An active energy ray-curable resin composition is provided, including polyglycerol (meth)acrylate (A), a (meth)acrylic monomer (B), urethane (meth)acrylate (C) including a constitutional unit derived from the following compounds (c1), the following constitutional unit derived a compound (c2) and the following constitutional unit derived from the compound (c3), a (co)polymer (D) of a vinyl-based monomer, and a photopolymerization initiator (E). The compound (c1): isocyanate compound having at least two isocyanate groups, the compound (c2): at least one polyol compound selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol, and the compound (c3): compound having a hydroxyl group and a (meth)acryloyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable resin composition, and more particularly to an active energy ray-curable resin composition for metallization treatment. For forming a coating layer with excellent adhesion and moisture resistance, suitable for dark coat layers and top coat layers. The present invention relates to an active energy ray-curable resin composition. [Background technology]

[0002] An undercoat layer (primer layer) is formed on the surface of the plastic molded product, and then After forming a metal film by metallization processes such as ionized deposition or sputtering, a top coat is applied. Laminates with these layers are widely used in fields such as decorative items and home appliances. .

[0003] For example, Patent Document 1 discloses a method for producing a compound having an acrylic polymer and a trifunctional or higher (meth)- and aluminum-based polymer as a substrate. A method for forming a base coat by applying and curing a coating material comprising a chelate compound is described. Patent Document 2 describes a method for producing a polymerizable composition of urethane (meth)acrylate and poly(meth)acrylic acid ester. A coating made of rubber and photoreactive resin is applied and hardened to provide adhesion to plastics and metals. A method for forming a coating having the above properties is described. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-87274 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-77273 Summary of the Invention [Problem to be solved by the invention]

[0005] The undercoat and topcoat are installed in areas that are exposed to the outside air, so they are moisture resistant. In addition, adhesion is also important because the coating film loses its functionality if it peels off from the substrate or between layers. However, the undercoat layers described in Patent Documents 1 and 2 are adhesive. However, there were problems with insufficient durability and moisture resistance.

[0006] The object of the present invention is to provide a method for producing a coating having excellent adhesion and durability required for an undercoat layer, a topcoat layer, etc. Active energy ray curable resin composition capable of forming a cured coating film having moisture resistance, and curing method of the composition and a laminate having a cured coating film made of the cured product on the surface of a substrate. do.

[0007] As a result of extensive research into solving the above problems, the present inventors have discovered that an active energy ray curable composition By blending a specific (meth)acrylate monomer into the mold resin composition, the cured coating The inventors have found that the adhesion and moisture resistance of the film are improved, and have arrived at the present invention.

[0008] The present invention includes the following [1] to [7]. [1] A polyfunctional glycerin (meth)acrylate (A) and a (meth)acrylic monomer ( B) and the following structural units derived from compound (c1), structural units derived from compound (c2), and a urethane (meth)acrylate (C) containing a structural unit derived from a compound (c3) and a vinyl-based monomer; (D) a monomer (co)polymer and (E) a photopolymerization initiator. Finished product. Compound (c1): an isocyanate compound having at least two isocyanate groups Compound (c2): Polyether polyol, polyester polyol, polycarbonate at least one polyol selected from the group consisting of Compound (c3): a compound having a hydroxyl group and a (meth)acryloyl group [2] Component (A) is 5 to 40% by mass relative to 100% by mass of the total amount of components (A) to (D); 10 to 60 mass% of component (B), 10 to 40 mass% of component (C), and 1 to 40 mass% of component (D). % by mass of the active energy ray-curable resin composition according to [1]. [3] The compound (c2) is a polyol selected from the following (c21) or (c22): The active energy ray-curable resin composition according to any one of [1] and [2]. Compound (c21): A compound obtained from an aliphatic polycarboxylic acid having 2 to 22 carbon atoms and a polyhydric alcohol. Polyester polyol Compound (c22): Polyether polyol having 2 to 5 carbon atoms in the repeating unit [4] The compound (c21) is a sebacic acid polyester polyol, [1] to [ 3] The active energy ray-curable resin composition according to any one of the above items. [5] The molecular weight of the compound (c21) is 500 or more and less than 3,000. The active energy ray-curable resin composition according to any one of [1] to [4]. [6] The compound (c22) is polytetramethylene glycol, [1] to [3] The active energy ray-curable resin composition according to any one of the above items. [7] The molecular weight of the compound (c22) is 500 or more and less than 3,000. The active energy ray-curable resin composition according to any one of [1] to [3] and [6]. . [8] The active energy ray-curable resin composition according to any one of [1] to [7], A cured product obtained by irradiating with reactive energy rays. [9] A laminate having a cured coating film made of the cured product according to [8] on the surface of a substrate. [Effects of the Invention]

[0009] The present invention provides a film having excellent moisture resistance and excellent adhesion required for an undercoat layer, a topcoat layer, etc. Active energy ray curable resin composition capable of forming a cured coating film having adhesiveness and moisture resistance, and a laminate having a cured coating film made of the cured composition on the surface of a substrate. It is possible. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. "(Meth)acrylic" means "acrylate" and / or "methacrylate" "(Meth)acryloyl" means "acryloyl" and / or "methacryl"; and / or "methacryloyl", and "(meth)acrylonitrile" means "acrylonitrile" " and / or "methacrylonitrile", and "(co)polymerization" means "homopolymerization" and / or " It means "copolymerization."

[0011] [Active energy ray-curable resin composition] The active energy ray-curable resin composition of the present invention (hereinafter referred to as the present composition) is At least one polyfunctional glycerin (meth)acrylate (A) [referred to as component (A)] a monomer (B) other than component (A) having a (meth)acryloyl group [referred to as component (B)] ], and the compound (c1), the compound (c2), and the compound (c3) described below are reacted to obtain Urethane (meth)acrylate (C) [referred to as component (C)], vinyl monomer (copolymer) ) polymer (D) [referred to as component (D)], and a photopolymerization initiator (E) [referred to as component (E)] The active energy ray-curable resin composition includes the following:

[0012] [Component (A)] The component (A) blended in this composition is a (meth)acrylate having a structure derived from glycerin. It is a hydroxyl group monomer used to give the cured product adhesion and moisture resistance. The molecular weight of component (A) is preferably 100 to 1,000, more preferably 110 to 500. If the molecular weight is equal to or greater than the lower limit of the range, the toughness of the coating film is improved. When the content is below the upper limit of the range, the smoothness of the coating film is improved.

[0013] Examples of polyfunctional glycerin (meth)acrylates that can be used as component (A) include: Glycerin di(meth)acrylate, glycerin tri(meth)acrylate, ethylene glycol Oxide-modified glycerin di(meth)acrylate, ethylene oxide-modified glycerin Di(meth)acrylate, propylene modified glycerin di(meth)acrylate, propylene Modified glycerin tri(meth)acrylate, multifunctional polyglycerin (meth)acrylate Examples include: Among these, glycerin diacrylate and / or glycerin diacrylate are preferred from the viewpoint of providing adhesion and moisture resistance to the coating film. Alternatively, glycerin triacrylate is preferred.

[0014] [Composition ratio of component (A)] The blending ratio of component (A) is 5 to 40 mass % of the total amount of components (A) to (D). %, and more preferably 5 to 30 mass %. The more component (A) is added, the more improved the moisture resistance is. The smaller the amount, the more likely it is that the adhesion between the cured coating film and the metal film will improve.

[0015] [Component (B)] Component (B) is a monomer other than component (A) that has at least one (meth)acryloyl group. Component (B) may be selected appropriately depending on the performance required of the cured coating film. Monomers having one (meth)acryloyl group that can be used as component (B) include , for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Hydroxyl group-containing hydrocarbon skeletons such as acrylate, 4-hydroxybutyl (meth)acrylate, etc. (Meth)acrylates with acrylate; 2-ethylhexyl (meth)acrylate, Lauryl acrylate, 2-isobutyl-2-methyl acrylate, etc. (Meth)acrylate;Tetrahydrofurfuryl (meth)acrylate, 2-ethyl -2-methyl-1,3-dioxolan-4-yl-methyl (meth)acrylate, isobutanol norbornyl(meth)acrylate, norbornyl(meth)acrylate, adamantyl(meth)acrylate ) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethicone Clopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, phen Phenyloxyethyl (meth)acrylate, Phenyloxydiethylene glycol (meth) Acrylate, ethylene oxide modified cresol (meth)acrylate, nonylphenyl Paracumylphenyloxyethyl (meth)acrylate, Paracumylphenyloxyethyl (meth)acrylate acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate cyclohexyloxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, t-Butylcyclohexyloxyethyl (meth)acrylate, benzyloxyethyl ( (meth)acrylate, isobornyloxyethyl (meth)acrylate, norbornyloxyethyl (meth)acrylate oxyethyl (meth)acrylate, adamantyloxyethyl (meth)acrylate, etc. (Meth)acrylates with a ring skeleton; 2-Methoxyethyl (meth)acrylate, 3- Methoxybutyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol Lithium (meth)acrylate, methoxytripropylene glycol (meth)acrylate Methoxydibutylene glycol (meth)acrylate, Methoxytributylene glycol Ethoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol Triethylene glycol (meth)acrylate, ethoxydipropylene glycol ( (meth)acrylate, ethoxytripropylene glycol (meth)acrylate, ethoxy Dibutylene glycol (meth)acrylate, ethoxytributylene glycol (meth)acrylate Alkoxy group-containing hydrocarbon skeletons such as acrylate, butoxyethyl (meth)acrylate, etc. (Meth)acrylates having hydroxyl groups; (meth)acrylamides such as dimethylacrylamide (meth)acrylamides having a heterocycle such as acryloylmorpholine;

[0016] Monomers having two (meth)acryloyl groups that can be used as component (B) include: , tricyclodecane dimethanol di(meth)acrylate, cyclohexane dimethanol Di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, bisphenoxy Di(meth)acrylates having a ring skeleton such as difluoreneethanol di(meth)acrylate Bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate Di(meth)acrylates with an isocyanuric acid skeleton, such as neopentyl glycol modified diacrylates Trimethylolpropane di(meth)acrylate and other compounds with a trimethylolpropane skeleton di(meth)acrylate; 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate Tandanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate 3-Methyl-1,5-pentanediol di(meth)acrylate, 2,4-diethyl- 1,5-Pentanediol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate Acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanedio di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methylpropional 1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12- Dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate Hydrocarbon skeletons such as acrylates and 1,14-tetradecanediol di(meth)acrylate Di(meth)acrylates with acrylates; Tripropylene glycol di(meth)acrylate and di(meth)acrylates having a polyether skeleton, such as polybutylene glycol di(meth)acrylate. p) acrylates.

[0017] Monomers having three (meth)acryloyl groups that can be used as component (B) include: For example, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol Tri(meth)acrylate having a pentaerythritol skeleton, such as erythritol tri(meth)acrylate meth)acrylate; Trimethylolpropane tri(meth)acrylate, tris(ethoxy)acrylate Trimethylolpropanes such as acrylated trimethylolpropane tri(meth)acrylate Tri(meth)acrylate with a pan-anionic skeleton; Tris(2-acryloyloxyethyl) Examples include tri(meth)acrylates having an isocyanuric acid skeleton such as isocyanurate. do.

[0018] The monomer having four or more (meth)acryloyl groups that can be used as component (B) is Examples of suitable acrylates include dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol pentaacrylate (Meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate ) acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated Pentaerythritol tetra(meth)acrylate and other compounds having a pentaerythritol skeleton Poly(meth)acrylate; Ditrimethylolpropanetetra(meth)acrylate and the like.

[0019] Examples of epoxy poly(meth)acrylates that can be used as component (B) include: Sphenol-type epoxy di(meth)acrylate, novolac-type epoxy di(meth)acrylate Examples include Related.

[0020] Examples of polyester poly(meth)acrylates that can be used as component (B) include: , phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, Polybasic acids such as azelaic acid and adipic acid, and ethylene glycol, hexanediol, poly Esterification reaction with polyols such as polyethylene glycol and polytetramethylene glycol The reaction of the polyester polyol obtained by the reaction with (meth)acrylic acid or its derivatives The resulting compounds include:

[0021] As component (B), urethane (meth)acrylates other than component (C) can also be used. As component (B), one compound can be used alone, or two or more compounds can be used in combination. The molecular weight of component (B) is preferably 80 to 2500, more preferably 90 to 2300. If the molecular weight is equal to or greater than the lower limit of the range, the toughness of the coating film is improved. When the content is below the upper limit of the range, the smoothness of the coating film is improved.

[0022] [Component (B) blend ratio] The blending ratio of component (B) is 10 to 60 mass% of the total amount of components (A) to (D). The more the amount of component (B) is, the more the smoothness is improved, and the more the amount of component (B) is, the more the smoothness is improved. The toughness of the coating film tends to improve as the amount of

[0023] [Component (C)] The component (C) blended in this composition is a urethane (meth)acrylate having a structure derived from compound (c1). Examples of the component (C) include the compound (c1) and the compound (c2) described below. and urethane (meth)acrylate obtained by reacting compound (c2) with compound (c3). Component (C) is a cured coating film obtained by curing the composition (hereinafter simply referred to as the cured coating film). This contributes to the toughness of the steel.

[0024] [Compound (c1)] The compound (c1) is an isocyanate compound having at least two isocyanate groups. The compound (c1) contributes to the flexibility of the coating film. As the compound (c1), for example, a compound conventionally used for producing urethane (meth)acrylate can be used. Examples of the compound (c1) include 1,3-phenylene. Diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate; Diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexyl Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate aliphatic polyisocyanates such as lysine diisocyanate and lysine triisocyanate; Isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, Alicyclic polyisocyanates such as methylcyclohexylene diisocyanate; xylene diisocyanate Aromatic and aliphatic polyisocyanates such as isocyanate and tetramethylxylylene diisocyanate biuret and allophanate forms of these. Among these, 1,3-phenylenediisopropyl acrylate is preferred because it can impart excellent toughness to the coating film. Cyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate , 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4 ,4'-Diphenylmethane diisocyanate Isophorone diisocyanate, Bis(4-isocyanate) isocyanatocyclohexyl)methane, 1,2-hydrogenated xylylene diisocyanate, 1,4- Hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, nor Bornane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2 Aliphatic diisocyanates such as 2,4-trimethylhexamethylene diisocyanate is preferred. In the synthesis of component (C), one compound may be used alone as compound (c1), or two or more compounds may be used in combination. The compounds can be used in combination.

[0025] [Compound (c2)] Compound (c2) is a polyether polyol, polyester polyol, polycarbonate At least one polyol selected from the group consisting of hydroxyl polyols and the following compounds: Compound (c21) or compound (c22) is a compound that improves the crater resistance of the coating film, Contributes to smoothness. In the synthesis of component (C), one type of polyol is used as compound (c2). They can be used alone or in combination of two or more.

[0026] [Compound (c21)] Compound (c21) is obtained from an aliphatic polycarboxylic acid having 2 to 22 carbon atoms and a polyhydric alcohol. It is a polyester polyol that can be used. The aliphatic polycarboxylic acids having 2 to 22 carbon atoms used as raw materials for compound (c21) include , for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid Phosphoric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, aconitic acid Among these, polyesters are preferred. Oxalic acid, malonic acid, succinic acid, glycerol, and glycerol are preferred because they make it easier to control the molecular weight of the ester polyol. Arthric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid Among these, sebacic acid is preferred from the viewpoint of compatibility. is preferred.

[0027] Examples of polyols used as raw materials for compound (c21) include neopentyl glycol Coal, ethylene glycol, diethylene glycol, propylene glycol, 1,6- Hexanediol, 1,4-butanediol, 1,9-nonanediol, 1,10-decane Diol, 3-methylpentanediol, 2,4-diethylpentanediol, tricycle Rhodecane dimethanol, 1,4-cyclohexane dimethanol, 1,2-cyclohexane dimethanol Methanol, 1,3-cyclohexanedimethanol, cyclohexanediol, hydrogenated bis(cyclohexanediol) Examples include phenol A, trimethylolpropane, and pentaerythritol. The polyester polyol used as the compound (c21) is, for example, sebacic acid Polyester polyol, adipic acid polyester polyol, terephthalic acid polyester Among these, the coating film In view of moisture resistance, polyester polyol sebacic acid is preferred.

[0028] When compound (c21) is used as a raw material for component (C), component (C) contains compound (c2 1) The structure derived from aliphatic polycarboxylic acids with 2 to 22 carbon atoms and polyhydric alcohols The polyester polyol may have a structure in which at least two hydroxyl groups have been removed from the polyester polyol.

[0029] [Compound (c22)] Compound (c22) is a polyether polyol having a repeating unit with 2 to 5 carbon atoms. be. The compound (c22) is a polyether polyether having a repeating unit having 2 to 5 carbon atoms. Examples of the alcohol include polyethylene glycol, polypropylene glycol, and polypropylene glycol. Among these, polytetrafluoroethylene glycol is preferred from the viewpoint of moisture resistance of the coating film. Lamethylene glycol is preferred.

[0030] To synthesize component (C), compounds (c21) and (c22) were added as raw polyols. In addition, other polyols can be used in combination. For example, neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol Glycol, 1,6-hexanediol, 1,4-butanediol, 1,9-nonanediol 1,10-decanediol, 3-methylpentanediol, 2,4-diethylpentane Diol, Tricyclodecane Dimethanol, 1,4-Cyclohexane Dimethanol, 1,2 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexane Diol, hydrogenated bisphenol A, trimethylolpropane, pentaerythritol, etc. Polyols: These polyhydric alcohols are mixed with ethylene oxide, propylene oxide, Polyether modified polyols to which alkylene oxides such as ethylene oxide are added; These polyhydric alcohols, ε-caprolactone, γ-butyrolactone, and γ-valerolactone Polycaprolactone polycaprolactone obtained by reacting with lactones such as δ-valerolactone These polyhydric alcohols and polybasic acids, ε-caprolactone, γ-butyrolactone carboxylates obtained by reacting with lactones such as valerolactone, γ-valerolactone, and δ-valerolactone. Prolactone modified polyester polyol; 1,6-hexanediol, 3-methylpentene Tandiol, 2,4-diethylpentanediol, trimethylhexanediol, 1,4 -butanediol, 1,5-pentanediol, 1,4-cyclohexanediol, etc. ethylene carbonate, dimethyl carbonate, diethyl carbonate, di- n-Propyl carbonate, diisopropyl carbonate, dibutyl carbonate, diisopropyl carbonate Transesterification with carbonate esters such as cyclohexyl carbonate and diphenyl carbonate Polycarbonate diol obtained by reaction; polybutadiene glycol Among these, neopentyl glycol and ethyl glycol are preferred because they provide good curing properties for the present composition. Ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol 1,4-butanediol, 1,9-nonanediol, 1,10-decanediol, 3 -Methylpentanediol, 2,4-diethylpentanediol, tricyclodecanediol ethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, Cyclohexanediol, Hydrogenated Bisphenol A Polyols such as trimethylolpropane and pentaerythritol are preferred. The molecular weight of (c21) is preferably 500 or more and less than 3000. The molecular weight is preferably 500 or more and less than 3000. If the molecular weight is above the lower limit, the moisture resistance of the coating film is If it is equal to or less than the upper limit, the appearance of the coating film becomes good.

[0031] [Compound (c3)] The compound (c3) is a compound having a hydroxyl group and a (meth)acryloyloxy group. Compound (c3) is a compound in which the hydroxyl group is an isocyanate of compound (c1) or an isocyanate obtained from compound (c1). The compound (C) forms a urethane bond with the isocyanate group of the intermediate compound having the carboxylate group. Any compound capable of introducing a (meth)acryloyloxy group into the compound may be used. Examples of the compound (c3) include 2-hydroxyethyl (meth)acrylate, 2- Hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 6-hydroxyhexyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate Trimethylolpropane di(meth)acrylate, pentaerythritol (Meth)acrylates such as tri(meth)acrylate, and these (meth)acrylates Among these, the component (C) with low viscosity is Therefore, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( Among these, 4-hydroxybutyl (meth)acrylate is preferred. In the synthesis of the component (C), one compound may be used alone or two or more compounds may be used as the compound (c3). Can be used together.

[0032] [Synthesis method of component (C)] The component (C) can be synthesized by, for example, a conventionally known urethane (meth)acrylate synthesis method. As a specific synthesis method, for example, 2 molar of compound (c1) is placed in a flask. 1, and then add a known catalyst such as dibutyltin dilaurate. The temperature in the flask is raised to 4 While maintaining the temperature at 0 to 80°C, 1 mol of compound (c2) was added dropwise using a dropping funnel. A urethane prepolymer having an isocyanate group is obtained. Compound (c3) 2mo having a hydroxyl group equivalent to the isocyanate group remaining at the polymer terminal l is added dropwise, and the mixture is heated to 60 to 85°C to react with the isocyanate groups of the urethane prepolymer and compound (c3) Component (C) can be synthesized by carrying out an addition reaction with the hydroxyl group of The reaction rate at the end point can be determined by quantifying the remaining isocyanate groups. It is 97% or more, more preferably 99% or more.

[0033] [Composition ratio of component (C)] The blending ratio of component (C) in this composition is 10 to 100% based on the total amount of components (A) to (D). The blending ratio of component (C) is preferably 40% by mass, and more preferably 10 to 30% by mass. The smaller the amount, the more the toughness of the cured coating film improves, and the smaller the amount, the more the smoothness improves.

[0034] [Component (D)] Component (D) is a (co)polymer of a vinyl monomer. Component (D) can be produced by the following method: For example, one or more vinyl-based polymerization initiators may be used in the presence of a conventionally known radical polymerization initiator. Examples of the method include a method of polymerizing a monomer by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or the like. Examples of vinyl monomers that can be used as raw materials for component (D) include methyl (meth)acrylate. ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate Acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2 -Ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl Sil(meth)acrylate, benzyl(meth)acrylate, dicyclopentanyl(meth)acrylate ) acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxy Ethyl (meth)acrylate, isobornyl (meth)acrylate, methoxyethyl (meth)acrylate meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate Acrylate, methoxyethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate tetrahydrofurfuryl (meth)acrylate, etc., which do not contain hydroxyl groups (Meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl 3-Hydroxypropyl (meth)acrylate, 4-Hydroxypropyl (meth)acrylate hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl (meth)acrylate; Adduct of hydroxyethyl (meth)acrylate and ethylene oxide, 2-hydroxyethyl Adduct of 2-hydroxyethyl (meth)acrylate and propylene oxide, 2-hydroxyethyl (meth)acrylates such as adducts of acrylate and ε-caprolactone hydroxyl group-containing vinyl monomers such as adducts of vinylates with alkylene oxides or organic lactones; Styrene, α-methylstyrene, pt-butylstyrene, vinyltoluene, and other styrenes or styrene derivatives; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide p) acrylamide and other acrylamides; (meth)acrylic acid, itaconic acid, maleic acid unsaturated carboxylic acids such as fumaric acid; unsaturated nitriles such as (meth)acrylonitrile; Diethyl itaconate, dibutyl maleate, dibutyl fumarate, diethyl itaconate, Unsaturated carboxylic acid esters such as dibutyl phosphate; vinyl acetate, vinyl propionate, etc. Esters are included. As the component (D), one type of (co)polymer may be used alone, or two or more types of (co)polymers may be used in combination. It can be used in combination.

[0035] [Composition ratio of component (D)] The blending ratio of component (D) is preferably 1 to 40 mass % based on the total amount of components (A) to (D). The higher the blending ratio of component (D), the better the hardness of the cured coating film. Improves adhesion to metal films, and the less it is used, the more the smoothness of the cured coating film tends to improve. . The molecular weight of component (D) is preferably 10,000 to 60,000, and more preferably 13,000 to 400 00 is more preferable, and 15,000 to 30,000 is even more preferable. If it is below the upper limit range, the coating film will have improved toughness and chemical resistance. will improve.

[0036] [Component (E)] Component (E) is a photopolymerization initiator that cures the composition by irradiation with active energy rays. Component (E) is, for example, a benzophenone type, an anthraquinone type, an alkane type, Kilphenone type, thioxanthone type, acylphosphine oxide type, phenylglyon Examples of photopolymerization initiators include xylate-type photopolymerization initiators. Examples of the component (E) include benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, methyl orthobenzoylbenzoate and 4-phenyl Benzophenone-type anthraquinones such as benzophenone; t-butylanthraquinone and 2-ethylanthraquinone Anthraquinones such as 2-hydroxy-2-methyl-1-phenylpropane 1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propanone}, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl Benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]- 2-Morpholino-1-propanone and 2-hydroxy-1-{4-[4-(2-hydroxy dimethyl-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, Alkylphenone type such as 2,2-dimethoxy-1,2-diphenylethan-1-one;2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,di Thioxanthone types such as ethylthioxanthone and isopropylthioxanthone; 2,4, 6-Trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentylphosphine oxide and bis(2,4 ,6-trimethylbenzoyl)-phenylphosphine oxide and other acylphosphines Oxide type: Phenylglyoxylic acid methyl ester and other phenylglyoxylic acid Examples include silate-type photopolymerization initiators. Among these, benzophenone and 2-ethyl benzophenone are preferred in terms of dryness to the touch of the present composition. Laquinone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2 -diphenylethan-1-one is preferred. As component (E), one compound can be used alone, or two or more compounds can be used in combination.

[0037] [Amount of ingredient (E)] The amount of component (E) to be blended is 0.1 parts by mass relative to 100 parts by mass of the total amount of components (A) to (D). The amount of component (E) is preferably from 1 to 15 parts by mass, and more preferably from 1 to 10 parts by mass. The more the curing property of the composition in an air atmosphere is improved, and the less the amount of the component ( E) tends to be less.

[0038] [Photosensitizer] The composition may contain a photosensitizer as needed. Examples of the photosensitizer include: Methyl 4-dimethylaminobenzoate, Ethyl 4-dimethylaminobenzoate, 4-dimethyl Examples of known photosensitizers include amyl aminobenzoate and 4-dimethylaminoacetophenone. It is possible.

[0039] [Organic solvents] The composition may contain an organic solvent as needed to adjust the viscosity, etc. Examples of organic solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones, cyclohexanone and other ketone compounds; methyl acetate, ethyl acetate, butyl acetate, Ester compounds such as ethyl lactate and methoxyethyl acetate; diethyl ether, ethylene glycol Diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol Ether compounds such as cholesteryl monobutyl ether and dioxane; toluene, xylene, etc. Aromatic compounds; aliphatic compounds such as pentane, hexane, and petroleum naphtha; isopropyl alcohol Alcohol compounds such as ethanol, isobutanol, and n-butanol; 1-methoxypropanolic acid Examples of suitable compounds include propylene glycol compounds such as 1-methoxypropanol acetate and 1-methoxypropanol acetate. It is possible.

[0040] [Other ingredients] The composition may contain leveling agents, antifoaming agents, anti-settling agents, lubricants, abrasives, rust inhibitors, antistatic agents, Additives such as photo-curing agents, light stabilizers, ultraviolet absorbers, and polymerization inhibitors may also be added. In addition, as long as the effect of the present invention is not impaired, components other than component (D) such as alkyd resins may be used. Resins may also be blended.

[0041] [Laminate] The laminate of the present invention is a cured product obtained by curing the composition by irradiating it with active energy rays. The composition is a laminate having a cured coating film on the surface of a substrate. When forming a metal film by metallization treatment such as tarring, an anti-oxidant is formed on the surface of the base material in advance. The substrate is preferably a molded product made of resin. Examples of such molded articles include ABS resin, AES resin, polycarbonate, and acrylic. Resins such as styrene resins and polystyrene; polyolefins such as polypropylene and polyethylene; Examples of the composition include molded articles made of polyesters such as PET and PBT. Cosmetic containers and housings for home appliances made of recarbonate and acrylic resins, etc., where excellent appearance is desired. It is suitable as a material for the undercoat layer in the metallization treatment of molded articles.

[0042] The substrate as described above, the cured coating film (undercoat layer) made of the cured product of the present composition, and the metal A laminate in which the films are laminated in this order is a preferred example of the laminate of the present invention.

[0043] To form an undercoat layer on a substrate, the composition is applied to the surface of the substrate and activated energy is applied to the surface of the substrate. The thickness of the undercoat layer is preferably in the range of 3 to 40 μm. .

[0044] The composition is laminated on the surface of a metal film formed by a metallization process such as vapor deposition or sputtering. In this case, the undercoat layer of the metal film can be formed by the composition of this invention. It is not necessary that the composition be formed from an undercoat formed from the present composition as described above. The coating layer is preferably formed from the present composition because it has good moisture resistance and smoothness. It's nice.

[0045] To form a topcoat layer on a metal film, the composition is applied to the surface of the metal film, and activated energy is applied to the surface. The thickness of the top coat layer is preferably in the range of 3 to 40 μm. .

[0046] The composition can be applied by, for example, brush coating, spray coating, dip coating, or the like. These include the stencil method, spin coating method, and flow coating method. In terms of the efficiency and uniformity, spray coating and flow coating are preferred.

[0047] When the present composition contains an organic solvent, the applied composition is irradiated with active energy rays. It is preferable to volatilize the organic solvent before curing. In this case, an IR heater or hot air It is preferable to heat the mixture at 30 to 70°C for 2 to 8 minutes to volatilize the organic solvent.

[0048] The active energy rays used to cure the composition include ultraviolet rays, electron beams, and the like. For example, when irradiating ultraviolet rays using a high-pressure mercury lamp, the energy The amount is preferably 100 to 5000 mJ / cm2, more preferably 500 to 2000 mJ / cm2. I wish.

[0049] To form a metal film on the undercoat layer, which is a cured coating film of the present composition, a vapor deposition method or a sputtering method is used. Known metallization methods such as tarring can be used. [Example]

[0050] The present invention will be described in detail below with reference to examples. The examples below are not intended to limit the scope of the present invention. In the examples, "parts" and "%" refer to mass standards. do. The weight average molecular weight of each component is the weight average molecular weight converted into the molecular weight of standard polystyrene. This can be measured using a high performance liquid chromatograph.

[0051] [Synthesis Example 1: Production of urethane acrylate (UA-1)] In a flask equipped with an internal thermometer, a stirrer, and a condenser, compound (c1) was added isophorone diisocyanate. cyanate (hereinafter referred to as IPDI) 152.3 parts, compound (c22) "PTM G2000 (Mitsubishi Chemical, polytetramethylene glycol) 666.2 parts, reaction 0.04 parts of dibutyltin dilaurate (DBTDL) was added as a catalyst and the reaction was carried out at 70°C. When the residual isocyanate group was 3.6% or less, 2-hydroxybenzoates were converted into compound (c3). 81.5 parts of hydroxyethyl acrylate (HEA), 2,6-di-tert-butyl acrylate as a polymerization inhibitor t-Butylcresol (BHT) 0.05 parts, 4-Methoxyphenol (MEHQ) 0. Add 40 parts of the mixture, react at 70°C, and when the residual isocyanate group becomes 0.1% or less, The reaction was terminated to produce urethane acrylate UA-1, which is component (C).

[0052] [Synthesis Example 2: Production of urethane acrylate (UA-2)] In a flask equipped with an internal thermometer, a stirrer, and a condenser, compound (c1) was added isophorone diisocyanate. cyanate (hereinafter referred to as IPDI) 152.3 parts, compound (c21) "SE- 2003" (Ito Oil, Sebacic acid / 1,3-propanediol polyester polyol) 666.2 parts of dibutyltin diol (hydroxyl value 57.7 mg KOH / g), 0.04 parts of laurate (DBTL) was added and the reaction was carried out at 70°C. When the value of the compound (c3) becomes 3.6% or less, 2-hydroxyethyl acrylate is used. (HEA) 81.5 parts, 2,6-di-tert-butylcresol (B 0.05 parts of HT) and 0.40 parts of 4-methoxyphenol (MEHQ) were added and reacted at 70°C. The reaction is terminated when the residual isocyanate groups reach 0.1% or less, and component (C) A urethane acrylate UA-2 was prepared.

[0053] [Synthesis Example 3: Production of Copolymer (PA-1)] Put 500g of toluene into a 2L four-neck flask and heat it so that the internal temperature reaches 80℃. Next, 125 g (25% by mass) of N-(n-butoxymethyl)acrylamide, 200g (40% by mass) of methyl methacrylate, 175g (35% by mass) of styrene, and a polymerization catalyst A mixture of 1 g of azobisisobutylnitrile as a solvent was added dropwise to the flask at a constant rate for 2 hours. The dropping was carried out while stirring the contents of the flask and maintaining the internal temperature at 80°C. After that, 0.2 g of azobisisobutylnitrile was added every hour for a total of four times while the temperature was kept at 80°C. After stirring for 6 hours, copolymer PA-1, component (D), was produced. The measured weight average molecular weight was 25,000 in terms of polystyrene.

[0054] [Synthesis Example 4: Production of Copolymer (PA-2)] The mixing ratio of the monomer to be dropped is 120g ( 24% by mass), methyl methacrylate 100g (20% by mass), styrene 170g (34 % by mass, and isobornyl methacrylate 110 g (22% by mass). Copolymer PA-2, component (D), was produced in the same manner as in Example 4. GPC of PA-2 The weight average molecular weight measured by this method was 17,000 in terms of polystyrene.

[0055] [Synthesis Example 5: Production of Copolymer (PA-3)] The mixing ratio of the monomers to be dropped is 275g (55% by mass) of methyl methacrylate, 275g of isobutane Runil methacrylate 115g (23% by mass), FA-513M 110g (22% by mass) % ) was used to prepare the copolymer PA-3, which is the component (D), in the same manner as in Synthesis Example 4. The weight average molecular weight of PA-3 measured by GPC in terms of polystyrene was 59,000 It was.

[0056] [Example 1] Component (A) was glycerin diacrylate (manufactured by Toa Gosei, product name: Aronix M-9). 20) 12 parts by weight of caprolactone-modified dipentaerythritol hexahydrate as component (B) 12.3 parts by mass of acrylate (manufactured by Nippon Kayaku, product name: Kayarad DPCA-120), E O4 mole-modified bisphenol A diacrylate (Miwon, trade name MIRAMER) 5 parts by mass of M240), and urethane acrylate UA- synthesized in Synthesis Example 1 as component (C). 10 parts by mass of copolymer PA-1 obtained in Synthesis Example 3 as component (D) (solid 12 parts by mass (solids equivalent) and PA-2 12 parts by mass (solids equivalent), 1-hydroxybenzoxazole as a photopolymerization initiator 1.65 parts cyclohexyl phenyl ketone and 0.82 parts benzophenone, as additives Trismethacryloyloxyphosphate (Osaka Organic Chemical Industry Co., Ltd., product name: Viscoat) 3PMA) 0.57 parts by mass, acrylic polymer (BYK product name BYK-3440) 2 Parts by mass, perfluoroalkyl compound (AGC product name Surflon S-651), and 13.5 parts of n-butanol, 17.4 parts of toluene, and 11 parts of xylene as organic solvents. The components were mixed and dissolved to produce an active energy ray curable composition (undercoat material).

[0057] This active energy ray curable composition (undercoat material) will be described below. The smoothness was evaluated by the method, and test pieces were prepared to evaluate the initial adhesion and moisture resistance. The results are shown in Table 1.

[0058] [Evaluation of smoothness] The composition was sprayed onto an ABS substrate so that the film thickness after curing was 15 μm. The organic solvent was then evaporated by heating in an oven at 60°C for 2 minutes. After that, a high-pressure mercury lamp was used from above the coated surface in the air, and the accumulated light amount was 100 0mJ / cm2 (integrated energy of ultraviolet rays with wavelengths of 340nm to 380nm) After curing by irradiation, the appearance of the coating film was visually observed. Smoothness was evaluated according to the following criteria. ⊚: The surface is smooth and highly glossy. ◯: The surface is smooth, but the gloss is somewhat dull. △: The surface is slightly uneven. ×: The surface is very uneven and not smooth.

[0059] [Creating test pieces] PA-3 20 parts by mass (10 parts by mass in terms of solid content) and dipentaerythritol hexahydrate 30 parts by weight of acrylate (Miwon product name MIRAMER M600), trimethyl Rolled propane triacrylate (Miwon, product name MIRAMER M300) 2 0 parts by mass, EO 4 mole modified bisphenol A diacrylate (manufactured by Miwon, trade name MI RAMER M240) 25 parts by mass, tetrahydrofurfuryl acrylate (Osaka Organic Chemical) 10 parts by weight of Viscoat #150 (manufactured by Gakushu Kogyo Co., Ltd.), 5 parts by weight of benzophenone, and Toluene 30 parts by mass of ethanol, 30 parts by mass of xylene, 30 parts by mass of n-butanol, and 20 parts by mass of ethyl acetate The above components were mixed and stirred to form a top coating material (1) (corresponding to the active energy ray curable composition of the present invention). (not included) was prepared. The active energy ray curable composition (undercoat material) for evaluation was placed on a vertical 9cm The film thickness of the cured coating was 15 μm on a rectangular sheet measuring 5 cm in width and 3 mm in thickness. The plate was then heated in an oven at 60°C for 2 minutes to remove the organic solvent. After that, a high-pressure mercury lamp was used to irradiate the coated surface in the air with an integrated light intensity of 1 000mJ / cm2 (integrated energy of ultraviolet rays with wavelengths of 340nm to 380nm) The undercoat layer was then cured by irradiation with light. Aluminum is deposited by vacuum deposition, and the above-mentioned top coat is used to prevent corrosion of the metal film. A topcoat layer was formed using the topcoat material (1) under the same conditions as the undercoat layer, and evaluated. A laminate for use (hereinafter referred to as a test piece) was prepared.

[0060] [Evaluation of initial adhesion] Make grid cuts with a cutter knife at 1mm intervals on the test piece, reaching down to the base material. 1mm 2 Make 100 grids of the above and stick Nichiban Cellotape (registered trademark) on them. Apply and then quickly peel off to separate the substrate and undercoat, undercoat and metal film, or metal film The state of the cross-cut areas that had peeled off between the adhesive and the top coat was observed. The initial adhesion was evaluated according to the following criteria: It was worth it. ◎...No peeling in the cross-cut peeling test. ◯: No peeling in the cross-cut test, but the cut grooves are slightly chipped. △: Slight peeling in the cross-cut test. ×...Complete peeling in the cross-cut test.

[0061] [Moisture resistance evaluation] The test piece is left in an atmosphere of 50°C and 98% RH for 5 to 20 days, then removed. The appearance was visually observed and evaluated according to the following criteria. and evaluation was carried out. (Appearance evaluation criteria) 〇...No abnormalities. △: The coating is slightly whitened. ×: Significant whitening of the coating film.

[0062] [Examples 2 to 5, Comparative Example 1] The same procedure as in Example 1 was carried out except that the blending and composition shown in the composition column of Table 1 were used. A radiation-curable composition (undercoat material) was prepared and evaluated. The results are shown in Table 1.

[0063] [Example 6] The same procedure as in Example 1 was repeated except that the formulation and composition shown in the composition column of Table 2 were used. A curable composition (top coat material) was prepared. The smoothness of the surface of the coated material was evaluated in the same manner as in Example 1. The initial adhesion and moisture resistance were evaluated in the same manner as in Example 1. Shown in Table 1.

[0064] [Creating test pieces] PA-1 12 parts by mass (6 parts by mass in solid content equivalent) and epoxy acrylate (Miwo 10 parts by weight of MIRAMER PE210 (manufactured by N), polyester acrylate (M 5 parts by weight of MIRAMER PS4140 (manufactured by iwon), caprolactone-modified PEG-10 Pentaerythritol hexacrylate (Nippon Kayaku, product name: DPCA-20) 5 parts by weight PO-modified neopentyl glycol diacrylate (Miwon, product name MIRAME) RM216) 4 parts by weight, benzophenone 0.4 parts by weight, 2,2-dimethoxy-2-phenanthroline 0.8 parts by mass of acetophenone, 30 parts by mass of toluene, 30 parts by mass of xylene, n-butadiene 30 parts by mass of alcohol and 20 parts by mass of ethyl acetate were mixed and stirred to prepare an active energy ray curable composition. Product (2) (undercoat material, not applicable to the present invention) was prepared. The active energy ray curable composition (2) (undercoat material) was applied to a 9 cm long ABS resin The coating was spread onto a rectangular sheet 5cm wide and 3mm thick so that the thickness of the cured coating was 15μm. The organic solvent was then removed by heating in an oven at 60°C for 2 minutes. After that, a high-pressure mercury lamp was used to irradiate the coating surface in air with an integrated light intensity of 10 00mJ / cm2 (integrated energy of ultraviolet rays with wavelengths of 340nm to 380nm) The undercoat layer was formed by irradiating the undercoat with light to form a cured coating film. Aluminum is deposited on the surface of the coating layer by vacuum deposition, and the metal film is then coated to prevent corrosion. The active energy ray curable composition (top coat material) for evaluation was used to form an undercoat layer. A topcoat layer was formed under the same conditions as in the above to prepare a test piece.

[0065] [Examples 7 to 11, Comparative Example 2] The same procedure as in Example 6 was repeated except that the formulation and composition shown in the composition column of Table 2 were used. A curable composition (top coating material) was prepared and evaluated. The results are shown in Table 2.

[0066] [Table 1]

[0067] [Table 2]

[0068] The units of values ​​other than the compounding ratio in the table are parts by mass. The abbreviations in Tables 1 and 2 are as follows: Indicates a compound. M-920: Aronix M-920 (product name, glycerin diacrylate) manufactured by Toa Gosei (Route) M-930: Aronix M-930 (product name, glycerin triacrylate) manufactured by Toa Gosei rate) DPCA-120: Nippon Kayaku Kayarad DPCA-120 (product name, Caprolactam) (Ton-modified dipentaerythritol hexaacrylate) M600: MIRAMER M600 (product name, dipentaerythritol) manufactured by Miwon (hexaacrylate) M340: Miramer M340 (trade name, pentaerythritol) manufactured by Miwon Tetraacrylate) M240: Miramer M240 (trade name, EO2 mol-modified bisphenol A) manufactured by Miwon Enol A diacrylate) M216: Miramer M216 (trade name, PO2 mole modified neopentyl) manufactured by Miwon (butyl glycol diacrylate) M150: Miramer M150 (trade name, tetrahydroxyfulvinyl alcohol) manufactured by Miwon Furyl acrylate) M140: Miramer M140 (trade name, EO modified phenyl acrylate) manufactured by Miwon Related 2-EHA: 2-ethylhexyl acrylate (Mitsubishi Chemical) PS4140: MIRAMER PS4140 (product name, polyester) acrylate) UA-1: Urethane acrylate UA-1 obtained in Synthesis Example 1 UA-2: Urethane acrylate UA-2 obtained in Synthesis Example 2 PA-1: Copolymer PA-1 obtained in Synthesis Example 3 PA-2: Copolymer PA-2 obtained in Synthesis Example 4 PA-3: Copolymer PA-3 obtained in Synthesis Example 5 HCPK: 1-hydroxycyclohexyl phenyl ketone BP: Benzophenone MBF: Methyl benzoyl formate 3PMA: Viscoat 3PMA (trade name, Trismethacryloy) manufactured by Osaka Organic Chemical Industry Co., Ltd. (hydroxyphosphate) BYK-3440: BYK BYK-3440 (product name, acrylic copolymer) S-651: AGC Surflon S-651 (product name, perfluoroalkyl compound) thing) ·F-477: Manufactured by DIC Megafac F-477 (product name, fluorine-containing group, hydrophilic group, parent Oily group-containing oligomer PM-21: Kayamar PM-21 (trade name, 2-methacryloyloxy) manufactured by Nippon Kayaku Kogyo Co., Ltd. Diethyl Caproate Acid Phosphate) LHP91: Disparlon LHP-91 (trade name, vinyl polymer and silicone) manufactured by Kusumoto Chemicals ricone mixture) Eb350: Daicel Allnex Ebecryl 350 (product name, silicone acrylate) (Route)

[0069] From the above examples, it can be seen that the cured coating film formed from the active energy ray-curable resin composition of the present invention On the other hand, the active ingredients of Comparative Examples 1 and 2, which did not contain component (A), were excellent in adhesion and moisture resistance. The cured coating film formed from the reactive energy ray curable resin composition has insufficient adhesion and moisture resistance. It was.

Claims

1. A polyfunctional glycerin (meth)acrylate (A), a (meth)acrylic monomer (B); a urethane (meth)acrylate (C) containing a structural unit derived from the following compound (c1), a structural unit derived from the following compound (c2), and a structural unit derived from the following compound (c3); a (co)polymer (D) of a vinyl-based monomer; a photopolymerization initiator (E); Including, The amount of component (A) is 5 to 40 mass%, the amount of component (B) is 10 to 60 mass%, the amount of component (C) is 10 to 40 mass%, and the amount of component (D) is 1 to 40 mass%, based on 100 mass% of the total amount of components (A) to (D). An active energy ray-curable resin composition for forming a coating layer in a metallization treatment. Compound (c1): an isocyanate compound having at least two isocyanate groups Compound (c2): at least one polyol selected from the group consisting of polyether polyols, polyester polyols, and polycarbonate polyols Compound (c3): a compound having a hydroxyl group and a (meth)acryloyl group

2. 2. The active energy ray-curable resin composition for forming a coating layer in a metallization treatment according to claim 1, wherein the compound (c2) is a polyol selected from the following compounds (c21) and (c22): Compound (c21): polyester polyol obtained from an aliphatic polycarboxylic acid having 2 to 22 carbon atoms and a polyhydric alcohol Compound (c22): Polyether polyol having a repeating unit with 2 to 5 carbon atoms

3. The active energy ray-curable resin composition for forming a coating layer in a metallization treatment according to claim 2, wherein the compound (c21) is a sebacic acid polyester polyol.

4. 4. The active energy ray-curable resin composition for forming a coating layer in a metallization treatment according to claim 2 or 3, characterized in that the molecular weight of the compound (c21) is 500 or more and less than 3,000.

5. The active energy ray-curable resin composition for forming a coating layer in a metallization treatment according to any one of claims 2 to 4, wherein the compound (c22) is polytetramethylene glycol.

6. The active energy ray-curable resin composition for forming a coating layer in a metallization treatment according to any one of claims 2 to 5, characterized in that the molecular weight of the compound (c22) is 500 or more and less than 3,000.

7. A cured product obtained by curing the active energy ray-curable resin composition for forming a coating layer in a metallization treatment according to any one of claims 1 to 6 by irradiating it with active energy rays.

8. A laminate having the cured product according to claim 7 on the surface of a substrate.

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