Active energy ray-curable coating material composition and laminate

Abstract

To provide a coating material composition capable of forming an undercoat layer for metal vapor deposition excellent in adhesion and appearance on various substrates.SOLUTION: An active energy ray-curable coating material composition according to the present invention contains a resin A, a (meth)acrylate B, and a silane coupling agent C. The resin A is a polymer A1 having hydroxyl groups with a hydroxyl value of 20-200 mg KOH / g and / or an alkyd resin A2. The content of the resin A is 20-60 mass% and the content of the (meth)acrylate B is 40-80 mass% in 100 mass% of the total amount of the resin A and the (meth)acrylate B. The content of the silane coupling agent C is 0.3-15 pts.mass based on 100 pts.mass of the total amount of the resin A and the (meth)acrylate B.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coating composition, and more particularly to a coating composition suitable for forming an undercoat layer for metal deposition that has excellent adhesion to various substrates and excellent appearance when irradiated with active energy rays. [Background technology]

[0002] Resins have advantages such as productivity, moldability, and light weight. Molded resin products are used as substrates, and an undercoat layer (primer layer) is formed on the surface. Metallization treatments such as ionization deposition and sputtering are then applied to the undercoat layer. These products are widely used as automobile parts, decorative items, and components for home appliances.

[0003] In recent years, substrates used in automotive parts include resin substrates such as ABS (acrylonitrile butadiene styrene), PC (polycarbonate), high-heat PC, and acrylic, as well as difficult-to-adhere resin substrates such as BMC (bulk molding compound; a molding material consisting of a mixture of unsaturated polyester resin, fillers, and fibrous materials), PPS (polyphenylene sulfide), ALD (aluminum die-cast), and PBT (polybutylene terephthalate) / PET (polyethylene terephthalate) alloy. These difficult-to-adhere resin substrates are lightweight and have excellent impact resistance and heat resistance. Forming an undercoat layer on these substrates and then subjecting them to a metallized treatment makes them suitable for use as reflectors for automotive lamps, for example.

[0004] Automotive lamp reflectors often use a combination of multiple resin substrates. For example, a substrate with excellent heat resistance is used in areas closer to the lamp light source, while a substrate with excellent processability is used in areas farther from the lamp light source so that complex shapes can be accommodated. Compositions for forming undercoats on resin substrates such as ABS and PC have problems, such as poor adhesion when applied to poorly adherent resin substrates such as BMC and PPS, and difficulty in forming metallic coatings through metallization. Furthermore, the high heat resistance of BMC and PPS can lead to the problem of rainbows appearing in the coating during heat resistance tests after metallization. Therefore, when forming an undercoat layer, it is necessary to switch to a composition suitable for the type of substrate.

[0005] For example, Patent Document 1 proposes an undercoat composition for metal vapor deposition that contains a homopolymer or copolymer of a specific amide group-containing (meth)acrylamide monomer as an undercoat composition for metal vapor deposition that can be applied to poorly adherent resin substrates. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-131653 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the undercoat composition for metal vapor deposition described in Patent Document 1 has the problem that the adhesion and appearance of the coating film after a heat resistance test are poor depending on the substrate. An object of the present invention is to provide a coating material composition that can form an undercoat layer for metal vapor deposition that has excellent adhesion and appearance on various substrates. Another object of the present invention is to provide a laminate having an undercoat layer and a metal vapor deposition layer formed by curing this coating material composition. [Means for solving the problem]

[0008] As a result of extensive research to solve the above problems, the present inventors discovered a coating material composition that, by blending a specific polymer and specific additives in specific amounts, can form an undercoat layer for metal vapor deposition that has excellent adhesion and appearance to various resins, and thus arrived at the present invention.

[0009] The above problems are solved by any one of the following present inventions [1] to

[16] .

[0010] [1] Comprising a resin A, a (meth)acrylate B, and a silane coupling agent C, the resin A is a polymer A1 and / or an alkyd resin A2 having a hydroxyl group with a hydroxyl value of 20 to 200 mgKOH / g, The resin A is 20% by mass of the total amount of the resin A and the (meth)acrylate B (100% by mass). to 60% by mass, and the (meth)acrylate B is 40 to 80% by mass, The active energy ray-curable coating material composition contains 0.3 to 15 parts by mass of the silane coupling agent C relative to 100 parts by mass of the total amount of the resin A and the (meth)acrylate B.

[0011] [2] The active energy ray-curable coating material composition according to [1], wherein the resin A is 30 to 60 mass % and the (meth)acrylate B is 40 to 70 mass % in a total of 100 mass % of the resin A and the (meth)acrylate B.

[0012] [3] The active energy ray-curable coating material composition according to [1], wherein the polymer A1 has a mass average molecular weight of 10,000 to 80,000.

[0013] [4] The active energy ray-curable coating material composition according to [1] above, wherein the polymer A1 has a hydroxyl value of 40 to 180 mgKOH / g.

[0014] [5] The active energy ray-curable coating material composition according to [1], wherein the polymer A1 contains a structural unit derived from a hydroxyalkyl (meth)acrylate.

[0015] [6] The active energy ray-curable coating material composition according to [1], wherein the polymer A1 contains a structural unit derived from a monomer represented by the following formula (1):

[0016] [ka]

[0017] In formula (1), R1 and R2 are each independently H or CH3. R3 and R4 are each independently H or C n H 2n+1 where n is 1 to 10.

[0018] [7] The active energy ray-curable coating material composition according to [1], wherein the alkyd resin A2 is an oil-modified alkyd resin.

[0019] [8] The active energy ray-curable coating material composition according to [1], wherein the (meth)acrylate B contains a polyfunctional (meth)acrylate having 2 to 6 (meth)acryloyloxy groups.

[0020] [9] The active-energy ray-curable coating material composition according to [8], wherein the (meth)acrylate B comprises at least one (meth)acrylate selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-acryloyloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and polyester (meth)acrylate.

[0021]

[10] The active energy ray-curable coating material composition according to [1], wherein the silane coupling agent C has an amino group or a glycidyl group.

[0022]

[11] The active energy ray-curable coating material composition according to

[10] , wherein the silane coupling agent C contains at least one silane coupling agent selected from the group consisting of N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.

[0023]

[12] The active energy ray-curable coating material composition according to the above [1], further comprising a photopolymerization initiator D.

[0024]

[13] The active energy ray-curable coating material composition according to

[12] , wherein the photopolymerization initiator D is 0.1 to 20 parts by mass per 100 parts by mass of the total amount of the resin A and the (meth)acrylate B.

[0025]

[14] The active energy ray-curable coating material composition according to [1], wherein the active energy ray-curable coating material composition is used as an undercoat material for metal vapor deposition.

[0026]

[15] A laminate comprising a coating layer of the active energy ray-curable coating material composition according to

[14] above and a metal vapor deposition layer laminated in this order on the surface of a resin substrate.

[0027]

[16] The laminate according to

[15] , which is a component for an automobile lamp. [Effects of the Invention]

[0028] According to the present invention, a coating material composition suitable for forming an undercoat layer for metal vapor deposition that has excellent adhesion and appearance to various substrates can be provided. The coating material composition of the present invention can be cured in a short time by irradiation with active energy rays. Furthermore, the coating material composition of the present invention can also form an undercoat layer for metal vapor deposition on aluminum, glass, and other substrates other than poorly adherent substrates and plastic substrates. Furthermore, according to the present invention, a laminate having an undercoat layer consisting of a cured layer of this coating material composition and a metal vapor deposition layer can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0029] [Covering material composition] The present invention will be described in detail below. In this specification, "(meth)acrylate" means "acrylate" and / or "methacrylate," "(meth)acrylic" means "acrylic" and / or "methacrylic," "(meth)acryloyl" means "acryloyl" and / or "methacryloyl," and "(meth)acrylonitrile" means "acrylonitrile" and / or "methacrylonitrile." Furthermore, resin A will also be referred to as "component A," polymer A1 as "component A1," alkyd resin A2 as "component A2," (meth)acrylate B as "component B," silane coupling agent C as "component C," and photopolymerization initiator D as "component D." Furthermore, an active energy ray-curable coating material composition will also be referred to as "coating material composition."

[0030] [Component A] The resin A blended in the coating material composition of the present invention is a polymer A1 and / or an alkyd resin A2 having a hydroxyl group with a hydroxyl value of 20 to 200 mgKOH / g. This component A imparts adhesion to the cured coating film of the coating material composition.

[0031] [A1 component] The polymer A1 is a homopolymer or copolymer having a hydroxyl group and a hydroxyl value of 20 to 200 mgKOH / g, and can be obtained by polymerizing a monomer having a hydroxyl group. The polymer A1 may contain "other monomer units" as needed.

[0032] Examples of the hydroxyl group-containing monomer include the following hydroxyl group-containing vinyl monomers: hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; ethylene oxide adducts of 2-hydroxyethyl (meth)acrylate; propylene oxide adducts of 2-hydroxyethyl (meth)acrylate; ε-caprolactone adducts of 2-hydroxyethyl (meth)acrylate; and organic lactone adducts of 2-hydroxyethyl (meth)acrylate. Among these, from the viewpoint of adhesion between the cured film obtained from the coating material composition and the substrate, hydroxyalkyl (meth)acrylates are preferred, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are more preferred. The hydroxyl group-containing monomers can be used alone or in combination of two or more.

[0033] The monomers that serve as raw materials for constituting the "other monomer units" are monomers that are copolymerizable with the monomers having a hydroxyl group, and examples thereof include the following monomers: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, Acrylic acid esters such as ethoxyethoxyethyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate; styrene or styrene derivatives such as styrene, α-methylstyrene, pt-butylstyrene, and vinyltoluene; acrylamide compounds such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, maleic acid, and fumaric acid; polymerizable unsaturated nitriles such as (meth)acrylonitrile; unsaturated carboxylic acid esters such as diethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, diethyl fumarate, and dibutyl fumarate; vinyl esters such as vinyl acetate and vinyl propionate.

[0034] As a monomer serving as a raw material for constituting the "other monomer units", a monomer represented by the following formula (1) is preferred from the viewpoint of adhesiveness.

[0035] [ka]

[0036] In formula (1), R1 and R2 are each independently H or CH3. R3 and R4 are each independently H or Cn H 2n+1 and n is 1 to 10. n is preferably 1 to 8, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the monomer represented by formula (1) include diethyl maleate, dibutyl maleate, diethyl fumarate, and dibutyl fumarate. These monomers serving as raw materials for constituting the "other monomer units" may be used alone or in combination of two or more.

[0037] The mass average molecular weight of polymer A1 is preferably 10,000 to 80,000, more preferably 15,000 to 70,000, and even more preferably 20,000 to 50,000. By setting the mass average molecular weight of polymer A1 to 10,000 to 80,000, when the coating material composition is applied to the surface of a substrate, a coating film with excellent smoothness can be obtained and sagging of the coating film can be suppressed.

[0038] The hydroxyl value of polymer A1 is 20 to 200 mgKOH / g, preferably 40 to 180 mgKOH / g, more preferably 60 to 160 mgKOH / g, and even more preferably 80 to 140 mgKOH / g. By adjusting the hydroxyl value of polymer A1 to 20 to 200 mgKOH / g, it is possible to improve the adhesion between a cured film obtained from the coating material composition and a substrate.

[0039] In the present invention, the mass average molecular weight is determined by GPC measurement in terms of polystyrene. The hydroxyl value is determined by determining the amount of free hydroxyl groups contained in 1 g of vinyl polymer from the composition ratio of the monomers used in polymerization, and then calculating the amount of potassium hydroxide (unit: mg) required to neutralize the acetic acid required for acetylating the free hydroxyl groups.

[0040] The content of the monomer unit having a hydroxyl group in the polymer A1 is preferably an amount such that the hydroxyl value of the polymer A1 is 20 to 200 mgKOH / g.

[0041] The polymerization method for obtaining polymer A1 is not particularly limited, and polymer A1 can be obtained by a conventional polymerization method such as solution polymerization in the presence of a radical polymerization initiator, bulk polymerization, or emulsion polymerization.

[0042] [A2 component] The alkyd resin A2 can be synthesized from, for example, a polyhydric alcohol, a polybasic acid or its acid anhydride, and a fat or oil or its fatty acid. The polyhydric alcohol is not particularly limited, and examples thereof include glycerin and trimethylolpropane. Examples of polybasic acids or their acid anhydrides include phthalic acid, phthalic anhydride, and maleic anhydride. The fat or oil fatty acid is not particularly limited, and non-drying oil, semi-drying oil, drying oil, or their fatty acids can be used. Examples include coconut oil, soybean oil, castor oil, tall oil, linseed oil, tung oil, safflower oil, and their fatty acids. Furthermore, modified alkyd resins such as phenol-modified and vinyl-modified alkyd resins can also be used. From the perspective of appearance, the alkyd resin A2 is preferably an oil-modified alkyd resin. Examples of oil-modified alkyd resins include palm oil-modified alkyd resins, soybean oil-modified alkyd resins, castor oil-modified alkyd resins, tall oil-modified alkyd resins, linseed oil-modified alkyd resins, tung oil-modified alkyd resins, and safflower oil-modified alkyd resins.

[0043] The oil length (mass ratio of oil to resin content) of the alkyd resin A2 is preferably 20 to 50%, more preferably 30 to 50%, from the viewpoint of improving the appearance of the cured coating film and compatibility with other components.

[0044] As the alkyd resin A2, for example, the following commercially available products can be used: palm oil-modified alkyd resin, Beckosol 1323-60-EL (manufactured by DIC, oil length 32%); tall oil-modified alkyd resin, Beckosol ET-3061-60 (manufactured by DIC, oil length 30%); soybean oil-modified alkyd resin, Beckosol ES-4020-55 (manufactured by DIC, oil length 40%), Beckosol OD-E-198-50 (manufactured by DIC, oil length 28%), Beckosol 1307-60-EL (manufactured by DIC, oil length 41%); Examples of water-soluble alkyd resins include Beckosol EL-4501-50 (manufactured by DIC, oil length 45%) and Beckosol EQV-987 (manufactured by DIC, oil length 50%); phenol-modified alkyd resins include Beckosol 1341 (manufactured by DIC, oil length 28%) and Beckosol J608 (manufactured by DIC, oil length 43%); and safflower oil-modified alkyd resins include Beckosol ENV-241 (manufactured by DIC, oil length 50) and Beckosol ENV-243 (manufactured by DIC, oil length 50). These can be used alone or in combination of two or more.

[0045] The blending ratio of component A is 20 to 60 mass%, preferably 30 to 60 mass%, more preferably 35 to 55 mass%, and even more preferably 40 to 50 mass%, based on 100 mass% of the total amount of components A and B. The lower limit of the blending ratio of component A is set from the viewpoint of improving adhesion to the metal vapor deposition film, and the upper limit is set from the viewpoint of improving the smoothness of the cured coating film.

[0046] [B component] The (meth)acrylate component B may be selected appropriately depending on the required performance of the cured coating film.

[0047] Specific examples of monomers having one (meth)acryloyl group that can be used as component B include the following monomers: hydroxyl group-containing hydrocarbons such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; hydrocarbons such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and 2-isobutyl-2-methyl acrylate; tetrahydrofurfuryl (meth)acrylate, 2-ethyl-2-methyl-1,3-dioxolan-4-yl-methyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and furfuryl (meth)acrylate. ring skeletons such as phenyloxyethyl (meth)acrylate, phenyloxydiethylene glycol (meth)acrylate, ethylene oxide-modified cresol (meth)acrylate, nonylphenyloxyethyl (meth)acrylate, para-cumylphenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, t-butylcyclohexyloxyethyl (meth)acrylate, benzyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, norbornyloxyethyl (meth)acrylate, and adamantyloxyethyl (meth)acrylate;Alkoxyacrylates such as 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxydibutylene glycol (meth)acrylate, methoxytributylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, ethoxytripropylene glycol (meth)acrylate, ethoxydibutylene glycol (meth)acrylate, ethoxytributylene glycol (meth)acrylate, and butoxyethyl (meth)acrylate; amines such as dimethylacrylamide; heterocyclic compounds such as acryloylmorpholine;

[0048] Specific examples of monomers having two (meth)acryloyl groups that can be used as component B include the following monomers: ring skeletons such as tricyclodecane dimethanol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, and bisphenoxyfluorene ethanol di(meth)acrylate; isocyanurates such as bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate; trimethylolpropanes such as neopentyl glycol-modified trimethylolpropane di(meth)acrylate; 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, and 2,4-diethyl-1,5-pentanediol di(meth)acrylate. Hydrocarbons such as 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, and 1,14-tetradecanediol di(meth)acrylate; tripropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, etc.

[0049] Specific examples of the monomer having three (meth)acryloyl groups that can be used as component B include the following monomers: pentaerythritols such as pentaerythritol tri(meth)acrylate and ethoxylated pentaerythritol tri(meth)acrylate; trimethylolpropanes such as trimethylolpropane tri(meth)acrylate and tris-ethoxylated trimethylolpropane tri(meth)acrylate; isocyanurates such as tris(2-acryloyloxyethyl)isocyanurate; and the like.

[0050] Specific examples of monomers having four or more (meth)acryloyl groups that can be used as component B include the following monomers: pentaerythritols such as dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate; and trimethylolpropanes such as ditrimethylolpropane tetra(meth)acrylate.

[0051] Specific examples of epoxy poly(meth)acrylates that can be used as component B include bisphenol-type epoxy di(meth)acrylates and novolac-type epoxy di(meth)acrylates.

[0052] Specific examples of polyester (meth)acrylates that can be used as component B include compounds obtained by reacting a polybasic acid such as phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, or adipic acid with a polyhydric alcohol such as ethylene glycol, hexanediol, polyethylene glycol, or polytetramethylene glycol, and (meth)acrylic acid or a derivative thereof.

[0053] Specific examples of urethane (meth)acrylates that can be used as component B include those obtained by reacting an organic isocyanate compound with a hydroxy group-containing (meth)acrylate having one (meth)acryloyloxy group and one hydroxy group, and, if necessary, with a diol such as an alkanediol, a polyetherdiol, a polybutadienediol, a polyesterdiol, a polycarbonatediol, or an amidediol.

[0054] Among these, from the viewpoint of the curability and heat resistance of the coating film, it is preferable that Component B contains a polyfunctional (meth)acrylate having 2 to 6 (meth)acryloyloxy groups. As the polyfunctional (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-acryloyloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and polyester (meth)acrylate are preferred. These monomers can be used alone or in combination of two or more.

[0055] The proportion of component B used is 40 to 80 mass%, preferably 40 to 70 mass%, more preferably 45 to 65 mass%, and even more preferably 50 to 60 mass%, based on 100 mass% of the total amount of components A and B. The lower limit of the range of the blending proportion of component B is set from the viewpoint of improving the curability of the coating film, and the upper limit is set from the viewpoint of improving the adhesion of the coating film to the metal vapor deposition film.

[0056] [C component] Component C, which is a silane coupling agent, is a component that imparts adhesion to the cured coating film of the coating material composition. Examples of silane coupling agents that can be used as component C include the following compounds:

[0057] Examples of suitable silanes include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride, and N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine. These can be used alone or in combination of two or more.

[0058] Among these, silane coupling agents having an amino group or a glycidyl group are preferred because they have excellent adhesion to both poorly adherent substrates and metal vapor-deposited films, and amino group-containing alkylalkoxysilanes such as N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane and N-(2-aminoethyl)3-aminopropyltrimethoxysilane, and glycidyl group-containing alkylalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are more preferred.

[0059] The blending ratio of Component C is 0.3 to 15 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the combined total of Components A and B. The lower limit of the blending ratio of Component C is set from the viewpoint of improving the adhesion of the resulting cured coating film to the substrate, and the upper limit is set from the viewpoint of improving the adhesion of the cured coating film to the substrate after a heat resistance test.

[0060] [D component] Component D, which is a photopolymerization initiator, is an optional component that cures the coating material composition by irradiation with active energy. Examples of component D include benzophenone-type, anthraquinone-type, alkylphenone-type, acylphosphine oxide-type, thioxanthone-type, and phenyl glyoxylate-type photopolymerization initiators, and specific examples include the following compounds:

[0061] Benzophenone-type compounds such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, and 4-phenylbenzophenone; anthraquinone-type compounds such as t-butylanthraquinone and 2-ethylanthraquinone; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-hydroxy-1-[4-[4-(2-hydroxyphenyl)phenyl]propanone. alkylphenone types such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, and isopropylthioxanthone; acylphosphine oxide types such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and phenyl glyoxylate types such as phenyl glyoxylic acid methyl ester. These can be used alone or in combination of two or more.

[0062] Among these, benzophenone, 2-ethylanthraquinone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferred from the viewpoint of dryness to touch of the coating material composition.

[0063] When Component D is included, the amount of Component D included is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the total amount of Components A and B. The lower limit of the range of the amount of Component D included is set from the viewpoint of curing the coating material composition in an air atmosphere, and the upper limit is set from the viewpoint of reducing the amount of photopolymerization initiator remaining in the resulting cured coating film.

[0064] [Photosensitizer] Furthermore, if necessary, known photosensitizers such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone can be added to the coating material composition of the present invention within a range that does not impair performance. These can be used alone or in combination of two or more.

[0065] [Organic solvents] The coating material composition of the present invention can be blended with an organic solvent to adjust the viscosity to a desired level, if necessary. Examples of organic solvents include the following compounds: ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and dioxane; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane, hexane, and petroleum naphtha; alcohol compounds such as isopropyl alcohol, isobutanol, and n-butanol; and propylene glycol compounds such as 1-methoxypropanol and 1-methoxypropanol acetate. These compounds can be used alone or in combination.

[0066] [Other ingredients (additives)] The coating material composition of the present invention may also contain additives such as leveling agents, antifoaming agents, antisettling agents, lubricants, abrasives, rust inhibitors, antistatic agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, etc. Furthermore, an acrylic polymer other than component A1 may be added to improve adhesion, provided that the effects of the present invention are not impaired.

[0067] [Molded products, laminates] The molded articles to which the coating composition of the present invention can be applied include, but are not limited to, various molded articles containing poorly adherent substrates such as thermosetting resins such as BMC, super engineering plastics such as PPS, metals such as ALD, PBT / PET alloy resins, ABS resins, AES (acrylonitrile-ethylene-propylene-diene-styrene) resins, PC resins, high-heat PC resins, acrylic resins, and polystyrene resins, as well as polyolefin resins such as polypropylene and polyethylene, and polyester resins such as PET resins and PBT resins. A coating layer of the coating composition of the present invention on these molded articles can be formed by applying the coating composition of the present invention to the surface of the resin molded article (resin substrate) and then irradiating it with active energy rays. The thickness of the undercoat layer, as measured by the thickness of the cured coating, is preferably in the range of 3 to 40 μm.

[0068] The coating composition can be applied by brush coating, spray coating, dip coating, spin coating, flow coating, or the like, with spray coating and flow coating being preferred in terms of ease of application and the smoothness and uniformity of the coating. When the coating composition is applied, if the organic solvent described above is blended into the coating composition, it is preferable to volatilize the solvent before curing the coating film of the coating composition. In this case, it is preferable to volatilize the organic solvent by heating the coating film with an IR heater and / or hot air at a temperature of 30 to 70°C for a heating time of 2 to 8 minutes.

[0069] Examples of active energy rays used to cure the coating material composition of the present invention include ultraviolet rays and electron beams. Examples of ultraviolet light sources include high-pressure mercury lamps. The amount of ultraviolet energy irradiated to cure the coating material composition is 300 to 4000 mJ / cm. 2 It is preferable that the degree of

[0070] The coating composition of the present invention is suitable as an undercoat material for metal vapor deposition when forming a metal vapor deposition film on a resin molded article. The formation of a metal vapor deposition film on a resin molded article provided with an undercoat layer of the coating composition of the present invention is carried out by a known method for metal vapor deposition. This allows for the production of a laminate in which a coating layer of the coating composition of the present invention and a metal vapor deposition film are laminated in this order on the surface of a resin substrate. This laminate can further include a thermosetting topcoat layer, an ultraviolet-curing topcoat layer, or a plasma-polymerized film formed on the surface of the formed metal vapor deposition film for the purpose of preventing corrosion of the metal vapor deposition film.

[0071] The undercoat layer for metal vapor deposition formed from the coating material composition of the present invention has excellent adhesion to various plastic substrates and excellent heat resistance, and therefore a laminate in which a coating layer of the coating material composition of the present invention and a metal vapor deposition film are laminated in this order is suitably used in applications requiring heat resistance, such as automotive lamp components such as reflectors for automotive lamps. [Example]

[0072] The present invention will be explained in more detail below with reference to Production Examples and Examples.

[0073] [Production Example 1] Production of Copolymer A-1 The materials shown in the Component 1 column of Table 1 were placed in a 2 L four-neck flask and heated to a liquid temperature of 110°C. The liquid in the flask was then stirred while maintaining the internal temperature at 110°C. A monomer-containing mixture consisting of the materials shown in the Component 2 column of Table 1 was added dropwise to the flask at a constant rate over 4 hours, followed by the material shown in the Component 3 column of Table 1. Subsequently, 1 g of azobisisobutylnitrile was added to the flask every hour for a total of four times (4 g in total), and the mixture was stirred for another 2 hours to obtain Copolymer A-1. The mass average molecular weight of Copolymer A-1 measured by GPC in terms of polystyrene was 2.5 x 10 4 The hydroxyl value was 108 mg KOH / g.

[0074] [Table 1]

[0075] [Production Example 2] Production of Copolymer A-2 A polymer having a mass average molecular weight of 4.3 × 10 was prepared in the same manner as in Production Example 1, except that 3.8 g of Perbutyl O (registered trademark, manufactured by NOF Corp.) was used as the polymerization initiator for component 2 and 10 g of Perbutyl O was used as the polymerization initiator for component 4. 4 Thus, a copolymer A-2 having a hydroxyl value of 108 mgKOH / g was obtained.

[0076] [Production Example 3] Production of Copolymer A-3 A polymer having a mass average molecular weight of 2.2 × 10 was prepared in the same manner as in Production Example 1, except that the monomers used for component 2 were 150 g of styrene (30% by mass of all monomers) and 175 g of 2-hydroxyethyl methacrylate (35% by mass of all monomers). 4 Thus, a copolymer A-3 having a hydroxyl value of 129 mg KOH / g was obtained.

[0077] [Production Example 4] Production of Copolymer A-4 A polymer having a mass average molecular weight of 2.3 × 10 was prepared in the same manner as in Production Example 1, except that 62.5 g of 2-hydroxyethyl methacrylate (12.5 mass% of all monomers) and 62.5 g of methyl methacrylate (12.5 mass% of all monomers) were used instead of 125 g of 2-hydroxyethyl methacrylate (25 mass% of all monomers) as the monomer used as component 2. 4 Thus, a copolymer A-4 having a hydroxyl value of 53 mgKOH / g was obtained.

[0078] [Production Example 5] Production of Copolymer A-5 A polymer having a mass average molecular weight of 6.2 × 10 was prepared in the same manner as in Production Example 1, except that 1.4 g of azobisisobutylnitrile and 2.4 g of Perbutyl Z (registered trademark, manufactured by NOF Corp.) were used as the polymerization initiator for component 2, and the liquid temperature was set to 100°C. 4 Thus, a copolymer A-5 having a hydroxyl value of 108 mgKOH / g was obtained.

[0079] [Production Example 6] Production of copolymer PA-1 A polymer having a mass average molecular weight of 2.0 × 10 was prepared in the same manner as in Production Example 1, except that the monomers used for component 2 were 75 g of styrene (15% by mass of all monomers) and 250 g of 2-hydroxyethyl methacrylate (50% by mass of all monomers). 4 Thus, copolymer PA-1 having a hydroxyl value of 215 mgKOH / g was obtained.

[0080] [Production Example 7] Production of copolymer PA-2 A polymer having a mass average molecular weight of 2.0 × 10 was prepared in the same manner as in Production Example 1, except that 125 g of methyl methacrylate (25% by mass of all monomers) was used instead of 125 g of 2-hydroxyethyl methacrylate (25% by mass of all monomers). 4 Thus, copolymer PA-2 having a hydroxyl value of 0 mgKOH / g was obtained.

[0081] [Example 1] 1. Preparation of Coating Composition A coating material composition was obtained by mixing and dissolving 100 parts by mass of copolymer A-1 synthesized in Production Example 1 as component A1 (50 parts by mass in terms of solid content), 25 parts by mass of DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name KAYARAD DPHA) and 25 parts by mass of M-8030: polyester acrylate (manufactured by Toagosei Co., Ltd., product name ARONIX M-8030) as component B, 1 part by mass of KBM-403: 3-glycidoxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-403) as component C, 5 parts by mass of benzophenone and 1.5 parts by mass of 2-ethylanthraquinone as component D, and 5 parts by mass of toluene, 70 parts by mass of 1-methoxypropanol, 30 parts by mass of butyl acetate, and 15 parts by mass of ethyl acetate as organic solvents.

[0082] 2. Preparation of laminate for evaluation The coating material composition prepared in 1 above was spray-coated onto the surface of a rectangular, flat BMC test piece, measuring 9 cm in length, 5 cm in width, and 3 mm in thickness, so that the thickness of the cured coating film was approximately 20 μm.

[0083] The organic solvent was then evaporated by heating in an oven at 60°C for 3 minutes. After that, a high-pressure mercury lamp was used to irradiate the coated surface in air with an integrated light intensity of 2000 mJ / cm. 2The coating film was cured by irradiating it with ultraviolet light. The light intensity was measured using an actinometer (manufactured by Oak Manufacturing, product name: UV-351 (SN type)) to measure the integrated energy of ultraviolet light with wavelengths of 340 nm to 380 nm. Subsequently, aluminum was vacuum-deposited onto the cured film (undercoat layer) using a vacuum deposition apparatus (manufactured by ULVAC, product name: EBA-800) to a film thickness of approximately 20 nm, forming an aluminum vapor-deposited film. Furthermore, to prevent corrosion of the aluminum vapor-deposited film, an acrylic melamine curing clear paint (manufactured by Mitsubishi Rayon, product name: Diabeam UT-047A) was spray-coated onto the aluminum vapor-deposited film to a film thickness of 5 μm after curing. This was followed by heat treatment at 120°C for 10 minutes to cure the film, forming a topcoat layer. In this way, a laminate for evaluation was prepared, with three coating layers formed on the surface of the substrate.

[0084] In the same manner, five types of laminates for evaluation were prepared using test pieces made of PPS, PBT / PET alloy, PC, and high-heat PC.

[0085] 3. Evaluation Method 3-1. Appearance of the coating To evaluate the appearance of the undercoat layer, the appearance of the metal vapor deposition film of each evaluation laminate was visually evaluated. The visual evaluation was judged according to the following criteria. E (EXCELLENT): The surface of the metal vapor deposition film is smooth and free of citrus peel. G (GOOD): The surface of the metal vapor deposition film has a slight yuzu peel appearance and is not smooth. B (BAD): The metal vapor deposition film has an orange peel appearance, is not smooth, and exhibits whitening, clouding, and blemishes.

[0086] 3-2. Coating adhesion A cross-shaped cut was made in the metal vapor deposition film and undercoat layer formed on the surface of the evaluation laminate using a cutter knife, reaching the substrate. Next, a cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.) was applied to the surface and then rapidly peeled off (peel test), which was repeated up to three times to observe delamination between the undercoat layer and the substrate, and the results were evaluated according to the following criteria. No delamination between the undercoat layer and the metal vapor deposition film was observed. E (EXCELLENT): No peeling occurs on the third peeling test. G (GOOD): No peeling occurred in the third peeling test, but the cross-shaped notch groove was slightly chipped. P (POOR): Peeling occurs after 2 or 3 peeling tests. B (BAD): Peeled off in the first peel test.

[0087] 3-3. Performance before and after heat resistance test For each evaluation laminate on which a coating film was formed, the appearance of the coating film and adhesion to the substrate were evaluated (initial). In addition, each evaluation laminate on which a coating film was formed was left for 24 hours in the atmosphere shown in Table 3, then removed and heat-treated, and the appearance of the coating film and adhesion to the substrate were evaluated (after heat resistance test). The evaluation results were judged according to the following criteria. -Appearance of the coating E (EXCELLENT): No whitening, clouding, bleeds, or swelling across the entire coating. G (GOOD): There is whitening, clouding, fading, or swelling in some areas of the paint film. B (BAD): Whitening, clouding, fading, or swelling is observed over the entire coating. - Coating adhesion E (EXCELLENT): No peeling occurs on the third peeling test. G (GOOD): No peeling occurred in the third peeling test, but the cross-shaped notch groove was slightly chipped. P (POOR): Peeling occurs after 2 or 3 peeling tests. B (BAD): Peeled off in the first peel test.

[0088] [Examples 2 to 20, Comparative Examples 1 to 9] A coating material composition was prepared, and a laminate for evaluation was fabricated and evaluated in the same manner as in Example 1, except that the blending and composition were as shown in the composition column of Table 2, Table 4, or Table 7. The evaluation results are shown in Table 3, Table 5, or Table 8. The abbreviations in Table 2 and Table 4 represent the materials in Table 6, and the abbreviations in Table 7 represent the materials in Table 9. All numerical values ​​in Table 2, Table 4, and Table 7 are in parts by mass.

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] [Table 6]

[0094] [Table 7]

[0095] [Table 8]

[0096] [Table 9]

[0097] The above examples demonstrate that the active energy ray-curable coating material composition of the present invention can provide an undercoat layer for metal vapor deposition that exhibits excellent adhesion to various substrates, adhesion to metal vapor deposition films, appearance, and heat resistance. In Comparative Example 1, Component C was not used, resulting in insufficient adhesion of the coating film to BMC. In Comparative Example 2, a large amount of Component C was used, resulting in insufficient adhesion of the coating film to PPS after a heat resistance test. In Comparative Example 3, a large amount of Component A was used, resulting in insufficient initial appearance of the coating film and appearance after a heat resistance test. In Comparative Example 4, a small amount of Component A was used, resulting in insufficient adhesion of the coating film. In Comparative Example 5, Component A was not used, resulting in insufficient appearance of the coating film. In Comparative Example 6, Component A was not used, resulting in insufficient appearance of the coating film to PPS and PBT / PET alloy. In Comparative Example 7, Component C was not used, resulting in insufficient adhesion of the coating film to PPS substrates and PBT / PET substrates. In Comparative Example 8, a large amount of Component A was used, resulting in insufficient initial appearance of the coating film and appearance after a heat resistance test. In Comparative Example 9, the amount of component A used was small, and therefore the adhesion of the coating film to the BMC substrate was insufficient.

[0098] This application claims priority based on Japanese Patent Application No. 2016-42408, filed March 4, 2016, and Japanese Patent Application No. 2016-107456, filed May 30, 2016, the disclosures of which are incorporated herein in their entireties.

[0099] Although the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the above-described embodiments and examples. Various modifications that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

Claims

1. The composition comprises a resin A, a (meth)acrylate B, and a silane coupling agent C, the resin A is a polymer A1 and / or an alkyd resin A2 having a hydroxyl group with a hydroxyl value of 20 to 200 mgKOH / g, the resin A accounts for 20 to 60 mass% and the (meth)acrylate B accounts for 40 to 80 mass% of the total amount of the resin A and the (meth)acrylate B, 100 mass%; The active energy ray-curable coating material composition contains 0.3 to 15 parts by mass of the silane coupling agent C relative to 100 parts by mass of the total amount of the resin A and the (meth)acrylate B.

2. 2. The active energy ray-curable coating material composition according to claim 1, wherein the resin A accounts for 30 to 60 mass% and the (meth)acrylate B accounts for 40 to 70 mass%, relative to a total of 100 mass% of the resin A and the (meth)acrylate B.

3. 2. The active energy ray-curable coating material composition according to claim 1, wherein the polymer A1 has a mass average molecular weight of 10,000 to 80,000.

4. 2. The active energy ray-curable coating material composition according to claim 1, wherein the polymer A1 has a hydroxyl value of 40 to 180 mgKOH / g.

5. 2. The active energy ray-curable coating material composition according to claim 1, wherein the polymer A1 contains a structural unit derived from a hydroxyalkyl (meth)acrylate.

6. 2. The active energy ray-curable coating material composition according to claim 1, wherein the polymer A1 contains a structural unit derived from a monomer represented by the following formula (1): 【Chemical 1】 In formula (1), R １ and R ２ are each independently H or CH ３ It is. ３ and R ４ are each independently H or C ｎ H ２ｎ＋１ and n is 1 to 10.

7. 2. The active energy ray-curable coating material composition according to claim 1, wherein the alkyd resin A2 is an oil-modified alkyd resin.

8. 2. The active energy ray-curable coating material composition according to claim 1, wherein the (meth)acrylate B comprises a polyfunctional (meth)acrylate having 2 to 6 (meth)acryloyloxy groups.

9. 9. The active-energy ray-curable coating material composition according to claim 8, wherein the (meth)acrylate B comprises at least one (meth)acrylate selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-acryloyloxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and polyester (meth)acrylate.

10. 2. The active energy ray-curable coating material composition according to claim 1, wherein the silane coupling agent C has an amino group or a glycidyl group.

11. 11. The active-energy ray-curable coating material composition according to claim 10, wherein the silane coupling agent C comprises at least one silane coupling agent selected from the group consisting of N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.

12. The active energy ray-curable coating material composition according to claim 1 , further comprising a photopolymerization initiator D.

13. 13. The active energy ray-curable coating material composition according to claim 12, wherein the photopolymerization initiator D is 0.1 to 20 parts by mass per 100 parts by mass of the total amount of the resin A and the (meth)acrylate B.

14. 2. The active energy ray-curable coating material composition according to claim 1, which is used as an undercoat material for metal deposition.

15. A laminate comprising a coating layer of the active energy ray-curable coating material composition according to claim 14 and a metal vapor-deposited film laminated in this order on the surface of a resin substrate.

16. The laminate according to claim 15, wherein the laminate is a component for an automobile lamp.

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