JP5521936B2 - The present invention relates to an active energy ray-curable resin composition, an active energy ray-curable resin composition for FRP metal deposition, and a coated product. - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition that is excellent in storage stability and further has a high level of appearance, adhesion to a substrate and heat resistance of a cured coating film.

A molded body having a metal layer such as a reflector of an automobile light is obtained by vacuum-depositing or sputtering a metal such as aluminum or tin on the surface of a substrate made of a fiber reinforced composite material (hereinafter abbreviated as “FRP”). Have been made. At this time, a resin layer called an undercoat layer is formed in advance on the surface of the base material in order to improve the adhesion between the substrate and the metal layer and further improve the optical characteristics of the metal layer. As the coating resin used for the undercoat layer, for example, various lacquers made of acrylic resin and digested cotton-based resin, urethane resin coating, alkyd resin coating, ultraviolet curable coating, etc. are known, Among these, alkyd resin-containing ultraviolet curable paints having a short curing time and excellent heat resistance are attracting attention.

  As such an ultraviolet curable coating, a quinone-based polymerization is prohibited in a resin composition containing a urethane-modified alkyd resin having a molecular weight distribution (Mw / Mn) in the range of 20 to 50 and a polyfunctional (meth) acrylate compound. A technique of adding an agent is known (see Patent Document 1). However, although the quinone-based polymerization inhibitor has a high ability to trap radicals, it tends to be deactivated by dimerization, so it cannot suppress thickening or gelation over a long period of time and has sufficient storage stability. Could not be given.

Japanese Patent No. 3720770

  Therefore, the problem to be solved by the present invention is an active energy ray-curable resin composition excellent in storage stability and excellent in appearance, heat resistance, and substrate adhesion of a cured coating film, and FRP metal using the same An object of the present invention is to provide an active energy ray-curable resin composition for vapor deposition and a coated product having an undercoat layer excellent in heat resistance and substrate adhesion.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an oil-modified alkyd resin (A) obtained by using an unsaturated fatty acid or an unsaturated fatty acid ester as an active energy ray-curable resin composition, By containing the monomer (B) having a (meth) acryloyl group as an essential component, a cured coating film excellent in appearance, heat resistance and substrate adhesion of the coating film can be obtained. By adding the compound (C) having the molecular structure represented by the structural formula of the formula (1) or (2), it is possible to effectively increase the viscosity and gelation over time due to the double bond of the alkyd resin. The present inventors have found that it is suppressed and have completed the present invention.

(Wherein R ₁ is any _one of H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ , R ₃ Are each a hydrocarbon group having 2 to 10 carbon atoms)

(Wherein R ₄ and R ₅ are each H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₆ and R ₇ are each a hydrocarbon group having 2 to 10 carbon atoms)

  That is, the present invention relates to an oil-modified alkyd resin (A) obtained using an unsaturated fatty acid or an unsaturated fatty acid ester, a monomer (B) having a (meth) acryloyl group, the following general formula (1) or ( The present invention relates to an active energy ray-curable resin composition containing, as an essential component, a compound (C) having a molecular structure represented by the structural formula 2).

(Wherein R ₁ is any _one of H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ , R ₃ Are each a hydrocarbon group having 2 to 10 carbon atoms)

(Wherein R ₄ and R ₅ are each H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₆ and R ₇ are each a hydrocarbon group having 2 to 10 carbon atoms)

  The present invention further relates to an active energy ray-curable undercoating agent for FRP metal vapor deposition comprising the active energy ray-curable resin composition.

  The present invention further relates to a molded article having an undercoat layer made of the active energy ray-curable undercoat agent for FRP metal deposition.

  The present invention further relates to a method for producing the molded body.

  According to the present invention, an active energy ray-curable resin composition having excellent storage stability and a cured coating film excellent in heat resistance and substrate adhesion is obtained as compared with conventional resin compositions for powder coatings. I can do it.

  The oil-modified alkyd resin (A) used in the present invention is obtained by reacting a raw material containing an alcohol, a carboxylic acid, and an unsaturated fatty acid or an unsaturated fatty acid ester. Among these, what is obtained by making unsaturated fatty acid ester react is preferable at the point which the alkyd resin (A) obtained is hard to color.

  Examples of the alcohols include hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n -Octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol Monoalcohols such as diol and 2-decyltetradecanol;

Ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4 -Butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, Aliphatic polyols such as 1,4-bis (hydroxymethyl) cyclohesane, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, hexanetriol, pentaerythritol;

  Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;

  Obtained by ring-opening polymerization of the aliphatic polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Modified polyether polyols;

  Examples thereof include lactone polyester polyols obtained by a polycondensation reaction between the aliphatic polyols and various lactones such as ε-caprolactone. These may be used alone or in combination of two or more. Among these, a trihydric or higher polyhydric alcohol is preferable in that the crosslink density is improved and a tougher film property can be obtained, and trimethylolethane, trimethylolpropane, or pentaerythritol is more preferable.

  Examples of the carboxylic acids include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid Monocarboxylic acids such as benzoic acid;

  Aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid;

  (Anhydrous) aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid;

  Alicyclic dicarboxylic acids such as hexahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid;

  Aliphatic unsaturated dicarboxylic acids such as tetrahydrophthalic acid, (anhydrous) maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid;

  Various tricarboxylic acids such as 1,2,5-hexanetricarboxylic acid, trimellitic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, etc. Can be mentioned. These may be used alone or in combination of two or more. Among these, aromatic carboxylic acids such as benzoic acid, (anhydrous) phthalic acid, terephthalic acid, and isophthalic acid having a relatively high Tg are preferable in that tougher coating film properties can be obtained.

  Examples of the unsaturated fatty acids include monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, ellagic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid; linoleic acid, eicosadienoic acid , Diunsaturated fatty acids such as docosadienoic acid; triins such as linolenic acid, γ-linolenic acid, pinolenic acid, eleostearic acid, β-eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid Unsaturated fatty acids; tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid; pentaunsaturated fatty acids such as boseopentanoic acid, eicosapentaenoic acid, ozbond acid, sardine acid, tetracosapentaenoic acid; Examples include hexaunsaturated fatty acids such as docosahexaenoic acid and nisic acid. These may be used alone or in combination of two or more.

  Examples of the unsaturated fatty acid ester include those obtained by esterifying the unsaturated fatty acid with various alcohols. Examples of the various alcohols include various polyhydric alcohols listed as the alcohols. These alcohols may be used alone or in combination of two or more. As unsaturated fatty acid ester, fats and oils are preferable.

  The fats and oils may be any of drying oil, semi-drying oil, or non-drying oil, and specific examples include linseed oil, soybean oil, drill oil, tall oil, coconut oil, safflower oil, castor oil, and the like. . These may be used alone or in combination of two or more. Among these, linseed oil is preferable in that the coating film has excellent curability.

  The oil-modified alkyd resin (A) is obtained by, for example, reacting an unsaturated fatty acid or an unsaturated fatty acid ester with an alcohol for 1 to 5 hours in a temperature range of 200 to 240 ° C. in the presence of an esterification catalyst. Then, esterification reaction or transesterification reaction is performed, carboxylic acids are then added, and the reaction is performed for 6 to 15 hours under a temperature condition in the range of 200 to 240 ° C., so that the remaining hydroxyl groups in the system and the carboxyl groups of the carboxylic acids are reacted. Obtained by a method of esterification reaction.

  Examples of the esterification catalyst include lithium hydroxide. The amount of the catalyst used is, for example, in the range of 50 ppm to 500 ppm with respect to the total mass of the raw material of the oil-modified alkyd resin (A).

  In the present invention, various organic solvents may be added to the oil-modified alkyd resin (A). Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone, cyclic ethers such as tetrahydrofuran (THF) and dioxolane, esters such as methyl acetate, ethyl acetate, and butyl acetate, toluene, xylene Aromatics such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

  Commercially available products of such oil-modified alkyd resin (A) include, for example, beccosol 45-163 (DIC Corporation, 28% oil length), beccosol EL-4501-50 (DIC Corporation) as linseed oil-modified alkyd resin. Manufactured, oil length 45%), beccosol EL-6501-70 (DIC Corporation, oil length 65%); as soybean oil modified alkyd resin, beccosol ES-6505-70 (DIC Corporation, oil length 65%) , Beccosol OD-E-198-50 (DIC Corporation, oil length 28%), Beccosol ES-4020-55 (DIC Corporation, oil length 40%), Beccosol P-470-70 (DIC Corporation, Oil length 65%); Beccosol ET-6502-60 (DIC Corporation, oil length 65%) as tall oil-modified alkyd resin; As the oil-modified alkyd resin, Beccosol 1323-60-EL (DIC Corporation, oil length 28%); As the safflower oil-modified alkyd resin, Beccosol J-577 (DIC Corporation, oil length 51%); Can be mentioned.

  In the oil-modified alkyd resin (A), the mass ratio of the fat and oil component to the total mass of the alcohols, carboxylic acids, and unsaturated fatty acids or unsaturated fatty acid esters as raw materials is referred to as oil length, and the oil-modified alkyd of the present invention The oil length of the resin is preferably in the range of 20 to 70%, more preferably in the range of 20 to 50%, from the viewpoint of excellent compatibility with the compound (B) and adhesion to the substrate.

  Moreover, it is preferable that the weight average molecular weight (Mw) of the said oil-modified alkyd resin (A) is the range of 10,000-500,000 at the point which is excellent in coating work property and coating-film physical property. Among them, the weight average molecular weight (Mw) is more preferably in the range of 20,000 to 100,000, and more preferably in the range of 30,000 to 60,000 in terms of excellent appearance such as leveling properties of the coating film. Is more preferable. Moreover, it is more preferable that the weight average molecular weight (Mw) is in the range of 100,000 to 500,000, and in the range of 200,000 to 400,000 in that the coating film is more excellent in heat resistance and substrate adhesion. More preferably. According to the present invention, high storage stability can be obtained even when the oil-modified alkyd resin (A) having any molecular weight is used.

  The monomer (B) having a (meth) acryloyl group used in the present invention includes, for example, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, and propoxylated hexane. Diol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, Di (meth) acrylate compounds such as hydroxypivalic acid neopentyl glycol di (meth) acrylate;

  Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) ) Tri (meth) acrylate compounds such as acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate;

Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meta) 4) or more functional (meth) acrylate compounds such as acrylate and ditrimethylolpropane hexa (meth) acrylate;

And the (meth) acrylate compound etc. which substituted a part of above-mentioned (meth) acrylate with the alkyl group and (epsilon) -caprolactone, etc. are mentioned. These may be used alone or in combination of two or more. Among these, a compound having three or more (meth) acryloyl groups in one molecule is preferable in that the obtained resin composition is excellent in curability, and pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) are preferable. Acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are more preferable.

  Mass ratio of the content of the oil-modified alkyd resin (A) and the monomer (B) having a (meth) acryloyl group in the active energy ray-curable resin composition of the present invention [(A) / (B) ] Is preferably in the range of 80/20 to 20/80 from the viewpoint of good compatibility and obtaining a tough coating film. Especially, it is more preferable that it is the range of 60 / 40-40 / 60 at the point from which a tough coating film is obtained.

  The compound (C) used in the present invention is a compound having a molecular structure represented by the structural formula of the following general formula (1) or (2), and serves as a polymerization inhibitor for enhancing the storage stability of the resin composition. Function. Although these compounds (C) have a phenolic hydroxyl group having a substituent at the ortho position, radical trapping performance is slightly lower than those having a phenolic hydroxyl group without a substituent at the ortho position. Inactivation due to dimerization hardly occurs, and there is an effect that it is possible to suppress thickening and gelation for a long period of time. In the ultraviolet curable resin which has a monomer and an oligomer as a main component, since there are many highly reactive (meth) acryloyl groups, radicals are easily generated. For this reason, it is necessary to trap the generated radicals instantaneously, and the polymerization inhibitor is selected in preference to the radical trapping performance. In contrast, the double bond of the alkyd resin is less reactive than the (meth) acryloyl group and the frequency of occurrence of radicals is low, but the molecular weight is large, so even if polymerization proceeds slightly, the viscosity increases significantly. Become. Although the alkyd resin-containing UV-curable resin composition has a low (meth) acryloyl group content, it contains an alkyd resin that causes a significant increase in viscosity even with a small amount of polymerization as described above. For this, the polymerization inhibitor (C) of the present invention, which is less prone to inactivation due to its own dimerization and maintains the polymerization inhibiting ability for a longer period, is effective.

(Wherein R ₁ is any _one of H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ , R ₃ Are each a hydrocarbon group having 2 to 10 carbon atoms)

(Wherein R ₄ and R ₅ are each H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₆ and R ₇ are each a hydrocarbon group having 2 to 10 carbon atoms)

  The above compounds (C) may be used alone or in combination of two or more. Among these, the compound represented by the general formula (2) is preferable in that the compatibility with the mixture of the oil-modified alkyd resin (A) and the monomer (B) having a (meth) acryloyl group is excellent.

  The compound (C) has a hydrocarbon group having 2 to 10 carbon atoms in the ortho position of the phenolic hydroxyl group, and H, OH, and 1 carbon atom in the para position of the phenolic hydroxyl group. It has either an alkoxy group in the range of -10 or a hydrocarbon group in which the number of carbon atoms is in the range of 1-10. The hydrocarbon group in the ortho position of the phenolic hydroxyl group is preferably a hydrocarbon group having 2 to 7 carbon atoms, and a hydrocarbon group having 2 to 4 carbon atoms in terms of excellent compatibility and durability of the polymerization inhibition effect. Is more preferable, and a tertiary butyl group is more preferable. In addition, the substituent at the para position of the phenolic hydroxyl group is preferably an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms from the viewpoint of excellent compatibility and durability of the polymerization inhibition effect.

  Among the compounds (C), compounds having a molecular structure represented by the structural formula of the general formula (1) are 2,6-di-ethylphenol, 2,6-di-ethyl-4-hydroxyphenol, 2 , 6-Di-ethyl-4-methoxyphenol, 2,6-di-ethyl-4-ethoxyphenol, 2,6-di-ethyl-4-methylphenol, 2,6-di-ethyl-4-ethylphenol 2,6-di-ethyl-4-n-propylphenol, 2,6-di-ethyl-4-i-propylphenol, 2,6-di-ethyl-4-n-butylphenol, 2,6-di -Ethyl-4-t-butylphenol, 2,6-di-ethyl-4-cyclohexylphenol, 2,6-di-n-propylphenol, 2,6-di-n-propyl-4-hydroxyphenol, 2, 6-di- -Propyl-4-methoxyphenol, 2,6-di-n-propyl-4-ethoxyphenol, 2,6-di-n-propyl-4-methylphenol, 2,6-di-n-propyl-4- Ethylphenol, 2,6-di-n-propyl-4-n-propylphenol, 2,6-di-n-propyl-4-i-propylphenol, 2,6-di-n-propyl-4-n -Butylphenol, 2,6-di-n-propyl-4-tert-butylphenol, 2,6-di-n-propyl-4-cyclohexylphenol, 2,6-di-i-propylphenol, 2,6-di -I-propyl-4-hydroxyphenol, 2,6-di-i-propyl-4-methoxyphenol, 2,6-di-i-propyl-4-ethoxyphenol, 2,6-di-i-propyl- -Methylphenol, 2,6-di-i-propyl-4-ethylphenol, 2,6-di-i-propyl-4-n-propylphenol, 2,6-di-i-propyl-4-i- Propylphenol, 2,6-di-i-propyl-4-n-butylphenol, 2,6-di-i-propyl-4-tert-butylphenol, 2,6-di-i-propyl-4-cyclohexylphenol, 2,6-di-n-butylphenol, 2,6-di-n-butyl-4-hydroxyphenol, 2,6-di-n-butyl-4-methoxyphenol, 2,6-di-n-butyl- 4-ethoxyphenol, 2,6-di-n-butyl-4-methylphenol, 2,6-di-n-butyl-4-ethylphenol, 2,6-di-n-butyl-4-n-propyl Phenol, 2,6 -Di-n-butyl-4-i-propylphenol, 2,6-di-n-butyl-4-n-butylphenol, 2,6-di-n-butyl-4-t-butylphenol, 2,6- Di-n-butyl-4-cyclohexylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-hydroxyphenol, 2,6-di-t-butyl-4-methoxyphenol 2,6-di-t-butyl-4-ethoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6- Di-t-butyl-4-n-propylphenol, 2,6-di-t-butyl-4-i-propylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6- Di-t-butyl-4-t-butyl 2,6-di-tert-butyl-4-cyclohexylphenol, 2,6-dicyclohexylphenol, 2,6-dicyclohexyl-4-hydroxyphenol, 2,6-dicyclohexyl-4-methoxy Phenol, 2,6-di-cyclohexyl-4-ethoxyphenol, 2,6-di-cyclohexyl-4-methylphenol, 2,6-di-cyclohexyl-4-ethylphenol, 2,6-di-cyclohexyl-4 -N-propylphenol, 2,6-dicyclohexyl-4-i-propylphenol, 2,6-dicyclohexyl-4-n-butylphenol, 2,6-dicyclohexyl-4-t-butylphenol, 2 , 6-Di-cyclohexyl-4-cyclohexylphenol, 2,6-di- (1-methylcyclone) Hexyl) phenol, 2,6-di- (1-methylcyclohexyl) -4-hydroxyphenol, 2,6-di- (1-methylcyclohexyl) -4-methoxyphenol, 2,6-di- (1-methyl) Cyclohexyl) -4-ethoxyphenol, 2,6-di- (1-methylcyclohexyl) -4-methylphenol, 2,6-di- (1-methylcyclohexyl) -4-ethylphenol, 2,6-di- (1-methylcyclohexyl) -4-n-propylphenol, 2,6-di- (1-methylcyclohexyl) -4-i-propylphenol, 2,6-di- (1-methylcyclohexyl) -4-n -Butylphenol, 2,6-di- (1-methylcyclohexyl) -4-tert-butylphenol, 2,6-di- (1-methylcyclohexyl) -4-cyclohexylphenol and the like.

  The compounds having a molecular structure represented by the structural formula of the general formula (2) are 2,2'-methylenebis (6-ethylphenol) and 2,2'-methylenebis (6-ethyl-4-hydroxyphenol). 2,2'-methylenebis (6-ethyl-4-methoxyphenol), 2,2'-methylenebis (6-ethyl-4-ethoxyphenol), 2,2'-methylenebis (6-ethyl-4-methylphenol) ), 2,2'-methylenebis (6-ethyl-4-ethylphenol), 2,2'-methylenebis (6-ethyl-4-n-propylphenol), 2,2'-methylenebis (6-ethyl-4) -I-propylphenol), 2,2'-methylenebis (6-ethyl-4-n-butylphenol), 2,2'-methylenebis (6-ethyl-4-t-butylphenol) Nol), 2,2'-methylenebis (6-ethyl-4-cyclohexylphenol), 2,2'-methylenebis (6-n-propylphenol), 2,2'-methylenebis (6-n-propyl-4-) Hydroxyphenol), 2,2'-methylenebis (6-n-propyl-4-methoxyphenol), 2,2'-methylenebis (6-n-propyl-4-ethoxyphenol), 2,2'-methylenebis (6 -N-propyl-4-methylphenol), 2,2'-methylenebis (6-n-propyl-4-ethylphenol), 2,2'-methylenebis (6-n-propyl-4-n-propylphenol) 2,2'-methylenebis (6-n-propyl-4-i-propylphenol), 2,2'-methylenebis (6-n-propyl-4-n-) Tilphenol), 2,2'-methylenebis (6-n-propyl-4-tert-butylphenol), 2,2'-methylenebis (6-n-propyl-4-cyclohexylphenol), 2,2'-methylenebis ( 6-i-propylphenol), 2,2'-methylenebis (6-i-propyl-4-hydroxyphenol), 2,2'-methylenebis (6-i-propyl-4-methoxyphenol), 2,2 ' -Methylenebis (6-i-propyl-4-ethoxyphenol), 2,2'-methylenebis (6-i-propyl-4-methylphenol), 2,2'-methylenebis (6-i-propyl-4-ethyl) Phenol), 2,2'-methylenebis (6-i-propyl-4-n-propylphenol), 2,2'-methylenebis (6-i-propyl) -4-i-propylphenol), 2,2'-methylenebis (6-i-propyl-4-n-butylphenol), 2,2'-methylenebis (6-i-propyl-4-t-butylphenol), 2 2,2'-methylenebis (6-i-propyl-4-cyclohexylphenol), 2,2'-methylenebis (6-n-butylphenol), 2,2'-methylenebis (6-n-butyl-4-hydroxyphenol) 2,2'-methylenebis (6-n-butyl-4-methoxyphenol), 2,2'-methylenebis (6-n-butyl-4-ethoxyphenol), 2,2'-methylenebis (6-n- Butyl-4-methylphenol), 2,2'-methylenebis (6-n-butyl-4-ethylphenol), 2,2'-methylenebis (6-n-butyl-) -N-propylphenol), 2,2'-methylenebis (6-n-butyl-4-i-propylphenol), 2,2'-methylenebis (6-n-butyl-4-n-butylphenol), 2, 2'-methylenebis (6-n-butyl-4-tert-butylphenol), 2,2'-methylenebis (6-n-butyl-4-cyclohexylphenol), 2,2'-methylenebis (6-t-butylphenol) 2,2'-methylenebis (6-t-butyl-4-hydroxyphenol), 2,2'-methylenebis (6-t-butyl-4-methoxyphenol), 2,2'-methylenebis (6-t- Butyl-4-ethoxyphenol), 2,2'-methylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6-t-butyl-4) Ethylphenol), 2,2'-methylenebis (6-t-butyl-4-n-propylphenol), 2,2'-methylenebis (6-t-butyl-4-i-propylphenol), 2,2 ' -Methylenebis (6-t-butyl-4-t-butylphenol), 2,2'-methylenebis (6-t-butyl-4-t-butylphenol), 2,2'-methylenebis (6-t-butyl-4) -Cyclohexylphenol), 2,2'-methylenebis (6-t-butylphenol), 2,2'-methylenebis (6-t-butyl-4-hydroxyphenol), 2,2'-methylenebis (6-t-butyl) -4-methoxyphenol), 2,2'-methylenebis (6-tert-butyl-4-ethoxyphenol), 2,2'-methylenebis (6-tert-butyl-4-methyl) Tilphenol), 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2'-methylenebis (6-t-butyl-4-n-propylphenol), 2,2'-methylenebis (6-t-butyl-4-i-propylphenol), 2,2'-methylenebis (6-t-butyl-4-t-butylphenol), 2,2'-methylenebis (6-t-butyl-4-) t-butylphenol), 2,2'-methylenebis (6-t-butyl-4-cyclohexylphenol), 2,2'-methylenebis (6-cyclohexylphenol), 2,2'-methylenebis (6-cyclohexyl-4-) Hydroxyphenol), 2,2'-methylenebis (6-cyclohexyl-4-methoxyphenol), 2,2'-methylenebis (6-cyclohexyl) 4-ethoxyphenol), 2,2'-methylenebis (6-cyclohexyl-4-methylphenol), 2,2'-methylenebis (6-cyclohexyl-4-ethylphenol), 2,2'-methylenebis (6 -Cyclohexyl-4-n-propylphenol), 2,2'-methylenebis (6-cyclohexyl-4-i-propylphenol), 2,2'-methylenebis (6-cyclohexyl-4-t-butylphenol), 2, 2'-methylenebis (6-cyclohexyl-4-t-butylphenol), 2,2'-methylenebis (6-cyclohexyl-4-cyclohexylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) phenol] 2,2'-methylenebis [6- (1-methylcyclohexyl) -4 Hydroxyphenol], 2,2′-methylenebis [6- (1-methylcyclohexyl) -4-methoxyphenol], 2,2′-methylenebis [6- (1-methylcyclohexyl) -4-ethoxyphenol], 2, 2'-methylenebis [6- (1-methylcyclohexyl) -4-methylphenol], 2,2'-methylenebis [6- (1-methylcyclohexyl) -4-ethylphenol], 2,2'-methylenebis [6 -(1-Methylcyclohexyl) -4-n-propylphenol], 2,2'-methylenebis [6- (1-methylcyclohexyl) -4-i-propylphenol], 2,2'-methylenebis [6- ( 1-methylcyclohexyl) -4-tert-butylphenol], 2,2′-methylenebis [6- (1-methylcyclohexyl) Xyl) -4-t-butylphenol], 2,2′-methylenebis [6- (1-methylcyclohexyl) -4-cyclohexylphenol] and the like.

  The compound (C) used in the present invention exhibits high storage stability in a small amount as compared with a generally used methoquinone-based polymerization inhibitor. As described above, since it has a substituent at the ortho position of the phenolic hydroxyl group, it is difficult for deactivation due to its own dimerization, so it remains in the resin composition while maintaining its activity for a long time even with a small amount. It depends on what you can do.

  The content of the compound (C) in the active energy ray-curable resin composition of the present invention is the total solid content of the oil-modified alkyd resin (A) and the monomer (B) having a (meth) acryloyl group. It is the range of 10-1500 ppm with respect to mass, It is more preferable that it is the range of 50-1000 ppm, It is still more preferable that it is the range of 100-500 ppm. By making content of a compound (C) into the said range, sufficient inhibitory effect with respect to thickening and gelatinization is expressed, and hardening by subsequent active energy rays is not inhibited.

  The active energy ray resin composition of the present invention further contains a photopolymerization initiator (D). Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy. -2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one and the like.

  Commercially available photopolymerization initiators include, for example, Irgacure-184, 149, 261, 369, 500, 651, 754, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2959, 4043, Darocur-1173 (manufactured by Ciba Specialty Chemicals), Lucyrin TPO (manufactured by BASF), Kayacure-DETX, MBP, DMBI, EPA, OA (Manufactured by Nippon Kayaku Co., Ltd.), BiCure-10, 55 (manufactured by Stofa Chemical Co., Ltd.), Trigonal P1 (manufactured by Akzo Co., Ltd.), Sandley 1000 (manufactured by Sands Co., Ltd.), Deep (manufactured by Apjon Co., Ltd.) , ITX, and EPD (manufactured by Ward Brenkinsopp). These may be used alone or in combination of two or more.

  The photopolymerization initiator keeps good sensitivity of light, and does not cause crystal precipitation or deterioration of physical properties of the coating film. The active energy ray-curable resin composition 100 for simultaneous decorating of the present invention is used. It is preferable that it is the range of 0.05-20 mass parts with respect to a mass part, and it is more preferable that it is the range of 0.1-10 mass parts.

  The active energy ray-curable resin composition of the present invention further comprises a photosensitizer, an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent. You may contain various additives, such as an agent. These addition amounts can be used as long as the effect of the additive is sufficiently exhibited and ultraviolet curing is not inhibited.

  The active energy ray-curable resin composition of the present invention can be suitably used as an active energy ray-curable resin composition for FRP metal deposition. Specifically, it is used as an undercoat layer when forming a metal vapor deposition layer on the FRP substrate. Hereinafter, various conditions and the like when using the active energy curable resin composition of the present invention as an undercoat layer when forming a metal vapor deposition layer on an FRP substrate will be described in detail.

  In forming the undercoat layer, the active energy ray-curable resin composition of the present invention is applied onto the FRP substrate by a method such as spray coating. The coating amount at that time is preferably such that the film thickness after curing is in the range of 5 to 60 μm, and more preferably in the range of 10 to 40 μm. By setting the film thickness of the cured coating film within the above range, it is preferable in terms of expression of the adhesive effect and curable expression of the coating film.

  After applying the active energy ray-curable resin composition on the FRP substrate by the above method, preheating is performed for 5 to 25 minutes under the temperature condition in the range of 50 to 150 ° C. for the purpose of volatilizing the organic solvent in the resin composition. To do.

After completion of the preheating step, the resin composition is cured by irradiating active energy rays to form the undercoat layer. Examples of the active energy ray used in the present invention include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp as a light source can be used, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary. In the present invention, it is preferable to irradiate to ultraviolet integrated light quantity is 50 to 5000 mJ / cm ^2, integrated light quantity is more preferable to irradiate so that 500~2000mJ / cm ^2.

  As described above, the FRP substrate having the undercoat layer of the present invention is provided with a metal vapor deposition layer thereon, and a topcoat layer is further provided thereon. The film thickness of the metal vapor deposition layer in that case is the range of 30 nm-3 micrometers, and the film thickness after hardening of a topcoat layer is the range of 3-40 micrometers. Examples of such molded products include automobile reflectors. By using the active energy ray-curable resin composition of the present invention as an undercoat layer of a metal vapor-deposited layer, a molded product excellent in metallic luster of the metal layer, adhesion to an FRP substrate, and heat resistance can be obtained. Moreover, the active energy ray-curable resin composition of the present invention is characterized by excellent storage stability.

  Hereinafter, the present invention will be described in more detail with reference to specific synthesis examples and examples.

[Measurement method of weight average molecular weight (Mw)]
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

Alkyd resin (A) used in Examples and Comparative Examples
Synthesis example 1
Synthesis of oil-modified alkyd resin (A1) A flask having a stirrer, a temperature sensor, and a rectifying tube was charged with 1269 g of linseed oil as an unsaturated fatty acid ester, and then with 593 g of pentaerythritol. Dry nitrogen was allowed to flow into the flask at an amount of 10 ml / min, the temperature was raised to 190 ° C. over 2 hours while stirring, and 0.07 g of lithium hydroxide was added as an esterification catalyst. Then, it heated to 240 degreeC and transesterification was performed. After the transesterification reaction, the temperature was lowered to 140 ° C., 880 g of phthalic anhydride was charged, and the esterification reaction was performed at 220 ° C. Toluene was added and diluted so that the non-volatile content (NV) was 55% by mass to obtain an oil-modified alkyd resin (A1) having an acid value of 4.3 and a Gardner viscosity VW. The weight average molecular weight (Mw) of the oil-modified alkyd resin (A1) by gel permeation chromatography (GPC) was 303,000, and the oil length was 45% by mass.

Synthesis example 2
Synthesis of oil-modified alkyd resin (A2) A flask having a stirrer, a temperature sensor, and a rectifying tube was charged with 674 g of linseed oil as an unsaturated fatty acid, and then with 666 g of trimethylolethane and 266 g of benzoic acid. Dry nitrogen was allowed to flow into the flask at an amount of 10 ml / min, the temperature was raised to 190 ° C. over 2 hours while stirring, and 0.1 g of lithium hydroxide was added. Then, it heated to 240 degreeC and transesterification was performed. After the transesterification reaction, the temperature was lowered to 140 ° C., 936 g of phthalic anhydride was added, and the esterification reaction was performed at 220 ° C. Toluene was added and diluted such that the nonvolatile content (NV) was 50% by mass to obtain an oil-modified alkyd resin (A2) having an acid value of 5.1 and a Gardner viscosity MN. The weight average molecular weight (Mw) of the oil-modified alkyd resin (A2) by gel permeation chromatography (GPC) was 205,000, and the oil length was 26% by mass.

Synthesis example 3
Synthesis of oil-modified alkyd resin (A3) A flask having a stirrer, a temperature sensor and a rectifying tube was charged with 658 g of linseed oil as an unsaturated fatty acid, and then with 289 g of pentaerythritol and 163 g of benzoic acid. Dry nitrogen was allowed to flow into the flask at an amount of 10 ml / min, the temperature was raised to 180 ° C. over 2 hours while stirring, and 0.1 g of lithium hydroxide was added. Then, it heated to 240 degreeC and transesterification was performed. After the transesterification reaction, the temperature was lowered to 140 ° C., 387 g of phthalic anhydride was added, and the esterification reaction was performed at 220 ° C. Toluene was added and diluted so that the non-volatile content (NV) was 50% by mass to obtain an oil-modified alkyd resin (A3) having an acid value of 4.5 and a Gardner viscosity ST. The weight average molecular weight (Mw) by the oil permeation chromatography (GPC) of the oil-modified alkyd resin (A3) was 55,000, and the oil length was 45% by mass.

Monomer (B) having a (meth) acryloyl group used in Examples and Comparative Examples
Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were mixed so that the mass ratio [dipentaerythritol pentaacrylate] / [dipentaerythritol hexaacrylate] was 60/40 to obtain a composition (B1). .
The (meth) acryloyl equivalent of the mixture was 99.7 g / eq.

Compound (C) used in Examples and Comparative Examples
Polymerization inhibitor (C1): 2,6-di-t-butyl-4-methylphenol: “BHT Swanox” manufactured by Seiko Chemical Co., Ltd.

Polymerization inhibitor (C2): 2,2′-methylenebis (4-methyl-6-tert-butylphenol): “Nonflex MBP” manufactured by Seiko Chemical Co., Ltd.

Polymerization inhibitor (C3): 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol]: “Nonflex CBP” manufactured by Seiko Chemical Co., Ltd.

Polymerization inhibitor (C1 ′): Hydroquinone monomethyl ether: “Metoquinone” manufactured by Seiko Chemical Co., Ltd.

Polymerization inhibitor (C2 ′): phenothiazine: “Phenothiazine” manufactured by Seiko Chemical Co., Ltd.

Polymerization inhibitor (C3 ′): N-nitrosophenylhydroxylamine / aluminum salt: “Q-1301” manufactured by Wako Pure Chemical Industries, Ltd.

Polymerization inhibitor (C4 ′) 2,5-di-t-butylhydroquinone: “Nonflex Alba” manufactured by Seiko Chemical Co., Ltd.

Photoinitiator (D) used in Examples and Comparative Examples

“Irgacure 184” manufactured by Ciba Japan

Examples 1-9 and Comparative Examples 1'-9 '
[Method of creating a value coating film]
Example resin compositions 1 to 9 and comparative resin compositions 1 'to 9' were prepared with the formulations shown in Table 1 or Table 2. On the FRP molded article washed with isopropyl alcohol, the previously prepared resin composition was applied by air spray, and dried in an oven at 100 ° C. for 10 minutes in order to volatilize the solvent in the composition. Subsequently, an 80 W high pressure mercury lamp was used to irradiate ultraviolet rays with an integrated light quantity of 2000 mJ / cm ² to form an undercoat layer having a thickness of 10 to 20 μm on the surface of the FRP molded product. After aluminum is vacuum-deposited on the surface of the obtained undercoat layer, a topcoat resin composition (*) is further applied thereon with an air spray so that the dry film thickness is 3 μm. A topcoat layer was formed by baking for a minute, and an FRP reflector was manufactured.
* Resin composition for top coat layer: 20 parts by weight of "Iupica Coat 3002A" manufactured by Iupika Japan, 35 parts by mass of toluene, 40 parts by weight of industrial solvent ("Solvesso # 100" manufactured by Exxon Chemical Co., Ltd.), n-butanol 5 A mixture of parts by mass.

  The FRP reflector obtained by the above method was evaluated for coating film appearance, gloss, adhesion, heat resistance, and storage stability, and the results are shown in Table 1 for Examples and Table 2 for Comparative Examples. Summarized.

Evaluation method [Appearance of coating film]
The appearance was visually observed and inspected for the presence of rainbow, whitening, cracks, and blister defects, and evaluated as follows.

  ○ ... No defects of rainbow, whitening, cracks, and swelling.

X: There are defects such as rainbow, whitening, cracks, and swelling.
[Glossiness]
The glossiness was evaluated as follows by visual observation.

  ○ ・ ・ ・ Those with sufficient gloss.

X: Insufficient gloss.
[Adhesion]
Cut the surface of the reflector into 100 2 mm wide grids with a cutter knife, and apply cellophane adhesive tape (registered trademark “Cello Tape” made by Nichiban) on top of this to peel off, and the number of grids remaining without peeling Was measured.
[Heat-resistant]
About what was taken out after leaving still in a 180 degreeC hot-air circulation thought furnace for 100 hours, and cooled to room temperature, the external appearance and adhesiveness were evaluated by the method similar to the above.
[Storage stability]
The state of the composition after allowing each resin composition to stand at a temperature of 60 ° C. for 100 hours was evaluated as follows.

  O: Not colored, no increase in viscosity or gelation.

  Δ: Colored, but no increase in viscosity or gelation has occurred.

  X ... gelled.

Claims (9)

Structural formula of oil-modified alkyd resin (A) obtained by using unsaturated fatty acid or unsaturated fatty acid ester, monomer (B) having (meth) acryloyl group, and the following general formula (1) or (2) And an oil-modified alkyd resin (A) obtained by using the unsaturated fatty acid or unsaturated fatty acid ester, and a single compound having the (meth) acryloyl group. An active energy ray-curable resin composition containing 10 to 1500 ppm of the compound (C) with respect to the total mass of the monomer (B) .

(Wherein R ₁ is any _one of H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₂ , R ₃ Are each a hydrocarbon group having 2 to 10 carbon atoms)

(Wherein R ₄ and R ₅ are each H, OH, an alkoxy group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms, and R ₆ and R ₇ are each a hydrocarbon group having 2 to 10 carbon atoms) 2. The active energy ray-curable resin composition according to claim 1, wherein the unsaturated fatty acid ester is one or more types of fats and oils selected from the group consisting of linseed oil, soybean oil, tung oil, and tall oil. The active energy ray-curable resin composition according to claim 1, wherein the monomer (B) having the (meth) acryloyl group is a monomer having three or more (meth) acryloyl groups in one molecule. The monomer (B) having the (meth) acryloyl group is selected from the group consisting of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. 2. The active energy ray-curable resin composition according to claim 1, which is one or more kinds of compounds. Mass ratio [(A) / (B)] of the oil-modified alkyd resin (A) obtained using the unsaturated fatty acid or unsaturated fatty acid ester and the monomer (B) having the (meth) acryloyl group The active energy ray-curable resin composition according to claim 1, wherein is in the range of 80/20 to 20/80. The active energy ray-curable resin composition according to claim 1, wherein, in the general formula (1) or (2) representing the compound (C), R ₂ and R ₃ , or R ₆ and R ₇ are tertiary butyl groups. object. Oil-modified alkyd resin (A) obtained using unsaturated fatty acid or unsaturated fatty acid ester, monomer (B) having (meth) acryloyl group, and hindered cresol polymerization inhibitor (C) When, further photoinitiator (D) and claim 1 active energy ray curable resin composition according to any one of the 6, characterized in that it contains a. FRP metal deposition active energy ray-curable undercoating formulation comprising the active energy ray-curable resin composition according to any one of claims 1-7. The molded object which has an undercoat layer which consists of an undercoat agent of Claim 8 .