JP2017039792A - Active energy-ray curable resin composition, coating agent for undercoating and molded body containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an active energy-ray curable resin composition which is excellent in storage stability, and has coating properties to various base materials, adhesiveness with the base materials, and appearance and heat resistance of a cured coated film at high level; a metal deposition active energy-ray curable coating agent for undercoating using the same; and a molded body having an undercoat layer for metal deposition excellent in adhesiveness with various base materials.SOLUTION: There are provided: an active energy-ray curable resin composition which contains an alkyd resin (A) and a (meth)acrylate compound (B), where the total of the alkyd resin (A) and the (meth)acrylate compound (B) in 100 pts.mass of the total of the resin content is 65 pts.mass or more, and the (meth)acrylate compound (B) contains a (meth)acrylate compound (B1) having an alicyclic condensed polycyclic structure as an essential component; and a metal deposition active energy-ray curable coating agent for undercoating using the same.SELECTED DRAWING: None

Description

  The present invention is an active energy ray-curable resin composition that is excellent in storage stability and further has a high level of applicability to various substrates, adhesion, and appearance and heat resistance of a cured coating film. The present invention relates to an active energy ray-curable resin composition suitably used as an undercoating coating agent for performing metal vapor deposition on a molded body formed by combining a plurality of resin types.

  It is necessary to form a metal thin film on the surface of a base material such as a reflector of an exterior lamp lens of an automobile part that requires excellent heat resistance by vacuum deposition or sputtering. Base materials used for such applications include BMC (bulk molding compound), PPS (polyphenylene sulfide), ALD (aluminum die cast), PBT (polybutylene terephthalate) / PET (polyethylene terephthalate) alloy resin, PC (polycarbonate). ), ABS (acrylonitrile-butadiene-styrene copolymer resin), plastic substrates such as PC (polycarbonate) reinforced with fillers such as glass fiber, and metal substrates, which have excellent heat resistance and impact resistance. In particular, plastic base materials are often used from the viewpoint of weight reduction.

  However, when a metal such as aluminum is vapor-deposited on such a heat-resistant plastic substrate, there is a problem that the surface smoothness of the resulting component is lowered, and it is difficult to obtain a metallic glitter, particularly an automobile headlamp. When used for a reflecting mirror of a lens, it has been difficult to ensure optical characteristics necessary for the reflecting mirror. Therefore, before the metal thin film is formed, the surface of the base material is coated and cured in advance to form a coating layer, thereby maintaining the smoothness of the surface of the component and improving the optical properties ( For example, see Patent Documents 1 to 4).

  However, the reflector of the headlamp lens for automobile parts is a combination of a plurality of types of base materials. For example, a base material with excellent heat resistance is used for the part close to the lamp light source, and a base material with excellent workability is used for the part far from the lamp light source because the base material shape is complicated. In order to provide adhesion and heat resistance, it is necessary to use a coating agent depending on the type of substrate.

  Also, not only automotive headlamp lens reflectors, but parts with a metal-like surface appearance to give high appearance to automotive parts such as mobile phones, grills, emblems, cosmetic containers, home appliances, etc. Is often used. These are produced by combining various plastics to form a molded body and vacuum depositing a metal such as tin or aluminum on the surface thereof. When performing such a method, an active energy ray-curable undercoating coating agent that can be applied to various plastic substrates in order to smooth the surface and improve the adhesion between the plastic substrate and the metal vapor-deposited film. Is required.

Table 95/32250 JP 2003-221408 A JP 2011-021153 A JP 2012-066712 A

  Therefore, the problem to be solved by the present invention is an active energy ray that is excellent in storage stability and further has a high level of coating properties and adhesion to various substrates, and appearance and heat resistance of a cured coating film. The object is to provide a curable resin composition, an active energy ray-curable undercoating coating agent for metal vapor deposition using the same, and a molded article having an undercoat layer for metal vapor deposition that has excellent adhesion to various substrates. .

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have an active energy ray-curable resin composition containing, as essential components, an alkyd resin and a (meth) acrylate compound having an alicyclic condensed polycyclic structure. It has been found that the above problems can be solved by using a product, and the present invention has been completed.

  That is, the present invention is an active energy ray-curable resin composition containing an alkyd resin (A) and a (meth) acrylate compound (B), wherein the alkyd resin is contained in a total of 100 parts by mass of resin solids. The total of (A) and the (meth) acrylate compound (B) is 65 parts by mass or more, and the (meth) acrylate compound (B) has an alicyclic condensed polycyclic structure (B1). ) As an essential component, an active energy ray curable resin composition for metal deposition using the active energy ray curable resin composition, and an undercoat layer comprising the undercoat coating agent. The molded object which has is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type resin composition excellent in the coating appropriateness to various plastic base materials, adhesiveness, and storage stability can be obtained. The cured coating film obtained from the composition has good appearance and heat resistance, so it is excellent in applicability to a molded body having a complicated shape and a molded body formed by combining multiple types of substrates. It can be suitably used as a coating agent for undercoating metal vapor deposition.

  One of the characteristics of the active energy ray-curable resin composition of the present invention is that 65 parts by mass or more of the alkyd resin (A) and the (meth) acrylate compound (B) in a total of 100 parts by mass of the resin solids. The active energy ray-curable resin composition is excellent in adhesion to various plastic substrates, heat resistance, toughness, and the like. Furthermore, in a total of 100 parts by mass of the resin solids, it is more preferable to contain the alkyd resin (A) and the (meth) acrylate compound (B) in a total of 70 parts by mass or more, and particularly 80 parts by mass or more. preferable.

  Another feature of the active energy ray-curable resin composition of the present invention is that the (meth) acrylate compound (B) has the (meth) acrylate compound (B1) having an alicyclic condensed polycyclic structure as an essential component. It is in the point of containing, and, thereby, the outstanding heat resistance is expressed in hardened | cured material.

  In the sexual energy ray-curable resin composition of the present invention, the ratio of the alkyd resin (A) and the (meth) acrylate compound (B) can be arbitrarily adjusted according to various desired performances. Since it becomes an active energy ray-curable resin composition having excellent adhesion, heat resistance, toughness and the like, the mass ratio of the alkyd resin (A) and the (meth) acrylate compound (B) [(A ) / (B)] is preferably 25/75 to 75/25.

  The alkyd resin (A) is a polyester resin obtained using polybasic acid (a1), polyhydric alcohol (a2), and fat or fatty acid (a3) as essential components.

  Examples of the polybasic acid (a1) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. Aliphatic dibasic acids such as pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid; tetrahydrophthalic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, itacone Aliphatic unsaturated dibasic acids such as acid and glutaconic acid or anhydrides thereof; Alicyclic dibasic acids such as hexahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid; phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid Acids, aromatic dibasic acids such as orthophthalic acid or anhydrides thereof; 1,2,5-hexanetricarboxylic acid, 1,2 Aliphatic tribasic acids such as 4-cyclohexanetricarboxylic acid; aromatic tribasic acids such as trimellitic acid, trimellitic anhydride, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, or the like An anhydride etc. are mentioned. These may be used alone or in combination of two or more.

  In addition, in order to adjust the molecular weight of the resulting alkyd resin (A), etc., together with the polybasic acid (a1), methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octane Monobasic acids such as acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and p-tert-butylbenzoic acid may be used. These may be used alone or in combination of two or more. Among these, it is preferable to use a monobasic acid having a cyclic structure such as benzoic acid because the cured coating film of the obtained active energy ray-curable resin composition has excellent heat resistance and toughness.

  Examples of the polyhydric alcohol (a2) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 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 Diols such as glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohesan, 2,2,4-trimethyl-1,3-pentanediol; trimethylolethane, trimethylolpropane, glycerin, hexanetriol Polyols such as pentaerythritol; the diol or polyol, Modified polyether polyols obtained by ring-opening polymerization with various cyclic ether bond-containing compounds such as tylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether; Examples include lactone polyester polyols obtained by polycondensation reaction of diols or polyols with various lactones such as ε-caprolactone. These may be used alone or in combination of two or more. Among them, since the cured coating film of the obtained active energy ray-curable resin composition becomes excellent in heat resistance and toughness, polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, or These modified polyols are preferably used.

  The fat or oil (a3) is, for example, linseed oil, tung oil, rice oil, safflower oil, soybean oil, tall oil, rapeseed oil, palm oil, castor oil, dehydrated castor oil, coconut oil or the like; Fatty acids; these regenerated fats and oils; higher fatty acids having 12 to 30 carbon atoms such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, and the like. These may be used alone or in combination of two or more. Among them, since it becomes an active energy ray-curable resin composition excellent in adhesion to various plastic substrates, oils and fats having an iodine value of 100 or more, specifically drill oil, linseed oil, dehydrated castor oil, soybean oil, It is preferable to use either safflower oil or tall oil, and it is more preferable to use two or more of these oils having an iodine value of 100 or more.

  The alkyd resin (A) of the present invention may be a urethane-modified alkyd resin obtained by further reacting the polyisocyanate compound (a4) in addition to the components (a1) to (a3). Examples of the polyisocyanate compound used here include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m- Aliphatic diisocyanates such as tetramethylxylylene diisocyanate;

  Cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;

  1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate Aromatic diisocyanates such as 1,4-phenylene diisocyanate and tolylene diisocyanate;

  Examples thereof include nurate-modified polyisocyanates of the various diisocyanates, adduct-modified polyisocyanates obtained by reacting the various diisocyanates and polyols, and biuret-modified polyisocyanates of the various diisocyanates. These may be used alone or in combination of two or more.

  Moreover, the alkyd resin (A) of the present invention may be a phenol-modified alkyd resin obtained by further reacting the phenol resin (a5) in addition to the components (a1) to (a3). Examples of the phenol resin used here include a resol type phenol resin and a novolac type phenol resin.

  The production method of the alkyd resin (A) is not particularly limited. For example, the polybasic acid (a1), the polyhydric alcohol (a2), the fat or fatty acid (a3) and, if necessary, a monobasic acid or a polybasic acid. A method of reacting all raw materials such as isocyanate compound (a4) and phenolic resin (a5) at once, or a multi-stage reaction in which a part of the raw materials are reacted first to produce a precursor, and then the remaining raw materials are added to react. Examples thereof include a method of producing by reaction, a method of adding a part of raw materials and reacting them. When the alkyd resin is polybasic acid (a1), polyhydric alcohol (a2), oil or fat or fatty acid (a3), and monobasic acid as a raw material as necessary, these are all about 120 to 300 ° C. at a time. A method of reacting at a temperature is preferred. In the case of producing a urethane-modified alkyd resin, a basic acid (a1), a polyhydric alcohol (a2), an oil or fatty acid (a3) and, if necessary, a monobasic acid were reacted at a temperature of about 120 to 300 ° C. Then, it is preferable to add a polyisocyanate compound (a4) and to make it react at the temperature of about 50-100 degreeC. When the phenol-modified alkyd resin is produced, the polybasic acid (a1), the polyhydric alcohol (a2), the fat or fatty acid (a3), the phenol resin (a5), and the monobasic acid as necessary are all 120 in a lump. A method of reacting at a temperature of about ~ 300 ° C is preferred. The progress of the reaction can be monitored by measuring the amount of water distilled in the dehydration reaction, the acid value or the hydroxyl value, and the remaining isocyanate group. Moreover, you may use an esterification catalyst, a urethanization catalyst, etc. suitably as needed.

  The alkyd resin (A) may be reacted in an organic solvent as necessary. Moreover, an organic solvent may be added after completion | finish of reaction, and a viscosity, a non-volatile content, etc. may be adjusted. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone, cyclic ether solvents such as tetrahydrofuran (THF) and dioxolane, ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, toluene, xylene And aromatic solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

  Since the alkyd resin (A) is an active energy ray-curable resin composition having excellent adhesion to various plastic substrates, heat resistance, toughness, etc., the oil length is in the range of 30 to 70. It is preferable. The weight average molecular weight (Mw) is preferably in the range of 50,000 to 700,000, and the molecular weight distribution (Mw / Mn) is preferably in the range of 2 to 200. The hydroxyl value is preferably in the range of 30 to 150 mgKOH / g, and the acid value is preferably 40 mgKOH / g or less.

  The oil length of the alkyd resin (A) is the mass ratio of the fat or fatty acid (a3) to the total mass of the resin raw material of the alkyd resin (A) in percentage. In the present invention, the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) are values 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; Column temperature: 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

  The (meth) acrylate compound (B) contains a (meth) acrylate compound (B1) having an alicyclic condensed polycyclic structure as an essential component. The (meth) acrylate compound (B1) having an alicyclic condensed polycyclic structure includes, for example, a norbornene structure, a norbornane structure, an isobornyl structure, a dicyclopentanyl structure, a dicyclopentenyl structure, an adamantyl structure, etc. in the molecular structure. It will not specifically limit if it has an alicyclic condensed polycyclic structure, Various (meth) acrylate compounds can be utilized. Specifically, norbornene (meth) acrylate, norbornane (meth) acrylate, norbornane di (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopenta Compounds having a molecular structure in which a (meth) acryloyloxy group is directly linked to an alicyclic condensed polycyclic structure site, such as nildi (meth) acrylate; and the above various compounds such as dimethylol tricyclodecane di (meth) acrylate In the above various compounds such as dicyclopentenyloxyethyl acrylate, a compound having a molecular structure in which an alicyclic condensed polycyclic structure site and a (meth) acryloyloxy group are knotted via an alkylene group Cyclic condensed polycyclic moiety and (meth) acrylo Compounds having a nodule molecular structure and aryloxy groups via a (poly) oxyalkylene group; the following structural formula (1-1) or (1-2)

［式中Ｘはノルボルネン構造、ノルボルナン構造、イソボロニル構造、ジシクロペンタニル構造、ジシクロペンテニル構造、アダマンチル構造等の脂環式縮合多環構造を表す。Ｒ^１は水素原子又はメチル基であり、ｎは１〜５の整数である。Ｒ^２、Ｒ^３、Ｒ^５はそれぞれ独立に炭素原子数１〜２０の炭化水素基であり、Ｒ^４は炭素原子数１〜６のアルキレン基或いは（ポリ）オキシアルキレン基である。］
で表されるようなウレタン構造部位を有する化合物等が挙げられる。これらはそれぞれ単独で使用しても良いし、二種類以上を併用しても良い。中でも、耐熱性に一層優れる活性エネルギー線硬化型樹脂組成物となることから、ジシクロペンタニル構造又はジシクロペンテニル構造を有する（メタ）アクリレート化合物が好ましい。

[Wherein X represents an alicyclic condensed polycyclic structure such as a norbornene structure, a norbornane structure, an isoboronyl structure, a dicyclopentanyl structure, a dicyclopentenyl structure, an adamantyl structure, or the like. R ¹ is a hydrogen atom or a methyl group, and n is an integer of 1 to 5. R ² , R ³ and R ⁵ are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is an alkylene group or a (poly) oxyalkylene group having 1 to 6 carbon atoms. ]
And a compound having a urethane structure moiety represented by These may be used alone or in combination of two or more. Among these, a (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is preferable because it becomes an active energy ray-curable resin composition having further excellent heat resistance.

  In the present invention, as the (meth) acrylate compound (B), other (meth) acrylate compounds (B2) other than the (meth) acrylate compound (B1) having the alicyclic condensed polycyclic structure are used in combination. Also good. At this time, since the present invention with excellent heat resistance is fully expressed, the content of the (meth) acrylate compound (B1) having the alicyclic condensed polycyclic structure in the (meth) acrylate compound (B) is 10 The content is preferably at least mass%, more preferably at least 25 mass%, particularly preferably in the range of 35-80 mass%.

  The other (meth) acrylate compound (B2) used in the present invention is, for example, (b2-1) a (meth) acrylate monomer obtained by reacting a polyol and (meth) acrylic acid, or a (b2-2) molecule. Urethane (meth) acrylate obtained by adding a compound having a hydroxyl group and a (meth) acryloyl group to a compound having a terminal isocyanate group, (b2-3) At least two epoxy groups or glycidyl groups in the molecule (Meth) acrylic acid to a polyester polyol formed by condensation polymerization of an epoxy (meth) acrylate obtained by reacting a compound having (meth) acrylic acid with (b2-4) polyol and a polybasic acid or acid anhydride thereof Polyester (meth) acrylate, (b2-5) acrylic monomer and vinyl mono Chromatography is pendant acryloyl groups in copolymerized acrylic polymer obtained by polymerizing and acrylic acrylates obtained.

  In the (meth) acrylate monomer of the above (b2-1), the polyol is not particularly limited. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, trimethylene glycol, polypropylene glycol, Tetramethylene glycol, polytetramethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-hexylene glycol, 1 , 6-hexanediol, heptanediol, 1,10-decanediol, cyclohexanediol, 2-butene-1,4-diol, 3-cyclohexene-1,1-dimethanol, 4-methyl -3-cyclohexene-1,1-dimethanol, 3-methylene-1,5-pentanediol, (2-hydroxyethoxy) -1-propanol, 4- (2-hydroxyethoxy) -1-butanol, 5- ( 2-hydroxyethoxy) -pentanol, 3- (2-hydroxypropoxy) -1-butanol, 4- (2-hydroxypropoxy) -1-butanol, 5- (2-hydroxypropoxy) -1-pentanol, 1 -(2-hydroxyethoxy) -2-butanol, 1- (2-hydroxyethoxy) -2-pentanol, hydrogenated bisphenol A, glycerin, diglycerin, polycaprolactone, 1,2,6-hexanetriol, trimethylol Propane, trimethylolethane, pentanetriol, trishydroxymethyl Minomethane, 3- (2-hydroxyethoxy) -1,2-propanediol, 3- (2-hydroxypropoxy) -1,2-propanediol, 6- (2-hydroxyethoxy) -1,2-hexanediol, 1,9-nonanediol, neopentyl glycol hydroxypivalate, spiro glycol, 2,2-bis (4-hydroxyethoxyphenyl) propane, 2,2-bis (4-hydroxypropyloxyphenyl) propane, pentaerythritol, di Polyesters such as pentaerythritol, trimethylolpropane, trishydroxyethyl isocyanurate, di (2-hydroxyethyl) -1-acetoxyethyl isocyanurate, di (2-hydroxyethyl) -2-acetoxyethyl isocyanurate, mannitol, glucose In addition, alkylene oxide-modified or lactone-modified polyols obtained by addition reaction of ethylene oxide, propylene oxide, ε-caprolactone, γ-buterolactone, etc. with these polyols, excess of these polyols Also included are polyester polyols and polyether polyols having terminal hydroxyl groups obtained by condensing polybasic acids or acid anhydrides thereof.

  Specific examples of such (meth) acrylate monomers include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, Propylene oxide modified bisphenol A di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) a Relate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (Meth) acrylate, etc. [above, bifunctional (meth) acrylic monomer]; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin poly Glycidyl ether poly (meth) acrylate [more, three or more functional (meth) acrylic monomer], and.

  In the urethane (meth) acrylate of (b2-2), examples of the compound having a terminal isocyanate group in the molecule include those exemplified as polyisocyanate or polyol in the compound of (b2-1). And the like obtained by reacting polyisocyanate.

  The polyisocyanate in the above (b2-2) may be any of aliphatic, alicyclic, aromatic and aromatic-aliphatic, for example. As, for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane -2,6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, pheny Diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyanate, naphthylene diisocyanate, 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-funylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4′-diisocyanate diphenyl ether, 5, 6-dimethyl-1,3-phenylene diisocyanate, 4,4′-diisocyanate diphenyl ether, 2. Dizine diisocyanate, 9,10-anthracene diisocyanate, 4,4′-diisocyanate dibenzyl, 3,3-dimethyl-4,4′-diisocyanate diphenyl, 2,6-dimethyl-4,4′-diisocyanate diphenyl, Diisocyanates such as 3-dimethoxy-4.4'-diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,10-decanmethylene diisocyanate, 1,3-cyclohexylene diisocyanate A nurate body, a burette body and an adduct body of these diisocyanates; triisocyanates such as 2,4,6-tolylene triisocyanate and 2,4,4′-triisocyanate diphenyl ether; Can be mentioned.

  Examples of the compound having a hydroxyl group and a (meth) acryloyl group in the above (b2-2) include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, epoxy (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, glycerol di (meth) acrylate, and alkylene oxide-modified or lactone-modified compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone, etc. to these, Moreover, the compound which added polyisocyanate to these compounds can also be used.

  Examples of the compound having at least two epoxy groups or glycidyl groups in the molecule (b2-3) include bisphenol A, bisphenol F, 2,6-xylenol, brominated bisphenol A, phenol novolac and the like. Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin containing dimer acid, glycidyl ester type epoxy resin containing aromatic or heterocyclic amine, alicyclic epoxy resin, acrylic having epoxy group or glycidyl group Examples thereof include resins.

  In particular, as a compound having three or more epoxy groups or glycidyl groups in the molecule, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidyl ether, sorbitan tetraglycidyl ether, sorbitan pentaglycidyl ether , Triglycerol tetraglycidyl ether, tetraglycerol tetraglycidyl ether, pentaglycerol tetraglycidyl ether, triglycerol pentaglycidyl ether, tetraglycerol pentaglycidyl ether, pentaglycerol pentaglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl isocyanurate, etc. be able to

  In the above (b2-4), examples of the polyol, polybasic acid, or acid anhydride thereof include the same as described above.

  In the present invention, a compound having an unsaturated bond other than the (meth) acryloyl group such as diallyl fumarate and triallyl isocyanurate may be used in combination with the (meth) acrylate compound (B).

  The active energy ray-curable resin composition of the present invention preferably contains a photopolymerization initiator (C) in order to favorably advance the curing reaction with active energy rays. The photopolymerization initiator (C) is not particularly limited as long as it generates a radical by the action of light, and specifically, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxy. Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) 2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, Zoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 '-Dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone 4 ′, 4 ″ -diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester, acylphospho Sphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, dimethylaminobenzoic acid, dimethylaminobenzoic acid Examples thereof include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, dimethylaminobenzoic acid, and dimethylaminobenzoic acid alkyl ester are preferable, and dimethylaminobenzoic acid and dimethylaminobenzoic acid alkyl ester are particularly preferably used.

  Examples of the commercially available photopolymerization initiator (C) include Irgacure-184, 149, 261, 369, 500, 651, 754, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2850, 2959, 4043, Darocur-1173, Lucylin TPO (BASF), Kayacure-DETX, MBP, DMBI, EPA, OA (Nippon Kayaku Co., Ltd.) Company), BYCURE-10, 55 (Stofa Chemical), Trigonal P1 (Akzo), Sandley 1000 (Sands), Deep (Apjon), Quantacure-PDO, ITX, EPD (manufactured by Ward Brenkinsop) and the like can be mentioned. These may be used alone or in combination of two or more.

  With respect to 100 parts by mass of the active energy ray-curable resin composition of the present invention, the photopolymerization initiator maintains light sensitivity satisfactorily and does not cause precipitation of crystals or deterioration of physical properties of the coating film. The range is preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass.

  In the present invention, in addition to the above-described components, an amino resin may be included as necessary to further improve the heat resistance of the resulting coating film.

  Examples of the amino resin include a methylolated amino resin synthesized from at least one of melamine, urea, and benzoguanamine and formaldehyde; such a methylolated amino resin, wherein a part or all of the methylol group is obtained. , Alkyl etherified with a lower monohydric alcohol such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and the like.

  Specific examples of such amino resins include, for example, Cymel 303 (manufactured by Nippon Cytec Industries, Inc., methylated melamine resin), Cymel 350 (manufactured by Nippon Cytec Industries, Inc., methylated melamine resin), Uban 520 (Mitsui). Chemical Co., Ltd., n-butylated modified melamine resin), Uban 20-SE-60 (Mitsui Chemicals, n-butylated modified melamine resin), Uban 2021 (Mitsui Chemicals, Inc., n- Butylated modified melamine resin), Uban 220 (Mitsui Chemicals, Inc., n-butylated modified melamine resin), Uban 22R (Mitsui Chemicals, Inc., n-butylated modified melamine resin), Uban 2028 (Mitsui Chemicals) N-buterized modified melamine resin), Uban 165 (Mitsui Chemicals) Co., Ltd., isobutylated modified melamine resin), Uban 114 (Mitsui Chemicals Co., Ltd., isobutylated modified melamine resin), Uban 62 (Mitsui Chemicals Co., Ltd., isobutylated modified melamine resin), Uban 60R (Mitsui Chemical Co., Ltd., isobutylated modified melamine resin) and the like. When using these amino resins, it is preferable to contain 5-20 mass parts with respect to a total of 100 mass parts of alkyd resin (A) and (meth) acrylate compound (B) in a composition.

  Moreover, when using the said amino resin, you may add acid compounds, such as phosphate ester, as a hardening accelerator. It is preferable that the addition amount of a hardening accelerator is the range of 0.1-10 mass parts with respect to 100 mass parts of amino resins.

  The active energy ray-curable resin composition of the present invention may contain a solvent to facilitate dilution and coating. The solvent is not particularly limited, but a low surface tension solvent is preferable in order to improve wettability. Examples of such a solvent include alcohol solvents, ketone solvents, and the like. In addition, ethyl acetate, butyl acetate, toluene, xylene and the like can be used in combination in view of the evaporation rate and cost.

  The active energy ray-curable resin composition of the present invention may contain a surface conditioner. The surface preparation agent is not particularly limited, and examples thereof include a fluorine-based additive and a cellulose-based additive. The fluorine-based additive has a function of preventing repelling when applied to various substrates by reducing surface tension and increasing wettability. Specific examples of the fluorine-based additive include Megafac F-177 (manufactured by DIC Corporation).

  The cellulose-based additive has an effect of imparting film-forming properties during coating. The cellulose-based additive is preferably a high-molecular-weight product having a number average molecular weight of 15000 or more in order to reduce fluidity. Examples of such a cellulose-based additive include cellulose-acetate-butyrate resin.

  In the present invention, when the amount of the fluorine-based additive is increased, the adhesion of the deposited aluminum and the top coat is decreased, and when the amount of the cellulose-based additive is increased, the solid content of the composition of the present invention is increased. It is preferable to use a fluorine-based additive and a cellulose-based additive in combination.

  The amount of the surface preparation agent is such that the total amount of the fluorine-based additive and the cellulose-based additive is in the range of 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the non-volatile content in the composition. preferable. When using a fluorine-type additive independently, it is preferable that it is the range of 0.01-1.0 mass part, and when using a cellulose-type additive independently, 0.5-5.0 mass part is preferable. It is preferable that it is the range of these.

  The active energy ray-curable resin composition of the present invention further includes various additions such as a photosensitizer, an ultraviolet absorber, an antioxidant, a silicon-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent. An agent may be contained. These addition amounts can be used as long as the effect of the additive is sufficiently exhibited and the 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 undercoat coating agent for metal deposition. Specifically, it is used as an undercoat layer when a metal vapor deposition layer is formed on a 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 a substrate will be described in detail.

  Since the active energy ray-curable resin composition of the present invention has high adhesion to various materials, the substrate is not particularly limited, and various materials can be used. Specifically, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, PET / PBT alloy resin, unsaturated polyester resin, polyethylene resin, polypropylene resin, polyphenylene sulfide (PPS) resin, polycarbonate resin, acrylonitrile-butadiene -Various resin materials such as styrene copolymer resin (ABS), resin materials reinforced with glass fibers and fillers such as bulk molding compound (BMC), and aluminum die cast (ALD).

  In forming the undercoat layer, the active energy ray-curable resin composition of the present invention is applied onto a substrate by a method such as spray coating, dip coating, spin coating, flow coating, or roller 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 substrate by the above method, preheating for 5 to 25 minutes under the temperature condition 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 base material on which the undercoat layer of the present invention is installed is provided with a metal vapor deposition layer thereon, and a top coat layer and the like are further provided thereon. Examples of metal species for metal deposition include aluminum, iron, nickel, chromium, copper, silver, zinc, tin, indium, magnesium, oxides thereof, and alloys thereof. The film thickness of the metal vapor deposition layer is preferably in the range of 30 nm to 3 μm. The top coat layer is generally a clear paint such as an acrylic lacquer paint, an acrylic melamine curable paint, an aluminum chelate acrylic paint, and the thickness of the top coat layer after curing may be in the range of 3 to 40 μm. preferable. Examples of the molded body thus obtained include an automobile reflector. 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 having excellent metallic luster, adhesion to a substrate, and heat resistance of the metal layer 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. Hereinafter, “parts” and “%” are based on mass unless otherwise specified.

[Method of measuring weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were 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; Column temperature: 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

Production Example 1 Production of Alkyd Resin (A-1) In a flask having a stirring bar, a temperature sensor, a rectifying tube and a decanter, 1260 parts by mass of soybean oil, 208 parts by mass of benzoic acid, 630 parts by mass of trimethylolpropane, and phthalic anhydride 681 parts by mass, 195 parts by mass of isophthalic acid, 85 parts by mass of xylene and 0.5 parts by mass of an organic titanium compound are charged, and dry nitrogen is flowed into the flask and heated to 230 to 250 ° C. while stirring to perform a dehydration condensation reaction. It was. The reaction was stopped when the acid value reached 8.0 mgKOH / g, and after cooling to 150 ° C., a mixed solvent (xylene / toluene = 50/50 (weight ratio)) was added dropwise to dilute to a solid content of 60% by mass. An alkyd resin (A-1) solution was obtained. The number average molecular weight (Mn) of the obtained alkyd resin (A-1) was 4,300, the weight average molecular weight (Mn) was 89,000, the molecular weight distribution (Mw / Mn) was 20.7, and the hydroxyl value was 82 mgKOH / g, acid value was 7.8 mgKOH / g, oil length was 45.

Production Example 2 Production of Alkyd Resin (A-2) In a flask having a stirring bar, a temperature sensor, a rectifying tube and a decanter, 616 parts by weight of linseed oil, 299 parts by weight of soybean oil fatty acid, 53 parts by weight of p-tert-butylbenzoic acid Part, 211 parts by mass of pentaerythritol, 38 parts by mass of dipropylene glycol, 153 parts by mass of glycerin, 563 parts by mass of phthalic anhydride, 71 parts by mass of xylene, and 0.4 parts by mass of organic titanium compound, and flow dry nitrogen into the flask The mixture was heated to 230 to 250 ° C. with stirring to perform a dehydration condensation reaction. The reaction was stopped when the acid value reached 8.3 mgKOH / g, and after cooling to 150 ° C., a mixed solvent (xylene / toluene = 50/50 (weight ratio)) was added dropwise to dilute to a solid content of 60%. An alkyd resin (A-2) solution was obtained. The number average molecular weight (Mn) of the obtained alkyd resin (A-2) was 3,400, the weight average molecular weight (Mw) was 90,000, the molecular weight distribution (Mw / Mn) was 26.5, and the hydroxyl value was 108 mgKOH / g, the acid value was 8.3 mg KOH / g, and the oil length was 50.

Production Example 3 Production of Alkyd Resin (A-3) In a flask having a stirring rod, a temperature sensor, a rectifying tube and a decanter, 380 parts by mass of soybean oil, 890 parts by mass of safflower oil, 154 parts by mass of p-tert-butylbenzoic acid Part, 472 parts by weight of pentaerythritol, 754 parts by weight of phthalic anhydride, 56 parts by weight of xylene and 0.2 parts by weight of an organic titanium compound, heated to 220-240 ° C. with stirring and flowing dry nitrogen into the flask, A dehydration condensation reaction was performed. The reaction was stopped when the acid value became 12 mg KOH / g or less, and after cooling to 150 ° C., toluene and ethyl acetate were added dropwise to dilute to a solid content of 50% to obtain an alkyd resin (A-3) solution. The number average molecular weight (Mn) of the obtained alkyd resin (A-3) was 4,000, the weight average molecular weight (Mw) was 530,000, the molecular weight distribution (Mw / Mn) was 132.5, and the hydroxyl value was 70 mgKOH / g, acid value was 12 mgKOH / g, and oil length was 50.

Production Example 4 Production of Alkyd Resin (A-4) In a flask having a stirrer, a temperature sensor, a rectifying tube and a decanter, 751 parts by mass of soybean oil, 274 parts by mass of pentaerythritol, 305 parts by mass of phthalic anhydride, 147 benzoic acid A mass part and 0.3 part by mass of an organic titanium compound were charged, dry nitrogen was allowed to flow into the flask, and the mixture was heated to 220 to 240 ° C. with stirring to perform a dehydration condensation reaction. The reaction was stopped when the acid value became 10 mgKOH / g or less, and after cooling to 150 ° C., xylene was added dropwise to dilute to a solid content of 80% by mass. Next, 130 parts by mass of isophorone diisocyanate was added and urethanated at 70 to 80 ° C., and the reaction was stopped when the isocyanate weight ratio became 0.1% or less, and xylene was added dropwise to dilute to a solid content of 50% by mass. Thus, an alkyd resin (A-4) solution was obtained. The number average molecular weight (Mn) of the obtained alkyd resin (A-4) was 3,600, the weight average molecular weight (Mw) was 230,000, the molecular weight distribution (Mw / Mn) was 76.7, and the hydroxyl value was 21 mgKOH / g, the acid value was 9.5 mg KOH / g, and the oil length was 40.

Production Example 5 Production of Alkyd Resin (A-5) In a flask having a stirring bar, a temperature sensor, a rectifying tube and a decanter, 680 parts by mass of soybean oil, 309 parts by mass of glycerin, 601 parts by mass of phthalic anhydride, resol type phenol resin (“Beccasite M-342” manufactured by DIC Corporation) 100 parts by weight, 76 parts by weight of xylene and 0.2 parts by weight of an organic titanium compound were charged, and dried nitrogen was flowed into the flask and heated to 200 to 220 ° C. while stirring. Then, a dehydration condensation reaction was performed. When the acid value became 13 mgKOH / g or less, the reaction was stopped, and after cooling to 150 ° C., xylene was added dropwise to dilute to a solid content of 50% by mass to obtain an alkyd resin (A-5) solution. The number average molecular weight (Mn) of the obtained alkyd resin (A-5) was 3,200, the weight average molecular weight (Mw) was 90,000, the molecular weight distribution (Mw / Mn) was 28.0, and the hydroxyl value was 58 mgKOH / g, acid value was 13 mgKOH / g, and oil length was 40.

Production Example 6 Production of (Meth) acrylate Compound (B1-1) In a flask having a stirring bar, a temperature sensor, and a condenser, 88 parts by mass of tricyclodecane dimethanol, 35 parts by mass of 1,6-hexanediol, “Aronix M- 305 "(manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value 116 mg KOH / g), charged with 735 parts by weight and 0.1 part by weight of an organic tin catalyst, heated to 80 ° C and stirred Then, 333 parts of isophorone diisocyanate was charged to carry out a urethanization reaction. After confirming that the isocyanate group content was 0.03% by mass or less, the mixture was cooled to 70 ° C. or less, diluted with 1542 parts by mass of butyl acetate, and a (meth) acrylate compound (B1-1 having a solid content of 50% by mass). ) A solution was obtained.

Production Example 7 Production of (Meth) acrylate Compound (B2-5) To a flask having a stirrer, a temperature sensor, and a condenser, “Aronix M-305” (manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate and pentaerythritol tetraacrylate) Mixture, hydroxyl value 116 mgKOH / g) 1174 parts by mass, 1,6-hexanediol 35 parts by mass, organotin catalyst 0.1 part by mass, and with isophorone diisocyanate 333 parts by mass while stirring at 80 ° C. The urethanization reaction was performed. After confirming that the isocyanate group content was 0.03% by mass or less, the mixture was cooled to 70 ° C. or less, diluted with 1542 parts by mass of butyl acetate, and a (meth) acrylate compound (B2-5 having a solid content of 50% by mass). ) A solution was obtained.

In addition to the various compounds obtained in the above production examples, the details of the compounds used in the examples of the present application are as follows.
◆ (Meth) acrylate compound (B1-2): dicyclopentenyloxyethyl acrylate (DCPTE-A) (“Funkryl FA-512AS” manufactured by Hitachi Chemical Co., Ltd.)
◆ (Meth) acrylate compound (B1-3): dicyclopentanyl acrylate (DCPTA-A) (“Funkryl FA-513AS” manufactured by Hitachi Chemical Co., Ltd.)
◆ (Meth) acrylate compound (B1-4): Tricyclodecane dimethanol diacrylate (DCP-DA) (Shin-Nakamura Chemical Factory “A-DCP”)
◆ (Meth) acrylate compound (B2-1): Dipentaerythritol hexaacrylate (DPHA) (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
◆ (Meth) acrylate compound (B2-2): ditrimethylolpropane tetraacrylate (DTMPTA) (“Aronix M-408” manufactured by Toagosei Co., Ltd.)
◆ (Meth) acrylate compound (B2-3): trimethylolpropane triacrylate (TMPTA) (“Aronix M-309” manufactured by Toagosei Co., Ltd.)
◆ (Meth) acrylate compound (B2-4): Tripropylene glycol diacrylate (TPGDA) (“Kayarad TPGDA” manufactured by Nippon Kayaku Co., Ltd.)
◆ Amino resin (1): “Cymel 303” manufactured by Nippon Cytec Industries, Ltd.
◆ Amino resin (2): “Super Becamine L-105-60” manufactured by DIC Corporation
◆ Curing accelerator: “P-198” phosphate ester compound manufactured by DIC Corporation ◆ Photopolymerization initiator: “Irgacure 184” manufactured by BASF
Surface modifier: DIC Corporation “Megafac F-477”

Example 1
Each component was mix | blended in the ratio shown in Table 1, the active energy ray hardening-type resin composition was adjusted, and various evaluation was performed in the following way about this. The results are shown in Table 1.

◆ Manufacture of reflective material BMC (bulk molding compound) was used as a base material. The active energy ray-curable resin composition prepared above was air spray-coated on the surface of the substrate. The solvent was dried under conditions of 60 ° C. × 10 minutes, and an undercoat layer having a thickness of 20 μm was formed on the substrate by irradiating with an ultraviolet ray with an irradiation amount of 1500 mJ / cm ² with an 80 W / cm high-pressure mercury lamp. Next, an aluminum vapor deposition layer was formed on the surface of the undercoat layer using a vacuum vapor deposition apparatus. Furthermore, using a plasma polymerization (CVD) apparatus on the surface of the aluminum vapor deposition layer, silicon gas was polymerized in a plasma atmosphere to form a silicon-based polymer film, thereby creating a reflector.

◆ Evaluation of smoothness The smoothness of the reflector was visually evaluated. Evaluation was performed according to the following criteria.
“◎”: Smooth.
“◯”: A liquid pool is slightly formed at the edge of the base material, or irregularities are confirmed.
“X”: Obviously, a liquid pool is formed at the end of the substrate, or irregularities are confirmed.

◆ Evaluation of adhesion The adhesion was evaluated by a cross-cut peel test. Make 100 × 1 × ² grids on the reflector with a 10 × 10 grid pattern at 1mm intervals, make cellophane tape on top of it, and peel it off quickly. The number of grids remaining without counting was counted. Evaluation was performed according to the following criteria.
“◎”: The remaining number of grids is 100.
“◯”: The number of remaining grids is 50 to 99.
“×”: The number of remaining grids is 49 or less.

◆ Evaluation of heat resistance (appearance) The appearance after the reflecting plate was left in a hot air dryer at 220 ° C. for 96 hours was visually evaluated. Evaluation was performed according to the following criteria.
“◎”: No change.
“◯”: Appearance abnormalities such as “whitening”, “rainbow”, “crack”, “fluff” are observed on a part of the reflector.
“×”: Appearance abnormalities such as “whitening”, “rainbow”, “crack”, “fluff” and the like are observed on the entire reflector.

◆ Evaluation method of heat resistance (adhesiveness) The adhesiveness after leaving the reflector plate in a hot air dryer at 220 ° C. for 96 hours was evaluated by a cross-cut peel test. Make 100 × 1 × ² grids on the reflector with a 10 × 10 grid pattern at 1mm intervals, make cellophane tape on top of it, and peel it off quickly. The number of grids remaining without counting was counted. Evaluation was performed according to the following criteria.
“◎”: The remaining number of grids is 100.
“◯”: The number of remaining grids is 50 to 99.
“×”: The number of remaining grids is 49 or less.

◆ Evaluation of storage stability The sexual energy ray-curable resin composition was stored at 40 ° C. for 3 months, and the storage stability was visually evaluated. Evaluation was performed according to the following criteria.
“◎”: No change in appearance and viscosity.
"X": There exists a viscosity change or the gelled material has produced | generated.

Examples 2-10
As in Example 1, the active energy ray-curable resin composition was prepared by blending each component at the ratio shown in Table 1, and various evaluations were performed in the manner described above. The results are shown in Table 1.

Comparative Examples 1 and 2
As in Example 1, the active energy ray-curable resin composition was prepared by blending each component at the ratio shown in Table 2, and various evaluations were performed in the manner described above. The results are shown in Table 2.

Claims (5)

  An active energy ray-curable resin composition containing an alkyd resin (A) and a (meth) acrylate compound (B), wherein the alkyd resin (A) and the ( The (meth) acrylate compound (B1) having a total of 65 parts by mass or more with the (meth) acrylate compound (B) and the (meth) acrylate compound (B) having an alicyclic condensed polycyclic structure as an essential component An active energy ray-curable resin composition comprising:   The active energy ray-curable resin according to claim 1, wherein the mass ratio [(A) / (B)] of the alkyd resin (A) and the (meth) acrylate compound (B) is 25/75 to 75/25. Composition.   The active energy ray-curable resin composition according to claim 1, wherein 10% by mass or more of the (meth) acrylate compound (B) is the (meth) acrylate compound (B1) having the alicyclic condensed polycyclic structure.   An active energy ray-curable undercoating coating agent for metal vapor deposition comprising the active energy ray-curable resin composition according to any one of claims 1 to 3.   The molded object which has an undercoat layer which consists of a coating agent for undercoats of Claim 4.