JP2015000876A - Active energy ray-curable composition and synthetic resin molded product having cured coating film of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition capable of forming a cured coating film excellent in weather resistance, adhesiveness with a substrate, abrasion resistance and scratch resistance, and to provide a synthetic resin molded product having the cured coating film.SOLUTION: There is provided an active energy ray-curable composition which comprises: a poly(meth)acrylic polyurethane (A) having a mass average molecular weight of 5500 to 60000 obtained by reaction of a hydroxyl group-containing compound with an isocyanate group-containing compound; a given poly((meth)acryloyloxyalkyl) isocyanurate (B); a given ethylenically unsaturated compound (C) other than the (A) and (B); and an ultraviolet absorber (D), wherein the composition contains a non-aromatic di(meth)acrylate (a1) having two hydroxyl groups in the molecule as the hydroxyl group-containing compound and contains a non-aromatic diisocyanate (a2) as the isocyanate group-containing compound.

Description

  The present invention relates to an active energy ray-curable composition and a synthetic resin molded article having a cured film of the composition.

  Synthetic resin molded products including polymethyl methacrylate resin, polymethacrylimide resin, polycarbonate resin, polystyrene resin, AS (acrylonitrile-styrene) resin, etc. are lightweight, excellent in impact resistance, and highly transparent. For example, various lamp lenses It is used as plastic parts for automobiles such as glazing and instrument covers. In particular, for the headlamp lens, the synthetic resin molded product is increasingly used from the viewpoint of weight reduction for improving the fuel efficiency of automobiles, diversification of design, and the like. However, since the synthetic resin molded product has low surface wear resistance, the surface is easily damaged by contact with other hard objects, friction, scratching, etc., and the damage generated on the surface lowers the commercial value. Further, when the synthetic resin molded product is used as the above-described automotive plastic part, weather resistance is also important. In particular, when the synthetic resin molded product is a polycarbonate resin molded product, the weather resistance is low, the product is deteriorated by ultraviolet rays, the molded product is yellowed, and cracks are generated on the surface.

  As a method for solving the problems of the synthetic resin molded product, a method of forming a crosslinked film by applying a resin composition containing a radical polymerizable monomer and then irradiating active energy rays has been proposed. In particular, the active energy ray-curable composition is immediately cured by irradiating active energy rays such as ultraviolet rays, and can form a hard film on the surface of the synthetic resin molded product, so that the processing speed is high, and the hardness, The overall process cost is low because of excellent wear resistance and high productivity.

  However, when the crosslink density of the cured film is improved in order to obtain a harder film, the cured shrinkage rate of the cured film increases and the residual stress of the cured film increases. Since the cured film has low flexibility and is likely to crack due to aging, it is difficult to use the cured film in applications that require the above-described weather resistance. Therefore, Patent Documents 1 and 2 propose a composition containing urethane (meth) acrylate having excellent scratch resistance and small cure shrinkage. Patent Document 3 proposes a composition containing polyacryl polyurethane composed of epoxy (meth) acrylate having two hydroxyl groups in the molecule and diisocyanate. By using polyacryl polyurethane having a relatively high molecular weight and having a functional group in the side chain, both hardness and flexibility are achieved.

JP 2012-229412 A JP 2011-144309 A JP 2010-275339 A

  However, in the techniques disclosed in Patent Documents 1 to 3, when a cured film is formed on a polycarbonate resin molded product used in an environment such as outdoors, weather resistance (crack resistance) is insufficient, Cracks occur in the cured coating, resulting in defects in appearance.

  An object of the present invention is to provide an active energy ray-curable composition capable of forming a cured film excellent in weather resistance, adhesion to a substrate, abrasion resistance and scratch resistance, and synthetic resin molding having the cured film Is to provide goods.

  That is, the present invention includes the following [1] to [5].

[1] A poly (meth) acrylic polyurethane (A) having a mass average molecular weight of 5500 to 60000 obtained by reacting a hydroxyl group-containing compound with an isocyanate group-containing compound;
Poly (meth) acryloyloxyalkyl isocyanurate (B) represented by the following formula (1);
Ethylenically unsaturated compounds (C) other than (A) and (B),
UV absorber (D),
An active energy ray-curable composition containing
As the hydroxyl group-containing compound, a non-aromatic di (meth) acrylate (a1) having two hydroxyl groups in the molecule,
As the isocyanate group-containing compound, a non-aromatic diisocyanate (a2) is included,
Active energy ray-curable composition.

(In the formula (1), X ¹ , X ² and X ³ are each independently acryloyl group (CH ₂ ═CH—CO—), an acryloyl group modified with caprolactone [{CH ₂ ═CH—CO ( O (CH ₂ ) ₅ C═O) _a —} (a is an integer of 1 or more)]] represents a hydrogen atom or an alkyl group, and at least two of X ¹ , X ² and X ³ are acryloyl groups or An acryloyl group modified with caprolactone, R ¹ , R ² and R ³ each independently represents an oxyalkylene group or a polyoxyalkylene group);

  [2] The active energy ray-curable composition according to [1], wherein (a1) is an epoxy (meth) acrylate having a molecular weight of 300 to 500 represented by the following formula (2).

(In the formula (2), R ⁴ represents a hydrogen atom or a methyl group. Y represents an alkylene group, a cycloalkylene group, or a divalent organic group not containing an aromatic group having an ester bond or an ether bond.) .

  [3] The active energy ray-curable composition according to [1] or [2], wherein (a2) is a diisocyanate having an alicyclic skeleton.

  [4] A synthetic resin molded article coated with a cured film of the active energy ray-curable composition according to any one of [1] to [3].

  [5] The synthetic resin molded product according to [4], wherein the synthetic resin molded product is a polycarbonate resin molded product for an automotive headlamp lens or a polycarbonate resin molded product for an automotive resin glass.

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type composition which can form the cured film excellent in a weather resistance, adhesiveness with a base material, abrasion resistance, and abrasion resistance, and the synthetic resin molding which has the cured film Goods can be provided.

Hereinafter, embodiments of the present invention will be described in detail. The curable functional group represented by CH ₂ ═C (R) C (O) O— (where R is a hydrogen atom or a methyl group) is an acryloyloxy group (when R is a hydrogen atom). Or it is a methacryloyloxy group (when R is a methyl group), and is also shown below as a (meth) acryloyloxy group. Similarly, a general term for “acrylate” and “methacrylate” is shown as “(meth) acrylate”.

<Poly (meth) acrylic polyurethane (A)>
The active energy ray-curable composition (hereinafter referred to as “the present composition”) according to the present invention is from the viewpoint of reducing the volume shrinkage of the cured coating during curing and improving the surface hardness and toughness of the cured coating. And poly (meth) acrylic polyurethane (A) (hereinafter referred to as “component A” as appropriate). Moreover, when this composition contains A component, a weather resistance (crack resistance) can be improved, without impairing the abrasion resistance of a cured film. The component A is a compound having a mass average molecular weight of 5500 to 60000 obtained by reacting a hydroxyl group-containing compound and an isocyanate group-containing compound, and as the hydroxyl group-containing compound, a non-aromatic compound having two hydroxyl groups in the molecule. A di (meth) acrylate (a1) and a non-aromatic diisocyanate as the isocyanate group-containing compound.

<(A1)>
(A1) is an essential raw material for the component A, and is a non-aromatic di (meth) acrylate having two hydroxyl groups in the molecule. (A1) improves the surface hardness of the cured product by maintaining low shrinkage at the time of curing of the composition and introducing a photoreactive functional group into the molecular side chain of the component A.

  (A1) is not particularly limited as long as it has two hydroxyl groups and two (meth) acryloyl groups in the molecule and does not contain an aromatic ring in its structure. For example, as (a1), a non-aromatic tetrahydric alcohol di (meth) acrylate, an epoxy (meth) acrylate obtained by adding (meth) acrylic acid to a non-aromatic diepoxy compound, or the like is used. be able to.

  Specifically, as (a1), pentaerythritol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol diacrylate (for example, trade name: Kayrad R-167, manufactured by Nippon Kayaku Co., Ltd.), polyethylene Acrylic acid adduct of glycol diglycidyl ether (for example, trade names: Denacol DA-811, Denacol DM-811, Denacol DM-832, Denacol DM-851, manufactured by Nagase ChemteX Corporation), polypropylene glycol diglycidyl ether Acrylic acid adducts (for example, trade names: Denacol DA-911M, Denacol DA-920, Denacol DA-931, manufactured by Nagase ChemteX Corporation), epichlorohydrin-modified hydrogenated phthalic acid diacrylate (for example, trade name: Denacol DA -7 2, manufactured by Nagase Chemtex Co., Ltd.), and the like.

  Particularly, (a1) is preferably an epoxy (meth) acrylate represented by the formula (2) from the viewpoint of scratch resistance. The molecular weight of the epoxy (meth) acrylate is preferably 300 to 500, and more preferably 300 to 400. In said Formula (2), as an alkylene group of Y, a C3-C10 alkylene group is mentioned, for example. Specific examples of such Y include a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the cycloalkylene group for Y include a cyclohexylene group, a cyclopentylene group, a tricyclodecane dimethylene group, and the like. Examples of the divalent organic group not containing an aromatic group having an ester bond or an ether bond of Y include a diethylene glycol group, a triethylene glycol group, a dipropylene glycol group, a tripropylene glycol group, and a hydrogenated phthalic acid group. Specific examples of the epoxy (meth) acrylate having a molecular weight of 300 to 500 represented by the formula (2) include epichlorohydrin-modified 1,6-hexanediol diacrylate. These may use 1 type and may use 2 or more types together.

  (A1) can be synthesized from a diepoxy compound and a (meth) acrylic acid derivative. The synthesis method is not particularly limited, and a known synthesis method can be employed. For example, (a1) can be synthesized by mixing an epoxy compound, a (meth) acrylic acid derivative, a synthesis catalyst and a polymerization inhibitor such as hydroquinone monomethyl ether and reacting the mixture at 95 ° C.

  As the synthesis catalyst, a known catalyst used in an esterification reaction between an acid group and an epoxy group can be used. However, from the viewpoint of a high reaction rate, the synthetic catalyst is preferably a tertiary amine, a quaternary ammonium salt, or a quaternary phosphonium salt. Examples of the tertiary amine include dimethylaminoethyl methacrylate. Examples of the quaternary ammonium salt include tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, and tetrabutylammonium hydroxide. Examples of the quaternary phosphonium salt include tetraethylphosphonium bromide, tetrabutylphosphonium bromide, benzyltriphenylphosphonium chloride, and benzyltriphenylphosphonium bromide. These may use 1 type and may use 2 or more types together.

  The diepoxy compound is not particularly limited as long as it is non-aromatic. Specific examples of the diepoxy compounds include hydrogenated bisphenol A type, hydrogenated bisphenol F type diepoxy compounds, alkylene oxide adducts thereof, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclohexanediol, and cyclohexane. Diepoxy compounds of alicyclic glycols such as dimethanol, cyclohexanediethanol, norbornanediol, norbornanedimethanol, norbornanediethanol, decalindiol, decalindimethanol, decalindiethanol, diepoxy compounds of phthalic acid, isophthalic acid, terephthalic acid, 3, 4 -Epoxycyclohexyl methyl carboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclo Hexane - meta-dioxane, bis (3,4-epoxycyclohexyl) alicyclic epoxy compounds such as adipates, oxide such as divinylbenzene, and the like. These may use 1 type and may use 2 or more types together. Among these, hydrogenated bisphenol A diepoxy compounds and hydrogenated bisphenol F diepoxy compounds are preferable because high weather resistance and surface hardness can be obtained after curing.

<(A2)>
(A2) is an essential raw material for the component A and is a non-aromatic diisocyanate. (A2) is used for introducing a urethane bond into the molecular chain of the component A to make it polyurethane. (A2) is not particularly limited as long as it is a diisocyanate that does not contain an aromatic group in the molecular structure used in the production of urethane (meth) acrylate. Specific examples of (a2) include aliphatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate; isophorone diisocyanate , Diisocyanate having an alicyclic skeleton such as dicyclohexylmethane-4,4-diisocyanate and methylcyclohexylene diisocyanate. These may use 1 type and may use 2 or more types together. Among these, as (a2), a diisocyanate having an alicyclic skeleton is preferable from the viewpoint of physical properties of the obtained cured film. (A2) is more preferably isophorone diisocyanate or dicyclohexylmethane-4,4-diisocyanate.

  The synthesis method of the component A is not particularly limited, and a known polyurethane synthesis method can be employed. For example, A component can be obtained by mixing (a1) and a polyurethane-forming catalyst, and dropping (a2) and reacting at 50 to 90 ° C.

  As the polyurethane forming catalyst, an amine catalyst, an organometallic catalyst, or the like can be used. Examples of the amine catalyst include triethylamine, N, N-dimethylcyclohexylamine, dimethanolamine and the like. As the organometallic catalyst, an organotin compound is preferably used, and examples thereof include stannous octoate, stannous laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, and dioctyltin diacetate. These may use 1 type and may use 2 or more types together. Among these, from the viewpoint of obtaining a high catalytic effect with a small amount, an organometallic catalyst is preferable, and dibutyltin dilaurate is more preferable. Further, the reaction solution may be diluted with a solvent or the like as necessary for the purpose of facilitating temperature control during synthesis and reducing the viscosity of the resulting A component to improve workability.

  When synthesizing the component A, in addition to (a1) and (a2), other polyurethane raw materials such as a hydroxyl group-containing compound other than (a1) and an isocyanate group-containing compound other than (a2) may be used. . Examples of such other polyurethane raw materials include (meth) acrylates having a hydroxyl group in the molecule other than (a1), polyols other than (a1), and polyisocyanates other than (a2). When using these other polyurethane raw materials, it is preferably 50% by mass or less of all polyurethane raw materials, more preferably 30% by mass or less, further preferably 10% by mass or less, and substantially 0% by mass. Particularly preferred.

  The ratio of (a1) and (a2) when producing the component A is not particularly limited. However, the ratio of the total amount of hydroxyl groups contained in (a1) and the total amount of isocyanate groups contained in (a2) is 0.5 ≦ (total amount of isocyanate groups) / (total amount of hydroxyl groups) <0.9. It is preferable. When the ratio is 0.5 or more, the molecular weight of the resulting poly (meth) acryl polyurethane is not too low, and the volume shrinkage is reduced during curing. Moreover, when the ratio is less than 0.9, the molecular weight of the resulting poly (meth) acryl polyurethane does not become too high, and gelation due to thickening during synthesis can be prevented. (Total amount of isocyanate groups) / (Total amount of hydroxyl groups) is more preferably 0.65 to 0.85. In addition, the amount of hydroxyl groups and the amount of isocyanate groups are values calculated by multiplying the number of functional groups contained in one molecule by the number of moles used.

  The mass average molecular weight of A component is 5500-60000. When the mass average molecular weight of the component A is within the above range, both the scratch resistance and weather resistance of the resulting cured product can be achieved. The mass average molecular weight of the component A is preferably 5500 to 30000, and more preferably 5500 to 25000. When the mass average molecular weight is less than 5500, the weather resistance of the resulting cured product is lowered.

  In addition, the mass average molecular weight of A component is the value measured with the following method. After preparing a tetrahydrofuran solution (0.4% by mass) of this composition, a gel permeation chromatography apparatus (manufactured by Tosoh Corporation) equipped with columns (trade names: GE4000HXL and G2000HXL, manufactured by Tosoh Corporation) Inject 100 μL of the solution. The flow rate is 1 mL / min, the eluent is tetrahydrofuran, the column temperature is 40 ° C., measured by gel permeation chromatography, and the value converted to standard polystyrene is defined as the mass average molecular weight of component A.

  The content of the component A in the active energy ray curable composition is not particularly limited. However, the A component, the poly (meth) acryloyloxyalkyl isocyanurate (B) represented by the above formula (1) (hereinafter referred to as “B component” as appropriate), and ethylenic unsaturation other than the A component and the B component The content of the component A is preferably 10 to 70% by mass and is preferably 20 to 60% by mass with respect to 100% by mass of the total amount of the compound (C) (hereinafter referred to as “C component” as appropriate). Is more preferable. When the content of the component A is within the above range, the viscosity can be easily reduced, the workability is excellent, and the obtained cured product has good wear resistance and weather resistance.

<Poly (meth) acryloyloxyalkyl isocyanurate (B) represented by Formula (1)>
This composition contains B component from a viewpoint which shows favorable polymerization activity by irradiation of an active energy ray, and can improve heat resistance, without impairing the abrasion resistance of a cured film. In X ¹ , X ² and X ³ of the formula (1), a of the acryloyl group modified with caprolactone is preferably 5 or less from the viewpoint of wear resistance of the resulting cured film. It is more preferable that it is 2 or less. In X ¹ , X ² and X ³ of the formula (1), examples of the alkyl group include an alkyl group having 1 to 3 carbon atoms. Examples of the oxyalkylene group of R ¹ , R ² and R ^{3 in} the formula (1) include oxyalkylene groups having 1 to 5 carbon atoms. Examples of the polyoxyalkylene group represented by R ¹ , R ² and R ^{3 in} the formula (1) include those having a repeating structure of an oxyalkylene group having 1 to 5 carbon atoms.

  Specific examples of the poly (meth) acryloyloxyalkyl isocyanurate represented by the formula (1) include bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, and bis. (2-acryloyloxypropyl) hydroxyethyl isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, tris (2-acryloyloxyethyl) isocyanurate modified with one caprolactone per molecule (for example, trade name: Aronix M-325, manufactured by Toagosei Co., Ltd.) Tris (2-acryloyloxyethyl) isocyanurate modified with 3 caprolactones per molecule (for example, trade name: Aronix M-327, Toago) Adult Co., Ltd.), and the like. These may use 1 type and may use 2 or more types together.

  Content of B component in an active energy ray curable composition is not specifically limited. However, the content of the B component is preferably 10 to 60% by mass and more preferably 20 to 50% by mass with respect to 100% by mass of the total amount of the A component, the B component and the C component. When content of B component is in the said range, the reactivity with respect to an active energy ray is favorable, and the adhesiveness and water resistance with the base material of the cured film obtained are favorable.

<Ethylenically unsaturated compounds (C) other than (A) and (B)>
This composition contains C component from a viewpoint of further improving the surface hardness of a cured film, and adhesiveness with a base material. The C component is not particularly limited as long as it is an ethylenically unsaturated compound other than the A component and the B component that improves the surface hardness of the cured coating or the adhesion to the substrate, but the coating film is not colored when used outdoors. From the viewpoint, a compound having two or more (meth) acryloyl groups not containing an aromatic group is preferable. Examples of the compound include di (meth) acrylate, trifunctional or higher polyfunctional (meth) acrylate, polyurethane poly (meth) acrylate other than component A, polyester poly (meth) acrylate, and the like.

  Examples of the di (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and neopentyl glycol. Di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (repeating unit n = 2 to 15) di (meth) acrylate, polypropylene glycol (repeating unit n = 2 to 15) di (meth) acrylate, polybutylene Glycol (repeat unit n = 2 to 15) di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) ) Propane, trimethylolpropane di Meth) acrylate, tricyclodecane dimethanol diacrylate, and the like.

  Examples of the trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate modified with caprolactone, pentaerythritol tri (meth) acrylate, and caprolactone. Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate modified with caprolactone, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate modified with caprolactone Dipentaerythritol modified with (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone Pointer (meth) acrylate, dipentaerythritol hexa (meth) acrylate, modified dipentaerythritol hexa (meth) acrylate and the like by caprolactone.

  Other specific examples of component C are obtained by reacting an organic diisocyanate, one or more (meth) acryloyloxy groups in the molecule and a hydroxy group-containing (meth) acrylate having one hydroxy group. Urethane (meth) acrylate: Alkane diol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, amide diol, spiroglycol and other alcohols with an organic diisocyanate added to the isocyanate group of the resulting urethane prepolymer Urethane (meth) acrylate obtained by reacting one (meth) acryloyloxy group with one hydroxy group-containing (meth) acrylate; phthalic acid, succinic acid, hexahydrophthalic acid Polybasic acids such as tetrahydrophthalic acid, terephthalic acid, azelaic acid, adipic acid, and polyhydric alcohols such as ethylene glycol, hexanediol, polyethylene glycol, polytetramethylene glycol, trimethylolethane, trimethylolpropane, and (meth) Examples thereof include polyester (meth) acrylate obtained by reacting acrylic acid or a derivative thereof. These may use 1 type and may use 2 or more types together.

  Among these, from the viewpoint of improving the surface protection performance of the cured coating, the C component is preferably a trifunctional or higher polyfunctional (meth) acrylate, such as trimethylolpropane tri (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate modified with caprolactone, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate modified with caprolactone, pentaerythritol tri (meth) acrylate, caprolactone Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol modified with caprolactone La (meth) acrylate are more preferred. From the viewpoint of achieving both the weather resistance and scratch resistance of the cured coating, the C component includes dipentaerythritol hexa (meth) acrylate modified with caprolactone, trimethylolpropane tri (meth) acrylate modified with caprolactone, and these More preferred is a mixture of

  The content of the C component in the active energy ray-curable composition is not particularly limited. However, the content of the C component is preferably 20 to 60% by mass and more preferably 25 to 50% by mass with respect to 100% by mass of the total amount of the A component, the B component, and the C component. When content of C component exists in the said range, the surface hardness and weather resistance of a cured film are favorable.

<Ultraviolet absorber (D)>
This composition contains an ultraviolet absorber (D) (hereinafter, referred to as “component D” as appropriate). The component D is not particularly limited as long as it dissolves uniformly in the present composition and has good weather resistance, but from the viewpoint of high solubility in the present composition and good weather resistance, triazine-based, benzophenone UV absorbers having a maximum absorption wavelength in the range of 240 to 380 nm, which are compounds derived from benzotriazole, phenyl salicylate, and phenyl benzoate. In particular, a benzophenone-based ultraviolet absorber is more preferable from the viewpoint that it can be contained in a large amount in the present composition. Further, from the viewpoint of preventing yellowing of a substrate such as polycarbonate, triazine-based and benzotriazole-based ultraviolet absorbers are more preferable.

  Content of D component in an active energy ray curable composition is not specifically limited. However, the content of the D component is preferably 1 to 30 parts by mass and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the total amount of the A component, the B component, and the C component. When content of D component exists in the said range, the sclerosis | hardenability of this composition and the abrasion resistance of a cured film are favorable. Moreover, the weather resistance (yellowing resistance) of a cured film and a base material is favorable.

<Hindered amine light stabilizer (E)>
The composition preferably further contains a hindered amine light stabilizer (E) (hereinafter referred to as “E component” as appropriate) from the viewpoint of preventing deterioration of the substrate to which the composition is applied by ultraviolet rays.

  A known hindered amine light stabilizer can be used as the E component. However, as component E, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9 -(2,4,8,10-tetraoxaspiro [5,5]) undecane) condensate with diethanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-pentamethyl- 1,1-dimethyl, a condensate of 4-piperidinol with β, β, β, β-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5]) undecane) diethanol Condensate of ethyl hydroperoxide and octane (for example, trade name: Tinuvin 123, manufactured by BASF), 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetra) Methylpiperidine-4- Yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine. In addition, a hindered amine light stabilizer having a (meth) acryloyl group in the molecule can also be used. Examples of the hindered amine light stabilizer include {2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6. A reaction product of-(2-hydroxyethylamine) -1,3,5-triazine and 2-acryloyloxyethyl isocyanate is exemplified. The reactant can be produced, for example, by the method described in JP-A-2008-56906. Among these, from the viewpoint of maintaining weather resistance over a long period of time, the E component includes 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine- 4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, a hindered amine light stabilizer having a (meth) acryloyl group in the molecule is more preferred.

  The content of the E component in the active energy ray-curable composition is not particularly limited. However, the content of the E component is preferably 0.1 to 5 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the A component, the B component, and the C component. More preferred. When content of E component exists in the said range, the weather resistance (crack resistance) and abrasion resistance of a cured film are favorable.

<Photopolymerization initiator (F)>
This composition preferably contains a photopolymerization initiator (F) (hereinafter referred to as “F component” as appropriate) when the active energy ray irradiated when curing the composition is ultraviolet light.

  Examples of the F component include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl). ) Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 Acetophenones such as hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzov Non, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,4 , 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, etc. Benzophenones; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 , 4-Dimethyl-9 -Thioxanthones such as thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis ( And acylphosphine oxides such as 2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

  Among these, from the viewpoint of good curability of the composition and high surface hardness of the cured product, the F component includes benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -Hydroxycyclohexyl-phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one is preferred. These may use 1 type and may use 2 or more types together.

  The content of the F component in the active energy ray-curable composition is not particularly limited. However, the content of the F component is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the A component, the B component, and the C component. More preferred. When content of F component exists in the said range, sclerosis | hardenability of this composition is favorable and the surface hardness of hardened | cured material is high.

<This composition>
This composition contains A to D components, and can further contain E and F components, but if necessary, inorganic fillers other than A to F components, organic solvents, polymerization inhibitors, yellowing inhibitors, Various additives such as an infrared absorber, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent, an antistatic agent, and an antifogging agent may be included.

  This composition can contain an inorganic filler as needed from a viewpoint of surface hardness, heat resistance, and electroconductivity improvement. As the inorganic filler, from the viewpoints of shape stability, heat resistance, flame retardancy, insulation, etc. of the cured product, a metal oxide such as silica, alumina, titanium oxide or a composite oxide thereof, the metal oxide or A surface-treated metal oxide or surface-treated composite oxide obtained by coating the composite oxide with a silane coupling agent or the like, or a hydroxide such as aluminum hydroxide, magnesium hydroxide, or potassium hydroxide is preferable. In addition, as the inorganic filler, from the viewpoint of improving conductivity, metal particles such as gold, silver, copper, nickel and alloys thereof, conductive particles such as carbon, carbon nanotube, carbon nanohorn, fullerene, and glass, ceramic, Particles in which the surface of the core such as plastic or metal oxide is coated with metal, ITO (indium tin oxide) or the like are preferable. These may use 1 type and may use 2 or more types together. The conductive particles preferably have an aspect ratio of 5 or more from the viewpoint of conductivity. The aspect ratio is a value obtained from (major axis) / (minor axis). The particle diameter of the inorganic filler is optically preferably 1 μm or less in terms of area average particle diameter. The blending amount of the inorganic filler in the active energy ray-curable composition can be appropriately adjusted according to the use of the composition, required mechanical strength, fluidity, and the like. A known method can be used as a blending method of the inorganic filler.

  This composition can contain an organic solvent as needed from a viewpoint of adjusting a viscosity to the viscosity according to the coating method. Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, cyclohexyl alcohol, diacetone alcohol; methyl cellosolve, cellosolve, butyl cellosolve, methyl Ether solvents such as carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; “Swazole 1000” (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), “Supersol 100” (trade name, New Nippon Petrochemical Co., Ltd.), "Supersol 150" (trade name, manufactured by Nippon Petrochemical Co., Ltd.), aromatic solvents such as benzene, toluene, xylene; cyclic hydrocarbon solvents such as cyclohexane Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ketone solvents such as cyclohexanone, ethyl acetate, n- butyl acetate, isobutyl acetate, n- amyl acetate, include acetate-based solvents such as propylene glycol acetate. These may use 1 type and may use 2 or more types together. The organic solvent to be used is preferably selected as appropriate depending on the type of the substrate. For example, when polycarbonate is used as the substrate, it is preferable to use an alcohol solvent such as isobutanol and an ester solvent such as n-butyl acetate alone or in combination of two or more as the organic solvent.

  About content of the organic solvent, it is preferable from content of application | coating workability | operativity that content of the hardened | cured material component in the final composition before application | coating is 30 mass% or more of the final composition before application | coating. Moreover, the said content can be 80 mass% or less, for example. For example, when spraying the composition, the Ford Cup No. It is preferable to add an organic solvent so as to have a viscosity of 15 to 30 seconds at 20 ° C. using a four viscometer.

<Method for producing the present composition>
This composition can be manufactured by mixing each said component uniformly using a well-known method.

  This composition can be used to modify the surface of various synthetic resin molded articles that are base materials. After apply | coating this composition on a base material, it can bridge | crosslink by irradiating an active energy ray and can form a cured film. The amount of the composition applied to the substrate is preferably such that the cured film has a thickness of 1 to 50 μm, more preferably 3 to 40 μm. The coating method of the present composition on the substrate includes bar coater coating method, Mayer bar coating method, air knife coating method, gravure coating method, reverse gravure coating method, micro gravure coating method, brush coating method, spray coating method, shower Examples thereof include a flow coating method, a dip coating method, a curtain coating method, an offset printing method, a flexographic printing method, a screen printing method, and potting. Moreover, you may apply | coat after heating this composition in order to adjust a viscosity.

As the active energy ray, ultraviolet rays are preferable, and ultraviolet rays including a wavelength of 340 nm to 380 nm are more preferable. As the ultraviolet light source, a high-pressure mercury lamp, a metal halide lamp, or the like can be used. The irradiation amount of ultraviolet rays can be set to 1000 to 5000 mJ / cm ² with ultraviolet rays having a wavelength of 340 nm to 380 nm, for example. The active energy ray may be irradiated in air, or in an inert gas such as nitrogen or argon.

  After apply | coating this composition on a base material, you may heat-process before irradiating an active energy ray. The heat treatment can be performed by irradiation with a near infrared lamp, circulation of hot air, or the like. When performing heat treatment, from the viewpoint of maintaining adhesion over a long period outdoors, the substrate surface temperature in the furnace (hereinafter referred to as heating temperature) is 40 to 90 ° C., and the heating time is 60 to 180 seconds. Is preferred. More preferably, the heating temperature is 50 to 70 ° C., and the heating time is 90 to 120 seconds. When the heating temperature is 40 ° C. or higher, the organic solvent and the like inside the coating film can be sufficiently removed, and the hardness, water resistance and weather resistance are improved. Moreover, when the heating temperature is 90 ° C. or lower, the appearance is improved and the weather resistance is improved. When the heating time is 60 seconds or longer, the organic solvent and the like inside the coating film can be sufficiently removed, and the hardness, water resistance and weather resistance are improved. Moreover, when the heating time is 180 seconds or less, the appearance is improved and the weather resistance is improved.

  In the synthetic resin molded product according to the present invention, the surface of various synthetic resin molded products as a substrate is coated with a cured film of the present composition. Examples of the synthetic resin molded article that is a base material include molded articles containing various thermoplastic resins and synthetic resins such as thermosetting resins that are desired to be improved in wear resistance and weather resistance. Specific examples of the synthetic resin include polymethyl methacrylic resin, polycarbonate resin, polyester resin, polystyrene resin, ABS (acrylonitrile-butadiene-styrene) resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin, Examples include polyallyl diglycol carbonate resin. As the synthetic resin, excellent transparency and improvement in abrasion resistance are strongly desired, and from the viewpoint that application of the present composition is particularly effective, polymethyl methacryl resin, polycarbonate resin, polystyrene resin, polymethacrylate. An imide resin is preferred. These may use 1 type and may use 2 or more types together. Further, the synthetic resin molded product as the base material may be a sheet-shaped molded product, a film-shaped molded product, or various injection molded products containing these resins. 1-50 micrometers is preferable and, as for the film thickness of the cured film coat | covered with the synthetic resin molded product which concerns on this invention, 3-40 micrometers is more preferable.

  The cured film of the composition is excellent in wear resistance and weather resistance. Therefore, the resin molded product in which a cured film is formed by applying this composition to the surface of a polycarbonate resin molded product and irradiating with active energy rays is a polycarbonate resin molded product for automobile headlamp lenses, polycarbonate for automotive resin glass. It can be preferably used as a resin molded product.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. “Part” means “part by mass”.

<Synthesis Example 1: Synthesis of polyacryl polyurethane UA-1>
In a flask equipped with a dropping funnel, a reflux condenser, a stirring blade and a temperature sensor, epichlorohydrin modified 1,6-hexanediol diacrylate (trade name: Kayarad R-167, manufactured by Nippon Kayaku Co., Ltd.) as (a1) 187 parts by mass, 292 parts by mass of n-butyl acetate, and 0.2 parts by mass of di-n-butyltin dilaurate were charged and heated to 60 ° C. While maintaining the internal temperature at 60 ° C., 106 parts by mass of dicyclohexylmethane-4,4-diisocyanate (trade name: Desmodur W, manufactured by Sumika Bayer Urethane Co., Ltd.) was added dropwise as (a2) over 3 hours. Reaction was continued for 5 hours after completion | finish of dripping, and the target polyacryl polyurethane UA-1 (solid content 50%) was obtained. The weight average molecular weight of UA-1 was about 8,300 in terms of polystyrene. The mass average molecular weight was measured by the method described above.

<Synthesis Examples 2 to 7: Synthesis of polyacryl polyurethane UA-2 to 7>
Polyacryl polyurethanes UA-2 to 7 were synthesized in the same manner as in Synthesis Example 1 except that the raw materials and blending amounts shown in Table 1 were employed. In addition, the polyacryl polyurethane UA-6 obtained in Synthesis Example 6 gelled during synthesis.

<Synthesis Example 8: Synthesis of polyacryl polyurethane UA-8>
In a flask equipped with a dropping funnel, a reflux condenser, a stirring blade, and a temperature sensor, 264.8 g (1 mol) of isophorone diisocyanate and 300 ppm of di-n-butyltin dilaurate were charged and heated to 60 ° C. While maintaining the internal temperature at 60 ° C., 195.4 g (0.8 mol) of pentaerythritol diacrylate was added dropwise over 3 hours. Thereafter, the temperature was raised to 70 ° C. over 1 hour, and 119.3 g (0.4 mol) of pentaerythritol triacrylate was added dropwise over 2 hours while maintaining the internal temperature at 70 ° C. Then, it stirred at 70 degreeC for 3 hours, and obtained the target polyurethane polyacrylate UA-8. The weight average molecular weight of UA-8 was about 2,700 in terms of polystyrene.

In addition, the abbreviation of each compound in Table 1 is as follows. Since 3000A is an aromatic diacrylate and not (a1), it is represented as (a1 ′) in Table 1.
R-167: Epichlorohydrin modified 1,6-hexanediol diacrylate (trade name: Kayrad R-167, manufactured by Nippon Kayaku Co., Ltd.)
DA-722: Epichlorohydrin-modified hydrogenated phthalic acid diacrylate (trade name: Denacol acrylate DA-722, manufactured by Nagase ChemteX Corporation)
DA-811: Acrylic acid adduct of polyethylene glycol diglycidyl ether (trade name: Denacol acrylate DA-811, manufactured by Nagase ChemteX Corporation)
DA-920: Acrylic acid adduct of polypropylene glycol diglycidyl ether (trade name: Denacol acrylate DA-920, manufactured by Nagase ChemteX Corporation)
3000A: Acrylic acid adduct of bisphenol A diglycidyl ether (trade name: epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.)
PET-2A: Pentaerythritol diacrylate PET-3A: Pentaerythritol triacrylate H-MDI: Dicyclohexylmethane-4,4-diisocyanate (trade name: Desmodur W, manufactured by Sumika Bayer Urethane Co., Ltd.)
IPDI: Isophorone diisocyanate (trade name: Desmodur I, manufactured by Sumika Bayer Urethane Co., Ltd.).

<Example 1>
Active energy ray-curable compositions were prepared at the blending ratios shown in Table 2. The composition was spray-coated on a polycarbonate resin plate having a thickness of 3 mm (trade name: Panlite L-1225Z, manufactured by Teijin Chemicals Ltd.) so that the thickness of the cured film was 10 μm. The resin plate was heat-treated at 60 ° C. for 2 minutes in an IR heater furnace to volatilize the diluted solvent in the composition. Then, using a high-pressure mercury lamp in the air with respect to the coating film of the composition, a wavelength of 340 to 380 nm, an integrated light amount of 3000 mJ / cm ² (ultraviolet light meter (trade name: UV-351 (SN type), Co., Ltd.) The cured film was formed by irradiating with the energy of (measured value) manufactured by Oak Seisakusho. The obtained synthetic resin molded product was evaluated for abrasion resistance, scratch resistance, pencil hardness, adhesion, hot water resistance and weather resistance. The results are shown in Table 2. Each evaluation was performed by the following method.

(1) Wear resistance In accordance with JIS K7204 "Plastic wear test with wear wheels", using ROTARY ABRASION TESTER (manufactured by Toyo Seiki Co., Ltd.) with wear wheels CS-10F and 4.9N (500gf) load Worn 500 revolutions. Haze values before and after the abrasion test were measured with a haze meter (trade name, HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.), and abrasion resistance was evaluated based on the following criteria.
◎ Increase haze value is 0% or more and less than 15.0%.
○ Increase haze value is 15.0% or more and less than 20.0%.
X Increased haze value is 20.0% or more.

(2) Scratch resistance The steel wool # 000 was reciprocated 50 times with a load of 250 g / cm ² . The haze value before and after this scratch test was measured with a haze meter (trade name: HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.), and scratch resistance was evaluated based on the following criteria.
◎ Increase haze value is 0% or more and less than 1.5%.
○ Increase haze value is 1.5% or more and less than 2.0%.
X Increased haze value is 2.0% or more.

(3) Pencil hardness In accordance with JIS K5600, the pencil hardness was evaluated by scratching at a 45 degree angle using a Mitsubishi pencil uni and not scratching.

(4) Adhesiveness In accordance with JIS K5600, eleven vertical and horizontal cuts were made at 1 mm intervals on the surface of the cured coating to make 100 grids. Adhesiveness was evaluated based on the following criteria based on the presence or absence of peeling when cellophane tape (Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.) was brought into close contact with the surface, and peeled off at once.
○ There is no peeling.
× Peeling occurs.

(5) Warm water resistance After being immersed in warm water of 80 ° C. for 2 hours and taking out, an adhesion test was performed according to the procedure described in (4), and warm water resistance was evaluated based on the following criteria.
○ There is no peeling.
× Peeling occurs.

(6) Weather resistance Sunshine weather meter (WEL-SUN-HC-B type, manufactured by Suga Test Instruments Co., Ltd.) using a weather resistance tester, black panel temperature 63 ± 3 ° C, rainfall 12 minutes, irradiation 48 minutes cycle Tested. The following evaluation was performed after 3000 hours and 4000 hours after the test time. The increased haze value and increased yellow index (YI) value after 3000 hours and 4000 hours after the test time both mean the increase before the test, that is, with respect to the test time of 0 hour.

(A) Appearance Appearance was evaluated based on the following criteria.
○ Neither cracks, whitening, nor peeling of the cured coating occurs.
X: At least one of cracking, whitening, and peeling of the cured film occurs.

(B) Transparency The haze value before and after the test was measured using a haze meter (trade name: HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.), and the transparency was evaluated based on the following criteria.
◎ Increase haze value is 0% or more and less than 1.0%.
○ Increase haze value is 1.0% or more and less than 2.0%.
X Increased haze value is 2.0% or more.

(C) Yellowing degree Tristimulus values (X, Y, Z) were measured using an instantaneous multi-photometry system (trade name: MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). The yellow index (YI) value before and after the test was calculated using the following formula, and the degree of yellowing was evaluated based on the following criteria.

Yellow index (YI) value = 100 × (1.28 × X−1.06 × Z) / Y
The increased yellow index (YI) value is 0 or more and less than 1.00.
○ Increased yellow index (YI) value is 1.00 or more and less than 2.00.
X Increased yellow index (YI) value is 2.00 or more.

<Examples 2-8, Comparative Examples 1-5>
Active energy ray-curable compositions were prepared at the compounding ratios shown in Table 2 and Table 3, and a cured film was formed in the same manner as in Example 1 to obtain a synthetic resin molded product. The evaluation results of the obtained synthetic resin molded product are shown in Tables 2 and 3.

In addition, the abbreviation of each compound in Table 2 and Table 3 is as follows. Since UA-7 and UA-8 do not correspond to (A), they are represented as (A ′) in Table 3.
TAIC: Tris (2-acryloyloxyethyl) isocyanurate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.)
DPCA-20: Dipentaerythritol hexaacrylate modified with one ε-caprolactone per molecule (trade name: Kayrad DPCA-20, manufactured by Nippon Kayaku Co., Ltd.)
PET-4A: Pentaerythritol tetraacrylate HHBT: 2- [4- (2-hydroxy-3-dodecyloxy-propyl) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) -1 , 3,5-triazine] (trade name: Tinuvin 400, manufactured by BASF)
LA-63P: 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) condensation product with diethanol (trade name: ADK STAB LA-63P, manufactured by ADEKA Corporation)
BNP: Benzophenone MPG: Methylphenylglyoxylate BDK: 2,2-dimethoxy-1,2-diphenylethane-1-one L-7001: Silicone leveling agent (trade name: Silwet L-7001, Toray Dow Corning (Made by Co., Ltd.)
PGM: propylene glycol monomethyl ether ECA: ethyl carbitol acetate.

  From the said evaluation result, since the active energy ray hardening-type composition of Examples 1-8 contains all (A)-(D), the various physical properties of the synthetic resin molded article obtained were favorable. On the other hand, since the active energy ray-curable compositions of Comparative Examples 1 to 3 did not contain (B) or (C), the scratch resistance and adhesion after the hot water test were insufficient. Moreover, since the active energy ray hardening-type composition of the comparative examples 4 and 5 does not contain (A), the weather resistance was inadequate.

  A synthetic resin molded article having a cured coating having particularly excellent weather resistance and excellent wear resistance and adhesion by applying the active energy ray-curable composition according to the present invention to the surface and irradiating the active energy rays. Can be obtained. In addition, by coating the active energy ray-curable composition according to the present invention on a plastic substrate such as an automobile headlamp lens or an automobile resin glass, the lens is protected from ultraviolet rays and scratches for a long period of time and has a good appearance. Can be maintained.

Claims (5)

A poly (meth) acrylic polyurethane (A) having a mass average molecular weight of 5500 to 60000 obtained by reacting a hydroxyl group-containing compound and an isocyanate group-containing compound;
Poly (meth) acryloyloxyalkyl isocyanurate (B) represented by the following formula (1);
Ethylenically unsaturated compounds (C) other than (A) and (B),
UV absorber (D),
An active energy ray-curable composition containing
As the hydroxyl group-containing compound, a non-aromatic di (meth) acrylate (a1) having two hydroxyl groups in the molecule,
As the isocyanate group-containing compound, a non-aromatic diisocyanate (a2) is included,
Active energy ray-curable composition.

(In the formula (1), X ¹ , X ² and X ³ are each independently acryloyl group (CH ₂ ═CH—CO—), an acryloyl group modified with caprolactone [{CH ₂ ═CH—CO ( O (CH ₂ ) ₅ C═O) _a —} (a is an integer of 1 or more)]] represents a hydrogen atom or an alkyl group, and at least two of X ¹ , X ² and X ³ are acryloyl groups or An acryloyl group modified with caprolactone, R ¹ , R ² and R ³ each independently represents an oxyalkylene group or a polyoxyalkylene group.) The active energy ray-curable composition according to claim 1, wherein (a1) is an epoxy (meth) acrylate having a molecular weight of 300 to 500 represented by the following formula (2).

(In the formula (2), R ⁴ represents a hydrogen atom or a methyl group. Y represents an alkylene group, a cycloalkylene group, or a divalent organic group not containing an aromatic group having an ester bond or an ether bond.)   The active energy ray-curable composition according to claim 1 or 2, wherein (a2) is a diisocyanate having an alicyclic skeleton.   The synthetic resin molded article with which the cured film of the active energy ray hardening-type composition of any one of Claims 1-3 is coat | covered.   The synthetic resin molded article according to claim 4, wherein the synthetic resin molded article is a polycarbonate resin molded article for an automobile headlamp lens or a polycarbonate resin molded article for an automobile resin glass.