JP6826417B2 - Active energy ray-curable resin composition - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition. More specifically, the present invention relates to an active energy ray-curable resin composition in which the cured product has excellent heat-stretchability and scratch resistance.

Conventionally, resin molded products that are often used for mobile information terminal devices such as mobile phones, notebook computers, home appliances, automobile interior / exterior parts, etc. are decorated with patterns and patterns on the molded resin surface. .. As one of the decoration methods for these molded resins, there is a decoration method using a decoration film. The decorative film has a design layer and a hard coat layer, and has a function of imparting a design and also having a function of protecting the resin surface. Hydraulic transfer and thermal transfer are the main methods for transferring a decorative film to a molding resin, but from the viewpoint of high design and high quality, in-mold molding that decorates at the same time as resin molding has begun to spread.
In recent years, there has been an increasing need for decoration of a molding resin having a complicated three-dimensional shape, and there is a strong demand for a decoration film that can follow the resin during heat molding and does not easily scratch the resin surface after molding.

In order to impart moldability and scratch resistance to the decorative film, it is required that the hard coat layer of the decorative film can be stretched during heat molding and has an excellent surface hardness after molding. As a method of achieving both heat stretchability and surface hardness of the hard coat layer, a method of incorporating inorganic oxide fine particles in the active energy ray-curable resin composition (for example, Patent Document 1), and a urethane oligomer in the active energy ray-curable composition. (For example, Patent Document 2) and the like have been proposed.

Japanese Unexamined Patent Publication No. 2014-069523 JP-A-2010-007049

However, although the method of Patent Document 1 can impart hardness to the resin surface after molding, the stretchability at the time of heating is insufficient. Further, although the method of Patent Document 2 is excellent in stretchability at the time of heating, it is insufficient to impart the required surface hardness to the hard coat layer.
An object of the present invention is to provide an active energy ray-curable resin composition that gives a cured product having excellent stretchability, scratch resistance, and chemical resistance when heated.

The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention comprises a bifunctional (meth) acrylate (A) having an alicyclic skeleton, a polyfunctional (meth) acrylate (B) having 3 to 12 (meth) acryloyl groups, and a nitrogen atom-containing monofunctional. An active energy ray-curable resin composition containing an unsaturated monomer (C) , wherein (A) has a urethane group, and the urethane group concentration is 3.0 to 3 based on the weight of (A). An active energy ray-curable resin composition (X) having a concentration of 5.0 mmol / g ; a cured product (P) obtained by curing the (X).

The active energy ray-curable resin composition (X) of the present invention has the following effects.
(1) The cured product has excellent stretchability (moldability) when heated.
(2) The cured product has excellent scratch resistance (surface hardness).
(3) The cured product has excellent chemical resistance.

[Bifunctional (meth) acrylate (A) having an alicyclic skeleton]
The bifunctional (meth) acrylate (A) having an alicyclic skeleton in the present invention is a bifunctional urethane (meth) acrylate (A1) having an alicyclic skeleton and a bifunctional polyester (meth) acrylate having an alicyclic skeleton. Examples thereof include bifunctional (meth) acrylates (A3) having an alicyclic skeleton other than (A2), (A1) and (A2), and mixtures thereof.

(A1) Bifunctional urethane (meth) acrylate having an alicyclic skeleton:
The bifunctional urethane (meth) acrylate (A1) having an alicyclic skeleton includes, for example, a polymer diol (A11) having an alicyclic skeleton, a diisocyanate (A12) having two isocyanate groups, and a carbon number (hereinafter, described below). It may be abbreviated as C.) By reacting a urethane prepolymer of a terminal isocyanate obtained by reacting 2 to 20 acyclic dihydric alcohols with a monofunctional (meth) acrylate (A13) having a hydroxyl group. can get.

The polymer diol (A11) having an alicyclic skeleton which is a raw material of the bifunctional urethane (meth) acrylate (A1) having an alicyclic skeleton is a polyester diol (A111) having an alicyclic skeleton and an alicyclic skeleton. Examples thereof include a polycarbonate diol (A112) having an alicyclic skeleton, a polylactone diol (A113) having an alicyclic skeleton, and a mixture thereof.

(A111) Polyester diol having an alicyclic skeleton:
Examples of the polyester diol (A111) having an alicyclic skeleton include alicyclic divalent carboxylic acids (anhydrous) of C8 to C20 and / or acyclic divalent carboxylic acids (anhydrous) of C2 to C20, and C6. A polyester diol obtained by a condensation reaction with an alicyclic dihydric alcohol of ~ C20 and / or an acyclic dihydric alcohol of C2 to C20, and the divalent carboxylic acid (anhydrous) used in the reaction and Examples thereof include polyesterdiol in which at least one of the dihydric alcohols is an alicyclic dihydric carboxylic acid (anhydrous) or an alicyclic dihydric alcohol.

Examples of the alicyclic divalent carboxylic acid (anhydride) of C8 to C20 include cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, and methylhexahydrophthalic acid. And these anhydrides and the like.

Examples of the acyclic divalent carboxylic acid (anhydrous) of C2 to C20 include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, hetic acid, maleic acid, fumaric acid, itaconic acid and these. Anhydrous and the like can be mentioned.

Examples of C6 to C20 alicyclic dihydric alcohols include 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, spiroglycol and dihydroxy. Examples thereof include methyltricyclodecane.

Examples of the acyclic dihydric alcohol of C2 to C20 include ethylene glycol, 1,2- or 1,3-propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-, 1,3-, 2, 3- or 1,4-butanediol, 3-methyl-1,2-butanediol, 1,2-, 1,4-, 1,5- or 2,4-pentanediol, 3-methyl-1,5 Pentandiol, 2,3-dimethyltrimethylethylene glycol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-, 1,5-, 1, 6- or 2,5-hexanediol, 2- or 3-methylpentanediol, 1,7-heptanediol, 2- or 3-methylhexanediol, 2-,3- or 4-methylheptanediol, 1,8 Examples thereof include −octanediol, 2-, 3- or 4-methyl 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, neopentyl glycol and the like.

(A112) Polycarbonate diol having an alicyclic skeleton:
Examples of the polycarbonate diol having an alicyclic skeleton include the alicyclic dihydric alcohols C6 to C20 or the acyclic dihydric alcohols C2 to 20 (preferably C6 to C10, more preferably C6 to C9). A mixture of one or more alkylene diols having an alkylene group) is mixed with a low molecular weight carbonate compound (for example, a dialkyl carbonate having an alkyl group C1 to C6, an alkylene carbonate having an alkylene group C2 to C6, and C6 to C9. Examples thereof include polycarbonate diols produced by condensing with a diaryl carbonate having an aryl group of the above) while dealcoholizing.

(A113) Polylactone diol having an alicyclic skeleton:
Examples of the polylactone diol having an alicyclic skeleton include a heavy addition of C4 to C12 lactones (for example, γ-butyrolactone, γ-valerolactone and ε-caprolactone) to the alicyclic dihydric alcohols C6 to C20. Can be mentioned.

The diisocyanate (A12) used as a raw material for the bifunctional urethane (meth) acrylate (A1) having an alicyclic skeleton is not particularly limited, and is, for example, isophorone diisocyanate, 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate. , Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalenediocyanate, norbornan diisocyanate, trizine diisocyanate, xylylene diisocyanate (XDI), hydrogenated Examples thereof include XDI, lysine diisocyanate and tetramethylxylene diisocyanate.

The monofunctional (meth) acrylate (A13) having a hydroxyl group as a raw material of the bifunctional urethane (meth) acrylate (A1) having an alicyclic skeleton is not particularly limited, and for example, hydroxyethyl (meth) acrylate and 2-hydroxy. Propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxyo-phenylphenolpropyl (meth) acrylate ) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like can be mentioned.

The high molecular weight diol (A11) used as a raw material for the bifunctional urethane (meth) acrylate (A1) having an alicyclic skeleton is preferably (A111) (A112) from the viewpoint of heat stretchability after curing. (A112) is particularly preferable, a polycarbonate diol consisting of 1,4-cyclohexanedimethanol and 1,6-hexanediol is preferable, a polycarbonate diol consisting of 1,4-cyclohexanedimethanol is particularly preferable, and 1,4- is most preferable. It is a polycarbonate diol composed of cyclohexanedimethanol and 1,6-hexanediol.

(A2) Bifunctional polyester (meth) acrylate having an alicyclic skeleton:
As the divalent carboxylic acid which is a constituent unit of the bifunctional polyester (meth) acrylate (A2) having an alicyclic skeleton, the above-mentioned alicyclic divalent carboxylic acid (anhydrous) of C8 to C20 and / or C2- Examples of the acyclic divalent carboxylic acid (anhydrous) and dihydric alcohol of C20 include the above-mentioned alicyclic dihydric alcohols of C6 to C20 and / or acyclic dihydric alcohols of C2 to C20. The terminal hydroxyl group of a polyester diol in which at least one of the divalent carboxylic acid (anhydrous) and the dihydric alcohol used in the reaction is an alicyclic divalent carboxylic acid (anhydrous) or an alicyclic dihydric alcohol. Can be obtained by esterifying with (meth) acrylic acid.

Bifunctional (meth) acrylate (A3) having an alicyclic skeleton other than the above (A1) and (A2):
Examples of the bifunctional (meth) acrylate (A3) having an alicyclic skeleton other than (A1) and (A2) include ethoxylated cyclohexanemethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1, Examples thereof include 3-adamantyldiol di (meth) acrylate.

Among the bifunctional (meth) acrylates (A) having an alicyclic skeleton, (A1) is preferable, and (A111) is more preferable, from the viewpoint of scratch resistance of the cured product and stretchability during heating. A bifunctional urethane (meth) acrylate, a bifunctional urethane (meth) acrylate having (A112), and most preferably a bifunctional urethane (meth) acrylate having (A112).

The alicyclic skeleton content of the bifunctional (meth) acrylate (A) having an alicyclic skeleton is 1.0 to 4.0 mmol / g from the viewpoint of scratch resistance of the cured product and stretchability during heating of the cured product. It is preferably 1.5 to 3.5 mmol / g, and particularly preferably 2.0 to 3.0 mmol / g.

When the bifunctional (meth) acrylate (A) having an alicyclic skeleton contains (A1), its urethane group concentration is 3.0 to 5 from the viewpoint of scratch resistance of the cured product and solubility in a solvent. It is preferably 0.0 mmol / g, more preferably 3.2 to 4.8 mmol / g, and particularly preferably 3.4 to 4.6 mmol / g.

The weight average molecular weight (hereinafter abbreviated as Mw) of (A) is measured by GPC using N, N-dimethylformamide or tetrahydrofuran as a solvent with reference to standard polystyrene. Mw in the present invention is based on the above method.
The Mw of (A) is, for example, 1,000 or more, preferably 10,000 to 50,000, more preferably 12,000 to 48,000, particularly from the viewpoint of scratch resistance and solubility in a solvent. It is preferably 15,000 to 45,000.

[Polyfunctional (meth) acrylate (B)]
The polyfunctional (meth) acrylate (B) in the present invention has 3 to 12 (meth) acryloyl groups.
If the number of the (meth) acryloyl groups is less than 3, the scratch resistance of the cured product may be deteriorated, and if the number is more than 12, the transparency of the cured product may be deteriorated.
Examples of the polyfunctional (meth) acrylate (B) include polyfunctional (meth) acrylates (B1) of C9 to C52, polyfunctional urethane (meth) acrylates (B2), polyfunctional polyester (meth) acrylates (B3), and these. A mixture of.

(B1) Polyfunctional (meth) acrylates of C9 to C52:
Examples of (B1) include trimethylolpropane tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, and dipentaeryth. Tri (meth) acrylate with 1 to 30 molar additions of alkylene oxides of C2 to C4 of rutor tri (meth) acrylate, trimethylol propantri ((meth) acryloyloxypropyl) ether, sorbitol tri (meth) acrylate, and pentaerythritol. , Ethoxyglycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol tetra ( Meta) acrylate, dipentaerythritol tetra (meth) acrylate of propionate, tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate with 1 to 30 mol of alkylene oxide 1 to 30 mol of C2 to C4 of pentaerythritol. ) Acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate;

(B2) Polyfunctional urethane (meth) acrylate:
The polyfunctional urethane (meth) acrylate (B2) is not particularly limited as long as it is a compound obtained by reacting a (meth) acrylic acid derivative having a bifunctional or higher (meth) acryloyl group having a hydroxyl group with isocyanate. For example, it can be obtained by reacting 1 equivalent of a compound having 2 isocyanate groups with 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group in the presence of a metal compound (for example, tin compound).

The isocyanate used as a raw material for the polyfunctional urethane (meth) acrylate (B2) is not particularly limited, and for example, the above-mentioned diisocyanate (A22), polypeptide MDI, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, 1, 6,10-Undecantry isocyanate can be mentioned.

The isocyanate may be obtained by reacting a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, or polycaprolactone diol with an excess of isocyanate. The resulting chain-extended isocyanate compound can also be used.

The (meth) acrylic acid derivative having a hydroxyl group as a raw material of the polyfunctional urethane (meth) acrylate (B2) and a bifunctional or higher (meth) acryloyl group is not particularly limited, and examples thereof include trimethylolethane, trimethylolpropane, and the like. Di (meth) acrylates of trihydric alcohols such as glycerin, tri (meth) acrylates of tetrahydric alcohols such as pentaerythritol and sorbitan, penta (meth) acrylates of hexahydric alcohols such as dipentaerythritol and sorbitol Can be mentioned.

(B3) Polyfunctional polyester (meth) acrylate:
Examples of the polyhydric alcohol which is a constituent unit of the polyfunctional polyester (meth) acrylate (B3) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanjiol, and neopentyl. Alkylene glycols such as glycols, 1,4-butenediols, 1,5-pentanediols and 1,6-hexanediols; alkylenes such as diethylene glycols, triethylene glycols, dipropylene glycols, polyethylene glycols, polypropylene glycols and polytetramethylene glycols. Ether glycol; bisphenol such as bisphenol A, bisphenol F, bisphenol S; alkylene oxide [EO, propylene oxide (PO), butylene oxide (BO)] adduct of bisphenol (average addition molar number 2-8), glycerin, trimethylol Examples thereof include propane and pentaerythritol.

Examples of the polyvalent carboxylic acid that is a constituent unit of the polyfunctional polyester (meth) acrylate (B3) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acid. , Adipic acid, sevantic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid , Isooctylsuccinic acid, aconitic acid, trimellitic acid, pyromellitic acid and the like, or anhydrides or lower alkyl esters of these acids.

Of the above polyfunctional (meth) acrylates (B), (B1) and (B2) are preferable from the viewpoint of scratch resistance of the cured product, (B1) is more preferable, and pentaerythritol tetra (meth) is particularly preferable. ) Acrylate, dipentaerythritol hexa (meth) acrylate, most preferably dipentaerythritol hexa (meth) acrylate.

[Nitrogen atom-containing monofunctional unsaturated monomer (C)]
Examples of the nitrogen atom-containing monofunctional unsaturated monomer (C) include vinylamine, N-methylvinylamine, N-ethylvinylamine, N-propylvinylamine, Nn-butylvinylamine, and Nt-butylvinyl. Amine, N-Butoxymethylvinylamine, N-Isopropylvinylamine, N-methylolvinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N-vinylmorpholine, allylamine, N-methylallylamine, N -Ethylallylamine, N-propylallylamine, Nn-butylallylamine, Nt-butylallylamine, N-butoxymethylallylamine, N-isopropylallylamine, N-methylolallylamine, N, N-dimethylallylamine and N, N- Examples thereof include diethylallylamine, N-allylmorpholine, N-vinylpyrrolidone, vinylformamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamide, and acryloylmorpholine. Of these, N, N-dimethylacrylamide, diacetoneacrylamide, and acryloyl morpholine are preferable, and N, N-dimethylacrylamide and acryloyl morpholine are particularly preferable, and acryloyl morpholine is particularly preferable, from the viewpoint of scratch resistance of the cured product. is there.
The above (C) may be used alone or in combination of two or more.

[Active energy ray-curable resin composition (X)]
The active energy ray-curable resin composition (X) of the present invention has a bifunctional (meth) acrylate (A) having the alicyclic skeleton and a polyfunctional (meth) having 3 to 12 (meth) acryloyl groups. ) The acrylate (B) and the nitrogen atom-containing monofunctional unsaturated monomer (C) are contained.
The content of each component based on the weight of (X) is based on the total weight of (A), (B) and (C), and the weight of (A) is the scratch resistance of the cured product and the heating of the cured product. From the viewpoint of stretchability at the time, for example, 40 to 95%, preferably 50 to 90%, further preferably 55 to 85%, particularly preferably 60 to 80%, most preferably 65 to 75%; (A) and ( Based on the total weight of B) and (C), the weight of (B) is, for example, 2 to 30%, preferably 5 to 20 from the viewpoint of scratch resistance of the cured product and stretchability when the cured product is heated. %, More preferably 7-18%, particularly preferably 9-15%, most preferably 10-13%; the weight of (C) based on the total weight of (A), (B) and (C). From the viewpoint of scratch resistance of the cured product and stretchability when the cured product is heated, for example, 3 to 40%, preferably 5 to 30%, more preferably 8 to 27%, particularly preferably 11 to 25%, most It is preferably 15 to 22%.

The active energy ray-curable resin composition (X) of the present invention has a polyfunctional (meth) acrylate (A) having the above-mentioned alicyclic skeleton and a polyfunctional (meth) having 3 to 12 (meth) acryloyl groups. ) In addition to the acrylate (B) and the nitrogen atom-containing monofunctional unsaturated monomer (C), other unsaturated monomers (D) can be used in combination as long as the effects of the present invention are not impaired.
Other unsaturated monomers (D) include the following (D1) to (D4) and mixtures thereof.

(D1) Monofunctional (meth) acrylates of C3 to C35:
(Meta) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl ( Meta) acrylate, 2,3-dimethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, icosyl (meth) Acrylate, n-docosyl (meth) acrylate, n-tetracosyl (meth) acrylate, n-hexaicosyl (meth) acrylate, n-octaicosyl (meth) acrylate, n-triacontyl (meth) acrylate, n-dotriacyl (meth) acrylate, n-Tetratriacontyl (meth) acrylate, n-hexatriacontyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, Bornyl (meth) acrylate, Isobornyl (meth) Acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene Mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (Meta) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4 -Butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, Glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidy Loxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) Acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene Glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol (meth) ) Acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO Modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate and EO-modified -2-ethylhexyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate;

Bifunctional (meth) acrylates other than (D2) and (A):
For example, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate. ) Acrylic, Butylethyl Propanediol Di (Meta) Acrylic, Polypropylene Glycoldi (Meta) Acrylic, Polyethylene Glycol Di (Meta) Acrylic, Oligoethylene Glycoldi (Meta) Axide, Ethylene Glycol Di (Meta) Axide, 2-Ethyl- 2-Butyl-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, ethylene oxide (hereinafter sometimes abbreviated as EO) modified bisphenol A di (meth) acrylate, EO modified bisphenol F Di (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate , 1,9-Nonandiol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate;

Compounds having a vinyl group other than (D3) and (C):
Examples of the compound having a vinyl group (D3) include a compound having one vinyl group (D31) and a compound having two or more (preferably 2 to 6) vinyl groups (D32).

(D31) Compound of C2 to C35 having one vinyl group For example, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, tert-octyl vinyl ether, 2,3-dimethylhexyl. Vinyl ether, isoamyl vinyl ether, decyl vinyl ether, isodecyl vinyl ether, stearyl vinyl ether, isostearyl vinyl ether, cyclohexyl vinyl ether, 4-n-butylcyclohexyl vinyl ether, bornyl vinyl ether, isobornyl vinyl ether, benzyl vinyl ether, 2-ethylhexyl diglycol vinyl ether, Butoxyethyl vinyl ether, 2-chloroethyl vinyl ether, 4-bromobutyl vinyl ether, butoxymethyl vinyl ether, methoxypropylene monovinyl ether, 3-methoxybutyl vinyl ether, alkoxymethyl vinyl ether, 2-ethylhexyl carbitol vinyl ether, alkoxyethyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 2- (2-butoxyethoxy) ethyl vinyl ether, 2,2,2-tetrafluoroethyl vinyl ether, 1H, 1H, 2H, 2H-perfluorodecyl vinyl ether, 4-butylphenyl vinyl ether, Phenyl vinyl ether, 2,4,5-tetramethylphenyl vinyl ether, 4-chlorophenylvinyl ether, phenoxymethyl vinyl ether, phenoxyethyl vinyl ether, glycidyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyethyl vinyl ether, glycidyloxypropyl vinyl ether, tetrahydroflu Frill vinyl ether, hydroxyalkyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, trimethoxysilylpropyl vinyl ether, trimethoxysilylpropyl vinyl ether, trimethylsilyl Propyl vinyl ether, polyethylene oxide monomethyl ether vinyl ether, oligoethylene oxide monomethyl ether vinyl ether, polyethylene oxide vinyl ether , Oligoethylene oxide vinyl ether, oligoethylene oxide monoalkyl ether vinyl ether, polyethylene oxide monoalkyl ether vinyl ether, dipropylene glycol vinyl ether, polypropylene oxide monoalkyl ether vinyl ether, oligopropylene oxide monoalkyl ether vinyl ether, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol vinyl ether, trifluoroethyl vinyl ether, perfluorooctyl ethyl vinyl ether, 2-hydroxy-3-phenoxypropyl vinyl ether, EO-modified phenol vinyl ether, EO-modified cresol vinyl ether, EO-modified nonylphenol vinyl ether, PO-modified nonylphenol vinyl ether and EO-modified -2-ethylhexyl vinyl ether;

(D32) Compounds C8 to C50 having 2 to 6 vinyl groups:
For example, 1,6-hexanediol divinyl ether, 1,10-decanediol divinyl ether, neopentyl glycol divinyl ether, 2,4-dimethyl-1,5-pentanediol divinyl ether, butylethylpropanediol divinyl ether, ethoxylated. Cyclohexanemethanol divinyl ether, polypropylene glycol divinyl ether, polyethylene glycol divinyl ether, oligoethylene glycol divinyl ether, ethylene glycol divinyl ether, 2-ethyl-2-butyl-butanediol divinyl ether, neopentyl glycol divinyl ether hydroxypivalate, EO modification Bisphenol A divinyl ether, EO modified bisphenol F divinyl ether, polypropylene glycol divinyl ether, oligopropylene glycol divinyl ether, 1,4-butanediol divinyl ether, 2-ethyl-2-butyl-propanediol divinyl ether, 1,9-nonane Didiol divinyl ether, propoxylated ethoxylated bisphenol A divinyl ether, trimethylolpropane trivinyl ether, trimethylolethanetrivinyl ether, alkylene oxide-modified trivinyl ether of trimethylolpropane, pentaerythritol trivinyl ether, dipentaerythritol trivinyl ether, trimethylol Propanetri (vinyloxypropyl) ether, sorbitol trivinyl ether, trivinyl ether with 1 to 30 molar additions of C2 to C4 alkylene oxide of pentaerythritol, glycerin trivinyl ether ethoxylated, dipentaerythritol trivinyl ether propionate, pentaerythritol tetravinyl ether , Sorbitol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol tetravinyl ether, dipentaerythritol tetravinyl ether propionate, tetravinyl ether with 1 to 30 molar additions of alkylene oxides of C2 to C4 of pentaerythritol, sorbitol pentavinyl ether, dipenta. Ellisritol pentavinyl ether, dipentaerythritol hexavinyl ether, sorbitol hexavinyl ether, caprolactone-modified dipentaerythritol hexavinyl ether.

(D4) Compound having an allyl group:
Examples of the compound having an allyl group (D4) include a compound having one allyl group (D41), a compound having 2 to 6 allyl groups (D42), a bifunctional or higher functional urethane allyl ether (D43), and a bifunctional compound. Examples thereof include the above polyester allyl ether (D44).

(D41) Compounds C3 to C35 having one allyl group:
For example, methyl allyl ether, ethyl allyl ether, butyl allyl ether, tert-butyl allyl ether, hexyl allyl ether, 2-ethylhexyl allyl ether, tert-octyl allyl ether, 2,3-dimethylhexyl allyl ether, isoamyl allyl ether, decyl. Allyl ether, Isodecyl allyl ether, Stearyl allyl ether, Isostearyl allyl ether, Cyclohexyl allyl ether, 4-n-butylcyclohexyl allyl ether, Bornyl allyl ether, Isobornyl allyl ether, benzyl allyl ether, 2-Ethylhexyldi To glycol allyl ether, butoxyethyl allyl ether, 2-chloroethyl allyl ether, 4-bromobutyl allyl ether, butoxymethylallyl ether, methoxypropylene monoallyl ether, 3-methoxybutyl allyl ether, alkoxymethylallyl ether, 2-ethyl Xylcarbitol allyl ether, alkoxyethyl allyl ether, 2- (2-methoxyethoxy) ethyl allyl ether, 2- (2-butoxyethoxy) ethyl allyl ether, 2,2,2-tetrafluoroethylallyl ether, 1H, 1H , 2H, 2H-perfluorodecylallyl ether, 4-butylphenylallyl ether, phenylallyl ether, 2,4,5-tetramethylphenylallyl ether, 4-chlorophenylallyl ether, phenoxymethylallyl ether, phenoxyethylallyl ether, Glysidylallyl ether, glycidyloxybutylallyl ether, glycidyloxyethylallyl ether, glycidyloxypropylallyl ether, tetrahydrofurfurylallyl ether, hydroxyalkylallyl ether, 2-hydroxyethylallyl ether, 3-hydroxypropylallyl ether, 2-Hydroxypropyl allyl ether, 2-hydroxybutyl allyl ether, 4-hydroxybutyl allyl ether, trimethoxysilylpropyl allyl ether, trimethoxysilylpropyl allyl ether, trimethylsilylpropyl allyl ether, polyethylene oxide monomethyl ether allyl ether, oligoethylene oxide Monomethyl ether allyl ether, polyethylene oxide allyl ether, oligoethylene oxide allyl ether, oligo ethyl Noxide monoalkyl ether allyl ether, polyethylene oxide monoalkyl ether allyl ether, dipropylene glycol allyl ether, polypropylene oxide monoalkyl ether allyl ether, oligopropylene oxide monoalkyl ether allyl ether, butoxydiethylene glycol allyl ether, trifluoroethyl allyl ether, Perfluorooctyl ethyl allyl ether, 2-hydroxy-3-phenoxypropyl allyl ether, EO modified phenol allyl ether, EO modified cresol allyl ether, EO modified nonylphenol allyl ether, PO modified nonylphenol allyl ether and EO modified -2-ethylhexyl allyl ether ;

(D42) Compounds C3 to C35 having 2 to 6 allyl groups:
For example, 1,6-hexanediol diallyl ether, 1,10-decanediol diallyl ether, neopentyl glycol diallyl ether, 2,4-dimethyl-1,5-pentanediol diallyl ether, butyl ethyl propanediol diallyl ether, ethoxylation. Cyclohexanemethanol diallyl ether, polypropylene glycol diallyl ether, polyethylene glycol diallyl ether, oligoethylene glycol diallyl ether, ethylene glycol diallyl ether, 2-ethyl-2-butyl-butanediol diallyl ether, neopentyl glycol diallyl ether hydroxypivalate, EO modification Bisphenol A diallyl ether, EO modified bisphenol F diallyl ether, polypropylene glycol diallyl ether, oligopropylene glycol diallyl ether, 1,4-butanediol diallyl ether, 2-ethyl-2-butyl-propanediol diallyl ether, 1,9-nonane Didiol diallyl ether, propoxylated ethoxylated bisphenol A diallyl ether, trimethylolpropane triallyl ether, trimethylol ethanetriallyl ether, alkylene oxide-modified triallyl ether of trimethylolpropane, pentaerythritol triallyl ether, dipentaerythritol tri Allyl ether, trimethylolpropantri (allyloxypropyl) ether, sorbitol triallyl ether, triallyl ether with 1 to 30 molar additions of C2-C4 alkylene oxide of pentaerythritol, glycerin triallyl ether ethoxylated, dipenta propionate Elythritol triallyl ether, pentaerythritol tetraallyl ether, sorbitol tetraallyl ether, ditrimethylol propanetetraallyl ether, dipentaerythritol tetraallyl ether, dipentaerythritol tetraallyl ether propionate, C2-C4 alkylene oxides 1 to pentaerythritol Tetraallyl ether, sorbitol pentaallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, sorbitol hexaallyl ether, caprolactone-modified dipentaerythritol hexaallyl ether;

The bifunctional or higher (preferably 2 to 8 functional, more preferably bifunctional) urethane allyl ether (D43) is not particularly limited as long as it is a compound obtained by reacting isocyanate with an allyl alcohol derivative having a hydroxyl group. For example, it can be obtained by reacting 1 equivalent of a compound having two isocyanate groups with 2 equivalents of an allyl alcohol derivative having a hydroxyl group in the presence of a metal compound (for example, tin compound).

The isocyanate used as a raw material for the bifunctional or higher functional urethane allyl ether (D43) is not particularly limited, and the isocyanate used as the raw material for the above-mentioned polyfunctional urethane (meth) acrylate (B2) can be used.

The allyl alcohol derivative having a hydroxyl group which is a raw material of bifunctional or higher functional urethane allyl ether (D43) is not particularly limited, and for example, 2-hydroxyethyl allyl ether, 2-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, etc. Divalent alcohol monoallyl ethers such as 2-hydroxybutylallyl ether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol, trimethylolethane. , Monoallyl ethers or diallyl ethers of trivalent alcohols such as trimethylol propane and glycerin, and epoxyallyl ethers such as bisphenol A-modified epoxy allyl ethers.

The bifunctional or higher (preferably 2 to 8 functional, more preferably bifunctional) polyester allyl ether (D44) has an allyl hydroxyl group of a polyester oligomer having a hydroxyl group at the terminal obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. It can be obtained by etherifying with bromide, or by etherifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with allyl bromide.

The polyhydric alcohol which is a constituent unit of the bifunctional or higher functional polyester allyl ether (D44) and the polyvalent carboxylic acid are not particularly limited, and the polyhydric alcohol used in the above-mentioned polyfunctional polyester (meth) acrylate (B3). Polyvalent carboxylic acid can be used.

The content of the other unsaturated monomer (D) is, for example, 10% or less based on the weight of the active energy ray-curable resin composition (X), and the stretchability, scratch resistance and scratch resistance of the cured product when heated. From the viewpoint of transparency, it is preferably 0.1% to 8%, more preferably 0.5% to 5%.

The active energy ray-curable resin composition (X) of the present invention contains, if necessary, a photopolymerization initiator (e1), a leveling agent (e2), an antioxidant (e3), as long as the effects of the present invention are not impaired. It may contain at least one additive (e) selected from the group consisting of the UV absorber (e4) and the filler (e5).

Examples of the photopolymerization initiator (e1) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2-methyl-1- (4-methylthio). Phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 1,2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- Hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy -1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 1, 2-octandion-1- (4- [phenylthio) -2- (O-benzoyloxime)], etanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (0-Acetyloxime), bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, etc. Can be mentioned.

As the leveling agent (e2), polydimethylsiloxane, a copolymer thereof, an acrylic polymer having a polydimethylsiloxane skeleton, a urethane polymer having a polydimethylsiloxane skeleton, and an acryloyl group or a methacryloyl group are introduced into these, and an active energy ray is used. Examples thereof include compounds having imparted reactivity.

Examples of the antioxidant (e3) include di-t-butylhydroxytoluene (BHT) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)-. 1,3,5-triazine, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5) -Di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexa Methylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4) -Hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, diphenylamine octylated, 2,4-bis [(octylthio) methyl] -O-cresol, isooctyl Examples thereof include -3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and dibutylhydroxytoluene.

Examples of the ultraviolet absorber (e4) include 2- (2-hydroxy-5-methyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole. , 2- (2'-Hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'- Hydroxy-3', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole- 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2'-hydroxy-3', 5'-t-pentylbenzotriazole, 2- [2'-hydroxy- 5'-(1,1,3,3, -tetramethylbutyl)] benzotriazole, 2- (2'-hydroxy-3'-s-butyl-5'-t-butylbenzotriazole, 2- (2') -Hydroxy-3-dodecyl-5'-methylbenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 5'-Methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl)] -6- (2H-benzotriazole-2-yl) phenol], 3-[ Examples thereof include 3- (2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and polyethylene glycol.
Examples of the filler (e5) include silica, alumina, and compounds obtained by introducing an acryloyl group or a methacryloyl group into these to impart active energy ray reactivity.

These additives (e) can be used alone or in combination of two or more. The amount of the additive (e) added is preferably 10% by weight or less, more preferably 0.1 to 5% by weight, based on the weight of the active energy ray-curable resin composition (X).

At the time of coating, the composition of the present invention may be diluted with a solvent, if necessary, in order to adjust the viscosity to be suitable for coating. The amount of the solvent used is, for example, 2,000% or less based on the weight of the composition before adding the solvent, and preferably 10 to 500% from the viewpoint of coatability and productivity. The viscosity of the coating material is, for example, 5 to 500,000 mPa · s at the temperature during use (for example, 5 to 60 ° C.), and preferably 50 to 10,000 mPa · s from the viewpoint of stable coating.

The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention, and specifically, aromatic hydrocarbons (for example, toluene, xylene and ethylbenzene), esters or ethers. Esters (eg ethyl acetate, butyl acetate and methoxybutyl acetate), ethers (eg diethyl ether, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol monoethyl ether), ketones (eg, diethyl ether, tetrahydrofuran, monoethyl ether of ethylene glycol), ketones ( For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone), alcohols (eg methanol, ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol and Benzyl alcohol), amides (eg, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (eg, dimethylsulfoxide), water, and mixed solvents of two or more of these.
Of these, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferable from the viewpoint of storage stability and productivity, and ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof are more preferable.

[Cured product]
The cured product of the present invention is a cured product of the active energy ray-curable composition (X). The active energy ray-curable resin composition is cured by the active energy ray to become a cured product. Examples of the active energy ray include ultraviolet rays and electron beams.
When irradiating the ultraviolet rays, a known ultraviolet irradiation device equipped with a high-pressure mercury lamp, a metal halide lamp, or the like can be used. The irradiation amount of ultraviolet rays is preferably 30 to 2,000 mJ / cm ² . If the irradiation amount is less than 30 mJ / cm ² , the curable composition is insufficiently cured, and if it exceeds 2,000 mJ / cm ² , the cured product may be yellowed and deteriorated.
When irradiating the electron beam, a known electron beam irradiating device can be used. The irradiation amount of the electron beam is preferably 1 to 10 Mrad. If the irradiation amount is less than 1 Mrad, the curable composition is insufficiently cured, and if it exceeds 10 Mrad, the cured product may be deteriorated.

The active energy ray-curable resin composition (X) of the present invention can impart stretchability, scratch resistance, and chemical resistance to a cured product when heated.
Therefore, the composition includes an optical lens (prism sheet, collimator lens, Fresnel lens, lenticular lens, back-reflection lens, hologram, etc.), a coating agent for a decorative film, a hard coat film, an antireflection film, and a decorative sheet (a decorative sheet). It is useful for applications such as floors, walls, ceilings, and other interior materials of buildings.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following examples, parts represent parts by weight and% represents% by weight.

<Manufacturing example 1>
154.2 parts of 1,2-cyclohexanedicarboxylic acid anhydride, 392.6 parts of tricyclodecanedimethanol, 153.4 parts of acrylic acid in a reaction vessel equipped with a stirrer, thermometer, air blow tube, water test tube, and condenser. Parts, 10.0 parts of paratoluenesulfonic acid, 2.0 parts of hydroquinone, and 300.0 parts of toluene were charged and heated. The produced water is distilled and condensed together with the solvent, only water is removed from the system with a water inspection pipe, the solvent is returned to the reaction vessel, and when a total of 72.0 parts of distilled water is produced, the reaction is stopped by cooling. It was. The reaction temperature was 105 ° C to 125 ° C. The reaction product was further diluted with 700.0 parts of toluene and neutralized with a 20% NaOH solution, washed with water, the toluene was removed under reduced pressure, and the precipitated inorganic salt was filtered off to obtain a bifunctional acrylate having an alicyclic skeleton (alicyclic skeleton). A-1) was obtained. The urethane group concentration of (A-1) was 0 mmol / g, and Mw was 1,900.

<Manufacturing example 2>
152.0 parts of tetrahydrophthalic anhydride, 388.0 parts of dihydroxymethyltricyclodecane, 10.0 parts of paratoluenesulfonic acid in a glass reaction vessel equipped with a stirrer, thermometer, air blow tube, water test tube, and condenser. , 2.0 parts of hydroquinone and 300.0 parts of toluene were charged and heated. The produced water is distilled and condensed together with the solvent, only water is removed from the system with a water inspection pipe, the solvent is returned to the reaction vessel, and when a total of 36.0 parts of distilled water is produced, the reaction is stopped by cooling. It was. The reaction temperature was 105 ° C to 125 ° C. The reaction product was further diluted with 700.0 parts of toluene, neutralized with a 20% NaOH solution, washed with water, the toluene was removed under reduced pressure, the precipitated inorganic salt was filtered off, and the polyester having an alicyclic skeleton of the terminal hydroxyl group was obtained. Got
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, 202.6 parts of synthetic terminal hydroxyl group polyester, IPDI [trade name "Death Module I", manufactured by Sumika Bayer Urethane Co., Ltd.] 778 .2 parts, 1,000 parts of THF, 0.1 part of Bismastris (2-ethylhexanoate) [trade name "Neostan U-600", manufactured by Nitto Kasei Co., Ltd.] was charged and reacted at 65 ° C. for 4 hours. After that, 19.2 parts of 2-hydroxyethyl acrylate [trade name "2-hydroxyethyl acrylate", manufactured by Nippon Shokubai Co., Ltd.] was added and reacted at 65 ° C. for 8 hours to obtain a bifunctional acrylate having an alicyclic skeleton. A-2) was obtained. The urethane group concentration of (A-2) was 1.9 mmol / g, and Mw was 23,700.

<Manufacturing example 3>
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, TDI [trade name "Coronate T-100", manufactured by Toso Co., Ltd.] 263.7 parts, a polycarbonate diol having an alicyclic skeleton [ Product name "ETERNACOLL UM-90 (1/1)", manufactured by Ube Industries, Ltd.] 670.7 parts, ethylene glycol 42.2 parts, THF 1,000 parts, bismastris (2-ethylhexanoate) [Product name "Neostan U-600", manufactured by Nitto Kasei Co., Ltd.] 1.0 part was charged and reacted at 65 ° C. for 4 hours, then 2-hydroxypropyl acrylate [trade name "Light Ester HOP-A", Kyoeisha Chemical Co., Ltd. )] 23.4 parts were added and reacted at 65 ° C. for 8 hours to obtain a bifunctional acrylate (A-3) having an alicyclic skeleton. The urethane group concentration of (A-3) was 3.0 mmol / g, and Mw was 22,800.

<Manufacturing example 4>
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, TDI [trade name "Coronate T-100", manufactured by Toso Co., Ltd.] 358.9 parts, a polycarbonate diol having an alicyclic skeleton [ Product name "ETERNACOLL UM-90 (1/1)", manufactured by Ube Industries, Ltd.] 531.9 parts, ethylene glycol 85.9 parts, THF 1,000 parts, bismastris (2-ethylhexanoate) [Product name "Neostan U-600", manufactured by Nitto Kasei Co., Ltd.] 1.0 part was charged and reacted at 65 ° C. for 4 hours, then 2-hydroxypropyl acrylate [trade name "Light Ester HOP-A", Kyoeisha Chemical Co., Ltd. )] 22.5 parts were added and reacted at 65 ° C. for 8 hours to obtain a bifunctional acrylate (A-4) having an alicyclic skeleton. The urethane group concentration of (A-4) was 4.1 mmol / g, and Mw was 23,700.

<Manufacturing example 5>
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, TDI [trade name "Coronate T-100", manufactured by Toso Co., Ltd.] 419.6 parts, a polycarbonate diol having an alicyclic skeleton [ Product name "ETERNACOLL UM-90 (1/1)", manufactured by Ube Industries, Ltd.] 444.4 parts, ethylene glycol 112.6 parts, THF 3,000 parts, bismastris (2-ethylhexanoate) [Product name "Neostan U-600", manufactured by Nitto Kasei Co., Ltd.] 1.0 part was charged and reacted at 65 ° C. for 4 hours, then 2-hydroxypropyl acrylate [trade name "Light Ester HOP-A", Kyoeisha Chemical Co., Ltd. )] 26.3 parts were added and reacted at 65 ° C. for 8 hours to obtain a bifunctional acrylate (A-5) having an alicyclic skeleton. The urethane group concentration of (A-5) was 4.8 mmol / g, and Mw was 20,300.

<Manufacturing example 6>
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, TDI [trade name "Coronate T-100", manufactured by Toso Co., Ltd.] 360.5 parts, a polycarbonate diol having an alicyclic skeleton [ Product name "ETERNACOLL UM-90 (1/1)", manufactured by Ube Industries, Ltd.] 533.7 parts, ethylene glycol 82.3 parts, THF1016 parts, bismastris (2-ethylhexanoate) [Product name "Neostan" U-600 ", manufactured by Nitto Kasei Co., Ltd.] 1.0 part was charged and reacted at 65 ° C. for 4 hours, after which 2-hydroxypropyl acrylate [trade name" light ester HOP-A ", manufactured by Kyoeisha Chemical Co., Ltd. ] 39.6 parts were added and reacted at 65 ° C. for 8 hours to obtain a bifunctional acrylate (A-6) having an alicyclic skeleton. The urethane group concentration of (A-6) was 4.1 mmol / g, and Mw was 11,600.

<Manufacturing example 7>
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, TDI [trade name "Coronate T-100", manufactured by Toso Co., Ltd.] 347.8 parts, a polycarbonate diol having an alicyclic skeleton [ Product name "ETERNACOLL UM-90 (1/1)", manufactured by Ube Industries, Ltd.] 544.7 parts, ethylene glycol 84.1 parts, THF 3,944 parts, bismastris (2-ethylhexanoate) [Product name "Neostan U-600", manufactured by Nitto Kasei Co., Ltd.] 1.0 part was charged and reacted at 65 ° C. for 4 hours, then 2-hydroxypropyl acrylate [trade name "Light Ester HOP-A", Kyoeisha Chemical Co., Ltd. )] 9.4 parts were added and reacted at 65 ° C. for 8 hours to obtain a bifunctional acrylate (A-7) having an alicyclic skeleton. The urethane group concentration of (A-7) was 4.1 mmol / g, and Mw was 47,000.

<Manufacturing example 8>
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, IPDI [trade name "Death Module I", manufactured by Sumika Bayer Urethane Co., Ltd.] 424.6 parts, polycarbonate with an alicyclic skeleton Diol [trade name "ETERNACOLL UC-100", manufactured by Ube Kosan Co., Ltd.] 468.4 parts, ethylene glycol 83.5 parts, THF 4,006 parts, bismastris (2-ethylhexanoate) [trade name "Neostan U" -600 ", manufactured by Nitto Kasei Co., Ltd.] 1.0 part was charged and reacted at 65 ° C. for 4 hours, after which 2-hydroxypropyl acrylate [trade name" light ester HOP-A ", manufactured by Kyoeisha Chemical Co., Ltd.] 24.9 parts were added and reacted at 65 ° C. for 8 hours to obtain a bifunctional polyurethane acrylate (A-8) having an alicyclic skeleton. The urethane group concentration of (A-8) was 3.8 mmol / g, and Mw was 21,400.

<Manufacturing example 9>
In another glass reaction vessel equipped with a cooling tube, agitator, and a thermometer, IPDI [trade name "Death Module I", manufactured by Sumika Bayer Urethane Co., Ltd.] 424.6 parts, polycarbonate diol [trade name "Duranol" T5651 ", manufactured by Asahi Kasei Chemicals Co., Ltd.] 468.4 parts, ethylene glycol 83.6 parts, THF 1,002 parts, bismastris (2-ethylhexanoate) [trade name" Neostan U-600 ", Nitto Kasei Co., Ltd. )] 1.0 part is charged and reacted at 65 ° C. for 4 hours, then 43.7 parts of glycerin dimethacrylate [trade name “Bremmer GMR-H”, manufactured by Nichiyu Co., Ltd.] is added and 8 hours at 65 ° C. The reaction was carried out to obtain a tetrafunctional acrylate (B-1). The urethane group concentration was 3.7 mmol / g, and Mw was 21,400.

Examples 1-17, Comparative Examples 1-3
According to the compounding composition (part) shown in Tables 1 and 2, the components were collectively compounded and stirred with a disperser until uniform to obtain each active energy ray-curable resin composition.
Next, the obtained active energy ray-curable resin composition is abbreviated as PC (polycarbonate) film having a thickness of 500 μm [trade name “Panlite PC-1151”, manufactured by Teijin Limited, hereinafter PC1151. ], Using an applicator so that the film thickness after curing is 20 μm, the solvent is dried at 80 ° C. for 1 minute, and under a nitrogen atmosphere, the EB tester [EC250: Eye Electron Co., Ltd.] A cured product was obtained by curing with an irradiation amount of 5 rad.
The active energy ray-curable resin composition of Example 16 was applied to PC1151 using an applicator so that the film thickness after curing was 20 μm, and the solvent was dried at 80 ° C. for 1 minute. Under a nitrogen atmosphere, a belt conveyor type UV irradiation device [“ECS-151U” manufactured by Eye Graphics Co., Ltd., and the same device was used for the following evaluation. ], The cured product was obtained by curing at an exposure amount of 500 mJ / cm ² .
The above cured product was evaluated according to the following evaluation methods (1) to (3).
The evaluation results are shown in Tables 1 and 2.

<Evaluation method>
(1) Pencil hardness [scratch resistance]
Pencil hardness was evaluated according to JIS K5600-5-4, and evaluated according to the following criteria.
<Evaluation criteria>
◎: H or more ○: F
Δ: HB
×: Less than HB

(2) Elongation at break [stretchability during heating]
In accordance with JIS-K6251, a tensile test was performed by an autograph at 150 ° C. using a dumbbell-shaped No. 3 test piece, and the elongation (%) at the time of cutting of the cured product was measured and evaluated according to the following evaluation criteria.
<Evaluation criteria>
⊚: 200% or more ○: 100% or more, less than 200% Δ: 50% or more, less than 100% ×: less than 50%

(3) Chemical resistance [Evaluation of chemical resistance]
After dropping a few drops of (i) ethanol and (ii) 1% NaOH aqueous solution with a dropper on another place on the coating surface and leaving them at room temperature for 1 hour and then in an 80 ° C. air circulation dryer for 1 hour. , The part of the coating surface where the chemical was dropped was wiped with a damp bleaching, and the change in appearance was visually judged by the following evaluation criteria.
⊚: No change ○: Spot traces remain but slight changes △: Changes can be confirmed but resin is not dissolved ×: Resin is partially dissolved and obvious changes are seen

The abbreviations in Tables 1 and 2 are as follows.
TCDDMDA (A-9):
Tricyclodecanedimethanol diacrylate [trade name "NK ester A-DCP", manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
DPHA (B-2):
Dipentaerythritol hexaacrylate [Product name "NK ester A-DPH", manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
PETA (B-3):
Pentaerythritol tetraacrylate [Product name "NK ester A-TMMT", manufactured by Shin Nakamura Chemical Industry Co., Ltd.]
ACMO (C-1):
Acryloyl morpholine [Product name "ACMO", manufactured by KJ Chemicals Co., Ltd.]
DMAA (C-2):
Dimethylacrylamide [Product name "DMAA", manufactured by KJ Chemicals Co., Ltd.]
HEA (D-1):
Hydroxyethyl acrylate [Product name "2-hydroxyethyl acrylate", manufactured by Nippon Shokubai Co., Ltd.]
MAPO (e1-1):
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [trade name "LUCIRIN TPO", manufactured by BASF Limited]]

From the results in Tables 1 and 2, the active energy ray-curable resin composition (X) of the present invention has excellent moldability and surface hardness in the cured product of the active energy ray-curable resin composition as compared with the comparative ones. , It can be seen that it imparts chemical resistance.

In the active energy ray-curable resin composition of the present invention, since the cured product is excellent in moldability, surface hardness, and chemical resistance, an optical lens (prism sheet, collimeter lens, frennel) having a fine structure on the surface is used. Lenses, lenticular lenses, back-reflection lenses, holograms, etc.), mobile phone members (decorative members such as buttons, touch panels, etc.), liquid crystal displays, plasma displays, electroluminescence displays, polarizing plate protective films, decorative films for building materials, etc. It can be widely used for decorative sheets (interior materials such as floors, walls, ceilings, etc. of buildings) such as hard coat films for molding, and is extremely useful.

Claims (5)

A bifunctional (meth) acrylate (A) having an alicyclic skeleton, a polyfunctional (meth) acrylate (B) having 3 to 12 (meth) acryloyl groups, and a nitrogen atom-containing monofunctional unsaturated monomer (C). An active energy ray-curable resin composition containing the above, wherein (A) has a urethane group, and the urethane group concentration is 3.0 to 5.0 mmol / g based on the weight of (A). A certain active energy ray-curable resin composition (X). The active energy ray-curable resin composition according to claim 1, wherein the content of (A) is 50 to 90% based on the total weight of (A), (B) and (C). The active energy ray-curable resin composition according to claim 1 or 2 , wherein the weight average molecular weight of (A) is 10,000 to 50,000. A cured product (P) obtained by curing the active energy ray-curable resin composition (X) according to any one of claims 1 to 3 . The cured product according to claim 4, which is an optical lens, a decorative film, a decorative sheet, a hard coat film or an antireflection film.