JP2017002105A - Urethane (meth)acrylate resin and laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane (meth)acrylate resin that imparts superior performances, such as scratch resistance, curling resistance, flexibility, and impact resistance, to a cured coating film, a curable composition that includes the urethane (meth)acrylate resin, a cured product of the composition, and a laminated film.SOLUTION: The present invention provides a urethane (meth)acrylate resin that has a molecular structure obtained by a reaction between the following essential components: a polyisocyanate compound (A) having an isocyanurate ring structure in a molecular structure; and a dihydroxydi(meth)acrylate compound (B).SELECTED DRAWING: None

Description

  The present invention relates to a urethane (meth) acrylate resin excellent in various properties such as scratch resistance, curl resistance, flexibility and impact resistance in a cured coating film, a curable composition containing the same, a cured product thereof, and a laminated film About.

  Plastic films manufactured using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc. are used in industrial applications such as polarizing plate protective films incorporated into flat panel displays and touch panel surface protective films. It is often used in. Since these plastic films are insufficient in performance, such as the surface is easily damaged by itself, the processability is low, and cracks and cracks are likely to occur, usually a coating layer made of active energy ray curable resin etc. is provided on the surface, It is used supplementing these performances.

  As a coating agent for reinforcing a plastic film, for example, an active energy ray-curable coating composition containing polyurethane polyacrylate obtained by reacting isophorone diisocyanate, pentaerythritol diacrylate, and pentaerythritol triacrylate (see Patent Document 1) And an ultraviolet curable composition containing urethane acrylate obtained by reacting an aliphatic diisocyanate with an acrylic ester of pentaerythritol having a hydroxyl value of 173 mg KOH / g (see Patent Document 2). Although these coating agents are excellent in scratch resistance, the toughness and flexibility of the coating film are not sufficient, and cracking due to external impact is likely to occur.

JP 2011-144309 A Japanese Patent Laying-Open No. 2015-021089

  In view of the above circumstances, the problem to be solved by the present invention includes a urethane (meth) acrylate resin excellent in various properties such as scratch resistance, curl resistance, flexibility, and impact resistance in a cured coating film, and this. The object is to provide a curable composition, a cured product thereof, and a laminated film.

  As a result of diligent studies to solve the above-mentioned problems, the present inventor obtained a urethane obtained by reacting a polyisocyanate compound having an isocyanurate ring structure in the molecular structure and a dihydroxydi (meth) acrylate compound as essential components. The present inventors have found that a (meth) acrylate resin solves the above problems and have completed the present invention.

  That is, the present invention has a molecular structure obtained by reacting the polyisocyanate compound (A) having an isocyanurate ring structure in the molecular structure with the dihydroxydi (meth) acrylate compound (B) as essential components. It is related with the urethane (meth) acrylate resin characterized.

  The present invention further relates to a curable composition containing the urethane (meth) acrylate resin and a photopolymerization initiator.

  The present invention further relates to a cured product obtained by curing the curable composition.

  The present invention further relates to a laminated film having a layer made of the cured product and another plastic film layer.

  According to the present invention, urethane (meth) acrylate resin excellent in various performances such as scratch resistance and curl resistance, flexibility, impact resistance in a cured coating film, a curable composition containing the same, and a cured product thereof, And a laminated film can be provided. The curable composition containing the urethane (meth) acrylate resin of the present invention can be suitably used as a reinforcing coating agent for various plastic films, and the laminated film obtained using the curable composition of the present invention is resistant to In addition to excellent scratch resistance and curl resistance, it has high flexibility and is resistant to cracking when bent or wound, and also has impact resistance that is resistant to cracking when there is a fallen object on the film.

  The urethane (meth) acrylate resin of the present invention is obtained by reacting a polyisocyanate compound (A) having an isocyanurate ring structure in the molecular structure and a dihydroxydi (meth) acrylate compound (B) as essential components. It has a molecular structure.

  Since the polyisocyanate compound (A) has an isocyanurate ring structure in the molecular structure, it is a urethane (meth) acrylate resin excellent not only in surface hardness in a cured coating film but also in flexibility and impact resistance. It becomes.

  Examples of the polyisocyanate compound (A) include those obtained by subjecting various diisocyanate compounds to nurate modification in the presence of monoalcohol or diol. Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. , Isophorone diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate and the like. These may be used alone or in combination of two or more.

  The monoalcohol is hexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n-octadecanol. , N-nonadecanol and the like. The diol is ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentane. Examples include diol, neopentyl glycol, 1,6-hexanediol. These monoalcohols and diols may be used alone or in combination of two or more.

  The polyisocyanate compound (A) may be used alone or in combination of two or more. Especially, since it becomes urethane (meth) acrylate resin excellent in the balance of each performance in hardened | cured material, the nurate modified body of an aliphatic or alicyclic diisocyanate compound is preferable.

  Moreover, it is preferable that it is the range of 13-30 mass%, and, as for the isocyanate group content of the said polyisocyanate compound (A), it is more preferable that it is the range of 15-25 mass%.

  Since the dihydroxydi (meth) acrylate compound (B) has two hydroxyl groups and two (meth) acryloyl groups in the molecule, the reaction with the polyisocyanate compound (A) not only causes molecular ends. A (poly) urethane acrylate resin having a (meth) acryloyl group also in the molecular chain can be obtained. Examples of the dihydroxy di (meth) acrylate compound (B) include di (meth) acrylate (B1) as a diglycidyl ether compound and di (meth) acrylate (B2) as a tetraol compound.

  Examples of the diglycidyl ether compound di (meth) acrylate (B1) include compounds obtained by reacting various diol compound diglycidyl ethers with (meth) acrylic acid or derivatives thereof to form (meth) acrylates. Examples of the diol compound include aliphatic diols such as ethylene glycol, propanediol, butanediol, pentanediol, neopentylglycol, and hexanediol;

  Aromatic ring-containing diols such as hydroquinone, 2-methylhydroquinone, benzene dimethanol, biphenyl diol, biphenyl dimethanol, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthalene diol, naphthalene diol methanol;

  Obtained by ring-opening polymerization of the aliphatic or aromatic ring-containing diol with various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyether-modified diols;

  Lactone-modified diol obtained by polycondensation of the aliphatic or aromatic ring-containing diol with a lactone compound such as ε-caprolactone:

  The aliphatic or aromatic ring-containing diol and an aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid, and an aromatic such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, and orthophthalic acid And polyester diols obtained by reacting group dicarboxylic acids or their anhydrides.

  Examples of the di (meth) acrylate (B2) of the tetraol compound include methanetetraol, 1,1,2,2-ethanetetraol, 1,1,3,3-propanetetraol, 1,2,3. , 4-butanetetraol, 1,1,4,4-butanetetraol, pentaerythritol, 1,1,5,5-pentanetetraol, pentane-1,2,4,5-tetraol, 1,2 , 5,6-hexanetetraol, 1,1,6,6-hexanetetraol, 2,2-bis (hydroxymethyl) -1,4-butanediol, and other di (meth) acrylates of aliphatic tetraol compounds Is mentioned.

  The above-listed dihydroxydi (meth) acrylate compounds (B) may be used alone or in combination of two or more. Among them, since it becomes a urethane (meth) acrylate resin excellent in curling resistance, flexibility and impact resistance in a cured product, di (meth) acrylate of an aliphatic diol diglycidyl ether compound or di (meth) of an aliphatic tetraol compound ( (Meth) acrylate is preferred.

  The urethane (meth) acrylate resin of the present invention has a molecular structure obtained by reacting the polyisocyanate compound (A) and the dihydroxydi (meth) acrylate compound (B) as essential components. A compound may be used as a reaction raw material. Specifically, in addition to the polyisocyanate compound (A) and the dihydroxy di (meth) acrylate compound (B), other polyisocyanate compounds (C), monohydroxy (meth) acrylate compounds (D), other What is obtained by reacting a polyol compound (E) etc. is mentioned.

  Examples of the other polyisocyanate compound (C) include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and xylylene diisocyanate. And diisocyanate monomers such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, adduct-modified products thereof, biuret-modified products, and the like. These may be used alone or in combination of two or more.

  When these other polyisocyanate compounds (C) are used, the polyisocyanate compound (A) is preferably 20% by mass or more in the total polyisocyanate raw material, since the effects of the present invention are sufficiently exhibited. It is more preferable that it is 40 mass% or more.

  The monohydroxy (meth) acrylate compound (D) includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, tri Aliphatic (meth) acrylate compounds such as methylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, acrylic acid Contains aromatic rings such as 4-hydroxyphenethyl, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate (Meth) acrylate compound; ring opening of the (meth) acrylate compound and various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether Examples include polyether-modified (meth) acrylate compounds obtained by polymerization; lactone-modified (meth) acrylate compounds obtained by polycondensation of the (meth) acrylate compounds and lactone compounds such as ε-caprolactone. These may be used alone or in combination of two or more. Especially, since it becomes urethane (meth) acrylate resin excellent in the softness | flexibility and impact resistance in hardened | cured material, an aliphatic (meth) acrylate compound or its polyether modified body and a lactone modified body are preferable. Furthermore, since it becomes urethane (meth) acrylate resin which is excellent in sclerosis | hardenability and has high surface hardness in a cured coating film, a trifunctional or more (meth) acrylate compound is preferable.

  Examples of the other polyol compound (E) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 3-methyl-1,3-butane. Polyol monomers such as diol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol; the polyol monomer, succinic acid, adipine Acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,4-cyclohexa Polyester polyol obtained by cocondensation with dicarboxylic acid such as dicarboxylic acid; obtained by polycondensation reaction between the polyol monomer and various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone. Examples of the lactone type polyester polyol include polyether polyols obtained by ring-opening polymerization of the polyol monomer and a cyclic ether compound such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds may be used alone or in combination of two or more.

  The method for producing the urethane (meth) acrylate resin of the present invention includes, for example, the polyisocyanate compound (A) and the dihydroxydi (meth) acrylate compound (B), an isocyanate group that the polyisocyanate compound (A) has, The molar ratio [(NCO) / (OH)] with the hydroxyl group of the dihydroxydi (meth) acrylate compound (B) is in the range of 1 / 0.95 to 1 / 1.05. Examples thereof include a method performed using a known and usual urethanization catalyst within a temperature range of 120 ° C., if necessary.

  In addition to the polyisocyanate compound (A) and the dihydroxy di (meth) acrylate compound (B), other polyisocyanate compounds (C), monohydroxy (meth) acrylate compounds (D), and other polyols When reacting the compound (E), a method of reacting these three components at once may be used, or a method of reacting a polyisocyanate component and a polyol component first to obtain an intermediate, and then reacting a monoalcohol component Alternatively, a method may be used in which the polyisocyanate component and the monoalcohol component are first reacted to obtain an intermediate, and then the polyol component is reacted. The reaction ratio of each component is such that the total molar ratio [(NCO) / (OH)] of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is 1 / 0.95 to 1 / 1.05. It is preferable that the ratio is

  When the di (meth) acrylate (B2) of a tetraol compound is used as the dihydroxy di (meth) acrylate compound (B), the (meth) acrylate (β) of the tetraol compound is used as a raw material for the urethane (meth) acrylate resin. May be. If the (meth) acrylate (β) of the tetraol compound contains the di (meth) acrylate (B2) of the tetraol compound as an essential component, the di (meth) acrylate (B2) of the tetraol compound alone Further, it may be a composition containing mono (meth) acrylate, tri (meth) acrylate or tetra (meth) acrylate. When such a (meth) acrylate (β) is used, it becomes a urethane (meth) acrylate resin excellent in flexibility and impact resistance in a cured product, so that the hydroxyl value thereof is in the range of 150 to 500 mgKOH / g. Is preferable, and the range of 190 to 480 mgKOH / g is more preferable. Moreover, it is preferable that 25 mol% or more in the (meth) acrylate (β) of the tetraol compound is di (meth) acrylate (B2).

  The (meth) acryloyl group equivalent of the urethane (meth) acrylate resin thus obtained is 100 to 500 g / eq because it becomes a urethane (meth) acrylate resin having excellent curability and high surface hardness in the cured coating film. A range is preferable. In the present invention, the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin is a value calculated as a theoretical value from the reaction raw materials.

  Moreover, since the weight average molecular weight (Mw) of the said urethane (meth) acrylate resin becomes a urethane (meth) acrylate resin excellent in the balance of each performance in hardened | cured material, it is the range of 2,000-60,000. Is preferred.

In the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the following conditions.

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

  The curable composition of this invention contains the said urethane (meth) acrylate resin and a photoinitiator. Examples of the photopolymerization initiator include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, and 4,4′-dichloro. Various benzophenones such as benzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Xanthones, thioxanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;

  Α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

  3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Tylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethyl Ketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4- Dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine, 2 , 4-Bis-trichloromethyl-6- (4-ethoxy Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, etc. Is mentioned. These may be used alone or in combination of two or more.

  Among the photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino One or more mixed systems selected from the group of phenyl) -butan-1-one By are more active against a broad range of wavelengths of light is preferred because the high curability curable composition.

  Commercially available products of the photopolymerization initiator include, for example, “Irgacure-184”, “Irgacure-149”, “Irgacure-261”, “Irgacure-369”, “Irgacure-500”, “Irgacure-” manufactured by Ciba Specialty Chemicals. "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800" "Irgacure-1850", "Irgacure-2959", "Irgacure-4043", "Darocur-1173"; "Lucirin TPO" manufactured by BASF; "Kayacure-DETX", "Kayacure-MBP" manufactured by Nippon Kayaku ”,“ Kayaki “A-DMBI”, “Kayacure-EPA”, “Kayacure-OA”; “Bicure-10”, “Bicure-55” manufactured by Stowa Chemical; “Trigonal P1” manufactured by Akzo; “Deep” manufactured by Apjon; “QuantaCure-PDO”, “QuantaCure-ITX”, “QuantaCure-EPD”, etc. manufactured by Ward Brenkinsop.

  The addition amount of the photopolymerization initiator is an amount that can sufficiently exhibit the function as a photopolymerization initiator, and is preferably in a range in which precipitation of crystals and deterioration of physical properties of the coating film do not occur. It is preferable to use it in the range of 0.05-20 mass parts with respect to 100 mass parts of curable compositions, and it is especially preferable to use in the range of 0.1-10 mass parts.

  The curable composition of the present invention may contain various photosensitizers in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

  The curable composition of the present invention further includes other photocurable compounds other than the urethane (meth) acrylate resin of the present invention, organic solvents, ultraviolet absorbers, antioxidants, silicon-based additives, and fluorine-based additives. Agents, silane coupling agents, organic beads, inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, antifogging agents, coloring agents, and the like may be contained.

  Examples of the other photocurable compound include various (meth) acrylate monomers, other urethane (meth) acrylates other than the urethane (meth) acrylate resin of the present invention, and epoxy (meth) acrylate. It is done.

  Examples of the (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate Relate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate , Ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- ( (Meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl ( (Meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, adamantyl Mono (meth) acrylates such as mono (meth) acrylate;

  Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylol Di (meth) acrylates such as propanedi (meth) acrylate and pentaerythritol di (meth) acrylate;

  Trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri Tri (meth) acrylates such as (meth) acrylate and dipentaerythritol tri (meth) acrylate;

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

  Examples thereof include (meth) acrylates in which some or all of the various polyfunctional (meth) acrylates are modified with a polyoxyalkylene chain or a polyester chain.

  Examples of the other urethane (meth) acrylate compounds include urethane (meth) acrylates composed of various polyisocyanate compounds and monohydroxy (meth) acrylate compounds. Examples of the polyisocyanate compound include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethyl. Aliphatic diisocyanates such as xylylene diisocyanate; Fatty acids such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate Cyclic diisocyanate; 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-bi (Paraphenyl isocyanate) Various kinds of aromatic diisocyanates such as propane, 4,4′-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, etc. These diisocyanate monomers and their nurate-modified products, adduct-modified products, and biuret-modified products.

  On the other hand, the monohydroxy (meth) acrylate compound includes various compounds listed as the monohydroxy (meth) acrylate compound (C).

  Examples of the epoxy (meth) acrylate compound include various compounds listed as di (meth) acrylate (B1) of the diglycidyl ether compound.

  These other photocurable compounds may be used alone or in combination of two or more. Especially, since it becomes a composition excellent in sclerosis | hardenability, it is preferable to use various (meth) acrylate monomers. When using these other photocurable compounds, the urethane (meth) acrylate resin of the present invention is 5 parts by mass in a total of 100 parts by mass of the urethane (meth) acrylate resin of the present invention and the other photocurable compounds. It is preferable to use it in the ratio which becomes above, and it is especially preferable to use it in the ratio which becomes 20 mass parts or more.

  Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone (ketone solvents such as tetrahydrofuran; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether These may be used alone or in combination of two or more.

  These organic solvents are used mainly for the purpose of adjusting the viscosity of the curable composition, but it is usually preferable to adjust so that the nonvolatile content is in the range of 10 to 80% by mass.

  Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Triazine derivatives such as 2,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These may be used alone or in combination of two or more.

  Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants. These may be used alone or in combination of two or more.

  Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl. Examples include polyorganosiloxanes having alkyl groups and phenyl groups, such as polysiloxane copolymers and amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes having polyether-modified acrylic groups, and polydimethylsiloxanes having polyester-modified acrylic groups. It is done. These may be used alone or in combination of two or more.

  Examples of the fluorine-based additive include DIC Corporation “Megafac” series. These may be used alone or in combination of two or more.

  Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) ) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl- N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special Aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropylate Ethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, etc., vinyl -Based silane coupling agents;

  Diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-bridoxypropyl Epoxy-based silane coupling agents such as triethoxysilane;

  styrenic silane coupling agents such as p-styryltrimethoxysilane;

  3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (meth) Acryloxy silane coupling agent;

  N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltri Amino-based silane couplings such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane Agent;

  Ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane;

  Chloropropyl-based silane coupling agents such as 3-chloropropyltrimethoxysilane;

  Mercaptopropyl silane coupling agents, such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethinesilane;

  Sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide;

  Examples thereof include isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane. These may be used alone or in combination of two or more.

  Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads. These may be used alone or in combination of two or more. The average particle diameter of these organic beads is preferably in the range of 1 to 10 μm.

  Examples of the inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. These may be used alone or in combination of two or more. The average particle diameter of these inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm. Further, when these inorganic fine particles are contained, a dispersion aid may be further used. Examples of the dispersion aid include phosphate esters such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphate dimethacrylate. Compounds and the like. These may be used alone or in combination of two or more.

  Examples of commercially available dispersion aids include “Kayamar PM-21” and “Kayamer PM-2” manufactured by Nippon Kayaku Co., Ltd., “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  The curable composition of the present invention can be used for coating applications, and the coating is applied as a coating layer that protects the surface of the substrate by coating on various substrates and irradiating and curing with active energy rays. be able to. In this case, the curable composition of the present invention may be directly applied to the surface-protecting member, or one applied on a plastic film may be used as the protective film. Or what applied the curable composition of this invention on the plastic film, and formed the coating film may be used as optical films, such as an antireflection film, a diffusion film, and a prism sheet. The cured coating film of the curable composition of the present invention is characterized by high surface hardness and excellent flexibility and impact resistance. Therefore, it is applied to various types of plastic films with a film thickness according to the application, and a protective film. It can be used as a use or a film-like molded product.

  The plastic film is, for example, a plastic film made of polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, cycloolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, polyimide resin, or the like. And plastic sheets.

  Among the plastic films, the triacetyl cellulose film is a film that is particularly suitably used for the polarizing plate application of a liquid crystal display. However, since the thickness is generally as thin as 40 to 100 μm, the surface even when a hard coat layer is installed. It is difficult to make the hardness sufficiently high, and there is a feature that it is easily curled. The coating film comprising the curable composition of the present invention has a high surface hardness even when a triacetyl cellulose film is used as a base material, and has an effect of excellent curling resistance, flexibility, transparency and impact resistance. Can be suitably used. When using the triacetyl cellulose film as a substrate, the coating amount when applying the curable composition of the present invention is such that the film thickness after drying is in the range of 1 to 20 μm, preferably in the range of 2 to 10 μm. It is preferable to apply to. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Among the plastic films, examples of the polyester film include polyethylene terephthalate, and the thickness thereof is generally about 20 to 300 μm. Although it is a cheap and easy to process film, it is a film used for various applications such as a touch panel display. However, it is very soft and has a feature that it is difficult to sufficiently increase the surface hardness even when a hard coat layer is provided. When using the polyethylene film as a substrate, the coating amount when applying the curable composition of the present invention is such that the film thickness after drying ranges from 1 to 100 μm, preferably from 1 to 20 μm, in accordance with the application. It is preferable to apply in such a range. In general, a cured coating film having a thickness exceeding 20 μm tends to curl greatly as compared with a case where the film thickness is small. However, the curable composition of the present invention also has a feature of excellent curling resistance, and therefore has a characteristic of 30 μm. Curling hardly occurs even when the film is applied with a relatively high film thickness exceeding 50, and can be suitably used. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Among the plastic films, the polymethyl methacrylate film is generally relatively thick and durable with a thickness of about 50 to 2,000 μm, so it is suitable for applications that require a particularly high surface hardness, such as applications for the front plate of liquid crystal displays. It is the film used for. When the polymethyl methacrylate film is used as a base material, the coating amount when applying the curable composition of the present invention is in the range of 1 to 100 μm, preferably 1 to 100 μm after drying according to the application. It is preferable to apply in a range of 20 μm. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Of the plastic films, cycloolefin polymer films are generally weak against lateral forces such as tearing, and are known to have poor folding resistance, but in recent years from the viewpoint of transparency and heat resistance. The area of use is expanding. The cured coating film obtained from the curable composition of the present invention can effectively increase its flexibility and impact resistance even in such a fragile film. From the viewpoint of suitably exhibiting such an effect, the thickness of the cured coating film is preferably adjusted in the range of 1 to 10 μm. Examples of the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  Examples of the active energy rays irradiated when the curable composition of the present invention is cured to form a coating film include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED or the like as a light source is used, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 50 m / min for one lamp having a light quantity that is usually in the range of 80 to 160 W / cm. On the other hand, in the case of curing with an electron beam, it is preferably cured with an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min.

  Moreover, the base material to which the curable composition of the present invention is applied is suitably used not only as a plastic film but also as a surface coating agent for various plastic molded articles, for example, cellular phones, electric appliances, automobile bumpers and the like. be able to. In this case, examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.

  The coating method is a method in which the paint is spray-coated or coated as a top coat on a molded product using a printing device such as a curtain coater, roll coater, gravure coater, etc., and then cured by irradiation with active energy rays. is there.

  The laminated film of the present invention has a cured coating film or the like of the curable composition of the present invention and a plastic film layer, and additionally has functional film layers such as an antireflection film, a diffusion film, and a polarizing film. You may do it. These various layer configurations may be formed by a method in which a resin raw material is directly applied and dried or cured, or may be formed by a method of bonding through an adhesive layer.

  Hereinafter, the present invention will be described more specifically with reference to specific production examples and examples, but the present invention is not limited to these examples. Unless otherwise indicated, all parts and percentages in the examples are based on mass.

  In the examples of the present invention, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H _XL- H manufactured by Tosoh Corporation
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 1.0 ml / min Standard: Polystyrene sample: 0.4 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (100 μl)

Production Example 1 Production of Pentaerythritol Diacrylate A flask equipped with a thermometer, a stirrer, and a condenser was charged with 136 parts by mass of pentaerythritol and 600 parts by mass of N, N-dimethylformamide, and paratoluenesulfonic acid as a catalyst. 7 parts by weight were added. The temperature was raised to 80 ° C. with stirring, and pentaerythritol was dissolved in N, N-dimethylformamide, and then mass parts of cyclohexanone was added. While maintaining the reaction temperature at 80 ° C., the pressure in the reaction system was reduced to 140 mmHg, and the reaction was continued while distilling off the generated water. When generation of water could not be confirmed, the mixture was further refluxed for 1 hour. While continuing stirring, the mixture was cooled to room temperature and returned to normal pressure, and unreacted pentaerythritol was removed by filtration under reduced pressure. After removing N, N-dimethylformamide under reduced pressure from the obtained filtrate, ethyl acetate was added, and the precipitated pentaerythritol was again removed by filtration. The obtained filtrate was washed with a saturated aqueous solution of sodium hydrogencarbonate, then further washed with a saturated aqueous solution of sodium chloride, and the organic layer was dehydrated with magnesium sulfate. The reaction product after dehydration was concentrated to obtain a ketal compound (x1).

  A flask equipped with a thermometer, a stirrer, and a condenser was charged with 21.6 parts by mass of the ketal compound (x1) obtained above, 120 parts by mass of dichloromethane, and 46.5 parts by mass of triethylamine, and cooled to -5 ° C. A solution prepared by dissolving 29 parts by mass of 3-chloropropionyl chloride in 40 parts by mass of dichloromethane was added dropwise little by little while keeping the reaction system at 0 ° C. or lower. After completion of dropping, the temperature was gradually raised to room temperature, and the reaction was further continued for 4 hours. After confirming disappearance of the raw material ketal compound (x1) by gas chromatography, triethylamine hydrochloride was removed by vacuum filtration. The obtained filtrate was washed with a saturated aqueous sodium hydrogen carbonate solution, further washed with a saturated aqueous sodium chloride solution, and dehydrated over anhydrous magnesium sulfate. The reaction product after dehydration was concentrated to obtain 30 parts by mass of (meth) acrylate compound (x2).

  A flask equipped with a thermometer, a stirrer, and a condenser was charged with 6.5 parts by mass of the (meth) acrylate compound (x2) obtained above and 30 parts by mass of acetone, and cooled to 0 ° C. with stirring. 10 parts by mass of a 10% sulfuric acid aqueous solution was added dropwise little by little so that the inside of the reaction system did not exceed 10 ° C., and the whole was added and reacted at room temperature for 16 hours. After confirming disappearance of the (meth) acrylate compound (x2) as a raw material by gas chromatography, 10 parts by mass of water was added, and acetone was removed under reduced pressure. The obtained aqueous layer was extracted with ethyl acetate and washed with a saturated aqueous solution of sodium bicarbonate until the pH was 7. The organic layer was dehydrated with magnesium sulfate and then concentrated under normal temperature and reduced pressure conditions to obtain 4.1 parts by mass of pentaerythritol diacrylate.

Example 1 Production of Urethane (Meth) acrylate Resin (1) Composition 208 parts by mass of a mixture of pentaerythritol triacrylate and tetraacrylate (“Aronix M-305” manufactured by Toagosei Co., Ltd.) in a four-necked flask, Production Example 1 75.2 parts by mass of pentaerythritol diacrylate obtained in the above, 0.1 part by mass of dibutyltin dilaurate, and 0.1 part by mass of hydroquinone were added to obtain a uniform solution. The flask was heated until the internal temperature of the flask reached 50 ° C., and then polyisocyanate (“Burnock DN-901S” hexamethylene diisocyanate modified nurate produced by DIC Corporation, isocyanate group content 23.5 mass%) 44.7 Part by mass and 63 parts by mass of hexamethylene diisocyanate (“Duranate 50M-HDI” manufactured by Asahi Kasei Chemicals Corporation) were added in portions over about one hour. After reacting at 80 ° C. for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectrum, the non-volatile content was adjusted to 80% using butyl acetate, and urethane (meth) acrylate resin (1) and pentaerythritol tetra A mixture with acrylate was obtained. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (1) was 10,000, and the acryloyl group equivalent calculated from the charged raw materials was 139 g / eq.
The hydroxyl value of “Aronix M-305” is 112.8 mgKOH / g, and the mixing ratio of pentaerythritol triacrylate and tetraacrylate calculated from the hydroxyl value is 60/40.
The hydroxyl value of the mixture of “Aronix M-305” and pentaerythritol diacrylate was 200 mgKOH / g.

Comparative Production Example 1 Production of Urethane (Meth) acrylate Resin (1 ′) Composition In a four-necked flask, a mixture of pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate (“Aronix M-306, manufactured by Toa Gosei Co., Ltd.”) “Hydroxyl value 165 mg KOH / g) 350.63 parts by mass, dibutyltin dilaurate 0.2 parts by mass, and hydroquinone 0.2 parts by mass were added to obtain a uniform solution. The flask was heated until the internal temperature of the flask reached 50 ° C., and then 84 parts by mass of hexamethylene diisocyanate (“Duranate 50M-HDI” manufactured by Asahi Kasei Chemicals Corporation) was dividedly charged over about one hour. After reacting at 80 ° C. for 3 hours and confirming the disappearance of the isocyanate group in the infrared absorption spectrum, the nonvolatile content was adjusted to 80% using butyl acetate, and the urethane (meth) acrylate resin (1 ′) and pentaerythritol were adjusted. A mixture with tetraacrylate was obtained. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (1 ′) was 1,500, and the acryloyl group equivalent calculated from the charged raw materials was 122 g / eq.

Example 2
125 parts by mass of the urethane (meth) acrylate resin (1) composition obtained in Example 1, 4 parts by mass of a photoinitiator (“Irgacure # 184” manufactured by Ciba Specialty Chemicals), and 75 parts by mass of methyl ethyl ketone are mixed and cured. A composition was obtained. This was coated on a PET film having a thickness of 125 μm by a bar coater and dried at 80 ° C. for 2 minutes. Subsequently, ultraviolet rays were irradiated at 300 mJ / cm 2 with an 80 W high-pressure mercury lamp in an air atmosphere to obtain a laminated film having a cured coating film having a thickness of 5 μm on the PET film. The laminated film was subjected to various evaluation tests by the following methods. The results are shown in Table 1.

Surface hardness test About the said laminated | multilayer film, based on JISK5600-5-4, the pencil hardness of the cured coating film surface of a laminated | multilayer film was measured on 500-g load conditions. The hardness was measured 5 times for each hardness, and the hardness of the cured coating film was determined as the hardness at which the measurement without scratches was 4 times or more.

Scratch resistance test 0.5 W of steel wool (“Bonstar # 0000” manufactured by Nippon Steel Wool Co., Ltd.) is wrapped with a disc-shaped indenter with a diameter of 2.4 cm, and a 500 g weight load is applied to the indenter to make it hard. An abrasion test was performed by reciprocating the cured coating film surface of the composition 200 times. The haze value of the coating film before and after the abrasion test was measured using an automatic haze computer (“HZ-2” manufactured by Suga Test Instruments Co., Ltd.), and the scratch resistance was evaluated by the difference value (dH). The smaller the difference value, the higher the resistance to scratches.

Flexibility test Using a mandrel tester (TP bending machine "flex tester"), the laminated film is wound around a test bar, and a test is performed to visually check whether or not cracks occur. The minimum diameter was taken as the evaluation result. Test bars having a diameter of 2 mm to 6 mm in 1 mm increments were used.

Curl resistance test A 5 cm square coating film was cut out from the laminated film to obtain a test piece. The test piece was measured for floating from four sides horizontally, and the average value (mm) was evaluated. The smaller the value, the smaller the curl and the better the curl resistance.

Impact resistance test A test was conducted with reference to JIS K5600-5-3. Specifically:
[apparatus]
Weight: A ball bearing steel ball (mass 300.0 ± 0.5 g, diameter 25.40 mm, grade 60) defined in JIS B 1501 “Steel Ball for Five Bearings” is hung with a thread at the tip.
Steel stand: A steel stand having a length of 300 mm, a width of 200 mm, and a thickness of 30 mm installed horizontally on a concrete floor.
[operation]
1. The laminated film was fixed on a steel table with the cured coating film surface facing upward.
2. The weight was hung at a position where the distance from the surface of the laminated film to the lower end of the weight was 50 mm, and after the vibration and rotation were confirmed to be stopped, the weight was dropped on the laminated film.
3. The laminated film after the drop test was left in the room for 1 hour, and then the coating surface was examined for damage.
4). The test was continued with the distance from the laminated film surface to the lower end of the weight 10 mm apart, and the evaluation was performed at the maximum distance at which the cured coating film did not break or peel off.

Comparative Example 1
A urethane (meth) acrylate resin (1 ′) composition or the like was used instead of the urethane (meth) acrylate resin (1) composition, and evaluation was performed in the same manner as in Example 2. The results are shown in Table 1.

Claims (8)

Urethane having a molecular structure obtained by reacting a polyisocyanate compound (A) having an isocyanurate ring structure in the molecular structure and a dihydroxydi (meth) acrylate compound (B) as essential components ( (Meth) acrylate resin. The urethane (meth) acrylate resin according to claim 1, wherein the polyisocyanate compound (A) is a urelate modified product of an aliphatic diisocyanate monomer or an alicyclic diisocyanate monomer. The urethane (meth) acrylate resin according to claim 1, wherein the dihydroxy di (meth) acrylate compound (B) is a di (meth) acrylate (B1) of a diglycidyl ether compound. The urethane (meth) acrylate resin according to claim 1, wherein the dihydroxy di (meth) acrylate compound (B) is a di (meth) acrylate (B2) of a tetraol compound. A tetraol compound (meth) acrylate (A) containing the polyisocyanate compound (A) and a tetraol compound di (meth) acrylate (B2) as essential components and having a hydroxyl value in the range of 150 to 500 mgKOH / g. The urethane (meth) acrylate resin according to claim 4, which is obtained by reacting β). A curable composition containing the urethane (meth) acrylate resin according to any one of claims 1 to 5 and a photopolymerization initiator. Hardened | cured material formed by hardening | curing the curable composition of Claim 6. A laminated film comprising a layer made of the cured product according to claim 7 and another plastic film layer.