JP6816348B2 - Urethane (meth) acrylate resin and laminated film - Google Patents

Description

The present invention relates to a urethane (meth) acrylate resin having excellent scratch resistance, curl resistance, flexibility, impact resistance, etc. in a cured coating film, a curable composition containing the same, a cured product thereof, and a laminate. Regarding film.

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 inside flat panel displays and surface protective films for touch panels. It is often used in. Since these plastic films have insufficient performance such as the surface is easily scratched by themselves, the workability is low, and cracks and cracks are easily formed, a coat layer made of an active energy ray-curable resin or the like is usually provided on the surface. It is used to supplement these performances.

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

JP 2011-144309 Japanese Unexamined Patent Publication No. 2015-021089

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

As a result of diligent studies to solve the above problems, the present inventor has reacted a polyisocyanate compound having two or more isocyanate methyl groups in the molecular structure with a dihydroxydi (meth) acrylate compound as an essential component. The urethane (meth) acrylate resin thus obtained has been found to solve the above-mentioned problems, and has completed the present invention.

That is, the present invention is a urethane (meth) obtained by reacting a polyisocyanate compound (A) having two or more isocyanate methyl groups in its molecular structure with a tetraol compound (meth) acrylate (B) as an essential component. ) An acrylate resin in which the (meth) acrylate (B) of the tetraol compound contains a di (meth) acrylate of the tetraol compound as an essential component, and the (meth) acrylate of the tetraol compound (meth) The present invention relates to a urethane (meth) acrylate resin characterized in that the hydroxyl value of B) is in the range of 180 to 500 mgKOH / g.

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, a urethane (meth) acrylate resin excellent in various performances such as scratch resistance, curl resistance, flexibility, and impact resistance in a cured coating film, a curable composition containing the urethane (meth) acrylate resin, 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. Further, the laminated film obtained by using the curable composition of the present invention is excellent in scratch resistance and curl resistance, has high flexibility, is less likely to crack when bent or wound, and is on the film. It has impact resistance that is hard to break even if there is a falling object.

In the urethane (meth) acrylate resin of the present invention, a polyisocyanate compound (A) having two or more isocyanate methyl groups in the molecular structure and a tetraol compound (meth) acrylate (B) are reacted as essential components. The (meth) acrylate (B) of the tetraol compound contained the di (meth) acrylate of the tetraol compound as an essential component, and the (meth) acrylate (B) of the tetraol compound was obtained. It is characterized in that the hydroxyl value is in the range of 180 to 500 mgKOH / g.

The polyisocyanate compound (A) is a compound having two or more isocyanate methyl groups in the molecular structure, that is, at least two of the isocyanate groups present in the molecular structure are bonded to a methylene group. By selectively using such a specific compound (A) among various polyisocyanate compounds, a urethane (meth) acrylate resin having excellent flexibility and impact resistance as well as surface hardness in a cured coating film can be obtained. Become.

Such a polyisocyanate compound (A) is, for example, a diisocyanate compound (A1) having two isocyanate methyl groups in its molecular structure, a nulate modified product (A2) of the diisocyanate compound (A1), or the diisocyanate compound (A1). Adduct modified product (A3), biuret modified product (A4) of the diisocyanate compound (A1), and the like.

The diisocyanate compound (A1) having two isocyanate methyl groups in the molecular structure is, for example, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-. Examples thereof include trimethylhexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and norbornan diisocyanate.

The nulate modified product (A2) of the diisocyanate compound (A1) is obtained, for example, by subjecting the diisocyanate compound (A1) having two isocyanate methyl groups in the molecular structure to a nucleolation reaction in the presence of a monoalcohol or a diol. Things can be mentioned. The monoalcohols include hexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n-octadecanol, n. -Nonadecanol and the like can be mentioned. The diols are ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, and 1,5-pentane. Examples thereof include diols, neopentyl glycols and 1,6-hexanediols. These monoalcohols and diols may be used alone or in combination of two or more.

Examples of the adduct modified product (A3) of the diisocyanate compound (A1) include those obtained by reacting a diisocyanate compound (A1) having two isocyanate methyl groups in the molecular structure with a polyol compound. The polyol compound is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5. -Lactone monomers such as pentanediol, neopentylglycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol; the polyol monomer and succinic acid, adipic acid, azelaic acid, Coexistence with dicarboxylic acids such as sebacic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,4-cyclohexanedicarboxylic acid Polyester polyol obtained by condensation; lactone-type polyester polyol obtained by polycondensation reaction of the polyol monomer with various lactones such as ε-caprolactone, δ-valerolactone, 3-methyl-δ-valerolactone; the polyol monomer And a polyether polyol obtained by ring-opening polymerization with a cyclic ether compound such as ethylene oxide, propylene oxide, tetrahydrofuran, ethylglycidyl ether, and propylglycidyl ether. Each of these polyol compounds may be used alone, or two or more kinds may be used in combination.

The biuret-modified form (A4) of the diisocyanate compound (A1) is, for example, a diisocyanate compound (A1) having two isocyanate methyl groups in the molecular structure in the presence of water, an acid anhydride, a tertiary alcohol, a diamine or the like. Examples thereof are those obtained by reacting with biuret.

The polyisocyanate compounds (A) listed above may be used alone or in combination of two or more. Among them, the diisocyanate compound (A1) or the nurate modified product (A2) of the diisocyanate compound (A1) is preferable because the urethane (meth) acrylate resin has an excellent balance of each performance in the cured product.

The isocyanate group content of the polyisocyanate compound (A) is preferably in the range of 13 to 30% by mass, and more preferably in the range of 15 to 25% by mass.

The (meth) acrylate (B) of the tetraol compound contains a di (meth) acrylate of the tetraol compound as an essential component. That is, the (meth) acrylate (B) of the tetraol compound may be the di (meth) acrylate form of the tetraol compound alone, or the di (meth) acrylate form of the tetraol compound and the mono (meth) compound. It may be a composition with an acrylate compound, a tri (meth) acrylate compound, or a tetra (meth) acrylate compound.

Since the di (meth) acrylate compound of the tetraol compound has two hydroxyl groups and two (meth) acryloyl groups in the molecule, the reaction with the polyisocyanate compound (A) causes not only the molecular terminal but also the molecular terminal. , A (poly) urethane acrylate resin having a (meth) acryloyl group in the molecular chain can be obtained.

The tetrafunctional polyols include, for example, 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, Examples thereof include 1,1,6,6-hexanetetraol and 2,2-bis (hydroxymethyl) -1,4-butanediol. Each of these may be used alone, or two or more types may be used in combination.

As described above, the (meth) acrylate (B) of the tetraol compound contains a di (meth) acrylate as an essential component, and together with this, a mono (meth) acrylate or a tri (meth) acrylate, It may contain a tetra (meth) acrylate compound. Above all, since it is a urethane (meth) acrylate resin having excellent curl resistance, flexibility, and impact resistance in a cured product, 25 mol% or more of the (meth) acrylate (B) of the tetraol compound is di (meth). It is preferably an acrylate compound.

The hydroxyl value of the (meth) acrylate (B) of the tetraol compound is in the range of 180 to 500 mgKOH / g, and further, the urethane (meth) acrylate resin having excellent curl resistance, flexibility, and impact resistance in the cured product. Therefore, it is more preferably in the range of 190 to 480 mgKOH / g, and particularly preferably in the range of 210 to 400 mgKOH / g.

The urethane (meth) acrylate resin of the present invention has a molecular structure obtained by reacting the polyisocyanate compound (A) with the tetraol compound (meth) acrylate (B) as an essential component, but other than these. Compound may be used as a reaction raw material. Specifically, in addition to the polyisocyanate compound (A) and the (meth) acrylate (B) of the tetraol compound, another polyisocyanate compound (C) and another monohydroxy (meth) acrylate compound (D). , Others obtained by reacting the polyol compound (E).

Examples of the other polyisocyanate compound (C) include tolylene diisocyanate, isophorone diisocyanate, tetramethylxylidene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and nulate modified products, adduct modified products, and biuret modified products thereof. Can be mentioned. Each of these may be used alone, or two or more types may be used in combination.

The other monohydroxy (meth) acrylate compound (D) is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate. , Glycerindi (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and other aliphatic (meth) Acrylate compounds; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy- Aromatic ring-containing (meth) acrylate compounds such as 3-phenoxypropyl acrylate; said (meth) acrylate compounds, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether. Polyether-modified (meth) acrylate compound obtained by ring-open polymerization with various cyclic ether compounds such as; lactone-modified (meth) obtained by polycondensation of the (meth) acrylate compound with a lactone compound such as ε-caprolactone. Examples include acrylate compounds. Each of these may be used alone, or two or more types may be used in combination.

The other polyol compound (E) is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-. Polyester monomers such as butanediol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol; the polyol monomer and succinic acid, Adipic 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-cyclohexanedicarboxylic acid, etc. Polyester polyol obtained by cocondensation with a dicarboxylic acid; a lactone type obtained by a polycondensation reaction between the polyol monomer and various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone. Polyester polyol; Examples thereof include a polyether polyol obtained by ring-opening polymerization of the polyol monomer and a cyclic ether compound such as ethylene oxide, propylene oxide, tetrahydrofuran, ethylglycidyl ether, and propylglycidyl ether. Each of these polyol compounds may be used alone, or two or more kinds may be used in combination.

In the method for producing a urethane (meth) acrylate resin of the present invention, for example, the polyisocyanate compound (A) and the tetraol compound (meth) acrylate (B) are combined with the isocyanate group contained in the polyisocyanate compound (A). , The molar ratio [(NCO) / (OH)] of the tetraol compound to the hydroxyl group of the (meth) acrylate (B) is in the range of 1 / 0.95 to 1 / 1.05. Examples thereof include a method of using a known and commonly used urethanization catalyst in a temperature range of 20 to 120 ° C., if necessary.

In addition to the polyisocyanate compound (A) and the (meth) acrylate (B) of the tetraol compound, the other polyisocyanate compound (C) and the other monohydroxy (meth) acrylate compound (D), When the other polyol compound (E) is reacted, a method of reacting these raw materials at once may be used, or the polyisocyanate component and the polyol component are first reacted to obtain an intermediate, and then the monoalcohol component. , Or the method of first reacting the polyisocyanate component with the monoalcohol component to obtain an intermediate, and then reacting the polyol component. 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 in the range of 1 / 0.95 to 1 / 1.05. It is preferable that the ratio is as follows.

The (meth) acryloyl group equivalent of the urethane (meth) acrylate resin thus obtained is 100 to 500 g / eq because it is a urethane (meth) acrylate resin having excellent curability and high surface hardness in the cured coating film. It is preferably in the range. 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 material.

Further, the weight average molecular weight (Mw) of the urethane (meth) acrylate resin is in the range of 2,000 to 60,000 because it is a urethane (meth) acrylate resin having an excellent balance of each performance in the cured product. Is preferable.

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
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

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

Xanthones such as xanthones, thioxanthones, 2-methylthioxanthones, 2-chlorothioxanthones, 2,4-diethylthioxanthones, and thioxanthones; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;

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

3,3'-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexylphenylketone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-hydroxy-2-methyl-1-one Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethylketal, benzyl-β-methoxyethylacetal, methyl o-benzoylbenzoate, bis (4-Dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyluni amount Body, 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-triazine anthraquinone, 2-t-butyl anthraquinone, 2-amyl anthraquinone, β-chloroanthraquinone and the like. Each of these may be used alone, or two or more types may be used in combination.

Among the photopolymerization initiators, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-Methyl-1-propane-1-one, thioxanthone and thioxanthone derivative, 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) By using one kind or a mixed system of two or more kinds selected from the group of phenyl) -butane-1-one, a curable composition showing activity to light of a wider range of wavelengths and having high curability can be obtained. Therefore, it is preferable.

Commercially available products of the photopolymerization initiator include, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", and "Irgacure-" manufactured by Ciba Specialty Chemicals. 651 ”,“ Irgacure-754 ”,“ Irgacure-784 ”,“ Irgacure-819 ”,“ Irgacure-907 ”,“ Irgacure-1116 ”,“ Irgacure-1664 ”,“ Irgacure-1700 ”,“ Irgacure-1800 ” , "Irgacure-1850", "Irgacure-2959", "Irgacure-4043", "DaroCure-1173"; "Lucillin TPO" manufactured by BASF; "Kayacure-DETX", "Kayacure-MBP" manufactured by Nippon Kayaku Co., Ltd. , "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA"; "BiCure-10", "BiCure-55" manufactured by Stofa Chemical Co., Ltd .; "Trigonal P1" manufactured by Axo; "Sandray" manufactured by Sands. 1000 ”;“ Deep ”manufactured by Apjon;“ Quantacure-PDO ”,“ Quantacure-ITX ”,“ Quantacure-EPD ”manufactured by WordBrenkinsop, and the like.

The amount of the photopolymerization initiator added is preferably an amount that can sufficiently exert the function as the photopolymerization initiator and does not cause precipitation of crystals or deterioration of the physical characteristics of the coating film. It is preferably used in the range of 0.05 to 20 parts by mass, and particularly preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable composition.

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

The curable composition of the present invention further comprises other photocurable compounds other than the urethane (meth) acrylate resin of the present invention, an organic solvent, an ultraviolet absorber, an antioxidant, a silicon-based additive, and a fluorine-based additive. It may contain an agent, a silane coupling agent, organic beads, inorganic fine particles, an inorganic filler, a rheology control agent, a defoaming agent, an antifogging agent, a colorant and the like.

Examples of the other photocurable compounds include various (meth) acrylate monomers, urethane (meth) acrylates other than the urethane (meth) acrylate resin of the present invention, epoxy (meth) acrylates, and the like. Be done.

The (meth) acrylate monomer includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. ) Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydroflufreele 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, 2-ethoxyethyl (meth) acrylate, 3-methoxy Butyl (meth) acrylate, ethylcarbitol (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 (Meta) acrylate, nonylphenol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolythylene glycol (meth) acrylate, methoxypropylene glycol (meth) ) Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl Hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, 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) acrylates;

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, Neopentyl glycol di (meth) acrylate ethoxylated, Neopentyl glycol di (meth) acrylate of hydroxypivalate, Glycerindi (meth) acrylate, Trimethylol Di (meth) acrylates such as propanedi (meth) acrylates and pentaerythritol di (meth) acrylates;

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

Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, ditrimethylolpropane hexa (meth) acrylate, or other tetrafunctional (meth) acrylate;

Examples thereof include (meth) acrylates in which some or all of the above-mentioned various polyfunctional (meth) acrylates are modified with polyoxyalkylene chains or polyester chains.

Examples of the other urethane (meth) acrylate compound include urethane (meth) acrylate composed of various polyisocyanate compounds and a monohydroxy (meth) acrylate compound. The polyisocyanate compound is, for example, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl. Alibo diisocyanates such as xylylene diisocyanate; fats such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate, etc. Cyclic diisocyanate; 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-bis (paraphenylisocyanate) propane, 4,4'-dibenzyldiisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate , 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, various diisocyanate monomers such as aromatic diisocyanate such as tolylene diisocyanate, and these nulate modified products, adduct modified products, and biuret modified products.

On the other hand, examples of the monohydroxy (meth) acrylate compound include 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. Above all, it is preferable to use various (meth) acrylate monomers because the composition has excellent curability. When these other photocurable compounds are used, 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 other photocurable compounds. It is preferably used in a ratio of 20 parts by mass or more, and particularly preferably 20 parts by mass or more.

The organic solvent is, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone (ketone solvent such as); cyclic ether solvent such as tetrahydrofuran, dioxolane; ester such as methyl acetate, ethyl acetate, butyl acetate; aromatic solvent such as toluene, xylene; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether can be mentioned. Each of these may be used alone, or two or more types may be used in combination.

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

The ultraviolet absorber is, for example, 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 , 5-Triazine derivatives such as triazine, 2- (2'-xanthencarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Examples thereof include xanthencarboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. Each of these may be used alone, or two or more types may be used in combination.

Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, phosphoric acid ester-based antioxidants, and the like. Each of these may be used alone, or two or more types may be used in combination.

The silicon-based additive includes, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl. Examples include polyorganosiloxane having an alkyl group or a phenyl group such as a polysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxane having a polyether-modified acrylic group, and polydimethylsiloxane having a polyester-modified acrylic group. Be done. Each of these may be used alone, or two or more types may be used in combination.

Examples of the fluorine-based additive include DIC Corporation's "Mega Fvck" series. Each of these may be used alone, or two or more types may be used in combination.

The silane coupling agent includes, for example, vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-. Glycydoxypropylmethyldiethoxysilane, 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-Dimethyl butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3-ureide Propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isopropylpropyltriethoxysilane, allyltrichlorosilane , Allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltricrolsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and other vinyl-based silane coupling agents. ;

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

Styrene-based silane coupling agents such as p-styryltrimethoxysilane;

3-Methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. (meth) Acryloxy-based 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;

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

A chloropropyl-based silane coupling agent such as 3-chloropropyltrimethoxysilane;

3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl trimetkinsilane, and other mercapro-based silane coupling agents;

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

Examples thereof include isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane. Each of these may be used alone, or two or more types may be used in combination.

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

Examples of the inorganic fine particles include fine particles such as silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. Each of these may be used alone, or two or more types may be used in combination. The average particle size 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 auxiliary agent may be further used, and the dispersion auxiliary agent is, for example, a phosphoric acid ester such as isopropylacid phosphate, triisodecylphosphite, or ethyleneoxide-modified dimethacrylate phosphate. Examples include compounds. Each of these may be used alone, or two or more types may be used in combination.

Examples of commercially available products of the dispersion aid include "Kajama PM-21" and "Kajama PM-2" manufactured by Nippon Kayaku Co., Ltd., and "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd.

The curable composition of the present invention can be used for paint applications, and the paint is applied as a coating layer that protects the surface of the base material by applying it on various base materials and irradiating it with active energy rays to cure it. be able to. In this case, the curable composition of the present invention may be directly applied to the surface protection member and used, or the one applied on the plastic film may be used as the protective film. Alternatively, the curable composition of the present invention may be applied onto a plastic film to form a coating film, which may be used as an optical film such as an antireflection film, a diffusion film, and a prism sheet. Since the cured coating film of the curable composition of the present invention has high surface hardness and excellent flexibility and impact resistance, it is applied on various types of plastic films with a film thickness suitable for the intended use to provide a protective film. It can be used for various purposes and as a film-shaped molded product.

The plastic film is, for example, a plastic film made of polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, cycloolefin, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin, AS resin, norbornene resin, polyimide resin and the like. And plastic sheets.

Of the above plastic films, the triacetyl cellulose film is a film that is particularly preferably used for polarizing plates of liquid crystal displays, but since it is generally as thin as 40 to 100 μm, it has a surface even when a hard coat layer is installed. It is difficult to increase the hardness sufficiently, and it is easy to curl large. The coating film made of the curable composition of the present invention has the effects of high surface hardness, curl resistance, flexibility, transparency, and impact resistance even when a triacetyl cellulose film is used as a base material. Can be preferably used. When the triacetyl cellulose film is used as a base material, 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, screen printing method and the like.

Among the above plastic films, the polyester film includes, for example, polyethylene terephthalate, and the thickness thereof is generally about 20 to 300 μm. It is a film used for various purposes such as touch panel displays because it is inexpensive and easy to process, but it is very soft and it is difficult to sufficiently increase the surface hardness even when a hard coat layer is installed. When the polyethylene film is used as a base material, the coating amount when the curable composition of the present invention is applied is such that the film thickness after drying is in the range of 1 to 100 μm, preferably 1 to 20 μm, depending on the application. It is preferable to apply so as to be within the range. In general, a cured coating film having a thickness of more than 20 μm tends to be larger and more likely to curl than when the film thickness is thin, but the curable composition of the present invention also has a feature of excellent curling resistance, and thus has a characteristic of excellent curling resistance. Even when it is applied with a relatively high film thickness exceeding the above, curling is unlikely to occur, and it can be preferably 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, screen printing method and the like.

Among the above plastic films, the polymethylmethacrylate film is generally relatively thick and durable with a thickness of about 50 to 2,000 μm, and is therefore suitable for applications requiring particularly high surface hardness such as front plate applications for liquid crystal displays. It is a film used for. When the polymethylmethacrylate 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, depending on the intended use. It is preferable to apply the film so as to have 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, screen printing method and the like.

Further, among the above plastic films, cycloolefin polymer films are generally known to be vulnerable to lateral forces such as tearing and have poor fold resistance, but in recent years, from the viewpoint of transparency and heat resistance, they have been used. The area of use is expanding. The cured coating film obtained from the curable composition of the present invention can effectively enhance its flexibility and impact resistance even in such a fragile film. From the viewpoint of preferably 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, screen printing method and the like.

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. When curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED, or the like is used as a light source, and the amount of light, the arrangement of the light source, and the like are adjusted as necessary. When a high-pressure mercury lamp is used, it is preferable to cure one lamp having a light amount usually in the range of 80 to 160 W / cm at a transport speed of 5 to 50 m / min. On the other hand, when curing with an electron beam, it is preferable to cure with an electron beam accelerator having an acceleration voltage usually in the range of 10 to 300 kV at a transport speed of 5 to 50 m / min.

Further, 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 products such as mobile phones, electric appliances, bumpers of automobiles 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 a molded product is coated as a top coat using a printing device such as a curtain coater, a roll coater, or a gravure coater, and then irradiated with active energy rays to cure. 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 also has a functional film layer 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 in which they are bonded together via an adhesive layer.

Hereinafter, the present invention will be described in more detail with reference to specific production examples and examples, but the present invention is not limited to these examples. All parts and% in the example are based on mass unless otherwise specified.

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
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard; Polystyrene sample; 0.4 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

Production Example 1 Production of pentaerythritol diacrylate A flask equipped with a thermometer, a stirrer, and a condenser is charged with 136 parts by mass of pentaerythritol and 600 parts by mass of N, N-dimethylformamide, and paratoluenesulfonic acid is used as a catalyst. 7 parts by mass was added. The temperature was raised to 80 ° C. with stirring to dissolve pentaerythritol in N, N-dimethylformamide, and then parts by mass of cyclohexanone was added. While maintaining the reaction temperature at 80 ° C., the pressure inside the reaction system was reduced to 140 mmHg, and the reaction was continued while distilling off the generated water. When the formation of water could not be confirmed, the mixture was refluxed for another hour. The mixture was cooled to room temperature while continuing stirring, returned to normal pressure, and unreacted pentaerythritol was removed by vacuum filtration. After removing N, N-dimethylformamide from the obtained filtrate under reduced pressure, ethyl acetate was added, and the precipitated pentaerythritol was removed by filtration again. The obtained filtrate was washed with a saturated aqueous solution of sodium hydrogen carbonate, 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), 120 parts by mass of dichloromethane, and 46.5 parts by mass of triethylamine obtained above, and cooled to −5 ° C. 29 parts by mass of 3-chloropropionyl chloride was dissolved in 40 parts by mass of dichloromethane, and the mixture was added dropwise little by little while keeping the temperature in the reaction system at 0 ° C. or lower. After completion of the dropping, the temperature was gradually raised to room temperature, and the reaction was further carried out for 4 hours. After confirming the disappearance of the ketal compound (x1) as a raw material by gas chromatography, triethylamine hydrochloride was removed by vacuum filtration. The obtained filtrate was washed with saturated aqueous sodium hydrogen carbonate solution, further washed with saturated aqueous sodium chloride solution, and dehydrated with anhydrous magnesium sulfate. The reaction product after dehydration was concentrated to obtain 30 parts by mass of the (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% aqueous sulfuric acid solution was added dropwise little by little so that the temperature inside the reaction system did not exceed 10 ° C., and after the total amount was added, the reaction was carried out at room temperature for 16 hours. After confirming the 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 saturated aqueous sodium hydrogen carbonate solution until the pH reached 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 Urethane (meth) acrylate resin (1) Production of composition 208 parts by mass of a mixture of pentaerythritol triacrylate and tetraacrylate (“Aronix M-305” manufactured by Toa Synthetic Co., Ltd.) in a four-necked flask, Production Example 1 75.2 parts by mass of pentaerythritol diacrylate, 0.1 part by mass of dibutyltin dilaurate, and 0.1 part by mass of hydroquinone obtained in the above were added to prepare a uniform solution. The flask was heated until the internal temperature reached 50 ° C., and then 84 parts by mass of hexamethylene diisocyanate (“Duranate 50M-HDI” manufactured by Asahi Kasei Chemicals Co., Ltd.) was added in portions over about 1 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 were used. A mixture with acrylate was obtained. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (1) was 3,000, and the acryloyl group equivalent calculated from the raw materials to be charged was 130 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.

Example 2 Production of Urethane (Meta) Acrylate Resin (2) Composition 173.9 parts by mass of a mixture of pentaerythritol triacrylate and tetraacrylate in a four-necked flask (“Aronix M-305” manufactured by Toa Synthetic Co., Ltd.) 81.07 parts by mass of pentaerythritol diacrylate, 0.1 parts by mass of dibutyltin dilaurate, and 0.1 parts by mass of hydroquinone obtained in Example 1 were added to prepare a uniform solution. The flask was heated until the internal temperature reached 50 ° C., and then 84 parts by mass of hexamethylene diisocyanate (“Duranate 50M-HDI” manufactured by Asahi Kasei Chemicals Co., Ltd.) was added in portions over about 1 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 (2) and pentaerythritol tetra were used. A mixture with acrylate was obtained. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (2) was 4,000, and the acryloyl group equivalent calculated from the raw materials to be charged was 136 g / eq.
The hydroxyl value of the mixture of "Aronix M-305" and pentaerythritol diacrylate was 220 mgKOH / g.

Example 3 Production of Urethane (Meta) Acrylate Resin (3) 125.9 parts by mass of pentaerythritol diacrylate obtained in Production Example 1 in a four-necked flask, (hydroxyl value 450 mgKOH / g), 0.1 mass of dibutyltin dilaurate Parts and 0.1 part by mass of hydroquinone were added to prepare a uniform solution. The flask was heated until the internal temperature reached 50 ° C., and then 84 parts by mass of hexamethylene diisocyanate (“Duranate 50M-HDI” manufactured by Asahi Kasei Chemicals Co., Ltd.) was added in portions over about 1 hour. After reacting at 80 ° C. for 3 hours and confirming the disappearance of the isocyanate group on the infrared absorption spectrum, the non-volatile content was adjusted to 80% using butyl acetate to obtain a urethane (meth) acrylate resin (3). The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (3) was 15,000, and the acryloyl group equivalent calculated from the raw materials to be charged was 208 g / eq.

Comparative Production Example 1 Production of Urethane (Meta) Acrylate Resin (1') Composition A mixture of pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate in a four-necked flask (“Aronix M-306” manufactured by Toa Synthetic Co., Ltd. A hydroxyl value of 165 mgKOH / g) 350.63 parts by mass, 0.2 parts by mass of dibutyltin dilaurate, and 0.2 parts by mass of hydroquinone were added to prepare a uniform solution. The flask was heated until the internal temperature reached 50 ° C., and then 84 parts by mass of hexamethylene diisocyanate (“Duranate 50M-HDI” manufactured by Asahi Kasei Chemicals Co., Ltd.) was added in portions over about 1 hour. After reacting at 80 ° C. for 3 hours and confirming the disappearance of the isocyanate group on the infrared absorption spectrum, the non-volatile content was adjusted to 80% using butyl acetate, and urethane (meth) acrylate resin (1') and pentaerythritol were used. 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 raw materials to be charged was 122 g / eq.

Example 4
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 curable. The composition was obtained. This was applied on a PET film having a thickness of 125 μm with a bar coater, and dried at 80 ° C. for 2 minutes. Next, in an air atmosphere, ultraviolet rays were irradiated at 300 mJ / cm2 with an 80 W high-pressure mercury lamp to obtain a laminated film having a cured coating film having a film thickness of 5 μm on the PET film. Various evaluation tests were carried out on this laminated film by the following methods. The results are shown in Table 1.

Surface hardness test For the laminated film, the pencil hardness of the cured coating film surface of the curable composition was measured under a load condition of 500 g in accordance with JIS K5600-5-4. The hardness was measured 5 times for each hardness, and the hardness at which the measurement was not scratched 4 times or more was defined as the hardness of the cured coating film.

Scratch resistance test Steel wool ("Bonster # 0000" manufactured by Nippon Steel Wool Co., Ltd.) wraps a disk-shaped indenter with a diameter of 2.4 cm with 0.5 g, and applies a load of 500 g to the indenter to form a laminated film. A wear test was conducted in which the surface of the cured coating film was reciprocated 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) between them. The smaller the difference value, the higher the resistance to scratches.

Flexibility test A mandrel tester (“bending tester” manufactured by TP Giken Co., Ltd.) is used to wrap the laminated film around a test rod, and a test is performed to visually check whether cracks occur. The minimum diameter (mm) of was used as the evaluation result. The test rods used were those having a diameter of 2 mm to 6 mm in 1 mm increments. In Example 6, cracks did not occur even with a 2 mm test rod.

Curl resistance test A 5 cm square coating film was cut out from the laminated film to obtain a test piece, and the horizontal lift of the four corners of the test piece was measured and evaluated by the average value (mm). The smaller the value, the smaller the curl and the better the curl resistance.

Impact resistance test The test was conducted with reference to JIS K5600-5-3. Specifically, it is as follows.
[apparatus]
Weight: A steel ball for ball bearings (mass 300.0 ± 0.5 g, diameter 25.40 mm, grade 60) specified in JIS B 1501 "Steel balls for five bearings" hung with a thread at the tip.
Steel table: A steel table with a length of 300 mm, a width of 200 mm, and a thickness of 30 mm installed horizontally on a concrete floor.
[operation]
1. 1. The cured coating film surface of the laminated film was turned upward and fixed on a steel table.
2. 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 confirming that the runout and rotation had stopped, the weight was dropped onto the laminated film.
3. 3. After the laminated film after the drop test was allowed to stand indoors for 1 hour, damage to the coated surface was examined.
4. The test was continued with a distance of 50 mm from the surface of the laminated film to the lower end of the weight, and the evaluation was made at the maximum distance at which the cured coating film did not crack or peel.

Examples 5 and 6 and Comparative Example 1
A urethane (meth) acrylate resin (2) composition or the like was used instead of the urethane (meth) acrylate resin (1) composition, and the evaluation was carried out in the same manner as in Example 4. The results are shown in Table 1.

Claims (7)

A method for producing a urethane (meth) acrylate resin obtained by reacting a polyisocyanate compound (A) with a tetraol compound (meth) acrylate (B).
The polyisocyanate compound (A) has two or more isocyanate methyl groups in its molecular structure.
The (meth) acrylate (B) of the tetraol compound is a mixture containing a di (meth) acrylate form of the tetraol compound, a tri (meth) acrylate form, and a tetra (meth) acrylate form.
The hydroxyl value of the (meth) acrylate (B) of the tetraol compound is in the range of 190 to 480 mgKOH / g.
The di (meth) acrylate compound of the tetraol compound is a urethane (meth) containing pentaerythritol di (meth) acrylate obtained by using pentaerythritol and 3-chloropropionyl chloride as essential reaction raw materials. A method for producing an acrylate resin. The method for producing a urethane (meth) acrylate resin according to claim 1, wherein the weight average molecular weight (Mw) is in the range of 2,000 to 30,000. The polyisocyanate compound (A) having two or more isocyanate methyl groups in the molecular structure is a diisocyanate compound (A1) having two isocyanate methyl groups in the molecular structure, and a nulate modified product of the diisocyanate compound (A1). The first aspect of claim 1, wherein the compound is one or more selected from the group consisting of A2), an adduct modified product (A3) of the diisocyanate compound (A1), and a biuret modified product (A4) of the diisocyanate compound (A1). A method for producing a urethane (meth) acrylate resin. A method for producing a curable composition containing the urethane (meth) acrylate resin according to any one of claims 1 to 3 and a photopolymerization initiator. A method for producing a cured product , which is obtained by curing the curable composition according to claim 4. A method for producing a laminated film having a layer made of a cured product according to claim 5 and another plastic film layer.
















































A method for producing a urethane (meth) acrylate resin obtained by reacting a polyisocyanate compound (A) with a tetraol compound (meth) acrylate (B).
The polyisocyanate compound (A) has two or more isocyanate methyl groups in its molecular structure.
The (meth) acrylate (B) of the tetraol compound is a mixture containing a di (meth) acrylate form of the tetraol compound, a tri (meth) acrylate form, and a tetra (meth) acrylate form.
All SANYO ranging hydroxyl value of 190~480mgKOH / g of said tetraol compound (meth) acrylate (B),
Wherein the di (meth) acrylate of tetraol compound, which pentaerythritol, characterized in der Rukoto those containing 3-chloro propionyl chloride and pentaerythritol di (meth) acrylate obtained as an essential reactant Item 2. The method for producing a urethane (meth) acrylate resin according to Item 1 .