KR101558338B1 - Energy ray-curable resin composition, and cured product and optical lens sheet thereof - Google Patents

Abstract

(식 중, R₁은 동일 또는 각각 다르며, 수소 원자 또는 탄소수 1 내지 4의 탄화 수소기이고, R₂는 동일 또는 각각 다르며, 탄소수 1 내지 4의 탄화 수소기이고, m 및 n은 평균 반복수로서, m＋n＝0.4∼12를 각각 나타냄).[PROBLEMS] To provide a resin composition having excellent releasability, mold reproducibility, adhesion to a substrate, high refractive index, high glass transition point, and low viscosity.
An energy ray curable resin composition for an optical lens sheet comprising a monoacrylate monomer (A) having a phenyl ether group, a compound (B) represented by the formula (1) and a photopolymerization initiator (C)
(Formula 1)

(Wherein R ₁ is the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms and R ₂ is the same or different and is a hydrocarbon group having 1 to 4 carbon atoms, And m + n = 0.4 to 12, respectively).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an energy ray-curable resin composition, a cured product thereof, and an optical lens sheet (ENERGY RAY-CURABLE RESIN COMPOSITION, AND CURED PRODUCT AND OPTICAL LENS SHEET THEREOF)

The present invention relates to an energy ray curable resin composition, a cured product thereof, and an optical lens sheet. More particularly, the present invention relates to a resin composition and a cured product particularly suitable for lenses such as a Fresnel lens, a lenticular lens, a prism lens, and a microlens.

Conventionally, the above-mentioned lenses have been molded by a method such as a pressing method, a casting method (casting forming method) or the like. Since the press method is manufactured by a plurality of cycles such as heating, pressurizing and cooling, the productivity is poor. The casting method has a problem in that it takes a long time to produce, and a large number of molds are required because the monomer is introduced (flowed into) and polymerized in the mold. In order to solve these problems, various proposals have been made for using an ultraviolet curable resin composition (Patent Document 1, Patent Document 2).

A method of producing an optical lens sheet for use in a transmissive screen or the like has been successful to some extent by using an ultraviolet curable resin composition. However, these conventional cured products of the resin composition have problems of poor adhesion to the substrate and poor releasability from the mold. If the adhesion is poor, the kind of usable substrate is limited, and it is difficult to obtain the intended optical properties. If the releasability is poor, the resin remains in the mold during mold release, and the mold can not be used. In addition, the resin composition which gives a cured product having good adhesiveness tends to have poor releasability due to improved adhesion to a mold, and on the other hand, a resin composition with good releasability tends to have poor adhesion. Therefore, it is desired to provide a resin composition capable of satisfying both the adhesion with the substrate and the releasability from the mold.

BACKGROUND ART [0002] A composition for a lens used in an optical lens sheet or the like is required to have a resin composition having a high refractive index in response to recent refinement of images and thinning of a final product, It is required to have a low viscosity in order to perform thin processing or continuous processing in a roll-like sheet or film. It is also necessary that the microstructure is not damaged well when the lens sheet is wound. In addition, even when it is actually used as a product, it is fatal that the lens shape changes due to heat caused by a light source or the like. In this case, it is required that the glass transition temperature Tg is high.

Among them, Patent Document 3 proposes a resin composition having both of adhesion and releasability. However, the viscosity for processing into a finer shape is not sufficient. In Patent Document 4, the (meth) acrylate of binaphthol Has been disclosed as a liquid crystal material. However, its use is limited to a liquid crystal material, and its optical characteristics are not specified.

As a result, it is difficult to combine a high refractive index, high Tg point, releasability, adhesion, and low viscosity as a composition for a lens used in an optical lens sheet or the like having a fine refractive index and a fine structure.

Japanese Patent Application Laid-Open No. 63-167301 Japanese Patent Application Laid-Open No. 63-199302 Japanese Patent No. 3209554 U.S. Patent Application Publication No. 2008/0090026

An object of the present invention is to provide a resin composition having a low viscosity suitable for the production of a lens sheet such as a Fresnel lens, a lenticular lens, a prism lens and a microlens, a cured product excellent in mold releasability, form reproducibility and adhesion, will be.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found out that an ultraviolet-curable resin composition having a specific composition and a cured product thereof solve the above problems, and completed the present invention.

That is, the present invention provides an energy ray curable resin composition comprising (1) a monoacrylate monomer (A) having a phenyl ether group, a compound (B) represented by the formula (1) and a photopolymerization initiator (C)

(Wherein R ₁ is the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms and R ₂ is the same or different and is a hydrocarbon group having 1 to 4 carbon atoms, M + n = 0.4 to 12, respectively)

(Meth) acrylate, p-phenylphenol (poly) ethoxy (meth) acrylate, o-phenylphenol epoxy (meth) acrylate, (Meth) acrylate or p-phenylphenol epoxy (meth) acrylate.

(1) or (2), further comprising (3) a monoacrylate monomer (A) having a phenyl ether group and a (meth) acrylate compound (D) other than the compound (B) , An energy radiation curable resin composition according to &

(4) The energy ray curable resin composition according to any one of (1) to (3), wherein the (meth) acrylate compound (D) is a compound having a structure containing a bisphenol A skeleton.

(5) The energy ray-curable resin composition according to any one of (1) to (4), wherein the viscosity at 25 ° C measured by an E-type viscometer is not more than 3000 mPa · s,

(6) A cured product obtained by curing the energy ray-curable resin composition according to any one of (1) to (5) above and having a refractive index at 25 ° C of 1.55 or more,

(7) An optical lens sheet using the cured product of (6)

.

The resin composition of the present invention has a low viscosity, and its cured product is excellent in releasability, mold reproducibility, adhesion with a substrate, and high refractive index. Therefore, it is particularly suitable for a lens sheet such as a Fresnel lens, a lenticular lens, a prism lens, and a microlens.

(Mode for carrying out the invention)

The resin composition of the present invention comprises a monoacrylate monomer (A) having a phenyl ether group, a compound (B) represented by the formula (1) and a photopolymerization initiator (C).

The monoacrylate monomer (A) having a phenyl ether group used in the present invention will be described.

Examples of the monoacrylate monomer (A) having a phenyl ether group include phenoxyethyl (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, tribromophenyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, phenylphenol epoxy Methacrylate, and the like. Among them, phenylphenol (poly) ethoxy (meth) acrylate and phenylphenol epoxy (meth) acrylate are preferable in the present invention. Among them, o-phenylphenol (poly) ethoxy p-phenylphenol (poly) ethoxy (meth) acrylate, o-phenylphenol epoxy (meth) acrylate and p-phenylphenol epoxy (meth) acrylate are preferable.

As the phenylphenol (poly) ethoxy (meth) acrylate, a compound in which the number of repeating units of the ethoxy structure moiety is an integer of 1 to 3 on the average is preferable. By reacting the reaction product of the raw material phenylphenol and ethylene oxide with (meth) acrylic acid Can be obtained. As the phenylphenol, commercially available o-tolylene-o-phenylphenol and para-phenylphenol can be used (for example, O-PP and P-PP, all available from Sanko Chemical Co., has exist). The reaction product of phenylphenol and ethylene oxide can be obtained by a known method, and commercially available products can also be used. The reaction product of phenylphenol and ethylene oxide is reacted with an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid in the presence of a polymerization inhibitor such as hydroquinone or phenothiazine, preferably in solvents (for example, toluene, cyclohexane, (Meth) acrylic acid at a temperature of preferably 70 to 150 DEG C in the presence of a solvent such as hexane, n-hexane, n-heptane, etc. to obtain a phenol (poly) ethoxy (meth) acrylate. The use ratio of (meth) acrylic acid is 1 to 5 mol, preferably 1.05 to 2 mol, per 1 mol of the reaction product of phenylphenol and ethylene oxide. The esterification catalyst is used in an amount of 0.1 to 15 mol%, preferably 1 to 6 mol%, based on the (meth) acrylic acid used.

The phenylphenol epoxy (meth) acrylate is obtained by reacting the phenylphenol with an epihalohydrin in the presence of an alkali metal hydroxide, and reacting the reaction product, epoxy resin, with (meth) acrylic acid.

As the epihalohydrin, epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin, epibromohydrin, and the like can be used. Of these epihalohydrin, industrially available epi Chlorohydrin is preferred.

The amount of epihalohydrin to be used is usually 2 to 20 mol, preferably 3 to 15 mol, per 1 mol of phenylphenol.

Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like, and a solid material may be used, or an aqueous solution thereof may be used. When an aqueous solution is used, an aqueous solution of the corresponding alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or under atmospheric pressure, and further water is removed by separating the water, Or a method of continuously returning halohydrin into the reaction system. The amount of the alkali metal hydroxide to be used is generally 0.1 to 10.0 moles, preferably 0.3 to 5.0 moles, more preferably 0.8 to 3.0 moles, per 1 mole of the phenylphenol.

To promote the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride as a catalyst. When a quaternary ammonium salt is used, the amount of the quaternary ammonium salt to be used is usually 0.1 to 20 g, preferably 0.2 to 15 g, per 1 mol of the phenylphenol.

At this time, it is preferable to carry out the reaction by adding an aprotic polar solvent such as aliphatic alcohols such as methanol, ethanol and isopropyl alcohol, dimethylsulfone, dimethylsulfoxide, tetrahydrofuran and dioxane.

When alcohols are used, the amount thereof is usually 1 to 50 mass%, preferably 2 to 30 mass%, based on the amount of epihalohydrin used. When an aprotic polar solvent is used, it is usually 3 to 100 mass%, preferably 5 to 80 mass%, based on the amount of epihalohydrin used.

The reaction temperature is usually from 30 to 100 캜, preferably from 35 to 90 캜. The reaction time is usually 0.2 to 10 hours, preferably 0.5 to 8 hours. Epihalohydrin and the like are removed under heating and decompression without rinsing the reaction solution of the reaction of phenylphenol and epihalohydrin in the presence of an alkali metal hydroxide or without washing with water. Further, in order to obtain an epoxy resin having little hydrolyzable halogen, the obtained epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction , And the closure can be ensured. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.5 mol, preferably 0.05 to 0.3 mol, per 1 mol of the phenylphenol used. The reaction temperature is usually from 50 to 120 캜, and the reaction time is usually from 0.5 to 2 hours.

After the completion of the reaction, the resulting salt is removed by filtration, washing with water, and the solvent or the like is distilled off under heating and decompression to obtain the desired epoxy resin. By the method represented by this prescription, an epoxy resin which can be used without special purification is obtained.

The phenylphenol epoxy (meth) acrylate is obtained by reacting the above-mentioned epoxy resin with (meth) acrylic acid. (Meth) acrylic acid is preferably used in an amount of 0.8 to 1.1 equivalents, more preferably 0.9 to 1.0 equivalents, per one epoxy equivalent of the epoxy resin.

The reaction may be carried out without using a solvent, but if necessary, a solvent having no alcoholic hydroxyl group such as ketones such as acetone, ethyl methyl ketone, and cyclohexanone, an aromatic ketone such as benzene, toluene, xylene, Glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether; ethers such as ethyl acetate, acetic acid Esters such as butyl, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether monoacetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as? -butyrolactone, petroleum ether, petroleum naphtha, Petroleum solvents such as hydrogenated petroleum naphtha and solvent naphtha and various monomers including a (meth) acrylate compound (D), for example, acryloylmorpholine, an ethylene oxide adduct of 2-phenylphenol (Meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane tri (methacrylate) (Meth) acrylates of? -Caprolactone adducts of hydroxypivalic acid neopentylglycol (eg, trimethylolpropane polyethoxy tri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, KAYARAD HX-220 and HX-620 manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, dipentaerythritol and? -Caprolactone Poly (meth) can be carried out from acrylate, dipentaerythritol poly (meth) single or mixed organic solvent such as an acrylate of a reaction product.

In the reaction, it is preferable to use a catalyst to accelerate the reaction. When the catalyst is used, the amount of the catalyst to be used is 0.1 to 10 mass% with respect to the reactant. The reaction temperature at that time is 60 to 150 占 폚, and the reaction time is preferably 5 to 60 hours. Examples of the catalyst to be used include catalysts such as triethylamine, benzyldiethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Chromium octanoate, zirconium octanoate, and the like.

Further, a thermal polymerization inhibitor may be used, and examples of the heat polymerization inhibitor include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, 2,6-di-tert-butyl- Diphenyl picrylhydrazine, diphenylamine and the like. When a thermal polymerization inhibitor is used, it is preferable to use about 0.1 to 10 mass% of the reaction product. The reaction is terminated when the acid value of the sample is 5 mg · KOH / g or less, and preferably 3 mg · KOH / g or less while appropriately sampling.

The compound (B) represented by the formula (1) used in the resin composition of the present invention will be described below.

The compound (B) used in the resin composition of the present invention can be obtained by reacting 1,1'-non-naphthol with an alkylene oxide or an alkylene carbonate, followed by dehydration condensation reaction in the presence of (meth) acrylic acid and an acid catalyst have. In the present invention, as the 1,1'-non-naphthol, (RS) -1,1'-non-2-naphthol is preferably used and is available from S & R CHIRAL CHEMICAL. In the reaction of 1,1'-non-naphthol with an alkylene oxide, 0.5 to 24 moles of alkylene oxide is reacted with 1 mole of 1,1'-non-naphthol. In the reaction of 1,1'-non-naphthol with an alkylene carbonate, 2 to 5 moles of alkylene carbonate is reacted with 1 mole of 1,1'-non-naphthol. The alkylene oxide or alkylene carbonate may be used singly or in combination of two or more.

Specific examples of the alkylene oxide include alkylene oxides having 1 to 4 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide. Specific examples of the alkylene carbonate include alkylene carbonates having 1 to 4 carbon atoms such as ethylene carbonate (ethylene carbonate), propylene carbonate (propylene carbonate), and butylene carbonate (butylene carbonate).

The reaction of 1,1'-non-naphthol with an alkylene oxide or an alkylene carbonate is carried out under an alkali catalyst such as sodium hydroxide or potassium hydroxide for a reaction time of 1 to 48 hours and a reaction temperature of 90 to 200 ° C. In the reaction of 1,1'-non-naphthol with the alkylene oxide, 0.01 to 5% by mass of the alkali catalyst may be used relative to 100% by mass of the reaction mixture. In the reaction of 1,1'-non-naphthol with an alkylene carbonate, 0.01 to 5 moles of an alkali catalyst is used relative to 1 mole of 1,1'-non-naphthol.

In the dehydration condensation reaction of (meth) acrylic acid with a reaction product of 1,1'-non-naphthol and an alkylene oxide or an alkylene carbonate, the (meth) acrylic acid is used in an amount of from 0.1 to 10 mol, 10 moles. As the reaction solvent in the dehydration condensation reaction, an azeotropic solvent capable of distilling off water generated in the reaction can be used. The azeotropic solvent used herein has a boiling point of 60 to 130 占 폚 and can be easily separated from water. Especially, azeotropic solvents such as benzene, toluene, n-hexane, n-heptane, cyclohexane, Or a mixture of two or more of them is preferably used. The amount thereof is arbitrary, but is preferably from 10 to 70 mass% with respect to the reaction mixture.

The reaction time in the dehydration condensation reaction may be in the range of 1 to 24 hours and the reaction temperature may be in the range of 60 to 150 占 폚, but it is preferably performed at 75 to 120 占 폚 in view of shortening of the reaction time and prevention of polymerization.

The (meth) acrylic acid which is a commercially available product used as a raw material has already been added with a polymerization inhibitor such as p-methoxyphenol, but a polymerization inhibitor may be added again at the time of the reaction. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxytiophenol, p-benzoquinone, 2,5-dihydroxy- -Benzoquinone, phenothiazine, and the like. The amount thereof is 0.01 to 1 mass% with respect to the reaction mixture.

The acid catalyst to be used in the dehydration condensation reaction may be selected from known ones such as sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and the like, and the amount thereof is preferably 0.01 to 10 mol% based on 1 mol of (meth) And preferably 1 to 5 mol%.

As the compound (B) used in the resin composition of the present invention, 0.5 to 4 moles of alkylene oxide is reacted with 1 mole of 1,1'-non-naphthol in consideration of the refractive index and compatibility with other components Or a compound obtained by reacting 2 to 4 moles of an alkylene carbonate with respect to 1 mole of 1,1'-non-naphthol. The alkylene oxide may be any alkylene oxide having 1 to 4 methylene groups, but ethylene oxide or propylene oxide is preferred. As the alkylene carbonate, any of alkylene carbonate having 1 to 4 methylene groups may be used, and ethylene carbonate (ethylene carbonate) or propylene carbonate (propylene carbonate) is preferable.

In addition to the monoacrylate monomer (A) having the phenyl ether group and the compound (B) represented by the formula (1), the viscosity and adhesion of the resin composition of the present invention obtained, the glass transition temperature (Tg) , The (meth) acrylate compound (D) other than the component (A) and the component (B) may be used singly or in combination of two or more. Examples of the (meth) acrylate compound (D) include (meth) acrylate monomers and (meth) acrylate oligomers.

Examples of the (meth) acrylate monomer include monofunctional (meth) acrylate monomers, bifunctional (meth) acrylate monomers, and trifunctional or higher polyfunctional (meth) acrylate monomers.

Examples of monofunctional (meth) acrylate monomers include acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol (Meth) acrylates such as mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, tribromophenyloxyethyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.

Examples of the bifunctional (meth) acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- (Meth) acrylate, dipentaerythritol hexaacrylate, decane dimethanol di (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di Di (meth) acrylate of polyethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epsilon -caprolactone adduct of hydroxypivalic acid neopentyl glycol (for example, KAYARAD HX- 220, HX-620, etc.).

Examples of the trifunctional or higher polyfunctional (meth) acrylate monomer include tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane polyethoxy tri Tetra (meth) acrylate, and the like.

Examples of the (meth) acrylate oligomer include urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer and polyester (meth) acrylate oligomer.

Examples of the urethane (meth) acrylate oligomer include diol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl Glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, Butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A Or a reaction product of these diol compounds with a dibasic acid or anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) Ester diols, and organic polyisocyanates (for example, tetra Chain saturated hydrocarbon isocyanates such as methylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, Cyclic saturated hydrocarbon isocyanates such as methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene isocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1 , 3-xylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate, 1,5-naphthalene di An aromatic polyisocyanate such as isocyanate) Come on hydroxyl group-containing (meth) acrylate reaction product was added. Further, compounds obtained by reacting the above organic polyisocyanate with a hydroxyl group-containing (meth) acrylate, and the like can be given.

Examples of the epoxy (meth) acrylate oligomer include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, terminal glycidyl ether of propylene oxide adduct of bisphenol A, fluorene epoxy resin and the like And (meth) acrylic acid.

Examples of the polyester (meth) acrylate oligomer include a reaction product of a polyester diol, which is a reaction product of the diol compound and the dibasic acid or anhydride thereof, and (meth) acrylic acid, and the like.

Among them, as the (meth) acrylate compound (D) which can be used in the resin composition of the present invention, a compound having a structure containing a bisphenol A skeleton is preferable in view of the refractive index. For example, bisphenol A polyethoxy di (Meta) acrylate oligomer having a skeleton of bisphenol A (bisphenol A polyethoxy diol, bisphenol A poly (meth) acrylate, bisphenol A poly A compound obtained by reacting a diol compound such as propoxydiol or a reaction product of these diol compounds with a dibasic acid or anhydride thereof, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate), a skeleton of bisphenol A (Bisphenol A type epoxy resin, terminal end of a propylene oxide adduct of bisphenol A), an epoxy (meth) acrylate oligomer The receiver ether such as reaction products of the epoxy resins with (meth) acrylic acid, etc.) is suitable.

(Meth) acrylate compound (D) is preferably a monofunctional or bifunctional (meth) acrylate monomer in view of the adhesion or viscosity of the cured product, and among these, acryloylmorpholine, tetrahydrofurfuryl Acrylate, isobornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (Meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.

In consideration of the glass transition temperature (Tg) of the cured product, examples of the (meth) acrylate compound (D) include tris (2-acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate monomers having three or more functional groups such as (meth) acrylate, dipentaerythritol penta (meth) acrylate and trimethylolpropane tri (meth) acrylate.

Examples of the photopolymerization initiator (C) contained in the resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, oligo [2- -2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]; Anthraquinones such as 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, and the like Pin oxide and the like. Preferred are acetophenones, more preferably 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone. In the resin composition of the present invention, the photopolymerization initiator (C) may be used singly or in combination of two or more kinds, and examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis , 6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, and the like are preferably used.

The use ratio of each component of the resin composition of the present invention can be determined in consideration of a desired refractive index, glass transition temperature, viscosity, adhesion, etc. However, the amount of component (A) + component (B) + component , The content of the component (A) + the component (B) is 50 to 100 parts by mass, particularly preferably 70 to 100 parts by mass, and therefore the content of the component (D) is less than 50 parts by mass, Is less than 30 parts by mass. When the total amount of the component (A) and the component (B) is 100 parts by mass, the content of the component (A) is 10 to 95 parts by mass, particularly preferably 20 to 90 parts by mass. The component (C) is preferably used in an amount of 0.1 to 10 parts by mass, particularly preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the total amount of the component (A) + the component (B) + the component (D).

The energy ray curable resin composition of the present invention may further contain additives such as release agents, defoaming agents, leveling agents, light stabilizers, antioxidants, polymerization inhibitors, antistatic agents, ultraviolet absorbers and the like in order to improve handling convenience, And may be contained in combination. If necessary, polymers such as acrylic polymers, polyester elastomers, urethane polymers and nitrile rubbers, inorganic or organic light-diffusing fillers, and the like may also be added. Although a solvent may be added, it is preferable not to add a solvent.

The resin composition of the present invention can be prepared by mixing and dissolving each component according to a conventional method. For example, it can be obtained by adding each component to a round bottom flask equipped with a stirrer and a thermometer, and stirring the mixture at 40 to 80 DEG C for 0.5 to 6 hours.

The viscosity of the resin composition of the present invention is a viscosity suitable for producing an optical lens sheet, and the viscosity of the resin composition measured using an E-type viscometer (TV-200 manufactured by Toki Sangyo K.K.) is not more than 3000 mPa · s Compositions are preferred.

The present invention also includes a cured product obtained by curing the resin composition of the present invention by irradiation with an energy ray such as ultraviolet ray according to a conventional method. The cured product is obtained by applying the resin composition of the present invention onto a stamper having a shape such as a Fresnel lens, a lenticular lens, a prism lens or the like to form a layer of the resin composition, (For example, a substrate or film made of a polymethacrylic resin, a polycarbonate resin, a polystyrene resin, a polyester resin, or a blend of these polymers) is adhered, and then a high pressure mercury lamp Or the like to cure the resin composition, and then peeling the cured product from the stamper. It is also possible to carry out these processes by continuous processing.

In this manner, an optical lens sheet having an optical lens portion such as a Fresnel lens, a lenticular lens, a prism lens, and a microlens having a refractive index (25 ° C) of 1.55 or more and excellent in releasability, mold reproducibility, These are also included in the present invention. The refractive index can be measured by Abbe's refractometer (DR-M2 manufactured by Atago Co., Ltd.).

The resin composition of the present invention is useful for an optical lens sheet as described above. Examples of applications other than the optical lens sheet include various coating agents and adhesives.

(Example)

Next, the present invention will be described in more detail with reference to Examples. The present invention is not limited in any way by the following examples. In the following, all units denoted by numbers are on a mass basis.

Synthesis of Compound (B)

Synthesis Example 1

286.3 g (1.0 mol) of (RS) -1,1'-bi-2-naphthol, 264.2 g (3.0 mol) of ethylene carbonate and 41.5 g of potassium carbonate in a flask equipped with a stirrer, (0.3 mol) and 2000 ml of toluene, and the mixture was reacted at 110 DEG C for 12 hours.

After the reaction, the obtained reaction solution was washed with water, washed with 1% NaOH aqueous solution, and then washed with water until the wash water became neutral. After washing with water, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 300.0 g of a reaction product of 2 mol of (RS) -1,1'-non-2-naphthol ethylene oxide.

Then, 187.2 g (0.5 mol) of the ethylene oxide 2 mol reaction product of (RS) -1,1'-non-2-naphthol, 86.5 g (2.4 mmol) of acrylic acid in a flask equipped with a stirrer, a reflux tube, a thermometer and a water separator 0.95 g of paratoluenesulfonic acid, 0.87 g of hydroquinone, 917.4 g of toluene and 2 g of cyclohexane 393. The resulting reaction mixture was reacted while removing the water produced at a reaction temperature of 95 to 105 ° C by azeotropic distillation with a solvent. After the reaction, the reaction solution was neutralized with a 25% NaOH aqueous solution and then washed three times with 200 g of 15% by mass of saline solution. The solvent was distilled off under reduced pressure to obtain 337.8 g of a product of the following formula 2 as a light yellow solid.

The physical properties of the compound (B) are shown below.

Liquid refractive index (D line, 25 캜) 1.62

_{^{1 H-NMR (CDCl 3,}} 300MHz), ppm:

4.00-4.30 ppm = 8H, 5.60-5.90 ppm = 4H, 6.05-6.15 ppm = 2H, 7.05-7.50 ppm = 8H, 7.80-8.00 ppm = 4H

Synthesis of Compound (D)

Synthesis Example 2

139.3 parts of 2,4-tolylene diisocyanate, 0.05 parts of di-n-butyl tin dilaurate and 0.16 parts of methoquinone were placed in a drying vessel, and the mixture was heated to 40 ° C and stirred. 185.6 parts of 2-hydroxyethyl acrylate was added dropwise over 1 hour while confirming the exotherm, and the mixture was reacted at 80 DEG C for 1 to 2 hours. The isocyanate value after the reaction was 0.1 or less, indicating that the reaction was almost finished quantitatively.

The resin composition and the cured product of the present invention were obtained from the compositions shown in the following examples (numerical values indicate parts by mass). The evaluation method and evaluation criteria for the resin composition and the cured film were as follows.

(1) Viscosity: Measured at 25 占 폚 using an E-type viscometer (TV-200; manufactured by Toki-San Kogyo Co., Ltd.).

(2) Dissimilarity: It represents the degree of difficulty when releasing the cured resin from the mold.

○ ... Good release from mold

△ · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

× · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

(3) Mold reproducibility: The surface shape of the cured ultraviolet-curable resin layer and the surface shape of the mold were observed.

○ · · · Reproducibility is good

× · · · Reproducibility is poor

(4) Adhesiveness: A resin composition was applied on a substrate to a thickness of about 50 mu m, and then irradiated with 1000 mJ / cm < 2 > with a high-pressure mercury lamp (80 W / cm, ozone) to prepare a cured test piece. JIS K5600- The adhesion was evaluated according to 5-6.

The evaluation results were 0 to 2 for o, and 3 to 5 for x.

(5) Refractive index (25 占 폚): The refractive index (25 占 폚) of the cured ultraviolet curable resin layer was measured with an Abbe's refractive index meter (DR-M2: manufactured by Atago Corporation).

(6) Glass transition temperature (Tg): The Tg point of the cured ultraviolet curable resin layer was measured in a tensile mode at a frequency of 1 Hz in a viscoelasticity measuring system (DMS-6000 manufactured by Seiko Denshi Kogyo Co., Ltd.).

Example 1

31 parts of o-phenylphenol monoethoxyacrylate as component (A), 20 parts of the compound obtained in Synthesis Example 1 as component (B), 3 parts of 1-hydroxy-cyclohexyl phenyl ketone as component (C) - (2,4,6-trimethylbenzoyl) phosphine oxide, 20 parts of KAYARAD R-551 (bisphenol A polyethoxy diacrylate, manufactured by Nippon Kayaku Co., Ltd.) as the component (D) (Manufactured by Nippon Kayaku Kabushiki Kaisha; bisphenol A epoxy acrylate), 18 parts of tris (2-acryloyloxyethyl) isocyanurate and 7 parts of acryloylmorpholine were heated to 60 ° C and mixed, To obtain the resin composition of the present invention. The viscosity of this resin composition was 904 mPa · s. The refractive index (25 占 폚) of the ultraviolet-curable resin layer having a thickness of 200 占 퐉 obtained by irradiating the resin composition with a high pressure mercury lamp (80 W / cm, ozone) at 600 mJ / cm2 was 1.587, and the glass transition temperature ) Was 94 ° C.

Further, this resin composition was coated on the prism lens mold so that the film thickness was 50 mu m, and an easy-bonding PET film (Cosmo Shine A4300, 100 mu m thick, Toyobo Co., Ltd.) Further, a prism lens sheet of the present invention was obtained by irradiating ultraviolet rays having a dose of 1000 mJ / cm < 2 >

Evaluation results

Dissimilarity:?, Pattern reproducibility:?, And adhesion:?.

Example 2

In Example 1, 52 parts of o-phenylphenol monoethoxyacrylate as component (A), 3 parts of 2-hydroxy-2-methyl-1-phenylpropane-1-one as component (C) D), 10 parts of the compound obtained in Synthesis Example 2, 13 parts of acryloylmorpholine, and 5 parts of tetrahydrofurfuryl acrylate. The viscosity of this resin composition was 195 mPa · s. The resin layer obtained in the same manner as in Example 1 had a refractive index (25 占 폚) of 1.597 and a glass transition temperature (Tg) of 69 占 폚.

Using the obtained resin composition, a prism lens sheet of the present invention was obtained in the same manner as in Example 1.

Evaluation results

Dissimilarity:?, Pattern reproducibility:?, And adhesion:?.

Comparative Example 1

70 parts of Aronix M-315 (tris (2-acryloyloxyethyl) isocyanurate) in accordance with Example 1 of Patent Document 1 (Japanese Unexamined Patent Publication No. 63-167301), 10 parts of tetrahydrofurfuryl Acrylate as a photopolymerization initiator and 3 parts of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one as a photopolymerization initiator were heated to 60 占 폚 and mixed to obtain a comparative resin composition. The viscosity of this resin composition was 134 mPa · s. The refractive index (25 DEG C) of the resin layer obtained in the same manner as in Example 1 was 1.52.

From these results, it can be seen that the composition of Comparative Example 1 has a lower refractive index than that of the composition of the present invention and is unsuitable for the production of the lenses of the present invention.

Comparative Example 2

According to Example 1 of Patent Document 3 (Japanese Patent No. 3209554), urethane acrylate (neopentyl glycol and adipic acid polyester diol, ethylene glycol, tolylene diisocyanate, and 2 -Hydroxyethyl acrylate) and the compound of Synthesis Example 3 (o-phenylphenol diethoxyacrylate) were synthesized, and 30 parts of the above-mentioned urethane acrylate, the above-mentioned o-phenylphenol diethoxyacrylate , 45 parts of KAYARAD R-551, 10 parts of tribromophenyl acrylate, and 3 parts of Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) were heated to 60 DEG C and mixed to obtain a comparative resin composition ≪ / RTI > The viscosity of this resin composition was 4420 mPa · s. The refractive index (25 DEG C) of the resin layer obtained in the same manner as in Example 1 was 1.574.

From this result, the composition of Comparative Example 2 is higher in viscosity than the composition of the present invention, and is not suitable for fine processing or continuous processing of a roll-shaped sheet or film.

As is clear from the evaluation results of Examples 1 and 2 and Comparative Examples 1 and 2, the resin composition of the present invention having a specific composition has a low viscosity, is excellent in releasability, moldability and adhesion to a substrate, The glass transition temperature (Tg) was high at the refractive index. Therefore, it is suitable for an optical lens sheet having a fine structure, for example, a Fresnel lens, a lenticular lens, a prism lens, a microlens, and the like. Particularly, it is suitable for production involving applications requiring fine processing or processes requiring continuous processing.

<Industrial applicability>

The ultraviolet-curable resin composition and the cured product thereof of the present invention are particularly suitable for optical lens sheets such as a Fresnel lens, a lenticular lens, a prism lens and a microlens.

Claims (7)

An energy ray curable resin composition comprising a monoacrylate monomer (A) having a phenyl ether group, a compound (B) represented by the formula (1) and a photopolymerization initiator (C)
(Formula 1)

(Wherein R ₁ is the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms and R ₂ is the same or different and is a hydrocarbon group having 1 to 4 carbon atoms, And m + n = 0.4 to 12, respectively). The method according to claim 1,
(Meth) acrylate, p-phenylphenol (poly) ethoxy (meth) acrylate, o-phenylphenol epoxy (meth) acrylate, Acrylate, or p-phenylphenol epoxy (meth) acrylate. The method according to claim 1,
Further, an energy ray curable resin composition comprising a monoacrylate monomer (A) having a phenyl ether group and a (meth) acrylate compound (D) other than the compound (B) The method of claim 3,
Wherein the (meth) acrylate compound (D) is a compound having a structure containing a bisphenol A skeleton. 5. The method according to any one of claims 1 to 4,
And a viscosity at 25 占 폚 measured by an E-type viscometer is 3000 mPa 占 퐏 or less. A cured product obtained by curing the energy ray-curable resin composition according to any one of claims 1 to 4 and having a refractive index at 25 占 폚 of 1.55 or more. An optical lens sheet using the cured product according to claim 6.