KR101635801B1 - (meth)acrylate compound, resin composition containing the same, cured product of the resin composition and energy ray-curable resin composition for optical lens sheet and cured product thereof - Google Patents

Abstract

The present invention relates to a photosensitive resin which is excellent in transparency and which has a high refractive index and high adhesiveness as a resin alone, and which provides a cured product having sufficient hardness, and which is excellent in releasability, form reproducibility, adhesion to a substrate, high refractive index, high glass transition point, A resin composition for an excellent optical lens sheet is provided. (1)

(B) with an aromatic polyisocyanate compound (c) in the presence of an epoxy resin (a) obtained by reacting a compound represented by the general formula (1) with epihalohydrin An energy ray curable resin composition for an optical lens sheet, which comprises a urethane compound (A), an urethane compound (A) and a photopolymerization initiator (B).

Transparency, refractive index, nonadhesive property, photosensitive resin, glass transition point, urethane compound

Description

(METH) ACRYLATE COMPOUND, RESIN COMPOSITION AND SURFACE COMPOSITION AND SURFACE COMPOSITION AND COMPOSITION AND COMPOSITION AND COMPOSITION AND COMPOSITION AND COMPOSITION AND COMPOSITION AND COMPOSITION AND SURFACE ENERGY RAY-CURABLE RESIN COMPOSITION FOR OPTICAL LENS SHEET AND CURED PRODUCT THEREOF}

The present invention relates to an unsaturated group-containing compound having a specific structure having a high refractive index and excellent transparency alone, a resin composition containing the unsaturated group-containing compound, and a cured product thereof. Examples thereof include a film forming material, a solder mask, a plating resistor, an adhesive, a lens, a display, an optical fiber, an optical waveguide, a hologram, and a coating agent when manufacturing a printed circuit (wiring circuit) substrate.

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

In recent years, development of a photosensitive material having a high heat resistance and a high refractive index, which is cured with an active energy ray, has been developed for various uses (Patent Documents 1 to 3). In these applications, in addition to high heat resistance and high refractive index, adhesion with a substrate, hardness of a cured product, solubility in alkali, and the like are required, and in many cases, additives such as a monomer and a filler are added in accordance with this demand. However, if these additives are added, it becomes difficult to manifest the characteristics of an organic material such as a decrease in refractive index, and therefore it is necessary to improve the heat resistance and the refractive index of the resin itself.

Patent Document 4 discloses the use of a reaction product of o-phenylphenol glycidyl ether and (meth) acrylic acid as an optical material. However, the compound obtained by this method is a monofunctional (meth) acrylate, and the hardness and heat resistance of the cured product may be low, and since the liquid refractive index is about 1.58, the compound is not yet satisfactory.

In Patent Document 5, the reaction products of an aromatic glycidyl compound and (meth) acrylic acid and a polyvalent isocyanate compound are described. However, in this case, the application is a dye-water-soluble resin, and in the examples, an aliphatic isocyanate compound is used and no optical characteristic is found.

Recently, a photosensitive acrylic hard coat agent has been used as a hard coat material having high hardness, high scratch resistance and adhesion, high refractive index, and low occurrence of curling in high and low shrinkage. Patent Document 6 Hardness, hardness, scratch resistance, continuous machining, antireflection, antistatic and other functions.

The lens described above such as a conventional Fresnel lens was molded by a method such as a pressing method, a casting method (mold forming method) or the like. The former press method is poor in productivity because it is manufactured by heating, pressurizing, and cooling cycles. In addition, the latter casting method has a problem in that the production cost is increased because a large number of molds are required at the same time as the production time is long because the monomer is polymerized by introducing the monomer into the mold. In order to solve such a problem, various proposals have been made for using an ultraviolet curable resin composition (Patent Document 7, Patent Document 8).

A method of producing an optical lens sheet for use in a transmissive screen or the like by using these ultraviolet-curable resin compositions is known. However, these conventional cured products of the resin composition have a problem of poor adhesion to the substrate and poor mold releasability. If the adhesion is poor, the kinds of usable substrates are limited, and it is difficult to obtain the intended optical properties. If the releasability is poor, the resin remains in the form at the time of releasing, and the form can not be reused. In addition, the resin composition providing the cured product having good adhesion to the substrate has a good adhesion with the form, and thus the releasability is liable to be deteriorated. On the other hand, the resin composition having good releasability tends to have poor adhesiveness. Therefore, a resin composition capable of satisfying both the adhesion with the substrate and the releasability from the shape is preferable, and Patent Document 9 has been proposed.

The resin compositions used for these optical lens sheets and the like have recently been required to have a low viscosity in order to process them into finer shapes or to be thinner in accordance with high definition of images or to enable continuous processing on rolls of sheets or films .

Further, it is also necessary that the microstructure is not easily damaged when the lens sheet is wound and taken out. In this case, a high glass transition temperature (Tg) is required.

In addition, there is a tendency that it is required to provide a cured product having a low glass transition temperature (Tg) at a low possible change in physical properties even when the optical lens sheet is used in a high temperature environment, , And good light resistance. However, it is difficult to combine high refractive index, high Tg point, releasability, adhesion, low viscosity, and light resistance, and nothing satisfying all of them exists.

Patent Document 1: International Publication 2002/033447 pamphlet

Patent Document 2: JP-A-2004-29042

Patent Document 3: JP-A-2005-274664

Patent Document 4: JP-A-9-272707

Patent Document 5: JP-A-4-316890

Patent Document 6: JP-A 2006-188588

Patent Document 7: JP-A-63-167301

Patent Document 8: JP-A-63-199302

Patent Document 9: Japanese Patent No. 3209554

DISCLOSURE OF INVENTION

Problems to be solved by the invention

It is an object of the present invention to provide a compound excellent in transparency and high in refractive index alone, and a resin composition containing the same, which has a high adhesiveness and a sufficient hardness. Accordingly, the photosensitive resin composition of the present invention is well suited for the production of film-forming materials, solder masks, plating resistors, adhesives, lenses, displays, optical fibers, optical waveguides, and holograms in the production of printed wiring boards. It is also suitable for a film having a cured film of a photosensitive resin composition and a compound suitable for a hard coat material capable of coating with a low curl thick film and free from cracks.

Another object of the present invention is to provide a resin composition having a low viscosity suitable for manufacturing a lens sheet such as a Fresnel lens, a wrench cure lens, a prism lens or a microlens, a cured product excellent in releasability, form reproducibility and adhesiveness, .

Means for solving the problem

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, they have found that unsaturated group-containing compounds and compositions thereof having a specific structure solve the above problems and have completed the present invention. That is, the first aspect of the present invention is

(1) A compound represented by the following general formula (1)

(B) and an aromatic polyisocyanate compound (c) are reacted with an epoxy resin (a) obtained by reacting a compound represented by the following general formula (1) with epihalohydrin The urethane compounds (A),

(1), wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is a reaction product of (meth) acrylic acid, (meth) acrylic acid and epsilon -caprolactone,

(3) the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is acrylic acid;

(4) The aromatic polyisocyanate compound (c) according to any one of (1) to (3), wherein the aromatic polyisocyanate compound (c) is a compound having an aromatic ring having 5 to 15 carbon atoms,

(5) A process for producing the aromatic polyisocyanate compound (A), the aromatic polyisocyanate compound (c) and the aromatic polyisocyanate compound (c)

(6) The liquid crystal composition according to any one of (1) to (5), wherein the liquid refractive index is 1.59 or more,

(7) A photosensitive resin composition characterized by containing a compound (A) described in any one of (1) to (6) and a polymerizable compound (B) other than (A)

(B-1), urethane (meth) acrylate (B-2), epoxy (meth) acrylate (B-3), (meth) acrylate (Meth) acrylate (B-4), alkyl (meth) acrylate or alkylene (meth) acrylate (B-5) (B-7), a maleimide group-containing compound (B-8), a (meth) acrylamide compound (B-9) and an unsaturated polyester (B-10) A photosensitive resin composition according to (7)

(9) The polymerizable liquid crystal composition according to any one of the above items (1) to (3), wherein the polymerizable compound (B) is at least one member selected from the group consisting of urethane (meth) acrylate (B-2), alkyl (meth) acrylate or alkylene (B-6), which is at least one compound selected from the group consisting of a photosensitive resin composition according to (7)

(10) The photosensitive resin composition according to any one of (7) to (9), which contains a photopolymerization initiator (C)

(11) A cured product of the photosensitive resin composition according to any one of (7) to (10)

(12) A film having the cured product described in (11)

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The inventors of the present invention have made intensive studies in order to solve the above problems, and as a result, they have found 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 second aspect of the present invention is

(13) A compound represented by the general formula (1)

(B) obtained by reacting an epoxy resin (a) which is a reaction product of a compound represented by the formula (1) with an epihalohydrin, a monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule and an aromatic polyisocyanate compound A), and a photopolymerization initiator (C);

(14) The composition according to any one of (14) to (17) above, wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is a reaction product of (meth) acrylic acid, (meth) acrylic acid and epsilon -caprolactone, or cinnamic acid, and the aromatic polyisocyanate compound The resin composition according to (13), which is a diisocyanate monomer;

(15) The resin composition according to (13) or (14), wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is acrylic acid and the aromatic polyisocyanate compound (c) is 2,4-tolylene diisocyanate;

(16) The resin composition according to any one of (13) to (15), further comprising a monoacrylate monomer (D) having a phenyl ether group;

(17) The composition according to any one of (17) to (18) above, wherein the monoacrylate monomer (D) having a phenyl ether group is at least one selected from the group consisting of o-phenylphenol (poly) ethoxy (meth) acrylate, (Meth) acrylate, and p-phenylphenol epoxy (meth) acrylate;

(18) The resin composition according to any one of (13) to (17), further comprising a urethane compound (A) or a (meth) acrylate compound (E) other than the monoacrylate monomer (D) ;

(19) A cured product obtained by curing the resin composition according to any one of (13) to (17) and having a refractive index of 1.55 or more at 25 占 폚;

(20) An optical lens sheet using the cured product described in (19) above;

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Effects of the Invention

The compound (A) of the present invention is excellent in transparency at a high refractive index with the resin alone, and the resin composition of the present invention containing the same has a low curling height and low hardening shrinkage. The cured product has high adhesiveness and sufficient hardness. ≪ / RTI > Therefore, the compound (A) of the present invention and the resin composition containing the same can be used for various kinds of lenses such as a Fresnel lens, a wrench cure lens, a prism lens, a microlens, a core material of an optical fiber, a clad material, an optical waveguide, And is useful for optical applications such as optical materials.

The energy ray curable resin composition of the present invention has a low viscosity, and the cured product has excellent releasability, shape reproducibility, adhesion with a substrate, and high light resistance with a high refractive index. Therefore, it is particularly suitable for optical lens sheets such as a Fresnel lens, a wrench cure lens, a prism lens, and a microlens.

Best Mode for Carrying Out the Invention

The compound (A) of the present invention is obtained by reacting an epoxy resin (a) obtained by reacting a compound represented by the following general formula (1) with epihalohydrin, a monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule, And a polyisocyanate compound (c).

The energy ray-curable resin composition of the present invention comprises an epoxy resin (a) which is a reaction product of the compound represented by the general formula (1) with epihalohydrin and a monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule, (A) and a photopolymerization initiator (C) obtained by reacting an aromatic polyisocyanate compound (c) with an aromatic polyisocyanate compound (c).

Examples of the compound represented by the general formula (1) include o-phenylphenol and p-phenylphenol. Commercially available products of these compounds include O-PP and P-PP (all manufactured by Sanko Co., Ltd.) .

In the present invention, the epoxy resin (a), that is, the phenylphenol epoxy (meth) acrylate can be obtained by reacting the compound of the general formula (1) with an epihalohydrin in the presence of an alkali metal hydroxide. The phenylphenol epoxy (meth) acrylate can be used as the monoacrylate monomer (D) having a phenyl ether group in the present invention.

As the epihalohydrin in the reaction for obtaining the epoxy resin (a) used in the present invention, epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin,? -Methyl epichlorohydrin, In the present invention, epichlorohydrin which is industrially easily available is preferable. The epihalohydrin is used in an amount of usually 2 to 20 mol, preferably 3 to 15 mol, per 1 mol of the hydroxyl group of the compound of the general formula (1).

Examples of the alkali metal hydroxide which can be used in the reaction include sodium hydroxide, potassium hydroxide, etc., and a solid material or an aqueous solution thereof may be used. When an aqueous solution is used, an aqueous solution of an alkali metal hydroxide is continuously added to the reaction system, and at the same time, water and epihalohydrin are continuously flowed out under reduced pressure or atmospheric pressure. Subsequently, water is removed by separating the water and epihalohydrin is added to the reaction system As shown in FIG. The amount of the alkali metal hydroxide to be used is generally 0.1 to 10.0 mol, preferably 0.3 to 5.0 mol, more preferably 0.8 to 3.0 mol, per 1 mol of the hydroxyl group of the compound of the general formula (1).

In order to accelerate 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 hydroxyl group of the compound of the general formula (1).

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% by weight, preferably 2 to 30% by weight based on the amount of epihalohydrin used. When an aprotic polar solvent is used, the amount of epihalohydrin is usually 3 to 100% by weight, preferably 5 to 80% by weight.

The reaction temperature is usually 30 to 100 ° C, preferably 35 to 90 ° C. The reaction time is usually 0.2 to 10 hours, preferably 0.5 to 8 hours. Epihalohydrin, a solvent, and the like are removed from the reaction product of the epoxidation reaction under heating and decompression after washing with water or without rinsing. Further, the epoxy resin thus recovered is dissolved in a solvent such as toluene or methyl isobutyl ketone to prepare an epoxy resin having little hydrolyzable halogen, and an alkali metal hydroxide aqueous solution such as sodium hydroxide or potassium hydroxide is added to carry out the reaction, You can be sure. 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, based on 1 mol of the hydroxyl group of the compound of the general formula (1) used for the epoxidation. The reaction temperature is usually from 50 to 120 ° C, and the reaction time is usually from 0.5 to 2 hours.

After completion of the reaction, the resulting salt is removed by filtration, washing with water, and the solvent is distilled off under reduced pressure again to obtain the epoxy resin of the present invention. An epoxy resin mixture which can be used without special purification can be obtained by a method represented by this method.

In the production of the compound (A) of the present invention, the epoxy resin (a) and the monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule are first reacted (hereinafter referred to as the first reaction) And reacting the aromatic polyisocyanate compound (c) (hereinafter referred to as the second reaction).

Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule include acrylic acid, crotonic acid,? -Cyano cinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl compound containing an unsaturated group have. Examples of the acrylic acids include (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, a reaction product of (meth) acrylic acid and? -Caprolactone, a saturated or unsaturated dibasic acid anhydride, (Meth) acrylate derivatives, and half esters, which are monohydric reactants of monoglycidyl (meth) acrylate derivatives with saturated or unsaturated dibasic acids and the like.

The monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is preferably a reaction product of (meth) acrylic acid, (metha) acrylic acid and epsilon -caprolactone or cinnamic acid in terms of sensitivity when made into a photosensitive resin composition Methacrylic acid is particularly preferable.

The first reaction may be carried out in the absence of a solvent, but if necessary, a solvent having no alcoholic hydroxyl group such as ketones such as acetone, ethyl methyl ketone, cyclohexanone, aromatic hydrocarbons 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, ethyl acetate, butyl acetate, methyl cell Esters such as rosorb acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether monoacetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, Cyclic esters such as lactone, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha , Solvent naphtha, and various monomers including a monoacrylate monomer (D) or a (meth) acrylate compound (E) described later, such as acryloylmorpholine, an ethylene oxide adduct of 2-phenylphenol (Meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like, as well as terminal acrylic acid esters such as OPP-1 and OPP- (Meth) acrylate of ε-caprolactone adduct of hydroxypivalic acid neopentyl glycol (for example, methacrylic acid esters such as trimethylolpropane polyethoxy tri (meth) acrylate, glycerin polypropoxytri (Metha) acrylate of a reaction product of pentaerythritol tetra (meth) acrylate, dipentaerythritol and epsilon -caprolactone, KAYARAD HX-220, HX- Acrylate, dipentaerythritol poly (meth) acrylate, and the like.

The amount of the monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule is preferably 60 to 140 equivalent%, more preferably 80 to 120 equivalent%, based on 1 equivalent of the epoxy resin (a) . When injected in this range, there is little possibility of gelation during the reaction, and the thermal stability of the finally obtained compound (A) is also enhanced.

In the reaction, a catalyst is preferably used to promote the reaction, and when the catalyst is used, the amount of the catalyst used is 0.1 to 10% by weight based on the reactants. The reaction temperature is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst to be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstilbine, methyltriphenylstyrene, Chromium carbonate, and zirconium octanoate.

Further, thermal polymerization inhibitors can be used. Specific examples thereof include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, diphenyl picrylhydrazine, Amine and the like. If used, it is preferable to use 0.1 to 10% by weight with respect to the reactant.

The reaction is terminated when the acid value of the sample becomes 5 mg · KOH / g or less, preferably 3 mg · KOH / g or less while appropriately sampling.

As the aromatic polyisocyanate compound (c) used in the second reaction, a compound having an aromatic ring having 5 to 15 carbon atoms is readily available and the density of the photoreceptor is consequently increased, which is preferable in view of the hardened film strength. , Tolylene diisocyanate such as 4-tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triazine diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene diisocyanate And diisocyanate monomers represented by the following general formula (1). Among them, 2,4-tolylene diisocyanate is particularly preferable.

The compound (A) of the present invention can be obtained by reacting the product obtained in the first reaction with the aromatic polyisocyanate compound (c). When the aromatic polyisocyanate compound (c) is used, the compound (A) of the present invention has a high refractive index and a low curing shrinkage of the resin composition of the present invention, and the cured product of the present invention has high adhesion and sufficient hardness . The amount to be used is not particularly limited, but it is preferable to conduct the reaction in an equivalence relationship in that NCO groups are not left after the reaction. When the addition (reaction) equivalent of the aromatic polyisocyanate compound (c) is within a preferable range, a resin having excellent heat resistance, hardness and refractive index can be obtained because the monofunctional (meth) acrylate is hardly retained, Gelation is difficult to occur because it is easy. Also, since the viscosity of the product can be appropriately controlled, workability is good. Specifically, the NCO group of the aromatic polyisocyanate compound (c) is added in an amount equivalent to 0.05 to 0.99 mol, preferably 0.1 to 0.95 mol, per 1.00 mol of the OH group of the product obtained by the first reaction.

The reaction can be carried out in the absence of a solvent, but it can be carried out in a solvent having no alcoholic hydroxyl group or in a solvent or in a mixed solvent of various monomers in order to increase the viscosity of the product and improve workability. In this case, the heat polymerization inhibitor may be further added.

The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is ascertained by the inverse titration method for the reduction of the amount of isocyanate. A catalyst may be added for the purpose of shortening the reaction time. As the catalyst, either a basic catalyst or an acid catalyst is used. Examples of basic catalysts include pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, amines such as ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of acidic catalysts include, but are not limited to, naphthenic acid, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, ditanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, 2-ethylhexanoate tin, And Lewis acid catalysts such as dibutyl tin dilaurate and octyl tin diacetate. The amount of these catalysts added is usually 0.001 to 1 part by weight based on 100 parts by weight of the total weight of the second reaction mixture.

The compound (A) of the present invention has a high refractive index and can be used for various optical materials such as various lenses such as a Fresnel lens, a wrench cure lens, a prism lens and a microlens, a core material of an optical fiber, a clad material, an optical waveguide, a hologram, And the like.

The photosensitive resin composition of the present invention is characterized by containing a compound (A) of the present invention and a polymerizable compound (B) other than the component (A). Specific examples of the usable polymerizable compound (B) include a compound having a (meth) acryloyloxy group, a maleimide compound, a (meth) acrylamide compound and an unsaturated polyester.

Specific examples of the compound having a (meth) acryloyloxy group that can be used in combination with the photosensitive resin composition of the present invention include (poly) ester (meth) acrylate (B-1); urethane (meth) acrylate (B-2); (Meth) acrylate (B-3); (poly) ether (meth) acrylate (B-4); alkyl (meth) acrylate or alkylene (Meth) acrylate (B-6) having an alicyclic structure, (meth) acrylate (B-7) having an alicyclic structure, and the like.

(Poly) ester (meth) acrylate (B-1) which can be used in combination with the photosensitive resin composition of the present invention is a generic term of (meth) acrylate having at least one ester bond in the main chain, -2) is a generic name of a (meth) acrylate having at least one urethane bond in its main chain, and epoxy (meth) acrylate (B-3) is a (meth) acrylate obtained by reacting an epoxy compound having at least one functional group with (meth) (Meth) acrylate (B-4) is a generic term of a (meth) acrylate having at least one ether bond in its main chain, and may be an alkyl (meth) acrylate or an alkylene (Meth) acrylate (B-5) is a generic term of a straight chain alkyl, branched alkyl, linear or branched (meth) acrylate which may have a halogen atom and / or hydroxyl group at the terminal, (B (Meth) acrylate (B-7) having an alicyclic structure includes an oxygen atom or a nitrogen atom in the constituent unit in the main chain or side chain, (Meth) acrylate having an alicyclic structure which may be substituted or unsubstituted.

Examples of the (poly) ester (meth) acrylate (B-1) which can be used in combination with the photosensitive resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide modified phthalic acid (Poly) ester (meth) acrylates such as ethylene oxide modified (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate and caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl Caprolactone-modified hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate, 1 mole of trimethylolpropane or 1 mole of glycerin Or a triol obtained by addition of a cyclic lactone compound such as? -Caprolactone,? -Butyrolactone, or? -Valerolactone, Tri (meth) acrylate;

Diol or tri (meth) acrylate obtained by adding at least one mole of a cyclic lactone compound such as ε-caprolactone, γ-butylolactone, δ-valerolactone to 1 mole of pentaerythritol or ditrimethylolpropane (Meta) acrylate obtained by adding a cyclic lactone compound such as? -Caprolactone,? -Butylolactone, or? -Valerolactone to 1 mole of dipentaerythritol, Mono (meth) acrylates or poly (meth) acrylates of polyhydric alcohols such as triols of acrylates, tetraols, pentaols or hexaols;

(Poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol, (Meth) acrylate of a polyester polyol which is a reaction product of a polybasic acid such as adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimeric acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, Acrylate of a cyclic lactone-modified polyester diol composed of the diol component, a polybasic acid, and anhydride thereof and an? -Caprolactone,? -Butyrolactone,? -Valerolactone, Ester (meth) acrylates, and the like, but are not limited thereto.

The urethane (meth) acrylate (B-2) that can be used in combination with the photosensitive resin composition of the present invention is a urethane (meth) acrylate compound having at least one (meth) acryloyloxy group- - (meth) acrylate obtained by the reaction of (meth) acrylate and (meth) acrylate.

Specific examples of the hydroxy compound (B-2-a) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (Meth) acrylate compound having various hydroxyl groups such as pentaerythritol tri (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ring-opening reaction products with? -caprolactone.

Specific examples of the isocyanate compound (B-2-) include, for example, P-phenylenediisocyanate, m-phenylenediisocyanate, P-xylenediisocyanate, m-xylenediisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenation Aliphatic or alicyclic diisocyanates such as xylylene diisocyanate, norbornenedisocyanate, and lidinedisocyanate, polyisocyanates such as one or more bisurets of isocyanate monomers or isocyanate compounds obtained by trimerizing the above diisocyanate compounds, And a polyisocyanate obtained by a urethane reaction between the polyol compound and the polyol compound.

The epoxy (meth) acrylate (B-3) which can be used in combination with the photosensitive resin composition of the present invention is a generic name of (meth) acrylates obtained by reacting an epoxy resin containing an epoxy group having one or more functional groups with (meth) acrylic acid. Specific examples of the epoxy resin as a raw material of the epoxy (meth) acrylate include phenyl diglycidyl ether such as hydroquinone diglycidyl ether, catechol diglycidyl ether and resorcinol diglycidyl ether; bisphenol A type Bisphenol such as epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3 - hydrogenated bisphenol type epoxy compounds such as epoxy compounds of hexafluoropropane, halogenated bisphenol type epoxy compounds such as brominated bisphenol A type epoxy resin and brominated bisphenol F type epoxy resin, Alicyclic diglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and diethylene glycol diglycidyl ether; A polysulfide diglycidyl ether compound such as polysulfide diglycidyl ether, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a trishydroxyphenyl methane type epoxy resin, Resin, dicyclopentadiene phenol type epoxy resin, biphenol type epoxy resin, bisphenol A novolac type epoxy resin, naphthalene skeleton containing epoxy resin, and heterocyclic epoxy resin.

Examples of (poly) ether (meth) acrylate (B-4) usable in combination with the photosensitive resin composition of the present invention include butoxy ethyl (meth) acrylate, butoxy triethylene glycol (meth) acrylate, epichlorohydrin (Meth) acrylate, phenoxyethyl (meth) acrylate, nonyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl Monofunctional (poly) ether (meth) acrylates such as phenoxypolyethylene glycol (meth) acrylate;

(Meth) acrylate such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and polytetramethylene glycol di Hydroxy polyols such as copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol, etc. Polyfunctional (meth) acrylates derived from (meth) acrylic acid and polyfunctional (meth) acrylates derived from diol having 1 mole or more of ethylene oxide, propylene oxide or butylene oxide added to 1 mole of neopentyl glycol, Methacrylate;

Di (meth) acrylates of alkylene oxide modified products of bisphenols such as bisphenol A, bisphenol F and bisphenol S; hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S, Di (meth) acrylate obtained by adding 1 mole or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to 1 mole of trimethylol propane or glycerin, ) Acrylate;

Mono-, di-, tri- or tetra (meth) acrylates of triols obtained by adding 1 mole or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to 1 mole of pentaerythritol or ditrimethylol propane; Polyfunctional (poly) ether (meth) acrylates such as hexaol trifunctional (meth) acrylate having 1 mole or more of ethylene oxide, propylene oxide or butylen oxide added to 1 mole of lithol And the like.

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (B-5) usable in the photosensitive resin composition of the present invention include octyl (meth) acrylate, isooctyl (meth) acrylate, decyl Monofunctional (meth) acrylates such as acrylate and dodecyl (meth) acrylate;

(Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (Meth) acrylate of 1, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylates;

Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, "poly" is used collectively as polyfunctional groups such as di-, tri- or tetra), glycerin mono- Mono- or poly (meth) acrylates of dipentaerythritol, mono- or poly (meth) acrylates of poly (meth) acrylate or poly Mono or poly (meth) acrylates of polyhydric alcohols such as triol, tetraol and hexanol;

(Meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Examples of the (meth) acrylate (B-6) having an aromatic ring which can be used in combination with the photosensitive resin composition of the present invention include a terminal of an ethylene oxide adduct of phenyl (meth) acrylate, benzyl (Meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate, and the like; monofunctional (meth) acrylates such as acrylic acid esters (for example, OPP-1 and OPP- Di (meth) acrylates, and the like, but are not limited thereto.

Examples of the (meth) acrylate (B-7) having an alicyclic structure that can be used in combination with the photosensitive resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobonyl (meth) (Meth) acrylates having an alicyclic structure such as dicyclopentenyl (meth) acrylate, di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F, tricyclodecane Alicyclic (meth) acrylates having cyclic structures such as dimethylol (meth) acrylate and dimethylol (meth) acrylate; and alicyclic (meth) acrylates having oxygen atoms in the structure such as tetrafurfuryl However, the present invention is not limited thereto.

Examples of the compound having a (meth) acryloyl group that can be used in combination with the photosensitive resin composition of the present invention include compounds obtained by reacting a reaction product of a (meth) acrylic acid polymer with glycidyl (meth) acrylate or glycidyl (meth) (Meth) acrylic acid polymer (meth) acrylate such as a reaction product of an acrylate polymer and (meth) acrylic acid; (meth) acrylate having an amino group such as dimethylaminoethyl (Meth) acrylate having a polysiloxane skeleton; polybutadiene (meth) acrylate, melamine (meth) acrylate, and the like can also be used.

Examples of the maleimide group-containing compound (B-8) which can be used in combination with the photosensitive resin composition of the present invention include N-n-butyl maleimide, N-hexyl maleimide, 2- maleimide ethyl ethyl carbonate, Monocyclic aliphatic maleimides such as N-methylmorpholine, propyl carbonate, N-ethyl- (2-maleimideethyl) carbamate, and alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; , Aliphatic bismaleimides such as polypropylene glycol-bis (3-maleimidepropyl) ether and bis (2-maleimideethyl) carbonate; 1,4-dimaleimidocyclohexane, isophorone bis- Ethyl maleimide); maleimide compounds obtained by esterifying maleimide acetic acid and polytetramethylene glycol; maleimide compounds obtained by copolymerizing maleimide caproic acid and pentaerythritol (Poly) maleimide compounds obtained by esterifying various (poly) alcohols with a carboxymimeimide derivative such as a maleimide compound by esterification with a tetraethylene oxide adduct, and the like. But is not limited thereto.

Examples of the (meth) acrylamide compound (B-9) usable in the photosensitive resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N- isopropyl (meth) And polyfunctional (meth) acrylamides such as bis (meth) acrylamide.

Examples of the unsaturated polyester (B-10) which can be used in combination with the photosensitive resin composition of the present invention include fumaric acid esters such as dimethyl fumarate and diethyl fumarate; esterification products of polyvalent unsaturated carboxylic acids such as maleic acid and fumaric acid with polyhydric alcohols .

The polymerizable compound (B) that can be used in combination with the photosensitive resin composition of the present invention is not limited to the above-described compounds. Any compound having a copolymerization with the component (A) may be used alone or in combination of two or more. can do. As the polymerizable compound, (B-2), (B-5) and (B-6) are preferably used.

The proportion of the component (A) and the component (B) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10 to 2000 parts by weight, more preferably 50 to 1000 parts by weight per 100 parts by weight of the component (A) It is desirable to be wife.

Specific examples of the photopolymerization initiator (C) used in the photosensitive resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, Acetophenones such as 2-methyl-1- (methylthio) phenyl-2-morpholinopropane-1-one, 2-amyl anthraquinone and the like; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; acetophenone dimethylketal, benzyldimethylketal, etc. Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bis Benzophenones such as aminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and the like . Preferred are acetophenones, more preferably 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone. The addition ratio thereof is generally 0.01 to 30% by weight, preferably 0.1 to 25% by weight based on 100% by weight of the solid content of the photosensitive resin composition.

These may be used alone or as a mixture of two or more kinds. Examples thereof include tertiary amines such as triethanolamine and methyldiethanolamine, benzoic acid such as N, N-dimethylaminobenzoic acid ethyl ester and N, N-dimethylaminobenzoic acid, A curing accelerator such as a derivative, and the like. As the amount of the accelerator to be added, an amount of not more than 100% by weight based on the photopolymerization initiator (C) is added if necessary.

It is preferable to use a monoacrylate monomer (D) having a phenyl ether group in consideration of the viscosity, the refractive index, and the adhesion property of the energy ray curable resin composition of the present invention. Examples of the monoacrylate monomer (D) having a phenyl ether group include phenoxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, tribromophenyloxyethyl (Meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, phenylphenol epoxy (meth) acrylate and the like. Of these, Phenylphenol epoxy (meth) acrylate, o-phenylphenol epoxy (meth) acrylate and p-phenylphenol epoxy (meth) acrylate are preferable.

The phenylphenol (poly) ethoxy (meth) acrylate is preferably a compound having an average number of repetition of the ethoxy moiety of 1 to 3, and reacting the reaction product of phenylphenol and ethylene oxide with (meth) acrylic acid Can be obtained. The reaction product of phenylphenol and ethylene oxide can be obtained by a known method, and commercially available products can also be used. Next, in the presence of an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid and a polymerization inhibitor such as hydroquinone or phenothiazine in the reaction product of phenylphenol and ethylene oxide, a solvent (for example, toluene, cyclohexane (meth) acrylic acid at a temperature of preferably 70 to 150 ° C in the presence of a catalyst (for example, n-hexane, n-heptane, etc.). (Meth) acrylic acid is used in an amount of 1 to 5 mol, preferably 1.05 to 2 mol, per 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 amount of (meth) acrylic acid used. As the phenylphenol, there can be mentioned o-phenylphenol and p-phenylphenol as described above, and O-PP and P-PP (both available from Sanko) are available. O-phenylphenol (poly) ethoxy (meth) acrylate or p-phenylphenol (poly) ethoxy (meth) acrylate are preferred.

The phenylphenol epoxy (meth) acrylate is the same as the above epoxy resin (a). o-phenylphenol epoxy (meth) acrylate or p-phenylphenol epoxy (meth) acrylate are preferred.

In consideration of the viscosity, adhesion, glass transition temperature (Tg) and hardness of the cured product of the energy ray curable resin composition of the present invention, the urethane compound (A) and the monoacrylate monomer (D) having a phenyl ether group (Meth) acrylate compound (E) are preferably used alone or in combination of two or more. (Meth) acrylate compounds (E) 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-dimethanolmono (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl Methacrylate, and the like.

Examples of the bifunctional (meth) acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- (Meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol Di (meth) acrylate, and polyethylene glycol di (meth) acrylate.

Examples of trifunctional or higher polyfunctional (meth) acrylate monomers include tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (metha) acrylate, dipentaerythritol Di (meth) acrylate of ε-caprolactone adduct of hydroxypivalic acid neopentyl glycol, di (meth) acrylate of ε-caprolactone adduct of hydroxypivalic acid (meth) acrylate, tripentaerythritol hexa (Meth) acrylates such as trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, and the like.

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

Examples of the urethane (meth) acrylate include diol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, Hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, Diethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxydiol < RTI ID = 0.0 > Etc.) or polyester diols which are a reaction product of these diol compounds with dibasic acids or anhydrides thereof (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) and organic polyisocyanates Tetramethylene diisocyanate, hexa Chain saturated hydrocarbon isocyanates such as methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornadiisocyanate, dicyclohexylmethane di Cyclic saturated hydrocarbon isocyanates such as isocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3 Aromatic polyamides such as xylylene diisocyanate, p-phenylenediisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate and 1,5- Isocyanate or the like) is reacted, and then the hydroxyl group-containing (meth) acrylate There may be mentioned a reaction product, such as adding a bit.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, polyethylene glycol mono Acrylate, ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenyl (meth) acrylate, (Meth) acrylate, and the like.

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

Examples of the polyester (meth) acrylate include a condensation reaction product of a polyester diol and (meth) acrylic acid as a reaction product of the diol compound and the dibasic acid or an anhydride thereof.

In particular, as the (meth) acrylate compound (E), monofunctional or bifunctional (meth) acrylate monomers are suitable considering the viscosity necessary for the energy ray curable resin composition of the present invention and the adhesion of the cured product. Among them, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobonyl (Meth) acrylate such as dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and bisphenol A polyethoxydi Functional (meth) acrylate monomers are suitable.

In consideration of the hardness and Tg required for the energy ray curable resin composition of the present invention, it is also preferable to use a trifunctional or more (meth) acrylate monomer in combination. Examples thereof include tris (2-acryloxyethyl) isocyanurate, di (Meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like.

The use ratio of each component in the energy ray curable resin composition of the present invention can be determined in consideration of the desired refractive index, glass transition temperature, viscosity, adhesion, etc. However, the ratio of the essential component (A), the optional component (D) The content of the component (A) is 3 to 100 parts by weight, particularly preferably 5 to 100 parts by weight, based on 100 parts by weight of the component (A) + the component (D) + the component (E) The content of the component (D) is 0 to 85 parts by weight, particularly preferably 0 to 75 parts by weight. The content of the component (E) is 0 to 60 parts by weight, particularly preferably 0 to 50 parts by weight. Component (C) is preferably used in an amount of 0.1 to 10 parts by weight, particularly preferably 0.3 to 5 parts by weight, based on 100 parts by weight of component (A) + component (D) + component (E).

In addition, the photosensitive resin composition of the present invention may contain a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, a releasing agent, a defoaming agent, a leveling agent, a plasticizer, a light stabilizer, an antioxidant, Antistatic agents, flame retardants, pigments, dyes and the like can be used without particular limitations within the range not impairing the curability and the resin characteristics. If necessary, polymers such as acrylic polymers, polyester elastomers, urethane polymers and nitrile rubbers, and inorganic or organic light-diffusing fillers may also be added.

Specific examples of the non-reactive compound include a liquid or solid oligomer or resin having low reactivity or no reactivity, and may be a (meth) acrylic acid alkyl copolymer, an epoxy resin, a liquid polybutadiene, a dicyclopentadiene derivative, a saturated polyester oligomer, But are not limited to, xylene resin, polyurethane polymer, ketone resin, diallyl phthalate polymer (Daff resin), petroleum resin, rosin resin, fluoric oligomer, and silicone oligomer.

Examples of the inorganic filler include inorganic fillers such as silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum oxide, Barium, alumina white, zeolite, silica balloons, glass balloons and the like. Such an inorganic filler may have a functional group of a halogen group, an epoxy group, a hydroxyl group or a thiol group by a method such as adding a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, have.

Examples of the organic filler include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene-acrylic acid copolymer, polystyrene, acrylic copolymer, polymethylmethacrylate resin, fluororesin, nylon 12, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like.

Examples of the silane coupling agent include silane coupling agents such as? -Glycidoxypropyltrimethoxysilane or? -Chloropropyltrimethoxysilane, tetra (2,2-diallyloxymethyl-1-butyl) bis Titanate-based coupling agents such as bis (tridecyl) phosphite titanate and bis (dioctylpyrophosphate) ethylene titanate; aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate; and zirconium-based coupling agents such as acetylacetone- Coupling agents and the like.

In order to obtain the photosensitive resin composition of the present invention, the above components may be mixed, and the order and method of mixing are not particularly limited.

The photosensitive resin composition of the present invention does not substantially require a solvent, but examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid esters such as ethyl acetate and butyl acetate, aromatic compounds such as benzene, toluene and xylene It is also possible to dilute the photosensitive resin composition of the present invention by using other commonly used organic solvents such as hydrocarbons.

In the present invention, active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, particle beams such as alpha rays, beta rays and electron rays. However, in consideration of a highly suitable use of the present invention, ultraviolet rays including visible rays, visible rays, or electron rays are preferred. At this time, it is preferable to contain a photopolymerization initiator (C) so that the curing rate can be practically achieved.

There are no particular restrictions on the method of forming various coatings. Examples of the methods for forming various coatings include intaglio printing methods such as gravure printing, iron plate printing methods such as Furekiso, stencil printing methods such as silkscreen, flat plate printing methods such as offset printing, Various coating methods such as coater, curtain coater, spin coater and the like can also be suitably used.

The photosensitive resin composition containing the compound (A) of the present invention can be used for a film forming material, a solder mask, a plating resistor, an adhesive, a lens, a display, an optical fiber, an optical waveguide, a hologram, The film-forming material is used for coating the substrate surface. Specific examples thereof include ink materials such as gravure ink, fresco ink, silkscreen ink and offset ink, and coating materials such as hard coat, top coat, overprint varnish, and crea coat. It is also possible to use various kinds of adhesives such as resist materials such as solder resists, etching resistors and resistors for micromachines, various other adhesives for laminates, adhesive materials such as adhesives, various adhesives such as adhesives for LEDs, Fresnel lenses, wrench cure lenses, prism lenses, Various optical materials such as various lenses of optical fibers, core materials of optical fibers, clad materials, optical waveguides, and holograms. It is also possible to use the resin composition as a so-called dry film in which the resin composition is temporarily coated on a releasable substrate to form a film, and then the film is bonded to a substrate intended for the intended purpose.

The energy ray-curable 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 injecting each component into a round bottom flask equipped with a stirrer and a thermometer, and stirring at 40 to 80 ° C for 0.5 to 6 hours.

The viscosity of the energy ray-curable resin composition of the present invention is suitable for the workability of shape transferability and workability when producing optical lens sheets, and the viscosity measured using an E-type viscometer (TV-200, And a composition in the range of 50 mPa · s to 4000 mPa · s at 25 ° C. is preferable.

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 has a refractive index (25 ° C) of 1.55 or more. The resin composition of the present invention is applied on a stenter having a shape such as a Fresnel lens, a wrench cure lens, a prism lens or the like to provide a resin composition layer, (For example, a polymethacrylic resin, a polycarbonate resin, a polystyrene resin, a polyester resin, or a substrate or a film made of a blend of these polymers) of a hard transparent substrate is adhered on the substrate, And then curing the resin composition by irradiating ultraviolet rays with a mercury lamp or the like, and then peeling the cured product from the stamper. It is also possible to carry out this application by continuous processing.

Thus, an optical lens sheet having an optical lens portion such as a Fresnel lens, a wrench cure lens, a prism lens, and a microlens having a refractive index (25 ° C) of 1.55 or more and excellent in releasability, form reproducibility, And these are also included in the present invention. The refractive index can be measured by an Abbe refractometer (product number: DR-M2, manufactured by Atago Co., Ltd.).

The energy ray curable resin composition of the present invention is particularly useful for an optical lens sheet. Examples of the optical lens sheet include sheets formed with optical lenses such as a Fresnel lens, a wrench cure lens, a prism lens, and a microlens. Examples of applications other than the optical lens sheet include various coating agents and adhesives.

The following examples further illustrate the present invention. The present invention is not limited by the following examples.

Synthesis Example 1 Synthesis of epoxy resin (a-1)

170 g of the compound of the following formula (2) (manufactured by O-PP Sanko Co., Ltd.), 370 g of epichlorohydrin and 74 g of methanol were poured into a flask equipped with a thermometer, a cooling tube and a stirrer and dissolved therein. Further, 41 g of sodium hydroxide on flakes was heated to 70 DEG C over 90 minutes, and then reacted at 70 DEG C for 60 minutes. After the completion of the reaction, the reaction mixture was washed twice with 200 g of water to remove the resulting salt and the like, and the reaction mixture was heated under reduced pressure (-70 ° C, -0.08 MPa to -0.09 MPa) And so on. 450 g of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 캜. 10 g of a 10% by weight aqueous solution of sodium hydroxide was added thereto under stirring, and the reaction was carried out for 1 hour. Thereafter, the reaction solution was washed with water until the washing water became neutral. The resulting solution was distilled off under reduced pressure using methyl isobutyl ketone To obtain 217 g of the intended epoxy resin (a). The obtained epoxy resin (a-1) had an epoxy equivalent of 233 g / eq. And liquid at room temperature.

Synthesis Example 2 Synthesis of epoxy resin (a-2)

181 g of the compound of the formula (3) (P-PP Sanko Co., Ltd.), 394 g of epichlorohydrin and 80 g of methanol were poured and dissolved in a flask equipped with a thermometer, a cooling tube and a stirrer while purging with nitrogen gas. Further, 44 g of sodium hydroxide on flaky was heated to 70 캜 over 90 minutes, and then reacted again at 70 캜 for 60 minutes. After completion of the reaction, the reaction mixture was washed twice with 200 g of water to remove the resulting salt and the like, and the reaction mixture was heated under reduced pressure (-70 ° C., -0.08 MPa to -0.09 MPa) And so on. 480 g of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 캜. 12 g of a 10% by weight aqueous solution of sodium hydroxide was added under stirring, and the reaction was carried out for 1 hour. Thereafter, the reaction solution was washed with water until the washing water became neutral, and methyl isobutyl ketone or the like was distilled off under reduced pressure using a rotary evaporator 227 g of the desired epoxy resin (a-2) was obtained. The obtained epoxy resin (a-2) had an epoxy equivalent of 242 g / eq. And a white crystalline phase at room temperature.

Example 1 (Synthesis of Compound (A-1)

139.8 g (0.6 eq.) Of the epoxy resin (a-1) obtained in Synthetic Example 1 was added to a 1 L flask equipped with a stirrer and a reflux tube, and 2,6-di-tert-butyl- (0.6 eq.) Of acrylic acid as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule and 0.55 g of triphenylphosphine as a reaction catalyst were charged and reacted at 98 占 폚 for 30 hours to obtain an acid value And the first reaction was terminated with 2.4 mg KOH / g.

After the completion of the first reaction, 151.1 g of a terminal acrylic acid ester of an ethylene oxide adduct of 2-phenylphenol (OPP-1 made by Nippon Gakuin KK) as an acrylate monomer was added as a reaction diluent at a reaction temperature of 40 캜 Followed by stirring and mixing. Then, 0.057 g of dibutyltin dilaurate was added as a urethane reaction catalyst and 43.6 g (0.5 eq.) Of 2,4-tolylene diisocyanate was added as an aromatic polyisocyanate compound (c) The temperature was raised, and the reaction was carried out for 24 hours to measure NCO (%). The reaction was terminated at 0.00%. By this step, 371 g of a transparent pale yellow resin-like product containing 60% by weight of the compound (A-1) of the present invention was obtained.

Example 2 (Synthesis of compound (A-2)

(0.6 eq.) Of the epoxy resin (a-2) obtained in Synthetic Example 2 and 2,6-di-tert-butyl-p-toluenesulfonic acid as a heat polymerization inhibitor were placed in a 1 L flask equipped with a stirrer, (0.6 eq.) Of acrylic acid as a monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule and 0.57 g of triphenylphosphine as a reaction catalyst were charged and reacted at 98 占 폚 for 30 hours to obtain an acid value And the first reaction was terminated with 1.2 mg KOH / g.

After the completion of the first reaction, 232.0 g of a terminal acrylic acid ester of an ethylene oxide adduct of 2-phenylphenol (OPP-1, manufactured by Nippon Yakuzaku Co., Ltd.) as an acrylate monomer was added as a reaction diluent at a reaction temperature of 40 캜 Followed by stirring and mixing. Then, 0.070 g of dibutyltin dilaurate was added as a urethane reaction catalyst, and 43.6 g (0.5 eq.) Of 2,4-tolylene diisocyanate was added as the aromatic polyisocyanate compound (c) The temperature was raised, and the reaction was carried out for 24 hours to measure NCO (%). The reaction was terminated at 0.00%. By this step, 460 g of a transparent yellowish resinous product containing 50% by weight of the compound (A-2) of the present invention was obtained.

Comparative Example 1 (Synthesis of Compound (H-1)

(0.6 eq.) Of the epoxy resin (a) obtained in Synthesis Example 1 and 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor were added to a 1 L flask equipped with a stirrer and a reflux tube 43.3 g (0.6 eq.) Of acrylic acid as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule and 0.55 g of triphenylphosphine as a reaction catalyst were charged and reacted at 98 DEG C for 30 hours to measure an acid value The reaction was terminated at 2.4 mg KOH / g. By this step, 180 g of a transparent pale yellow resinous compound (H-1) was obtained.

Comparative Example 2 (Synthesis of Compound (H-2)

139.8 g (0.6 eq.) Of the epoxy resin (a) obtained in Synthesis Example 1 and 0.5 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor were placed in a 1 L flask equipped with a stirrer and a reflux tube, 43.3 g (0.6 eq.) of acrylic acid as a monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule and 0.55 g of triphenylphosphine as a reaction catalyst were charged and reacted at 98 DEG C for 30 hours to measure an acid value The first reaction was terminated with 2.4 mg KOH / g of bar.

After the completion of the first reaction, the reaction temperature was adjusted to 40 占 폚, 159.1 g of methyl isobutyl ketone was added as a reaction diluent, and the mixture was stirred and mixed. Then, 0.06 g of dibutyltin dilaurate was added as a urethane reaction catalyst, 55.6 g (0.5 eq.) Of isophorone diisocyanate of aliphatic diisocyanate was added as a polyisocyanate compound, the reaction temperature was raised to 60 ° C, and 24 The reaction was terminated at 0.00% by measuring NCO (%). By this step, 390 g of a transparent yellow resin-like product containing 60% by weight of the compound (H-2) was obtained.

The liquid refractive indexes of the compounds of Examples and Comparative Examples were measured, and the liquid refractive indexes thereof were as shown in Table 1. (The monomer and solvent dilution products were diluted so that the compound concentration was changed by 3 points, and the refractive index of the compound itself was measured by measuring the refractive index of the solution by three points.) Measurement apparatus: Multi-wavelength Abbe refractometer DR-M2 Manufactured by Atago Co., Ltd., measurement wavelength: 589 nm (D line))

Table 1

From the above results, it can be seen from the above results that the compound (A) of the present invention has a high refractive index and transparency alone, and can be used for various lenses such as a Fresnel lens, a wrench cure lens, a prism lens and a microlens, a core material of an optical fiber, , A hologram, a display member, and other optical materials.

Examples 3 to 7 and Comparative Examples 3 to 4

A photosensitive resin composition prepared by compounding the compounds (A-1 and A-2) synthesized in the Examples and the compounds (H-1 and H-2) obtained in Comparative Examples 1 and 2 in the composition shown in Table 2 Since one compound contains OPP-1 as a reactive diluent, it is blended so as to have the composition shown in Table 2, and the compound (H-2) synthesized in Comparative Example 2 uses methyl isobutyl ketone as a solvent. H- (Hereinafter referred to as " OPP-1 ") was diluted so as to have the composition shown in Table 2, and methyl isobutyl ketone as a solvent was distilled off under reduced pressure. (Co., Ltd.): a-4300, the film was coated in a thickness 188μm), and allowed to stand 1 minutes while in the 80 ℃ dried and under an air atmosphere using a high pressure mercury of 120W / cm ² 5m from the distance of the lamp height 10cm / Minute, thereby forming a cured coating (10 to 15 mu m) To give a name.

Table 2

* 1: OPP-1: terminal acrylic acid ester of ethylene oxide adduct of 2-phenylphenol (manufactured by Nippon Yakushi Kogyo Co., Ltd.)

* 2: DPHA: KAYARAD DPHA-40H (polyfunctional urethane acrylate) manufactured by Nippon Yakuza Co.,

* 3: PET-30: KAYARAD PET-30 (a mixture of pentaerythritol triacrylate / pentaerythritol tetraacrylate)

* 4: Irg.184 (Irgacure 184): manufactured by Ciba Specialty Chemicals (1-hydroxycyclohexyl phenyl ketone)

* 5: MEK: 2-butanone

Test Example

The following items were evaluated for the films obtained in Examples 3 to 7 or Comparative Examples 3 to 4, and the results are shown in Table 3.

(Pencil hardness)

The pencil hardness of the coating film was measured using a pencil scratching tool (Jukka) according to JIS K 5400. That is, on a polyester film having a cured coating film to be measured, a pencil was rubbed with a load of 1 kg from an upper side at an angle of 45 to scratch about 5 mm, and the attachment state of the scratch marks was confirmed. Measure 5 times and count the number of scratch marks.

Rating 5/5: 5 out of 5 times No scars

0/5: All 5 incidents

(Scratch test)

On a steel wool # 0000, a load of 200 g / cm ² was applied, and the wool was reciprocated ten times to judge the condition of the wound marks as a visual indication.

Evaluation 5: No occurrence of scars was observed.

Evaluation 4: One to five wound marks were observed.

Evaluation 3: 6 to 50 wound marks were observed.

Evaluation 2: 51-100 incidence of scarring was observed.

Evaluation 1: Peeling of the coating film was observed.

(Adhesion)

According to JIS K 5400, 11 pieces of vertical and horizontal pieces are cut in 1 mm intervals on the surface of the film to form 100 checkerboard eyes. The cellophane tape was brought into close contact with the surface of the cellophane tape, and the number of mass eyes remained after peeling at once was not peeled off.

(curl)

The polyester film having the cured coating film to be measured was cut into 5 cm x 5 cm, left in a drying furnace at 80 캜 for 1 hour, and then returned to room temperature. The height of each of the four sides rising from the horizontal object was measured, and the average value was set as a measurement value (unit: mm). At this time, the curl of the substrate itself was 0 mm.

(Exterior)

Cracks, whitening, and cloudiness on the surface were judged to be visually observable.

Evaluation ○: Good

?: Small crack occurred

X: Significant cracks

Table 3

Compared with Comparative Examples 3 to 4, the epoxy resin (a) is superior in hardness, scratch resistance and adhesion and has the same curl height as the orthoester (Examples 3 to 5) and para-isomers (Examples 6 to 7) It can be seen that the hardening shrinkage is small. As compared with Comparative Example 3 in which the aromatic polyisocyanate compound (c) was not used, in Example 5, it was found that Example 5 was remarkably excellent in hardness, scratch resistance and adhesion, and hardened and shrunk. Further, when Example 5 is compared with Comparative Example 4 using an aliphatic polyisocyanate compound, it can be seen that Example 5 is excellent in hardness, scratch resistance, adhesion, and hardening shrinkage. From the above results, the resin composition of the present invention containing the compound (A) of the present invention having transparency is useful as a coating agent requiring transparency because it has less curing shrinkage and the cured product has sufficient hardness and high adhesiveness .

Next, an ultraviolet-curing resin composition and a cured product of the present invention were obtained with the compositions shown in the following examples (numerical values indicate parts by weight). The evaluation methods and evaluation criteria for the resin composition and the cured film are as follows.

(1) Viscosity: Measured at 25 캜 using an E-type viscometer (TV-200: manufactured by Sekisui Chemical Co., Ltd.).

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

○ · · · Releasing from the mold is good.

DELTA ... ... There are some difficulties in releasing or peeling in releasing.

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

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

Good reproducibility.

× ···· Reproducibility is poor.

(4) Adhesion: coating a resin composition on a base film to be about 50μm thick, and then a high pressure mercury lamp (80W / cm, an ozone-less) to 1000mJ / cm ² to manufacture a test piece was carried out by hardening the irradiation, and JIS K5600- The adhesion was evaluated in accordance with 5-6.

The evaluation result was 0 for no peeling at all, 1 for 2 and 3 for 5, respectively.

(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 Co.).

(6) Glass Transition Point Temperature (Tg): The Tg point of the cured ultraviolet ray-curable resin layer was measured in a viscoelasticity measuring system (DMS-6000, manufactured by Seiko Electronics Industry Co., Ltd.) at a frequency of 1 Hz.

(7) Light fastness: The hardened ultraviolet ray-curable resin layer was subjected to light fastness test at 60 DEG C and 60% RH for 2 hours in EYE SUPER UV TESTER SUV-W11 (manufactured by Iwasaki Kikai Co., Ltd.).

○ · · · · A little coloring can be seen, but transparency is good.

× · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · /

Example 8

16.7 parts of the compound (A-1) -containing product obtained in Example 1 as Component (A), 3 parts of 2-hydroxy-2-methyl-1-phenylpropane- , 70.3 parts of o-phenylphenol monoethoxyacrylate, 10 parts of acryloylmorpholine as component (E) and 3 parts of tris (2-acryloyloxyethyl) isocyanurate were heated to 60 ° C, To obtain a resin composition of the present invention. The viscosity of this resin composition was 195 mPa · s. The refractive index (25 占 폚) of the film cured with the resin composition was 1.606 and the glass transition temperature (Tg) was 50 占 폚.

Applied to this resin composition has a thickness of 50μm on a prism lens mold, and as the base material over the polycarbonate film 500μm sikimyeo adhesive thickness, the above that since curing by irradiating the irradiation quantity ultraviolet rays of 1000mJ / cm ² by a high pressure mercury lamp And then peeled off to obtain a prism lens sheet.

Evaluation results

Formability:?, Shape reproducibility:?, Adhesion:?, And light resistance:?.

Example 9

20 parts of the compound (A-2) -containing product obtained in Example 2 and 67 parts of o-phenylphenol monoethoxyacrylate instead of 70.3 parts of the compound (A-1) -containing product obtained in Example 1 were used as the component (A) The resin composition of the present invention was obtained in the same manner as in Example 8. The viscosity of this resin composition was 200 mPa · s. The refractive index (25 占 폚) of the film obtained by curing the resin composition was 1.607 and the glass transition temperature (Tg) was 51 占 폚.

This resin composition was coated on a prism lens mold so as to have a film thickness of 50 mu m, and a polycarbonate film having a thickness of 500 mu m was adhered as a base thereon. Ultraviolet rays of 1000 mJ / cm < ^{2 &} To obtain a prism lens sheet.

Evaluation results

Formability:?, Shape reproducibility:?, Adhesion:?, And light resistance:?.

Example 10

51 parts of the compound (A-2) -containing product obtained in Example 2, 3 parts of 1-hydroxycyclohexyl phenyl ketone as the component (C), 20 parts of acryloylmorpholine as the component (E) 5 parts of tris (2-acryloyloxyethyl) isocyanurate, 20 parts of bisphenol A (EO4 molar modified) diacrylate and 4 parts of bisphenol A epoxy acrylate were heated to 60 DEG C and mixed to prepare a resin composition of the present invention . The viscosity of this resin composition was 2600 mPa · s. The refractive index (25 占 폚) of the film obtained by curing the resin composition was 1.594 and the glass transition temperature (Tg) thereof was 88 占 폚.

The resulting resin composition was coated on a Fresnel lens mold so as to have a film thickness of 200 mu m, and 2 mm of methyl methacrylate / styrene base material was adhered as a base thereon. Ultraviolet rays of 1000 mJ / cm < ^{2 &} After curing and peeling, a Fresnel lens was obtained.

Evaluation results

Formability:?, Shape reproducibility:?, Adhesion:?, And light resistance:?.

Example 11

The resin composition of the present invention was obtained in the same manner as in Example 8 except that the component (D) in Example 8 was changed to 40.3 parts of o-phenylphenol monoethoxyacrylate and 30 parts of p-phenylphenol epoxy acrylate. The viscosity of this resin composition was 630 mPa · s. The refractive index (25 占 폚) of the film obtained by curing the resin composition was 1.600 and the glass transition temperature (Tg) was 54 占 폚.

This resin composition was coated on a prism lens mold so as to have a film thickness of 50 m, a polycarbonate film having a thickness of 500 m was adhered as a base thereon, and irradiated with ultraviolet rays of 1000 mJ / cm < ^{2 &} And peeled off to obtain a prism lens sheet.

Evaluation results

Formability:?, Shape reproducibility:?, Adhesion:?, And light resistance:?.

Example 12

The resin composition of the present invention was obtained in the same manner as in Example 9 except that the component (D) was changed to 27 parts of o-phenylphenol monoethoxyacrylate and 30 parts of o-phenylphenol epoxy acrylate in Example 9. The viscosity of this resin composition was 693 mPa · s. The refractive index (25 占 폚) of the film cured with this resin composition was 1.604 and the glass transition temperature (Tg) was 56 占 폚.

This resin composition was coated on a prism lens mold so as to have a film thickness of 50 m, a polycarbonate film having a thickness of 500 m was adhered as a base thereon, and irradiated with ultraviolet rays of 1000 mJ / cm < ^{2 &} And peeled off to obtain a prism lens sheet.

Evaluation results

Deformability:?, Shape reproducibility:?, Adhesion:?, And light resistance:?.

Example 13

Example 8 The film thickness of the resin composition on a prism lens mold of the coating to be 50μm, and sikimyeo station adhesive PET film 100μm adhesive thickness (Oriental room A4300) as described above that of 600mJ / cm ² by a high-pressure mercury lamp from above, Irradiated with ultraviolet rays, cured, and peeled to obtain a prismatic lens sheet.

Evaluation results

Releasability:?, Shape reproducibility:?, And adhesion:?.

Example 14

Example 9 The film thickness of the resin composition on the prism lens mold coating so that 50μm and sikimyeo station adhesive PET film 100μm adhesive thickness (Oriental room A4300) as described above that of 600mJ / cm ² by a high-pressure mercury lamp from above, Irradiated with ultraviolet rays, cured, and peeled to obtain a prismatic lens sheet.

Evaluation results

Releasability:?, Shape reproducibility:?, And adhesion:?.

Example 15

Embodiment the thickness of the resin composition on a prism lens mold 11 is applied such that the 50μm and sikimyeo station adhesive PET film 100μm adhesive thickness (Oriental room A4300) as described above that of 600mJ / cm ² by a high-pressure mercury lamp from above, Irradiated with ultraviolet rays, cured, and peeled to obtain a prismatic lens sheet.

Evaluation results

Releasability:?, Shape reproducibility:?, And adhesion:?.

Example 16

Embodiment the thickness of the resin composition on a prism lens mold 12 is applied such that the 50μm and sikimyeo station adhesive PET film 100μm adhesive thickness (Oriental room A4300) as described above that of 600mJ / cm ² by a high-pressure mercury lamp from above, Irradiated with ultraviolet rays, cured, and peeled to obtain a prismatic lens sheet.

Evaluation results

Releasability:?, Shape reproducibility:?, And adhesion:?.

Comparative Example 5

70 parts of Aronix M-315 (tris (2-acryloyloxyethyl) isocyanurate), 30 parts of tetrahydrofurfuryl acrylate, 30 parts of tetrahydrofurfuryl acrylate, And 3 parts of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one as a photopolymerization initiator were heated to 60 DEG C 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 film obtained by curing the resin composition was 1.52.

From this result, the composition of Comparative Example 5 has a lower refractive index than that of the composition of the present invention, and is not suitable for the production of the lenses of the present invention.

Comparative Example 6

According to the embodiment of Patent Document 9 (Japanese Patent No. 3209554), the urethane acrylate of the synthetic example 1 of the document (polyester diol of neopentyl glycol and adipic acid, ethylene glycol, tolylene diisocyanate and 2-hydroxyethyl acrylate And a compound of Synthesis Example 3 (o-phenylphenol diethoxyacrylate) were synthesized. Specifically, 120 parts of a polyester diol (polyester diol having neopentyl glycol and adipic acid, molecular weight 2000, OH value 56.1), 2.48 parts of ethylene glycol, and 34.8 parts of tolylene diisocyanate were charged. After the temperature was raised, the mixture was reacted at 80 DEG C for 10 hours Then, 24.4 parts of 2-hydroxyethyl acrylate and 0.1 part of methoquinone were charged and reacted at 80 DEG C for 10 hours to obtain urethane acrylate. Further, 258 parts of the compound represented by the following formula (6)

(Product name: Newpol OPE-20, OH value: 217.5), acrylic acid (86.5 parts), toluene (300 parts), sulfuric acid (21 parts), hydrotreated silica (1 part by mass of O-phenylphenol and 2 moles of ethylene oxide, manufactured by Sanyo Chemical Industries, And 5 parts of quinone were charged. The water produced by heating was distilled and condensed with the solvent, and the reaction mixture was cooled when 18 parts of water was produced by the separator. The reaction temperature was 130 to 140 ° C. The reaction mixture was dissolved in 500 parts of toluene, neutralized with a 20% aqueous solution of NaOH, and then washed three times with 100 parts of 20% aqueous NaCl solution. The solvent was distilled off under reduced pressure to obtain 303 parts of a compound (B) (liquid) (o-phenylphenol diethoxyacrylate). The viscosity (25 DEG C) was 204 CPS and the refractive index (23 DEG C) was 1.567. 30 parts of the urethane acrylate, 15 parts of o-phenylphenol diethoxyacrylate, 45 parts of KAYARAD R-551 (bisphenol A tetraethoxydiacrylate), 10 parts of tribromophenyl acrylate, 3 parts of Guria 184 (1-hydroxycyclohexyl phenyl ketone) were heated to 60 캜 and mixed to obtain a comparative resin composition. The viscosity of this resin composition was 4420 mPa · s. The refractive index (25 DEG C) of the film obtained by curing the resin composition was 1.574.

From this result, the composition of Comparative Example 6 has a higher viscosity than the composition of the present invention, and is not suitable for fine processing or continuous processing of roll-like sheets or films.

As can be seen from the evaluation results of Examples 8 to 16 and Comparative Examples 5 and 6, the resin composition of the present invention having a specific composition is excellent in releasability, form reproducibility and adhesion to a substrate, and the cured product has a glass transition point The temperature (Tg) was 50 DEG C or more and the light resistance was good. Therefore, it is suitable for an optical lens sheet having a fine structure, such as a Fresnel lens, a wrench cure lens, a prism lens, a microlens, or the like. Particularly, it is suitable for applications requiring fine processing or manufacturing including processes requiring continuous processing.

The ultraviolet ray 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 wrench cure lens, a prism lens and a microlens.

Claims (20)

(1)

(B) and an aromatic polyisocyanate compound (c) are reacted with an epoxy resin (a) obtained by reacting a compound represented by the following general formula (1) with epihalohydrin As the urethane compound (A) The urethane compound (A) wherein the compound represented by the general formula (1) is p-phenylphenol (P-PP). The compound (A) according to claim 1, wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is a reaction product of (meth) acrylic acid, (meth) acrylic acid and? -Caprolactone or cinnamic acid. The compound (A) according to claim 1, wherein the monocarboxylic acid compound (b) having an ethylenic unsaturated group in the molecule is acrylic acid. The compound (A) according to claim 1, wherein the aromatic polyisocyanate compound (c) is a compound having an aromatic ring having 5 to 15 carbon atoms. The compound (A) according to claim 1, wherein the aromatic polyisocyanate compound (c) is 2,4-tolylene diisocyanate. The compound (A) according to claim 1, which has a liquid refractive index of 1.59 or more. delete delete delete delete delete delete delete delete delete delete delete delete delete delete