TW200911862A - (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

Disclosed is a photosensitive resin which is excellent in transparency, while having high refractive index and high adhesion by the resin itself. This photosensitive resin provides a cured product having a sufficient hardness. Also disclosed is a resin composition for optical lens sheet, which is excellent in mold releasability, mold reproducibility, adhesion to a base, while having high refractive index, high glass transition temperature and good light resistance. Specifically disclosed is a urethane compound (A) characterized by being obtained by reacting an epoxy resin (a), which is obtained by reacting a compound represented by the general formula (1) below with epihalohydrin, a monocarboxylic acid compound (b) having an ethylenically unsaturated group in a molecule, and an aromatic polyisocyanate compound (c). Also specifically disclosed is an energy ray-curable resin composition for optical lens sheet, which is characterized by containing the urethane compound (A) and a photopolymerization initiator (B).

Description

200911862 IX. OBJECTS OF THE INVENTION: The present invention relates to a compound containing an unsaturated group having a specific structure and having excellent transparency and excellent transparency, and a tree-containing compound thereof Hardened material. Examples of the use thereof include a film coating material, a solder resist for printing (wiring circuit) substrate, a plating resist 'adhesive agent, a lens, a display, an optical fiber, an optical waveguide, a hologram, and a coating agent.

Further, the present invention relates to an optical lens sheet (four) energy ray-curable resin: and a cured product thereof. More specifically, it relates to a sapphire composition and a cured product which are particularly suitable for use in phenanthrene lenses, flat reading lenses, prism lenses, microlenses # lenses. [Prior Art] In recent years, development of a photosensitive material having a transparent energy-sensitive ray-heating and high refractive index, which has been made into an active energy ray, has been developed in various applications (Patent Documents 1 to 3). In these applications, in addition to high heat resistance and high refraction, 'the adhesion to the substrate, the hardness of the cured product, the solubility to the test, etc. are required'. In order to cope with such requirements, in most cases, monomer is added. Or additives such as fillers. However, it is difficult to express the characteristics of the organic material because the refractive index is lowered by adding such an additive, and therefore it is necessary to increase the heat resistance or refractive index of the resin itself. Further, Patent Document 4 discloses that a reaction product of o-phenyl phenyl iglycidil scale and (meth) acrylic acid is used as an optical material. However, this method is not a single g of this (fluorenyl) acrylate, and there is a hardened 130737.doc 200911862 degree heat resistance and a liquid refractive index of about 1.58, so as a compound Still not reaching the level of satisfaction. Further, in Patent Document 5, the product of the reaction of an aromatic glycidyl compound, a (meth)acrylic acid, and a polyvalent isocyanate compound. However, at this time, the use was a dye-receiving resin, and an aliphatic isocyanate compound was used in the examples, and finally no optical characteristics were found. In recent years, a photosensitive acrylic hard coater has been used as a hard coat material which has high hardness, scratch resistance, and adhesion, and has a high refractive index, a high hardness, and a low shrinkage. Patent Document 6 describes a hard coat layer which imparts various functions such as processing speed, hardness, scratch resistance, continuous processing, anti-reflection, and antistatic. Further, the above-mentioned lens such as the "previous" phenanthrene lens is formed by a method such as a pressing method or a casting method. The former pressing method is manufactured by heating, pressurizing, and cooling cycles, so that productivity is poor. Further, the latter casting method has a problem in that it is polymerized by injecting a monomer into a mold, so that a long production time is required and a plurality of molds are required, so that the manufacturing cost increases. In order to solve such a problem, various proposals have been made for the use of the ultraviolet curable resin composition (Patent Document 7 and Patent Document 8). There is known a method of producing an optical lens sheet for a transmissive screen or the like by using the ultraviolet curable resin composition. However, the cured product of these prior resin compositions has a problem in that the adhesion to the substrate and the mold release property from the mold are inferior. If the adhesion is poor, the type of the substrate that can be used is limited, and it is difficult to obtain the optical property having the desired properties. If the mold release property is poor, the resin remains on the mold at the time of demolding, and the mold can no longer be used. 130737.doc 200911862 In addition, the combination of the resin of the hardened material with good adhesion to the substrate is also good, so the mold release property is easy (four) is poor, and on the other hand, the mold release property is good. The problem that sex is prone to deterioration. Therefore, a resin composition which satisfies both properties of adhesion to a substrate and mold release property from a mold has been proposed, and Patent Document 9 has been proposed. The resin composition which can be used for such an optical lens sheet or the like is reinforced into a finer shape or carried out as the image of recent years is highly refined.

It is required to be processed at a lower thickness or in order to be continuously processed on a roll-shaped sheet or film. Further, it is also required that the fine structure is less likely to be broken when the lens sheet is wrapped, and at this time, a high glass transition temperature (Tg) is required. Further, there is a tendency that the physical property change is small even when the optical lens sheet is used in a high-temperature environment, and it is required to supply a cured product having a glass transition temperature (Tg) as high as possible; for the purpose of long-term use, it is not caused by coloring. Physical properties are declining, but those with good light cut are good. ❻, which has a higher refractive index, a higher Tg temperature, a mold release property, a denseness, a low viscosity, and a light resistance, is more difficult and cannot be obtained. [Patent Document 1] International Publication No. 2002/033447 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-188588 (Patent Document 7). Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. An object of the present invention is to provide a compound which is excellent in transparency and has a high refractive index in a resin alone, and further provides a cured product comprising a resin composition having a relatively high consistency and a sufficient hardness. Therefore, the photosensitive resin composition of the present invention is suitable for producing a film forming material, a solder resist for printing (wiring circuit) substrate, a plating resist, an adhesive, a lens, a display, an optical fiber, an optical waveguide, and the like. Photo film. Further, it is also suitable for use in a film having a hardened film of a compound and a photosensitive resin composition which can be applied to a low-cracking film which can be coated with a thick film and which does not cause cracking. Another object of the present invention is to provide a low-viscosity resin composition suitable for producing lens sheets such as Fresnel lenses, lenticular lenses, prism lenses, and microlenses, and excellent in mold release property, mold reproducibility, and adhesion. , & a high refractive index and good light resistance. [Means for Solving the Problem] The present inventors have made an effort to solve the above problems, and as a result, have found that a compound containing an unsaturated group having a specific structure and a composition thereof can solve the above problems and complete the present invention. That is, the first example of the present invention relates to: (1) a urethane compound (A) characterized in that it is an epoxy resin (4), a monocarboxylic acid having an ethylenically unsaturated group in its molecule. Acidification: 130737.doc 200911862 (b), which is obtained by reacting with an aromatic polyisocyanate compound (c), wherein the epoxy resin (a) is a compound represented by the following formula:

(2) The compound (A) according to (1), wherein the monosodium oxyacid compound (b) having an ethylenically unsaturated group in the molecule is (meth)acrylic acid, (meth) a reaction product of acrylic acid and ε-caprolactone or cinnamic acid; (3) a compound (a) according to (1) or (2), wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is acrylic acid (4) The compound of any one of (1) to (3) wherein the aromatic polyisocyanate compound (c) is a compound having an aromatic ring having a carbon number of 5 to 5; (5) as (1) The compound (A) in any one of (4) wherein the aromatic polyisocyanate compound (c) is 2,4-nonyl diisocyanate; (6) as in any one of (1) to (5) The compound (a) having a liquid refractive index of 159 (7) is a photosensitive resin composition containing the compound (A) according to any one of (1) to (6), and (A) (B) The photosensitive resin composition of (7), wherein the polymerizable compound (b) is selected from the group consisting of (poly)ester (meth)acrylate (7)-oxime, an amine Formate (meth) acrylate (B-2), (meth) acrylate epoxy (B-3), (poly) ether (fluorenyl) acrylate (B-4), (mercapto) acrylic acid An alkyl ester or alkyl (meth) acrylate 5), an aromatic ring (fluorenyl) acrylate (b_6) and an alicyclic structure 130737.doc 200911862 (meth) acrylate (B-7), containing One or more compounds of the group consisting of a compound of the maleimide group (B-8), a (meth)acrylamide compound (B_9), and an unsaturated polyester (b_i〇); (9) The photosensitive resin composition of (7), wherein the polymerizable compound (b) is selected from the group consisting of amino phthalate (methyl) phthalic acid vinegar (B 2 ), (meth) acryl, or (meth) a compound of more than one kind consisting of alkyl acrylate (B-5) and a group of (meth) acrylate (B-6) having an aromatic ring; (10) as in (7) to (9) The photosensitive resin composition of any one of the photosensitive resin composition of any one of (7) - (10), and the hardening of the photosensitive resin composition of any one of (7) - (10); ) a film, Has a hardened material such as (U). In order to solve the above problems, the present inventors have found that the ultraviolet curable resin composition having a specific composition and a cured product thereof can solve the above problems, and the present invention has been completed. That is, the second aspect of the present invention relates to: (13) An energy ray-curable resin composition for an optical lens sheet, which comprises a urethane compound (A) and a photopolymerization I δ Starting agent (C), the above amino phthalate compound (Α) is a compound of the following formula (1): [Chemical 2]

130737.doc • 11 - 200911862 Epoxy resin (a) of the reaction product with epi-alcohols (a) mono-retinoic acid compound (b) having an ethylenically unsaturated group in the molecule, and an aromatic polyisocyanate compound ( (C) a resin composition according to the above (η), a monobasic acid compound (8) having an ethylenically unsaturated group in the oxime, (meth) acetoic acid, (methyl) The reaction product of C (4) and ε·内内 S or cinnamic acid, the aromatic polyisocyanate compound (c) is an aromatic diisocyanate monomer; (15) as described in (13) or (14) above a resin composition, wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group, the acetoic acid vinegar compound (4) is 2,4·toluene diisocyanate; (16) as described above (13) The resin composition according to any one of (15), which further comprises a monoacrylic acid ester monomer (D) having a phenyl group; (17) The resin composition according to the above (16), which has a phenyl ether group Monoacrylic acid vinegar monomer (D) is o-phenylphenol (poly) (meth) acrylate ethoxy vinegar, p-phenyl benzene (poly) (meth) acrylate B Ester, o-phenylphenol (meth) acrylate epoxy ester, p-phenylphenol (meth) acrylate epoxy ester; (18) The resin composition according to any one of the above (13) to (17) Further, the (meth)acrylic acid vine compound (e) other than the urethane compound (A) or the monoacrylate monomer (D) having a phenyl ether group; (19) a cured product The resin composition obtained by curing the resin composition according to any one of the above (13) to (17), and having a refractive index of 251 or more at 251; (20) an optical lens sheet which is used as described above ( 19) Hardened material. [Effects of the Invention] The resin of the compound (A) of the present invention has a high refractive index alone and is excellent in transparency. 130737.doc -12-

200911862, the resin composition of the present invention containing the same has a low degree of crimping, so that the hardening shrinkage is less, and the hardened material is sturdy and has sufficient hardness due to the fact that it has a firmness. It can be effectively used as a coating agent for transparency. Therefore, the compound (4) of the present invention and the resin composition containing the same can be effectively used for various lenses such as a phenanthrene lens, a flat lens, a prism lens, a micro material, a core material of an optical fiber, a coating material, and a light wave. Optical applications such as various optical materials such as catheters and parts. "The energy ray-curable resin composition of the present invention has a low viscosity, and has excellent mold release property, mold reproducibility, and adhesion to a substrate, and has a high refractive index and good light resistance.邡%邡, w & sub-j is used for an optical lens sheet such as a Fresnel lens, a lentil lens, a prism lens, or a microlens. [Embodiment] The compound (4) of the present invention is characterized in that it is aromatic The polyisocyanate compound (4) is reacted with an epoxy resin (4) and a mono-reactive acid compound (8) having an ethylenically unsaturated group in the molecule, and the epoxy resin (4) is represented by the following formula (1). The compound is reacted with the epidentate alcohol. [Chemical 3]

(I) The energy ray-curable resin composition of the present invention is characterized by comprising an amino phthalate compound (A) and a photopolymerization initiator (c), and the urethane compound (A) An epoxy resin (a) which is a reaction product of a compound represented by the above formula (1) and an epihalohydrin, an ethylenic acid compound (8) having an ethylenic unsaturated J30737.doc 200911862 and a molecule, and The aromatic polyisocyanate compound (C) is reacted. Examples of the compound represented by the formula (1) include o-phenylphene and p-phenylphenol. Commercial products of such a compound include, for example, o_pp and p_pp (all manufactured by Sanguang Co., Ltd.). The epoxy resin (4) of this month, that is, phenyl benzene (meth) acrylate epoxy s 曰 can be used in the presence of a metal hydroxide to make the compound of the above formula (1)

Reacted with the table _. The phenyl (meth) acrylate acid acetonate can be used as the mono acrylate monomer (D) having a silyl ether group in the present month. In the reaction for obtaining the epoxy resin (4) used in the present invention, as the surface alcohol, an epigas alcohol, a " epichlorohydrin, γ-methylepichlorohydrin, an epi-lol, etc. may be used. In the invention, it is preferred that the industrially readily available surface chlorine is used in an amount of usually 2 to 20 moles, preferably 3 to 15 moles, based on the (IV) i mole of the compound of the formula (1). Examples of the metal hydroxide which can be used in the above reaction include gas oxygen (10) 'hydrogen (four)', which can be either a solid matter or an aqueous solution. When an aqueous solution is used, the method may be as follows: an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and the water is removed under reduced pressure or often = distilled water, and the liquid is removed to remove the water. The tooth alcohol continuously returns to the reaction system. The amount of the base metal hydroxide to be used with respect to the compound of the formula (1) is usually mountain (I). 〇 Mo Erguang, is 0.3~5.0 Moule, and better is 〇8~3〇 Mo Er. Oh, bromotetrazol. In order to promote the reaction, it is preferred to add a quaternary ammonium salt such as vaporized tetramethylammonium chloride or trimethylbenzylammonium chloride as the Ammonium I30737.doc-J4-200911862 level salt salt. (4) The amount 'with respect to the base of the compound of the formula (1) is generally (U~2Gg, preferably G2~i5g. 1) in terms of reaction progress, it is preferable to add methanol =, different = aliphatic alcohols such as alcohols, aprotic polar solvents such as dimethyl, dimethyl (tetra), tetrachlorine, and alkane, etc. When using alcohols, the amount of the opposite main k relative to the epihalohydrin It uses 1~50 weight 〇/〇, preferably “壬θ 里通吊马... 疋 2~30 weight 1%. Also, use aprotic pole. Life agent, relative to the dentate alcohol The reaction amount is usually 3 to 10 parts by weight / 〇', preferably 5 to 80% by weight. The reaction temperature is usually 3 G to 1 GG t, preferably deuteration. The reaction time is usually G. 2 to 1 G hour. Preferably, it is Q5 to 8 hours. After the reactants of the epoxidation reaction are washed with water or not, the epirudol or solvent is removed under heating and reduced pressure. Further, in order to produce an epoxy resin having less hydrolyzable dentate, the recovered epoxy resin may be dissolved in a solvent such as toluene or methyl isobutyl ketone, and a metal gas such as sodium hydroxide or potassium hydroxide may be added. The aqueous solution of the oxide is subjected to the reaction 'and the ring closure is accurately performed. At this time, the amount of the hydroxy oxime base metal hydroxide relative to the compound of the formula (1) used for the epoxidation is usually 〇.〇1 to 0.5. Mohr, preferably 〇〇5~〇3mol. The reaction temperature is usually 5〇~12〇t; and the reaction time is usually (1) hour. After the reaction is finished, it is removed by filtration, washing with water, etc. The resulting salt is further subjected to heating under reduced pressure to obtain a solvent of the present invention. By the method represented by such a formulation, an epoxy resin mixture which can be used without special purification can be obtained. .doc 15- 200911862 The production of the compound (A) of the present invention can be obtained by first reacting the above epoxy resin (a) with a monoacid compound (b) having an ethylenic group and a molecule in the molecule. (hereinafter, referred to as the first reaction Then, the generated radical is reacted with the aromatic polyisocyanate compound (c) (hereinafter referred to as a second reaction) as a mono-retensive compound having an ethylenically unsaturated group in the molecule (b) For example, acrylic acid or crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl compound containing an unsaturated group can be cited as an acrylic acid, for example, Listed: (meth)acrylic acid, β-styryl acrylic acid, β-furan methacrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, as a saturated or unsaturated dibasic acid anhydride and having 1 molecule a half ester of a molar reaction of one hydroxyl group (meth) acrylate derivative, a molar reactant such as a saturated or unsaturated dibasic acid and a (meth)acrylic acid monoglycidyl ester derivative Semi-esters and the like. As the sensitivity in the case where the molecule has an ethylenically unsaturated group and the photosensitive resin composition is formed in a dry state, it is preferred that (meth)acrylic acid or (mercapto)acrylic acid and The reaction product or cinnamic acid is particularly preferred as (meth)acrylic acid. The first reaction may be carried out in the absence of a solvent, or may be carried out in a solvent having no alcoholic radical or in a separate or mixed organic solvent of various monomers, as described above, for example, a solvent having no alcoholic hydroxyl group, for example : acetone, ethyl methyl ketone, ketones such as ketone, aromatic hydrocarbons such as benzene, toluene, xylene, tetramethylbenzene, ethylene glycol dimethyl hydrazine, ethylene glycol diethyl ether, dipropylene glycol dimethyl 130737. Doc • 16 - 200911862 Ether ethers such as ether, dipropylene glycol diethyl ether, triethylene glycol dioxime ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, B Cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether monoacetate, dialkyl glutarate, dialkyl succinate, adipate dioxane An ester such as an ester, a cyclic ester such as γ-butyrolactone, a petroleum solvent such as petroleum ether, petroleum brain, hydrogenated petroleum brain, or solvent petroleum brain; and the above various single systems contain a monoacrylate monomer (D) described later. Or various monomers of the (meth) acrylate compound (Ε), for example: acrylonitrile? , a terminal acrylate ester of an epoxy Ethylene burn adduct of 2-phenylphenol (for example, manufactured by Nippon Kayaku Co., Ltd., ΟΡΡ-1, ΟΡΡ-2), polyethylene glycol bis(indenyl) Acrylate, tripropylene glycol bis(indenyl) acrylate, trishydroxypropyl propane tris(decyl) acrylate, dipyridyl propyl alcohol polyethoxy tris(decyl) acrylate vinegar, glycerol polypropoxy bis ( Acetyl acrylate, hydroxypivalic acid, neopentyl glycol, mono-caprolactone, bis(indenyl) acrylate (for example, 曰本化药(股), KAYARAD ΗΧ- 220, ΗΧ-620, etc.), pentaerythritol tetrakis(mercapto) acrylate, a mixture of dipentaerythritol and bupreperrol, a poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, and the like. As the feed ratio of the raw material in the first reaction, the amount of the monocapric acid compound having an ethylenically unsaturated group in the molecule is preferably from 60 to 140 equivalent %, more preferably, relative to the epoxy resin (small equivalent weight). It is (10)~丨^, although it is %. When feeding in this range, there is less concern about gelation in the reaction, and the thermal stability of the obtained compound (Α) is also high. In order to promote the reaction, it is preferred to use a catalyst, a reagent, and the amount of the catalyst used when the catalyst is used is 反 for the inverse amount. The reaction temperature of this 130737.doc -17- 200911862 is 60 to 15 〇. 〇, again,; 5 + * " The time should be preferably 5 to 60 hours. As a specific example of the catalyst to be used, + for example, a tri-neck, benzyl dimethylamine , triethylammonium chloride, benzyl bromide, male: 3⁄4: it: r methyl ammonium, triphenyl phosphine, triphenyl sulfonium, methyl, soil - I 绨, octanoic acid, decanoic acid and so on. In the sucking, the thermal polymerization inhibitor is used again, and as p, and the system is exemplified by: p-|two-year-old monomethyl ether, 2-methyl hydroquinone, pair 5 phenol, 2,6-di-third

The amount of C-p-p-phenol, diphenyl-bitterin, diphenyl sulfonamide, etc. used is preferably 〇丨 丨〇 丨〇 by weight relative to the reactant. As for the reaction, one side is appropriately sampled, and the acid value of the sample is 5 mg.K0H/gM, preferably 3 times the gamma (four) is used as the end point. As the aromatic polyisocyanate compound (c) used in the first reaction, it is easy to obtain, and it is used to describe the strength of the cured film which is used for the density of the same precursor. Further, a compound having a carbon number of 5 to 15 and having an aromatic ring is, for example, a toluene diiso-acid such as 2,4-toluene diiso-acid, and a toluene diisocyanate. Diphenylmethane diisocyanate, D-naphthalene diisocyanate, tolidine diisocyanate, M-benzene diisocyanate: diisocyanate monomer such as 1,6-benzene diisocyanate Classes, etc. Among them, particularly preferred is 2,4·toluene diisocyanate. The compound (A) of the present invention can be obtained by reacting the product obtained in the above first reaction with the aromatic polyisocyanate compound (c). By using an aromatic polyisocyanate compound, the present invention can be achieved. The refractive index of the resin (A) is high, and the hardening shrinkage of the resin composition of the present invention is less. I30737.doc 200911862 Less, the cured product of the present invention has high adhesion and sufficient hardness. As the amount to be used, it is not particularly limited that it is preferred to carry out the reaction in an equivalent relationship such that no NCO group remains after the reaction. When the addition (reaction) equivalent of the aromatic polyisocyanate compound (4) is in a preferable range, the monofunctional (meth)acrylic acid vinegar hardly remains, so that a resin having excellent heat resistance, hardness, and refractive index can be obtained. Moreover, since the molecular weight in the reaction is easily controlled, it is not easy to cause gelation. Further, the viscosity of the product can be appropriately controlled, so that the workability is good. Specifically, 'relative to the product obtained in the first reaction, ^H^(10)], and the equivalent of ().()5~0.99 mob is equivalently fed to the Fangxiang family. Polyisocyanate compound (c) 2NC fluorenyl. The reaction can be carried out in the absence of a solvent, but in order to improve the viscosity of the product, the workability can be carried out in the above solvent having no alcoholic base or in separate or mixed organic solvents of various precursors. At this time, the above thermal polymerization inhibitor can be further added. The reaction temperature is usually 30 to 15 (TC' is preferably in the range of 5 Torr to 1 Torr. The end point of the reaction is confirmed by the back titration method to reduce the amount of isocyanide. In order to shorten the reaction At the time, a catalyst can be added. As the catalyst, any one of an inert catalyst and an acid catalyst can be used. As an experimental catalyst, an example can be cited as: (d) ... ratio, triethylamine, diethylamine, An amine such as dibutylamine or feng shui, such as tributylphosphine or triphenyl sulphate. Further, as an example of an acidic catalyst, there may be mentioned copper succinic acid, cyclosporic acid chain, and sulphuric acid sulphur. Butyl ketone, titanium tetraisopropoxide, tetrabutoxy oxychloride, chlorinated, 2-ethyl: tin, octyl tin trilaurate, dibutyltin dilaurate, octanoic diacetate 4 Lewis acid Catalyst. Total amount by weight of the second reaction mixture 130737.doc -19· 200911862 100 parts by weight 'The addition amount of the catalyst is usually 0.00H weight = the refractive index of the compound (4) of the invention is higher, preferably It is a kind of lens such as a Philippine lens, a lentil lens, a prism lens, a microlens, etc. The core material and cladding material of the light wind fiber , Optical waveguides, hologram displayed: Use the optical components and the like and other various optical materials °

The photosensitive resin composition of the present invention contains the compound (4) of the present invention and a polymerizable compound (8) other than the component (4). Specific examples of the polymerizable compound (B) which can be used include a compound having a (meth)acryloxy group, a maleimide compound, a (fluorenyl) group: an oxime compound, and an unsaturated group. Polyester, etc. Specific examples of the compound having a (meth)acryloxy group which can be used in combination in the photosensitive resin composition of the present invention include (poly)ester (meth)acrylate (B-1); and amine group A. Acid ester (meth) acrylate (B 2 ); (meth) acrylate epoxy ester (B-3); (poly) ether (meth) acrylate (B_4); alkyl (meth) acrylate or (A) (alkyl) acrylate (B_5); (meth) acrylate having an aromatic ring (B-6) having a alicyclic structure (B_7), etc., but is not limited thereto. The (poly)ester (meth)acrylate (B-1)' which can be used in combination in the photosensitive resin composition of the invention is used as a general term for (meth)propionate having i or more ester bonds in the main chain. a urethane (meth) acrylate acid vinegar (B 2 ), which is a general term for (meth) acrylate having one or more amino phthalate linkages in the main chain; (meth)acrylic acid; The epoxy ester (B-3) is a general term for (meth) acrylate obtained by reacting a monofunctional or higher epoxy compound with (mercapto)acrylic acid; (poly) (methyl)-propyl acetoacetate (B-4), which is used as a general term for (meth) acrylate having an ether bond at I30737.doc •20-200911862 in the main chain; The ester or alkylene (meth)acrylate (B_5) is used as a (meth) acrylate whose main chain is a linear alkyl group, a branched alkyl group, a straight chain or a terminal group having a hydroxyl atom and/or a hydroxyl group. A general term for a (meth) acrylate having an aromatic ring (B_6), which is used as a general term for a (meth) acrylate having an aromatic ring in a main chain or a side chain; (fluorenyl) acrylate having an alicyclic structure (Β·7) is a general term for (meth)acrylic acid vinegar having an alicyclic structure which may contain an oxygen atom or a nitrogen atom in a constituent unit in a main chain or a side chain. The photosensitive resin composition of the present invention The (poly)ester (meth)acrylic acid Ss (Β-1) which can be used together can be exemplified by hexyl vinegar modified (mercapto) propylene

鲅2 hydroxyethyl g 曰, ethylene oxide and / or propylene oxide modified phthalic acid (meth) acrylate vinegar, epoxy epoxide modified succinic acid (meth) acrylate vinegar, hexene Monofunctional (poly) vinegar (meth) acrylate vinegar such as modified (methyl) acrylate tetrahydrocyanate methyl vinegar; neopentyl glycol di(methyl) acrylate Vinegar, hexidine modification (4) pivalic acid S is neopentyl glycol di(methyl) propylene (four), surface alcohol alcohol modified J · raw neighbor _ formic acid di(methyl) acrylate vinegar; Adding more than 1 mole of ester to methyl propylene or molybdenum, butyl vinegar, δ pentane and other cyclic internal vinegar compounds to obtain the enoate; the second (f-based) propyl hydrazine a cyclic lactone compound such as ε-caprolactone of cockroaches, a triol of butanesine, a valerate of pentane vinegar, etc. to obtain i or tetra(meth) acrylate, and is added to dipentaerythritol 1 molar -1 early, or poly(methyl) obtained by the formation of a mono-lactone compound such as ε_caprolactone, P-butyrolactone, or δ-valerolactone in the ring Acrylate 130737.doc 200911862 diol, tetraol, pentaol or a mono (meth) acrylate of a polyol such as an alcohol, or a poly(meth) acrylate; (poly)ethylene glycol, (poly)propylene glycol, (poly) 14-butanediol, (poly)butanediol, a diol component such as 3-mercapto-pentanediol or hexanediol, and maleic acid, butyric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, and hexahydrogen a polybasic acid such as phthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, sebacic acid or sodium 5-thioisophthalate, and a reactant of the acid anhydride, that is, a polyester polyol (N-based) acrylate; modified by the above diol component and polybasic acid and the anhydride, and ?_caprolactone, 丫_butyrolactone, δ-valerolactone, etc. The (poly) vinegar (meth)acrylic acid vinegar or the like of the polyester diol (S) such as S (meth)acrylic acid is not limited thereto. The amino phthalate (meth) acrylate (B-2) which can be used in combination in the photosensitive resin composition of the present invention is a hydroxy compound (B-2) having at least one (meth) acryloxy group. -1) A general term for (meth) acrylate obtained by reaction with an isocyanate compound (B_2_2). Specific examples of the hydroxy compound (Β·2_1) having at least one (meth) propylene fluorenyloxy group include, for example, (meth)acrylic acid 2-hydroxyethyl ester and (meth)acrylic acid-2-hydroxyl group. Propyl ester, 2-hydroxybutyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Various (meth) acrylate compounds having a hydroxyl group such as ester, polypropylene glycol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-phenoxypropyl vinegar And the ring-opening reactant 130737.doc-22-200911862 and the like having the above-mentioned (meth) acrylate compound having a hydroxyl group and ε_caprolactone.

Specific examples of the isocyanate compound (B-2-2) include p-phenylene diisocyanate, isophthalic diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, and 2,4-nonylbenzene. Aromatic diisocyanates such as isocyanate, 2,6-nonyl diisocyanate, 4,4,-diphenylmethane diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, 6 hexane diisocyanate, 4, 4'_Dicyclohexyldecane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, diisocyanate or other diisocyanate of dicyclic isocyanate; one or more biuret of isocyanate monomer Or a polyisocyanate such as an isocyanate obtained by tri-polymerizing the above-mentioned diisocyanate compound; and a polyisocyanate obtained by the amide grouping reaction of the above isocyanate compound with the above-mentioned polyol compound. The (meth)acrylic epoxy vinegar (B.3) which can be used together in the resin composition is an epoxy resin Γ and (meth)acrylic acid containing an epoxy group having a monofunctional or higher functional group. It is obtained by (meth) acrylate, 8 general term for the purpose of. Specific examples of the epoxy resin which is a raw material of (meth)acrylic epoxy vinegar include: hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether Phenyl diglycidyl ether; bisphenol A type epoxy tree =, double 酴 F type epoxy resin, double s type epoxy tree, 2, 2 _ double (4_ 备基基基)-1, Bismuth type epoxy compound such as 1,1,3,3,3_hexa-1 propylene oxide compound; hydrogenated bisphenol eight type epoxy resin, hydrogenated double fat, hydrogenated bisphenol S type epoxy oxime, gas虱桠The main exhibition of yew tree 曰, 虱化 2,2_ bis(4_hydroxyphenyl)_ ^ to hydrogenate from six propylene-like epoxy compounds, such as epoxidized 130737.doc -23- 200911862 Double-aged A-type epoxy resin, desertified double-type epoxy resin, etc. _ bisphenol i% oxygen compound; ring. 巳 巳 一 T T T T T ; ; ; ; ; ; ;; Compound; hexane diol diglycidyl ether, _ diglycidyl ether, diethylene glycol diglycidyl ether and other fat-dicondensation: glycerol scaly compound; polysulfide diglycidyl (tetra) and other polysulfide 'shrinkage Gan, from ether compounds; phenol novolac type epoxy resin, nail = secret varnish type epoxy resin, tris-phenylene type U epoxy resin, two

Cyclopentadiene phenol type epoxy resin, biphenol type epoxy resin, bisphenol_A phenol varnish type epoxy resin, epoxy resin containing material rack, heterocyclic resin, and the like. The (poly)ether (fluorenyl) acrylate (B-4) which can be used in combination in the photosensitive resin composition of the present invention is, for example, butoxybutoxybutyric acid (meth)acrylate. (fluorenyl) acrylate, surface alcohol modified butyl (meth) acrylate, dicyclopentynyloxyethyl (meth) acrylate, (meth) propylene I 2 ethyl lactyl g 曰, ethyl Monofunctional (poly)ether (mercapto)acrylic acid such as carbitol (meth) acrylate vinegar, phenoxyethyl (meth) acrylate, decyl phenoxy polyethylene glycol (meth) acrylate Ester; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, polytetramethylene glycol di(meth) Alkyl diol di(indenyl) acrylates such as acrylate; copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, polyisoprene diol, hydrogenated polyisoprene a polyhydroxy compound such as a hydrocarbon-based polyol such as an olefin diol, a polybutadiene diol or a hydrogenated polybutadiene diol A polyfunctional (meth) acrylate of the genus B. sinensis; a cyclohexane or a propylene acrylate in the ear of neopentyl diol 1 Mo 130737.doc -24· 200911862 Burning, butyl epoxide, diol di(methyl) propylene soldering acid; Dingkeng and other double A, double F, double S and other double-anti-epoxy curing Body base) acrylic acid vinegar; gasification double hopping eight, chlorination double bismuth gasification double s S, etc. ^ bis double-type epoxy burning modified body of two (meth) acrylate; in three ... Burning or glycerin 1 molar addition of more than 1 mole of epoxy bake, epoxy:

a mono-, di- or tri(methyl) acrylate of a triol derived from a cyclic ether compound such as an alkane or a butylene oxide; S is in the quaternary tetral or di-trimethyl methacrylate 1 mil Adding mono-, mono-, di- or tetra (meth) acrylate of monohydric alcohol obtained by adding a cyclic ether compound such as oxyethylene bromide, propylene bromide or butyl epoxide to more than 1 mol; in dipentaerythritol 1 Polyfunctional (poly) such as 3- to 6-functional (sub) acrylate of hexaol obtained by adding a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to 1 mol or more Ether (methyl) propionic acid § class and the like. The (meth)acrylic acid ruthenium or (mercapto)acrylic acid sinter (B-5) which can be used together in the photosensitive resin composition of the present invention, for example, (meth)acrylic acid vinegar, (A) Monofunctional (meth) acrylates such as isooctyl acrylate, methacrylic acid (meth) acrylate vinegar, and dodecyl (meth) acrylate; ethylene glycol di(meth) acrylate, propylene glycol di(a) Acrylate, i,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid, neopentyl glycol di(meth)acrylate, 2·a Base-oxime, 8-octyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ι,1〇-nonanediol di(meth)propionate, etc. Di-(mercapto) acrylates of methacrylic acid; mono(meth) acrylate, di(meth) acrylate of trimethylolpropane 130737.doc •25- 200911862 or tris(decyl)acrylic acid Ester (hereinafter, "poly" is used as a general term for the second, third, and fourth polyfunctional groups.) 'Single (meth) acrylate or poly(methyl) Acrylate, mono- or poly(methyl) acrylate of pentaerythritol, mono- or poly(indenyl) acrylate of di-trihydroxydecylpropane, mono- or poly(indenyl) acrylate of dipentaerythritol Mono- or poly(meth)acrylates of polyols such as alcohols, tetraols, hexaols, etc.; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) A hydroxyl group-containing (meth) acrylate such as 4-hydroxybutyl acrylate.

The (meth) acrylate (B-6) having an aromatic ring which can be used in combination in the photosensitive resin composition of the present invention may, for example, be (meth)acrylic acid benzene vinegar or (mercapto)propionic acid vinegar. a monofunctional (mercapto) acrylic acid vinegar such as a terminal acrylate ester of a 2-phenylene oxide ethylene oxide addition product (for example, manufactured by Nippon Chemical Co., Ltd., Oppq, OPP-2) It is not limited to these, but it is a kind of di(meth)acrylic acid, etc., such as a di-(meth)acrylic acid 6 or a double-aged F (nonyl) acrylic acid. The (meth)acrylic acid vinegar (B_7) which has an alicyclic structure which can be used together in the photosensitive resin composition of this invention is mentioned, for example, (meth) propylene baking _ vinegar, (meth) propylene Dilute acid cyclopentanol, (meth)acrylic acid isobornyl vinegar, (methyl) acrylic acid dicyclopentene vinegar and other monofunctional (methyl acid hydrogenated (tetra) A 'hydrogenated double F and other hydrogenated Two-parallel class II (acrylic acid brewing; three-ring brothel two-molecular methyl di(meth)acrylic acid vinegar, etc.; structure tf functional (10)) acrylic acid vinegar; (methyl) acrylic acid ^ The serocyclic (meth) 4 having an oxygen atom or the like in the structure of the South A ^ structure is not limited to these. The known is 130737.doc -26· 200911862 * .

Further, as the compound having a (meth)acryl fluorenyl group which can be used in combination as the photosensitive resin composition of the present invention, in addition to the above compounds, for example, (mercapto)acrylic acid polymer and (mercapto)acrylic acid can be used. a reaction of glycerin or vinegar, or a (meth)acrylic polymer (meth) acrylate such as a reaction of a glycidyl (meth) acrylate polymer with (mercapto) acrylic acid; (meth) acrylate a methyl (meth) acrylate having an amine group such as methylaminoethyl ester; an isomeric cyanuric acid (meth) acrylate such as isotrimethylene di(meth) propylene oxyacetate; (Alkyl) acrylate of alkane skeleton; polybutadiene (mercapto) acrylate, melamine (meth) acrylate, and the like. In addition, examples of the compound (B-8) of the butylenediimide group of the photosensitive resin composition of the present invention include N-n-butylbutyleneimine and N-hexylmethyleneimine. Monoethyl 2 - maleimide ethyl ester monoethyl carbonate, mono- 2 - maleimide ethyl ester monopropyl carbonate, N-ethyl-(2-m-butylene diimide Monofunctional aliphatic maleimide such as urethane; alicyclic monofunctional cis-butyl iodide such as N-cyclohexyl maleimide; N, N _ hexyl bis-butane diimide diimine, polypropylene glycol bis (3_cis-butyl diimine iminopropyl) mystery, bis(2-m-butylene iminoethyl) carbonate and other aliphatic Bis-m-butylene diimide; 1,4-dimethyleneimine cyclohexane, isophorone bis-carbamate bis (N-ethyl maleimide) An alicyclic di-n-butylene iminoimide; a maleimide compound obtained by acetalizing maleic acid imide with polybutanediol, maleimide-hexanoic acid Shun Ding, who has been treated with the oxyethylene dahide adduct of pentaerythritol a carboxy-n-butyleneimine derivative such as an imine compound, which is esterified with various (poly) alcohols. 130737.doc •27· 200911862 (poly)ester (poly) maleimide compound Etc., but not limited to these. The (meth) acrylamide compound (IV) which can be used in combination in the photosensitive resin composition of the present invention may, for example, be monofunctional such as acrylonitrile or N-isopropyl (meth)acrylamide. (meth)acrylic amines; polyfunctional (meth) acrylamides such as methylene bis(methyl) acrylamide. The photosensitive resin composition of the present invention may be an unsaturated polyacetate (B, 'for example, a fumarate such as dibutyl succinate or diethyl butyl succinate may be mentioned. An esterification reaction product of a polyunsaturated carboxylic acid such as maleic acid or fumaric acid with a polyhydric alcohol. The polymerizable compound (B) which can be used in combination in the photosensitive resin composition of the present invention is not limited to When the compound having a copolymerization property with the component (4) is used, one of the compounds may be used, or a plurality of compounds may be used in combination without particular limitation. As the polymerizable compound, (B-2) is preferably used. (B-5), (B-6).

In the photosensitive resin composition of the present invention, the ratio of the components (A) and (B) is not particularly limited to $, and it is preferably 10 to 2000 parts by weight based on (4) parts by weight of the component (8). It is 5〇~1〇〇〇 by weight. Specific examples of the photopolymerization initiator (C) which can be used in the photosensitive resin composition of the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin iso- τ_ and the like. Ethylenesteel, 2,2'ethoxy-2-phenylphenyl ketone, u_diacetophenone, 2-hydroxyl methyl-phenylpropanol acetonide, diethoxyacetophenone, 1 , Cyclohexyl phenyl ketone, 2-methyl small [4 — (methylthio) phenyl] _2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _醌, 2_Third butyl onion, 2_ scallions, Xikun, ruthenium and so on; 2'4·diethyl (tetra) oxime, 2 isopropyl oxime, 2-chloroindole (4) Ketones such as ketones; acetophenone dimethyl lysine, ketal ketals, benzophenones, benzophenones, 4-benzyl fluorenyl _4, _methyl dioxin 4,4-dimethylamine Dibenzopyrenes such as dibenzophenone; 2,4,6-trimethylphenylnonyl-phenylphosphine oxide, bis(2,4,6•trimethylbenzylidene)-styl Phosphine oxides such as phosphine oxides. It is better to use acetophenones, and it is better to list them.

2-hydroxy-2-methylphenylpropane-indoleone, hydroxycyclohexyl phenyl ketone. The solid content of the photosensitive composition is set to 100% by weight, and is usually 〇〇1 to 3〇% by weight, preferably Ο:% by weight. These may be used singly or in combination of two or more kinds, and further may be combined with a tertiary amine such as triethanolamine or methyldiethanolamine, ν,ν·dimethylaminobenzoic acid ethyl ester, hydrazine, hydrazine _: A curing accelerator such as a benzoic acid derivative such as isoamyl benzoylbenzoate or the like is used in combination. The amount of the accelerator is added in an amount of 1% by weight or less to the photopolymerization initiator (c) as needed in the energy ray-curable resin composition of the present invention, considering the viscosity thereof. The refractive index, the adhesion, etc. are preferably used to further use a monoacrylic acid acrylate monomer (D) having a phenyl group. Examples of the monoacrylic acid acrylate monomer (9) having a phenyl ether group include (meth)acrylic acid phenoxyacetic acid, polyethoxy (meth)acrylic acid benzene, and (methyl acid to isopropyl group). Styrene phenoxyethyl ester, tribromophenoxyethyl (meth) acrylate, phenyl phenol (poly) ethoxylate (meth) acrylate, phenyl phenol (fluorenyl) acrylate epoxy ester, etc. , preferably 130737.doc -29- 200911862 疋. o-phenylphenol (poly) (meth) acrylate, p-phenylphenol (poly) (meth) acrylate, o-phenyl phenol ( Ethyl methacrylate epoxide, p-phenyl benzene (meth) propyl acrylate vinegar. As phenylphenol (poly) ethoxylate (meth) acrylate, preferably ethoxy moiety The compound having an average number of repeats of 丨~3 can be obtained by reacting a reaction of phenylphenol with ethylene oxide with (mercapto)acrylic acid. The reaction of phenylphenol with ethylene oxide can be obtained. It can be obtained by a known method, and a commercially available product can also be used. Then, an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid, p-benzene is used. In the presence of a polymerization inhibitor such as phenol or phenol sulphide, it is preferably in the presence of a solvent (for example, toluene, cyclohexane, n-hexane, n-heptane, etc.), preferably in the form of The reaction of phenylphenol with ethylene oxide at a temperature to react with (meth)acrylic acid, thereby obtaining phenylphenol poly(ethylene) acrylate. Relative to phenylphenol and epoxy The reactant of the alkane is 1 mole, and the ratio of (meth)acrylic acid is 1 to 5 moles, preferably 1.05 to 2 moles, and the esterification catalyst is 0 with respect to the (meth)acrylic acid used. '1 15 mol%, preferably 1 to 6 mol%. As the strepyl phenol, as described above, o-phenylphenol, p-phenylphenol, 〇_PP, P PP (both are available) The light (strand) is preferably produced by o-phenylphenol (poly) (meth) acrylate or p-phenylphenol (poly) (mercapto) acrylate. Benzophenol (meth) acrylate ring The oxyester is the same as the above epoxy resin (a). Preferred is o-phenylphenol (meth)acrylate epoxy ester or p-phenylphenol (A) Further, in view of the adhesion of the energy ray-curable resin composition of the present invention, the glass transition temperature (Tg), the hardness of the cured product, etc., compared with 130737.doc • 30- 200911862 '= before The exemplified amine-based acid compound (4), (meth) acetoacetate compound (8) other than benzene surface = acetoacetate monomer (9) = 吏 used in combination or in combination of two or more. Examples of the (meth) acrylate monomer (8) include a (meth) acrylate monomer or a (meth) acrylate oligomer. Examples of the (meth) acryl acrylate monomer include monoterpene energy (methyl). C, acid vinegar monomer, bifunctional (methyl) propylene glycol styrene monomer, trifunctional or higher polyfunctional (meth) acrylic acid styrene monomer, etc. as monofunctional (meth) acrylic acid vinegar single Examples of the body include acryloyl morpholine, 2-hydroxypropyl (meth) acrylate, _4-hydroxybutyrate (meth) acrylate, and cyclohexane-1,4-dimethanol ( Methyl) acrylate, tetrahydrofuranyl (meth) acrylate, isobornyl (mercapto) acrylate, (fluorenyl) propyl Acid cyclopentyl ester, (meth) acrylate, dicyclopentenyl acrylate, (meth) acrylate, dicyclopentenyl oxyethyl S baked purpose like. Examples of the bifunctional (meth) acrylate monomer include hydrazine, 4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, hydrazine, and 9- fluorene. Alcohol di(meth)acrylate, tricyclic terpineol di(decyl)propionate, bisphenol A polyethoxy di(meth)acrylate, bisphenol a polypropoxy di(曱) Acrylate, bisphenol F polyethoxy di(indenyl) acrylate, ethylene glycol di(indenyl) propionate vinegar, polyethylene glycol di(meth) acrylate, and the like. Examples of the trifunctional or higher polyfunctional (meth) acrylate monomer include triiso(methacryloxyethyl) isocyanurate, pentaerythritol tetrakis(mercapto)propionate, and dipentaerythritol. (Meth) acrylate, dipentaerythritol penta(indenyl) acrylate, tripentaerythritol hexakisyl acrylate, three seasons 130737.doc -31 · 200911862 pentaerythritol penta(indenyl) acrylate vinegar, hydroxypivalic acid Neopentyl glycol esters of di(meth)acrylates of vinegar addition products (for example, manufactured by Nippon Kayaku Co., Ltd. 'KAYARAD ΗΧ220, HX_620, etc.), trimethylolpropane tris(methyl) Acrylic vinegar, trimethylolpropane polyethoxy tri(meth)acrylic acid, di-trimethylolpropane tetra(meth)acrylate, and the like. Examples of the (meth) acrylate oligomer include urethane (meth) acrylate, (meth) acrylate epoxy, and polyester (meth) acrylate. Ο

Examples of the urethane (meth) acrylate include a diol compound or a polyester diol which is a reaction product of the diol compound with a dibasic acid or an anhydride thereof, and an organic polyisocyanate, followed by addition. a reactant such as a hydroxyl group-containing (meth)acrylic acid vinegar, etc. 'The above diol compound, for example: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4- Butylene glycol, neopentyl glycol, hydrazine, 6-hexanediol, hydrazine, 8-octanediol, 1,9-nonanediol, 2·methyl-1,8-octanediol, 3-methyl ], 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-M-propylene glycol, cyclohexane_1,4-sterol, poly Ethylene glycol, polypropylene glycol, bisphenol A polyethoxy diol, bisphenol A polypropoxy diol, etc.; the above dibasic acid or its anhydride, for example: succinic acid, adipic acid, sebacic acid, two Polyacid, isophthalic acid, terephthalic acid, phthalic acid or such acid liver; the above organic polyisophthalic acid vinegar, for example: diisocyanate-1,4-butanediacetate, diiso Amino acid ^, 卜己二§, diisocyanate-2,2, Chain-like saturated hydrocarbon isocyanate such as 4-trimethyl·1,6-hexane triacetate, triisoxo acid _2,4,4-trimethyl-1,6-hexane diester, isophora-diisocyanate, lower Borneane diisocyanate, dicyclohexylmethane diisocyanate, sub-130737.doc •32· 200911862 methyl bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, deuterated xylene diisocyanate, hydrogenation Toluene: isocyanate g is equivalent to cyclic saturated hydrocarbon isocyanate, 2,4-toluene diisocyanate, 153-diphenylene diisocyanate, p-phenylene diisocyanate, 3,3,_dimethyl An aromatic polyisocyanate such as 4,4,-diisoacyl acid, isopropyl-1,3-phenyl diisocyanate, hydrazine or 5-naphthalene diisocyanate.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydrazine, and 'butanediol mono(methyl). Acrylate, polyglycolic acid (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, (mercapto) -2-hydroxyethyl acrylate An ester adduct, a hydroxyl group of (meth)acrylic acid, 3-phenyloxypropyl ester, and the like. Examples of the (fluorenyl) acrylate epoxy ester include a bisphenol fluorene type epoxy eucalyptus, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a bisphenol a propylene oxide adduct. An epoxy resin such as a terminal glycidyl ether or an anthracene epoxy resin, or a reaction product with (meth)acrylic acid. Examples of the polyester (meth) acrylate include a polyester diol which is a reaction product of the above diol compound with the above dibasic acid or an acid anhydride thereof, and a condensation reaction product with (meth)acrylic acid. In particular, as the (meth) acrylate compound (E), it is considered that the viscosity or the hardening property of the hardening type resin composition of the month b of the present invention is good. Or a bifunctional (meth) acrylate monomer. Among them, propylene sulfonium carbaryl, (meth) acrylic acid tetrahydrofuran methyl ester, I4-butanediol di(meth) acrylate, diol di(meth)acrylic acid 130737.doc -33· 200911862 Vinegar, isobornyl (meth)acrylate, (meth)propane-dicyclopentanacetic acid, (meth)acrylic acid dicyclopentanyl 81, (meth)acrylic acid dicyclopentene oxyethylene vinegar A monofunctional or bifunctional (meth) acrylate monomer such as bisphenol A polyethoxy di(indenyl) acrylate. In view of the hardness or Tg necessary for the energy ray-curable resin composition of the present invention, it is also preferred to use a trifunctional or higher (meth)acrylic acid S 曰 monomer as the above. Tris(2·acetamidooxyethyl) S-cyanate, pentaerythritol hexa(indenyl)acrylic acid vinegar, dipentaerythritol penta(indenyl) acrylate vinegar, trishydroxypropyl propane tris(methyl) ) Acrylate and the like. The ratio of use of each component in the energy ray-curable resin composition of the present invention can be determined in consideration of a desired refractive index, glass transition temperature, viscosity, adhesion, etc. 'For essential component (A), optional component ( D) and the optional component (E), when the component (A) + the component (D) + the component (E) is made ι by weight, the content of the component (A) is 3 to 1 part by weight, particularly preferably It is 5 to 1 〇〇 heavy. The content of the component (D) is 〇 to 85 parts by weight, and particularly preferably 〇 to 75 parts by weight. The content of the component (E) is 〇 6 〇 by weight, particularly preferably 〇 5 〇 by weight. When the component (A) + the component (D) + the component (E) is made ι by weight, the component (c) is preferably used in an amount of from 01 to 1 part by weight, particularly preferably from 〇·3 to 5. Parts by weight. The photosensitive resin composition of the present invention can be used without any particular limitation, such as a non-reactive compound, an inorganic filler, an organic filler, a decane coupling agent, or the like, depending on the application. Adhesives, mold release agents, defoamers, leveling agents, plasticizers, light stabilizers, anti-130737.doc •34· 200911862 oxidizing agents, UV absorbers, polymerization inhibitors, antistatic agents, flame retardants, Pigments, dyes, etc. Further, a polymer such as an acrylic polymer, a polyester elastomer, a urethane polymer or a nitrile rubber, an inorganic or organic light-diffusing filler, or the like may be added as needed. Specific examples of the non-reactive compound are liquid or solid oligomers or resins having low reactivity or non-reactivity, and examples thereof include (meth)acrylic acid ester copolymer, epoxy resin, and liquid. Polybutylene diketone, dicyclopentadiene derivative, saturated polyester oligomer, xylene resin, polyaminophthalate polymer, ketone resin, diallyl phthalate polymer (DAP resin) The petroleum resin 'rosin resin, fluorine-based oligomer, fluorene-based polymer, and the like are not limited thereto. Examples of the inorganic fillers include cerium oxide, oxidized cerium oxide, calcium carbonate, calcium citrate, magnesium carbonate, magnesium oxide, talc, kaolin, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, and aluminum oxide. , glass, mica, barium sulfate, alumina white, zeolite, helium balloon, glass balloon, etc. In addition, a halogen-based group may be added to the inorganic filler by adding a decane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, or the like, and reacting the same. a functional group of an epoxy group, a hydroxyl group, or a thiol group. Examples of the organic filler include benzomelamine laurel polyoxyl resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene acrylic acid copolymer, polystyrene, acrylic copolymer, and poly Ethyl methacrylate resin, fluororesin, nylon 12, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimine resin, and the like. 130737.doc -35- 200911862: For the decane coupling agent, for example, γ'glycidoxypropyltrioxy: shixi appearance or γ-gas propyl trimethoxy zexi-burning, etc.; '匕 丙 丙 曱 曱 丁基 ) ) 双 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二^"Aluminum coupling agent such as acetoxy alkoxydisilazide; an oxime coupling agent such as an acetamidine conjugate; and the like. The order or method in which the photosensitive resin composition of the present invention is obtained by mixing the above-mentioned respective components with Sm can be 'unmixed' is not particularly limited. The photosensitive resin composition of the present invention does not require a solvent, but can be, for example, ketones such as methyl ethyl ketone or methyl isobutyl ketone, acetic acid vinegar such as ethyl acetate or butyl sulfonate, and benzene. An aromatic fumes such as toluene or xylene, etc., are usually used as an organic solvent, and the photosensitive resin composition of the present invention is diluted and used. Examples of the active energy ray shown in the invention include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, ray rays, and laser rays, and particle lines such as read rays and electron beams. However, it is preferable to include the ultraviolet light, the visible light, or the laser beam of the laser if the invention is taken into consideration. At this time, the curing rate is practical, and the photopolymerization initiator (c) is preferred. : There are no special restrictions on the method of forming various coating films: Γ printing method, flexographic printing method such as flexographic printing, screen printing method, lithographic printing method, roll coating, blade Various coating methods such as coating, die coating, curtain coating, and spin coating. The photosensitive resin composition containing the compound (4) of the present invention can be used for 130737.doc -36 - 200911862: film forming material, printing (wiring circuit) substrate plating anti-synthesis agent, adhesive, lens, and drying It blocks the tube, the full-image pen optical fiber, and the optical waveguide surface! The material for film formation is used to cover the surface of the substrate. As a specific use of W, „ /, 丹子目田's 疋: gravure oil', flexo ink, screen ink, lithographic ink and other ink materials, hard coating outer coating, overprint varnish, clear coating and other coating materials, etc. Also: used as a barrier agent, an etch resist, a resist for a micro-machine, etc., and other various adhesives, adhesives, etc. Adhesives, (four) ear lenses, lenticular lenses, prismatic lenses, microlenses and other lenses, core materials of optical fibers, coated optical waveguides, full-image films and other optical materials, etc. In other words, the resin composition is temporarily applied onto a release substrate to form a film, and then bonded to the original target substrate to form a film. The energy ray-curable resin composition of the present invention can be processed according to a conventional method. The components are mixed and dissolved to prepare a composition. For example, the components are fed into a round bottom flask equipped with a stirring device and a thermometer, and stirred at 40 to 8 (TC for 0.5 to 6 hours), thereby obtaining the energy of the present invention. Wire hardening resin combination The viscosity of the material is suitable for the workability of the transfer property or the workability of the shape of the optical lens sheet. It is preferable to use an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.). The measured viscosity is in the range of 50 mPa·s to 4000 mPa·s at 25 ° C. The cured product obtained by curing the resin composition of the present invention by irradiating an energy line such as ultraviolet rays according to the usual method is also included in the present invention. In the invention, the hardening 130737.doc •37·200911862 can be obtained by: setting the refractive index (25° C.) of the object to 1.55 or more, and setting the resin composition by a Fresnel lens or a lenticular shape. The resin composition of the invention is applied to a stamper having a shape such as a mirror or a prism lens: a layer on which a mask sheet as a rigid transparent substrate is bonded (for example, 'polymethacrylic acid resin, a polycarbonate resin, a polystyrene resin, a "resin or a substrate or film formed of a blend of such polymers", and then a side view of the hard transparent substrate by a high pressure mercury lamp or the like

After the ultraviolet ray was irradiated to cure the resin composition, the cured product was peeled off from the stamper. X, as such applications, can also be performed by continuous processing. In this way, an optical lens sheet having an optical lens portion having a refractive index (wind) of 155 or more and excellent in mold release property, mold reproducibility, adhesion, and green resistance (four) material lens, lentil lens, prism lens, and microlens can be obtained. Materials, and these are also included in the present invention. Further, the refractive index can be measured by an Abbe refractometer (Model: DR-M2, manufactured by Atago). The energy ray-curable resin composition of the present invention is particularly effective as an optical lens material. Examples of the optical lens sheet include a sheet # which forms an optical lens such as a phenanthrene lens, a lentil lens, a prism lens, or a microlens. Examples of the application other than the use of the photonic lens sheet include various coating agents and adhesives. [Examples] The present invention will now be described in more detail by way of examples. Further, the present invention is not limited by the following examples. Synthesis Example 1 Synthesis of Epoxy Resin (a-丨) 130737.doc -38- 200911862 A nitrogen purge was carried out in a flask equipped with a thermometer, a condenser, and a stirrer, and a compound of the following formula (2) was fed (〇 _pp, manufactured by Sanko Co., Ltd.) 170 g, 37 〇g of alcohol, and 74 g of sterol, so as to dissolve. Further, the mixture was heated to 70 ° C, and 41 g of flaked sodium hydroxide was added thereto in 90 minutes, and further, 70. (: The reaction is carried out for 60 minutes. After the completion of the reaction, the mixture is washed twice with water 2 〇〇g, and the resulting salt or the like is removed, and then heated under reduced pressure (~7 〇, 〇 〇 (10) MPa to -0.09 MPa) 'Agitating and distilling excess surface gas alcohol or the like over 3 hours. 45 〇g of decyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 C. 1 〇% by weight of sodium hydroxide was added under stirring. The aqueous solution was 丨〇g, and after reacting for 1 hour, it was washed with water until the washing water reached neutrality, and the obtained solution was distilled off to remove methyl isobutyl ketone or the like under a reduced pressure using a rotary evaporator. Resin (a) 2 丨 7 g. The obtained epoxy resin (a-1) had an epoxy equivalent of 233 g/eq. ' and was liquid at normal temperature.

Synthesis Example 2 The epoxy resin (a_2) was synthesized in a flask equipped with a thermometer, a condenser, and a stirrer, and was subjected to nitrogen gas = and was fed with a compound of the following formula (3) (p_pp, manufactured by Sanko Co., Ltd.) 181 g, 394 g of surface gas alcohol, 80 g of methanol, to dissolve. Further, the mixture was heated to 7 ° C, and 44 g of flaked sodium hydroxide was added thereto in an amount of 90 minutes, and then further reacted at 7 ° C for 60 minutes. After completion of the reaction, the mixture was washed twice with 200 g of water, and the resulting salt and the like were removed, and then heated under reduced pressure (~7〇t, -〇.〇8 130737.doc -39- 200911862 MPb o.〇9MPa) , search and mix, and go to the alcohol store in 3 hours. . Methyl isobutyl ketone was added to the residue and dissolved, 2 to 70 C. 1 〇% by weight of aqueous sodium hydroxide solution was added under stirring - after i hours of reaction, washing with water until the washing water reached neutrality was carried out by using a rotary evaporator, and the obtained solution was distilled off under reduced pressure. Thus, 227 g of the target epoxy resin (a_2) was obtained. The obtained ring = moon 曰 (a-2) has an oxygen equivalent of 242 g/eq ' and a white knot at normal temperature [Chemical 5]

Example 1 (Synthesis of Compound (A_1}) In an L flask equipped with a stirring device and a reflux tube, the epoxy resin (a.1) obtained in Synthesis Example i was fed 139.8 g (G.6 eq). As a thermal polymerization inhibition sword, 2,6-di-t-butyl-p-to-one shot 55 g, as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, U 3 Lu (〇6 .), 35 g of triphenylphosphine as a reaction catalyst, reacted at 98 t for 3 hours, and the acid value was measured, and as a result, it was 2.4 mg·K〇H/g, and the first reaction was terminated. Thereafter, the reaction temperature was set to 4{rc, and an acrylate monomer which is an acrylate monomer as a reaction diluent, that is, an ethylene oxide adduct of 2-phenylphenol was added (manufactured by Sakamoto Chemical Co., Ltd.) , 〇Pjm)i5i丨§, ', stirring and mixing. Then, as an amino phthalate reaction catalyst, adding - 57 g of dibutyltin laurate, added as an aromatic polyisocyanate 4, toluene diisocyanate 43.6 g (0.5 eq·), the reaction temperature was 130737.doc 200911862 degrees, the temperature was raised to 6 (TC, the reaction was allowed to react for 24 hours, and Nc was determined. (%), the result was Ο.ΟΟ/ό and the reaction was terminated. By this step, 371 g of a transparent pale yellow resin product containing 60 parts by weight of the compound of the present invention (Α·1) was obtained. (Synthesis of Compound (A-2)) In a 1 L flask equipped with a stirring apparatus and a reflux tube, the epoxy resin (a_2) 145, 2 g (0.6 eq) obtained in Synthesis Example 2 was fed as a heat. The polymerization inhibitor 2,6·di·t-butyl-p-methyl G.57 g, as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, 43 3 g of acrylic acid (〇6 is called. The reaction catalyst was set to 4 〇 Adding a terminal acrylate compound of the acrylic acid-derived adduct of 2 - phenyl benzene as a reaction diluent (manufactured by Nippon Kayaku Co., Ltd., g, and mixing and mixing) Then, dibutyltin dilaurate · _ g ' added as a urethane reaction catalyst is added as an aromatic polyacetic acid vinegar = (4) 2,4-toluene diisocyanate vinegar 43 6 g (〇 5 eq ), the reaction was warmed to 60 C, and allowed to react for 24 hours, and Nc 〇 (%) was measured, and the result was 〇·〇〇%, and the reaction was terminated. By this step, a transparent pale yellow resin-like product containing 50% by weight of the compound (A-2) of the present invention was obtained, and Comparative Example 1 (synthesis of the compound (H-1)) was mounted on a stirring device and a reflux tube. τ 睡 ,,, s Λ ^ 中 中 ^ ^ 1 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Inhibition, 6_--di-dibutyl-p-nonylphenol 0.55 g, as a fraction, Ά wg as a single acid of the monounic acid compound (b) having an ethylenic unsaturated group in the knife _ 13〇737.do, - 41- 200911862 0.55 g of triphenylphosphine as a reaction catalyst, which was reacted at 98 ° C for 3 hours, and the acid value was determined to be 2.4 mg.KOH/g, and the reaction was terminated. By this step, 180 g of a transparent pale yellow resinous compound (H-1) was obtained. Comparative Example 2 (Synthesis of Compound (H_2)) Ο

In the 1 L flask equipped with a stirring device and a reflux tube, 139.8 g (0.6 eq.) of the epoxy resin (a) obtained in Synthesis Example i, 2,6-di-the first as a thermal polymerization inhibitor were fed. Tributyl _p-cresol 0,55 g, 43.3 g (0.6 eq.) of acrylic acid as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, triphenylphosphine ruthenium as a reaction catalyst · 55 g, at 98. (: The reaction was carried out for 30 hours, and the acid value was measured, and as a result, it was 2.4 mg.KOH/g, and the first reaction was terminated. After the end of the first reaction, the reaction temperature was set to 4 ° C, and methyl group as a reaction diluent was added. Isobutyl _159.ig, and stirred and mixed. Then, 6 g of dibutyltin dilaurate as an amine phthalate reaction catalyst is added, and aliphatic diisocyanate as a polyisocyanate compound is added. Isophorone diisocyanate 55*6 g (〇.5 eq.), the reaction temperature was raised to 6 〇t:, and the reaction was allowed to proceed for 24 hours, and NC〇 (%) was measured, and the result was 〇〇〇%, and the reaction was terminated. By this step, 390 g of a transparent pale yellow resin product containing the compound (H 2 ) 6 〇 by weight was obtained. The liquid refractive index of the compound of the examples and the comparative examples was as shown in Table 1. (The monomer and solvent dilution products were diluted by diluting the concentration of the compound by three concentrations to prepare a sample, measuring the refractive index of the liquid at a degree of f, and calculating the refractive index of the liquid of the compound itself. Pi Chang Abe refractometer DR_M2. Manufactured, measured wavelength: 589 nm (D line) 130737.doc -42· 200911862 [Table 1] Liquid refractive index (A-1) 1.601 (Α-2) 1.610 (Η-1) 1.580 (Η-2) 1.564 According to As a result of the above, the compound (A) of the present invention has a high refractive index and transparency, and is effectively used for various lenses such as a Fresnel lens, a lenticular lens, a cymbal, and a microlens, and a core material of the optical fiber. Optical applications such as coating materials, optical waveguides, holograms, and display members, etc. Examples 3 to 7 and Comparative Examples 3 to 4 Using a bar coater (No. 20) 'The composition shown in Table 2 A photosensitive resin composition (the compound synthesized in the examples) in which the compounds (A_丨, A_2) synthesized in the examples and the compounds (Η-1, H-2) obtained in Comparative Examples 1 and 2 were prepared. Since OPH was contained as a reactive diluent, it was formulated in the form of the composition of Table 2, and the compound (H-2) synthesized in Comparative Example 2 was used as a solvent of methyl isobutyl ketone. The formulation shown in 2 is diluted with OPP-1 and will act as a solvent for the methyl group. The butyl ketone is reduced, and the obtained one is used, and it is applied to an easy-adhesive polyester film (manufactured by Toyobo Co., Ltd.: A4300, film thickness: 188 μm), and placed in a drying oven of 8 (TC). After a minute, a high-pressure mercury lamp of 12 〇w/cm2 was used in an air atmosphere, and ultraviolet rays were irradiated at a conveying speed of 5 m/min from the height of the lamp at a height of 1 〇cm to obtain a film having a hardened film (1 〇 to 15 μη1). 130737.doc -43· 200911862 [Table 2] Formulation amount (g) Example Comparative Example 3 4 5 6 7 3 4 (A-1) 5 5 10 (A-2) 5 10 (H-1) 10 (H -2) 10 OPP-1 * 1 10 10 10 10 10 10 10 DPHA-40H *2 35 30 35 30 30 30 PET-30 *3 35 Irg.184 Ben 4 3 3 3 3 3 3 3 MEK *5 50 50 50 50 50 50 50 * 1 : OPP-1 : Manufactured by Nippon Chemical Co., Ltd. (end acrylate acetate of ethylene oxide adduct of 2-phenylphenol) * 2 : DPHA : 曰本化药)Manufacture, KAYARAD DPHA-40H (polyfunctional amine phthalate acrylate) * 3 : PET-30 : 曰本化药(股), KAYARAD PET-30 (pentaerythritol triacrylate / pentaerythritol tetrapropyl Mixture of acid esters) * 4 : Irg.l84 (Irgacure-184): Ciba Specialty Chemicals (Ciba Specialty 01^] 114315) Manufacture (1-cyclohexylphenylene 1) * 5 : MEK : 2-butyl Ketone Test Examples The films obtained in Examples 3 to 7 or Comparative Examples 3 to 4 were evaluated for the following items, and the results are shown in Table 3. (Pencil hardness) 130737.doc -44- 200911862 The erroneous pen hardness of the coated film was measured using a stray scratch tester according to m κ 54〇〇'. That is, on the polyacetal film having the hardened film measured, the load of i kg was hung from the pen at an angle of 45 degrees, and the scratch was about 5 _ to confirm the damage. The measurement was performed 5 times, and the number of times without scratches was counted. Evaluation 5/5: No damage in 5 of 5 times 〇/5 : All of the 5 occurrences of scratches (scratch resistance test)

Hang 200 gW load on steel wool # 0000, and reciprocate 1 time to visually determine the scar condition. Evaluation 5: No scratch evaluation was observed 4: 1 to 5 scars were observed 3: 6 to 50 scars were observed 2: 51 to 1 flaws were observed Evaluation 1 : Film peeling was observed ( Adhesion) According to JIS K54, a grid of 11 slits was formed on the surface of the film at intervals of 1 mm. When the transparent tape is adhered to the surface thereof, the number of the grids remaining without being peeled off is displayed when the breath is peeled off. (Curling) The measured tempered film having a hardened skin was cut into 5 cm x 5 cm, placed in a drying oven of 8 ° C for 1 hour, 11 μM, and returned to room temperature. The height of each of the four sides on the water platform was measured, and the average value was taken as the measured value (single axis). At this time, the substrate itself was curled to 0 mm. (Appearance) 130737.doc -45- 200911862 Visually judge the surface crack, evaluation 〇: Good ‘Defect point and other status. A. Very few cracks generated x: significant cracks were produced [Table 3] Evaluation results Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 3 Comparative Example 4 Degree 2H 5/5 5/5 5/5 5/5 5/5 1/5 4/5 Scratch Adhesive 5 5 5 5 5 3 4 100 100 100 100 100 87 96 Retracted 10 8 6 9 5 5 6 Appearance - Epoxy resin (a) adjacent to you ^ chest) is wider than Comparative Examples 3 to 4: Examples 3 to 5), and the opposite body (the degree of implementation is less, so the hardening shrinkage is less. It is known that the actual example 5 Compared with Comparative Example 3 in which the aromatic polyisocyanate compound (4) was not used, the 'hardness of Example 5' was excellent in scratch resistance and adhesion, and the number of hardening shrinkage was small. X' is known: Example 5 and use of fat In comparison with Comparative Example 4 of the polyisocyanuric acid compound, the hardness, scratch resistance, and adhesion of Example 5 were excellent, and the hardening shrinkage was small. According to the above results, the compound (A) of the present invention having transparency was contained. The resin composition of the present invention has less hardening shrinkage, and the cured product has sufficient hardness and high adhesion, so it can be effectively used in 130737.doc -46- 200911862 A coating agent which is required to be transparent, and dust, # is obtained by the composition shown in the following examples (numerical value indicates weight damage), and the ultraviolet curable resin composition and cured product of the present invention are obtained. The evaluation method and evaluation criteria of the hardening enthalpy are carried out as follows. The soil () is also measured using a £-type viscometer (tv-200: manufactured by Toki Sangyo Co., Ltd.) at 2 5 C. (2) Modulus·Table does not make the hardened resin easy to release from the mold. 〇...It is good to release from the mold △...It is difficult to release the mold or there is peeling sound when demoulding X...The mold is difficult to mold or mold Residual (3) Reproducibility: The surface shape of the cured ultraviolet curable resin layer and the surface shape of the mold are observed. 〇...Reproducibility is good x...Reproducibility is poor (4) Adhesion·· The resin composition was applied to a film thickness of about 5 Å, and then a sample hardened by irradiation with 1000 mj/cm 2 by a high pressure mercury lamp (8 〇 w/cm, no ozone) was prepared, according to JIS K56〇〇_5_6, Carry out the evaluation of adhesion. "Ping 4 shell results will be completely The peeling 0 is set to ◎, 丨~2 is set to 〇, and 3 to 5 is set to X. (5) Refractive index (25. 〇: measured by Abbe refractometer (DR_M2: manufactured by Atag®) Refractive index of the hardened ultraviolet curable resin layer (25. 〇). (6) Glass transition temperature (Tg): by viscoelasticity measurement system (DMS_6〇〇〇: 130737.doc -47- 200911862 Seiko Instruments (8) The Tg temperature of the cured ultraviolet curable resin layer was measured in a tensile mode at a frequency of 1 Hz. (7) Light resistance [·sheng. With the eye SUPER UV TESTER SUV-W11 (manufactured by Iwasaki Electric Co., Ltd.), the cured UV curable resin layer was subjected to a light resistance test for 2 hours under conditions of 6 〇t and 60% RH. Thereafter, the state of the film was visually evaluated. 〇 虽 虽 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 若干 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显3 parts of 2-hydroxy-2-mercapto-1-phenylpropan-1-yrene of component (C), 7 parts of o-phenylphenol monoethoxy acrylate as component (D), as a component ( 10 parts of propylene decylmorpholine and 3 parts of tris(2-propenyloxyethyl) isocyanurate of E), and the mixture is heated to 6 (TC and mixed to obtain a resin composition of the invention. The viscosity of the composition was 195 mPa·s. Further, the refractive index of the film obtained by hardening the resin composition (25 it) was 丨6〇6, and the glass transition temperature (Tg) was 5 (TC. The object is coated on a prismatic lens mold so as to have a thickness of 5 μμηι′ on the polycarbonate film as a substrate, and then irradiated with a thickness of 1000 mj/cm 2 by a high pressure mercury lamp. The ultraviolet rays were hardened, and then peeled off to obtain a prismatic lens sheet. Evaluation results Release property: 〇 'mode reproducibility : 〇, adhesion: 〇, light resistance: 〇. Example 9 130737.doc -48· 200911862 Using the product containing the compound (A_2) obtained in Example 2, 2 parts, obtained in place of Example 1. The present invention was obtained in the same manner as in Example 8 except that the product (product of Α_υ was used as a component (Α), and 67 parts of o-phenylphenol monoethoxy acrylate was used instead of 7 〇·3 parts. The resin composition of the invention has a viscosity of 2 〇〇 mPa s. Further, the resin composition is cured to obtain a refractive index of ruthenium, and the glass transition temperature (Tg) is 51 ° C. The resin composition It is coated on a prismatic lens mold to have a film thickness of 5 〇μηι, and a polycarbonate film as a substrate is bonded thereto to have a thickness of 5 Å, and then irradiated with a high pressure mercury lamp by 1 〇〇〇mJ/cm 2 . After the ultraviolet rays were irradiated, the particles were cured, and then peeled off to obtain a prism sheet. Evaluation results Release property: 〇, mold reproducibility: 〇, adhesion: 〇, light resistance: 〇. Example 10 The content obtained in Example 2 of the component (A) 51 parts of the product of the compound (A_2), as a component ((3 parts of hydroxycyclohexyl phenyl ketone), 20 parts of acryloyl morpholine as component (E), and triisopropane cyanide (2-propylene) 5 parts of decyloxyethyl) vinegar, and 2 parts of bisphenol A (E04 molar modified) diacrylate and 4 parts of A epoxy acrylate are heated to 60 ° C and mixed. The resin composition of the present invention has a viscosity of 26 〇〇 mPa·s. Further, the refractive index (2 〇 〇) of the film obtained by hardening the smear resin composition is 1.594, and the glass transition temperature ( Tg) is 88 ° C. The obtained resin composition is applied to a phenanthrene lens mold to a film thickness of 200 μm, and a methyl methacrylate/130737.doc as a substrate is adhered thereto. 49· 200911862 The styrene substrate was 2 mm, and it was hardened by irradiating ultraviolet rays of an irradiation amount of 10 μm/cm 2 from a high-pressure mercury lamp, and then peeled off to obtain a Fresnel lens. Evaluation results Release property: 〇, mold reproducibility: 〇 'Adhesiveness: 〇, light resistance: 〇. Example 11 The same procedure as in Example 8 was carried out except that the component (D) in Example 8 was changed to 40.3 parts of o-phenylphenol monoethoxy acrylate and 3 parts by weight of p-phenylphenol epoxy acrylate. The resin composition of the present invention is obtained in the same manner. The viscosity of the resin composition was 630 mPa.s. Further, the refractive index of the film obtained by curing the resin composition (25. 〇 was 1.600, and the glass transition temperature (dg) was 54 〇 C. The resin composition was applied onto a prism lens mold to achieve a film thickness. 5〇μηι, on which a polycarbonate film as a substrate is bonded to a thickness of 5 Å, and further cured by irradiation of ultraviolet rays of 1 〇〇〇mJ/cm 2 from a high-pressure mercury lamp, followed by The prism sheet was obtained by peeling off. The evaluation result was mold release property. 〇, mold reproducibility: 〇, adhesion: 〇, hydroxy property: 〇. Example 12 The component (D) in Example 9 was changed to A resin composition of the present invention was obtained in the same manner as in Example 9 except that 27 parts of o-phenylphenol monoethoxy lactone and 3 parts of o-phenylphenol epoxy acrylate were used. The viscosity of the material was 693 mPa·s. Further, the refractive index of the film obtained by hardening the resin composition (25. 〇 was 1.604, and the glass transition temperature (Tg) was 56. 130. 130737.doc -50- 200911862 The resin composition is applied to a prismatic lens mold to have a film thickness of 5 μm The polycarbonate film as a substrate is bonded to a thickness of 5 μm, and is cured by irradiating ultraviolet rays of an irradiation amount of 1000 mJ/cm 2 from a high-pressure mercury lamp, and then peeling off to obtain a prism sheet. Evaluation results Release property 〇 模 mold reproducibility: 〇, adhesion: ◎, hydroxy property: 〇. Example 13 The resin composition of Example 8 was applied to a prism lens mold to achieve a film thickness 50 μιη 'bonded to the substrate as an easy-to-adhere pET film 1 〇〇μιη thickness (Toyo A4300), which was then hardened by irradiation of ultraviolet rays of 600 mJ/cm 2 from a high-pressure mercury lamp. Then, peeling was performed to obtain a prismatic lens sheet. Evaluation results Release property: 〇, mold reproducibility: 〇, adhesion: ◎ Example 14 The resin composition of Example 9 was applied onto a prism lens mold so that The film thickness is 50 μηι, and the thickness of the easily attachable pET film ι〇〇μηι (Toyobo 4300) as a substrate is adhered thereto, and the ultraviolet light of 600 mJ/cm 2 is irradiated thereon by a high pressure mercury lamp. Hardening, The peeling was performed to obtain a prismatic lens sheet. Evaluation results Release property: 〇' mold reproducibility: 〇, adhesion: ◎ Example 1 5 The resin composition of Example 11 was applied onto a prism lens mold so that Film thickness 130737.doc 51 200911862 Up to 50 μηι, adhered to the substrate as an easy-to-adhere pET thin 臈ι〇〇μηι thickness (Toyobo A4300), and then irradiated with 600 mJ/cm2 from a high-pressure mercury lamp After the ultraviolet rays were irradiated, the particles were cured, and then peeled off to obtain a prism sheet. Evaluation results Release property: 〇 'mode reproducibility: 〇, adhesion: ◎. Example 1 6 The resin composition of Example 12 was coated on a prismatic lens mold to have a film thickness of 50 μm, and the thickness of the easily adhered pet thin 臈1〇〇μηη as a substrate was adhered thereto (Toyo A4300). Further, it was hardened by irradiating ultraviolet rays of an irradiation amount of 600 mJ/cm 2 from a high-pressure mercury lamp thereon, and then peeled off to obtain a prism sheet. Evaluation results Release property: 〇, mold reproducibility: 〇, adhesion: Comparative Example 5 According to Example 1 of Patent Document 7 (Japanese Patent Laid-Open Publication No. SHO 63-169-103), ARONIX M-315 (iso-poly-cyanuric acid tris(2-propenyloxyethyl) ester) 7 parts, 30 parts of tetrahydrofuran methyl acrylate, 3 parts of isopropyl basic group - 2 - mercapto-2-mercaptopropen-1-one as a photopolymerization initiator, and heated to 6 Torr. The mixture was kneaded and mixed to obtain a resin composition for comparison. The resin composition had a viscosity of 134 mPa·s. Further, the refractive index (25 ° C) of the film obtained by curing the resin composition was 1.52. According to the results, the composition of Comparative Example 5 has a lower refractive index than the composition of the present invention, and thus is not suitable for producing the lens of the present invention. 130737.doc -52- 200911862 Comparative Example 6 According to the example of Patent Document 9 (Japanese Patent No. 3209554), the urethane acrylate of Synthetic Example 1 of the document (neopentylene glycol and adipic acid) was synthesized. A reaction product of a polyester diol, ethylene glycol, toluene diisocyanate, and hydroxyethyl acrylate), and a compound of the synthesis example 3 (o-phenylphenol diethoxy acrylate). Specifically, 'Feeding a polyester diol (a polyester diol of neopentyl glycol and adipic acid, a molecular weight of 2000, an OH value of 56.1), 20 parts, 2.48 parts of ethylene glycol, and 34.8 parts of toluene diisocyanate. After the temperature is raised, the reaction is carried out at 80 ° C for ίο hours, and then 24 parts of 2-hydroxyethyl acrylate and 24 parts of p-methoxybenzene are fed, and the reaction is carried out at 80 ° C for 10 hours to obtain urethane acrylate. The compound shown by vinegar and '(6) was 258 parts. [Chemical 6]

(6)

0-eCH2CH2-〇-^-H is fed (Sanyo Chemical Co., Ltd.) to produce 'o-phenylphenol 1 molar and ethylene oxide 2 molar reaction, product name: NEWPOLOPE-20, OH value 217.5) Acrylic acid 86.5 parts, 300 parts of toluene, 21 parts of sulfuric acid, and 5 parts of hydroquinone, the water formed by heating was distilled together with a solvent to be condensed, and the reaction mixture was cooled while generating 18 parts of water by a separator. The reaction temperature is 130 to 140 °C. The reaction mixture was dissolved in 500 parts of toluene, neutralized with a 20% Na〇H aqueous solution, and then washed three times with a 20% aqueous NaCl solution. The solvent was distilled off under reduced pressure to give 303 parts of Compound (B) (liquid) (o-phenylphenoldiethoxypropane 130737.doc -53 - 200911862). The viscosity (25 ° C) was 204 CPS and the refractive index (23. 〇) was 1.567. 30 parts of the above urethane acrylate, 15 parts of the above o-phenylphenol diethoxy acrylate, KAYARAD R-551 (bis bis-A tetraethoxy diacrylate), 45 parts, propionate Tribromophenyl ester 1 part, iragacure 184 (1-hydroxycyclohexyl phenyl ketone) 3 parts, heated to 6 (TC and mixed, and the comparative resin composition was obtained. The viscosity of the resin composition was 4420 Further, the refractive index (25 Å) of the film obtained by hardening the resin composition was 1.574.

According to the result, the composition of Comparative Example 6 has a higher viscosity than the composition of the present invention, and thus is not suitable for microfabrication or continuous processing of a roll-shaped sheet or film. According to the evaluation results of Examples 8 to 16 and Comparative Examples 5 and 6, it is clear that the resin composition of the present invention having a special composition has excellent mold release property, mold reproducibility, and adhesion to a base material, and is hardened. The material has a high refractive index and a glass transition temperature (Tg) of 50 ° C or more, and is also good in light. Therefore, it is suitable for an optical lens sheet having a fine structure such as a phenanthrene lens, a lentil lens, a prism lens, a microlens, etc. It is also suitable for use in a process requiring microfabrication or a process including a step of continuous processing. [Industrial Applicability] Optical Lens Sheet The ultraviolet curable resin composition of the present invention and a cured product thereof are mainly applied to a phenanthrene lens, a lentil lens, a prism lens, and a mirror f 130737.doc -54 -

Claims (1)

200911862, the scope of patent application: a urethane compound (A) characterized in that it is an epoxy resin (4), a mono-compound (8) having an ethylenically unsaturated group in the molecule, and an aromatic system. The polyisocyanate compound (c) is obtained by reacting the epoxy resin (a) with a compound represented by the following formula (1): 2. The monocarboxylic acid compound (b) is a reaction product of (meth)acrylic acid, (meth)acrylic acid and ε-caprolactone or cinnamic acid. 3. 4. 5. 6. 8. The compound (4)' of claim 1 wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is acrylic acid. The compound (4) according to claim 1, wherein the aromatic polyisocyanate compound (c) is a compound having an aromatic ring having an anisotropy of 5 to 15. Such as the request item! The compound (4) wherein the aromatic polyisophthalic acid compound (c) is 2,4-nonyl diisocyanate. The compound (A) of claim 1 has a liquid refractive index of 丨59 or more. A photosensitive resin composition containing the compound (A) as claimed in the item (i) and the polymerizable compound (b) other than (A). The photosensitive resin composition of claim 7, wherein the polymerizable compound (B) is selected from the group consisting of (poly) vinegar (mercapto) acrylic acid _ υ, amino phthalic acid vinegar (mercapto) 130737.doc 200911862 acrylic vinegar ( B-2), (fluorenyl) acrylate (B-3), (poly)ether (meth) acrylate (B-4), alkyl (meth) acrylate or (meth) acrylate Stretching S (B-5), (meth) acrylate having an aromatic ring (Β·6), and (meth) acrylate (Β-7) having an alicyclic structure, containing maleicene A compound of the group consisting of an amine group (Β-8), a (meth)acrylamide compound (Β_9), and an unsaturated polyester (Β-10). 9. The photosensitive resin composition of claim 7, wherein the polymerizable compound (b) is selected from the group consisting of amino phthalate (7) _2), (mercapto) propyl acetoate or sulfhydryl One or more compounds of the group consisting of alkyl acrylate (B-5) and (meth) acrylate (B-6) having an aromatic ring. 10. The photosensitive resin composition of claim 7, which comprises a photopolymerization initiator (C), which is a hardened material of the photosensitive resin composition of claim 7. A film having a layer of a cured product as claimed in claim 11. An energy ray-curable resin composition for an optical lens sheet, comprising: a urethane compound (A) and a photopolymerization initiator (C) 'the above urethane compound ( A) is a compound of the following formula (丨): [Chemical 8] 130737.doc 200911862 Epoxy resin (a) which reacts with epihalohydrin, monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and aromatic polyisocyanate compound (c) By. 14. The resin composition of claim 13, wherein the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is a reaction product of (mercapto)acrylic acid, (meth)acrylic acid and ε-caprolactone Or cinnamic acid, the aromatic polyisocyanate compound (c) is an aromatic diisocyanate monomer. 15. The resin composition of claim 13, wherein the mono-ortho-acid compound (b) having an ethylenically unsaturated group in the molecule is acrylic acid, and the aromatic polyisocyanate compound (c) is 2,4-toluene diisocyanate. 16. The resin composition of claim 13, which further comprises a monoacrylate monomer (D) having a phenyl ether group. 17. The resin composition of claim 16, wherein the monoacrylate monomer (D) having a phenyl ether group is o-phenylphenol (poly)(mercapto)acrylic acid ethoxylate, p-phenylphenol (poly) ( Ethyl methacrylate, epoxy phthalate (meth) acrylate, p-phenyl phenyl (meth) acrylate epoxy. The resin composition of claim 13, which further contains a (meth) acrylate compound other than the urethane compound (A) or the monoacrylate monomer (7) having a phenyl ether group ( E). A cured product obtained by hardening the resin composition of claim 13 and having a refractive index of 1.55 or more at 25 °C. 20. An optical lens sheet using the hardened material of claim 19. 130737.doc 200911862 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 130737.doc