TW201250386A - Energy ray-curable resin composition for optical lens sheet and cured product thereof, and the optical lens sheet - Google Patents

Abstract

This invention provides a resin composition suitable for an optical lens sheet formed on a substrate, having excellent releasing ability, refoming ability, adherence to the substrate film and high durability (abrasion-resistant, scratch-resistant). Provided is an energy ray-curable resin composition for optical lens sheet formed on a substrate, comprising: (A) a polyethylene oxide modified bisphenol A type di(meth)acrylate represented by the following general formula (1): (wherein, R1 and R2 respectively, independently represent a hydrogen atom or a methyl group, m and n respectively, independently represent an integer of 5 to 10), 30 to 70 mass parts, (B) a mono(meth)acrylate having phenyl ether structure, 3 to 50 mass parts, (C) a caprolactone or ethylene oxide modified polyfunctional (meth)acrylate having at least three (meth)acryloyl groups, 3 to 20 mass parts, (D) an urethane (meth)acrylate oligomer having tetraethylene glycol structure, 3 to 20 mass parts, and (E) a photopolymerization initiator, 1 to 10 mass parts.

Description

201250386 VI. Description of the Invention: [Technical Field] The ultraviolet curable resin composition is a prism lens used for backlighting of a liquid crystal display device, a Fresnel lens used for a projection television, and the like. An optical lens film formed on a substrate such as a lenticular lens, a transmissive screen, or the like. [Prior Art] These optical lens diaphragms have a tendency to reduce the number of optical films due to the increase in cost reduction in recent years, and also require durability when contacted with other optical films that have not been in direct contact with each other (also called For the abrasion resistance, scratch resistance, etc.) is the southern standard. The resin layer itself has durability, and in Patent Document i, durability is exhibited by using a material having a small acrylic acid equivalent, but a resin composition containing a material having a small acid equivalent () has a tendency to become curled. Optical films are not good. In addition, it is tested whether the material having a small amount of c-equivalent is durable: when the cured film is hard and brittle, especially when it comes into contact with an optical film containing an organic or inorganic filler, there is a problem that scratches are likely to be left. ^ Read 2 towel proposed (4) Heavy-duty total of 0 to 8 of Ethylene Ethylene to change one of the (methyl) acrylate acid, and the ancient 9 propylene brewing compound, with a fragrant apricot ^ aroma The ring and one (meth) group and a compound having an ethylenically unsaturated group having three or more (meth) propyl groups are optionally used as the resin for optical lenses. It is repeated that the number of epoxy oxime f to 8 is 324097 5 201250386 The scratch resistance (scratch resistance) is not suitable for the case where scratch resistance (scratch resistance) is required. This is because the alkylene oxide is hardened if it is modified, but it also becomes brittle. Further, in the examples of Patent Document 2, only the disulfide ester of the sulfide skeleton is used. However, when a resin containing a sulfur atom is used, the refractive index tends to increase, but the odor is too strong, and further, light resistance is known. Sex will also be significantly worse. Therefore, there has been a problem in use of the resin composition for optical lens diaphragms in recent years. As described above, it is not possible to obtain a resin composition having high light transmittance, mold release property, substrate adhesion, and high durability which are properties of a general optical lens sheet. [Prior Art Document] (Patent Document) Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-126670 (Patent Document 2) Patent No. 4457960 (Invention) The object of the present invention is to provide a lenticular lens. A resin composition for an optical lens film formed on a substrate such as a 稜鏡 lens or a microlens, and a cured product having excellent light transmittance and mold release property and high durability (scratch resistance and scratch resistance). . (Means for Solving the Problem) The present inventors have intensively studied in order to solve the above problems, and as a result, have found that the ultraviolet curable resin composition having a specific composition and the cured product thereof can be solved by the above-described teachings. 324097

S 201250386 In other words, the present invention is as follows: (1) An energy ray-curable resin composition for an optical lens film formed on a substrate, which comprises a polyepoxy resin represented by the following formula (1) Alkyl modified bisphenol A type bis(indenyl) acrylate (A) 30 to 70 parts by mass, mono(indenyl) acrylate (B) having a diphenyl ether structure, 3 to 50 parts by mass, and 3 or more a (meth)acrylonitrile group and a polyfunctional (fluorenyl) acrylate (C) modified with caprolactone or epoxy oxime (C) 3 to 20 parts by mass, having a tetramethylene glycol structure The amine amidate (meth) acrylate oligomer (D) is 3 to 20 parts by mass, and the photopolymerization initiator (E) is 1 to 10 parts by mass.

(In the formula, Ri and R2 each independently represent a hydrogen atom or a fluorenyl group, and m and η are repeating numbers and each independently represent a positive number of 5 to 10) (2) The energy ray-curable resin composition as described in (1) Among them, the (fluorenyl) acrylate having a diphenyl ether structure is composed of phenoxyethyl (mercapto) acrylate, phenoxy (methyl) polyethoxy acrylate, o-phenylphenol (Meth) acrylate, o-phenyl phenol monoethoxy (meth) acrylate, o-phenyl phenol polyethoxy (fluorenyl) acrylate, p-phenyl phenol (A) One or more selected from the group consisting of acrylate, p-phenylphenol monoethoxy(fluorenyl) acrylate, and p-phenylphenol polyethoxy(fluorenyl) acrylate. (3) The energy ray-curable resin composition according to (1), wherein the urethane (meth) acrylate oligomer (D) having a butylene glycol structure has a molecular weight of 500 to 510 Å An amine oxime (meth) acrylate oligomer obtained by reacting a diol compound, a polyisocyanate compound, or a hydroxyl group-containing (mercapto) acrylate. (4) The energy ray-curable resin composition according to any one of (1) to (3) wherein the polyisocyanate compound has a ring structure. (5) The energy ray-curable resin composition as described in any one of (1) to (4) wherein the viscosity measured at 25 ° C by an E-type viscosity meter is 2000 mPa·s or less (6) The energy ray-curable resin composition according to any one of (1) to (5), which is obtained by irradiation with an energy ray and hardened. (7) An optical lens film having the cured product as described in (6). (Effects of the Invention) The resin composition of the present invention has excellent ampoule properties, and is excellent in mold release property, mold reproducibility, and adhesion to a base film. Further, it is excellent in durability (deterioration and scratch resistance). Therefore, it is particularly suitable for an optical lens diaphragm formed on a substrate such as a lenticular lens, a 稜鏡 lens, or a microlens. [Embodiment] The total number of repeats used in the present invention (m + η in the above formula (1)) is a polyethylene oxide modified di-type bis(indenyl) acrylate (A) of 10 to 20 It has the effect of improving the scratch resistance (scratch resistance) of the hardened material. The total number of repetitions is from 10 to 20, and although it is hard, it becomes a brittle hardened material. Specific examples include ethoxy 10 mo-modified bisphenol A bis(indenyl) acrylate, 324097

S 8 201250386 ethoxy 18 mol modified bisphenol A bis(indenyl) acrylate, ethoxy 20 molar modified bisphenol A di(meth) acrylate, etc., which are readily available from commercial products . Specifically, NEW FRONTIER BPE-10 manufactured by First Industrial Pharmaceutical Co., Ltd. (Ri=H, R2=H, m=5, n=5 in the general formula (1)), First Industrial Pharmaceutical Co., Ltd. NEW FRONTIER BPEM-10 (RfCIL·, R2=CH3, m=5, n=5), NEW FRONTIER BPE-20C manufactured by Daiichi Kogyo Co., Ltd. In the general formula (1), Ri=H, R2=H, m=10, n=20), FANCRYL FA-321A manufactured by Hitachi Chemical Co., Ltd. (Ri=H, R2=H, m=5, n=5), FANCRYL manufactured by Hitachi Chemical Co., Ltd. Person (1=1, R2=H, m=9, n=9), FANCRYL FA-321MCRFCH3, R2=CH3, m=5, n=5) manufactured by Hitachi Chemical Co., Ltd., Hitachi Chemical Co., Ltd. FANCRYL FA-3218M (ΚΗ3, R2=CH3, m=9, n=9), NK ESTER A-BPE-UKRfH, R2=H, m=5, n=5), Xinzhongcun Chemical Industry Co., Ltd. NK ESTER A-BPE-20C manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (1) R^H, R2=H, m=10, n=20), NK ESTER BPE-made by Shin-Nakamura Chemical Industry Co., Ltd. SOiKRFCiL·, R2=CH3, m=5, n=5), Xinzhongcun Chemical Industry Co., Ltd. NK ESTER ΒΡΕ-900 (Κ=(:Η3, R2=CH3, m=8, η=9), BLEMMER PDBE-450 manufactured by Nippon Oil Co., Ltd. (Ri=CH3, R2=CH3, m=5, n= 5), Sartomer system SR602 (Ri = H, R2 = H, m = 5, n = 5), Sartomer system SR480 (Ri = CH3, R2 = CH3, m = 5, n = 5), MIWON system MIRAMER Μ 2100 ( Ι^=Η, R2=H, m=5, n=5), etc. The (meth) acrylate (B) having a diphenyl ether structure used in the resin composition of the present invention may be exemplified below. 201250386 Pair of isopropyl basic ethoxyethyl phenoxyethylene glycol (P_cumyl phenoxyethyleneglycol), tribromophenyl (meth) acrylate, ethoxylated tribromophenyl (mercapto) acrylic acid Ester, propoxy modified Sankun phenyl (methyl) propionate, phenoxy hydroxypropyl (meth) acrylate, phenoxy polyethyl (meth) acrylate vinegar , nonylphenoxy polyethylene glycol (fluorenyl) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy poly Oxy (mercapto) acrylate, nonylphenol (meth) acrylate, Oxygen-modified nonylphenol (fluorenyl) acrylate, polyethoxylated nonylphenol (fluorenyl) acrylate, o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy ( Methyl) yttrium acrylate, o-based phenol polyethoxy (fluorenyl) acrylic acid, p-phenyl benzene (meth) acrylate, p-phenyl phenol monoethoxy (fluorenyl) acrylate Ester, p-phenylphenol polyethoxy (fluorenyl) acrylate, o-phenylphenol epoxy (meth) acrylate, p-phenylphenol epoxy (fluorenyl) acrylate, and the like. Particularly preferred are phenoxyethyl (decyl) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenyl phenol polyethoxy (meth) acrylate. These (fluorenyl) acrylates having a diphenyl ether structure may be used singly or in combination of plural kinds. The polyfunctional (fluorenyl) acrylate (C) having three or more (meth) acrylonitrile groups and modified by caprolactone or ethylene oxide has an effect of improving the scratch resistance (scratch resistance) of the cured product. In the case of a person who has not been modified with caprolactone or ethylene oxide, the hardened material is hard but brittle. Specific examples of the polyfunctional (fluorenyl) acrylate (C) having three or more (meth) acryloyl fluorenyl groups modified with caprolactone or ethylene oxide include polyethoxylated trimosine Propane tris(indenyl)propene 324097

S 10 201250386 enoate, polyethoxy modified pentaerythritol tetrakis(meth) acrylate, polyethoxy modified glycerol tris(decyl) acrylate, polyethoxy modified dipentaerythritol Alcohol penta(indenyl) acrylate, polyethoxy modified dipentaerythritol hexa(meth) acrylate, polycaprolactone modified trihydroxy decyl propane tri(meth) acrylate, polyhexene Ester-modified dipentaerythritol penta(indenyl) acrylate, polycaprolactone modified dipentaerythritol hexa(indenyl) acrylate, caprolactone modified tris(propenyloxyethyl) Isocyanurate (iS0Cyanurate), polycaprolactone modified tris(propylaphthaleneoxyethyl)isocyanurate, polyethoxylated modified tris(propyleneoxyethyl)isocyanuric acid Ester and the like. Particularly preferred is polyethoxy modified trimethylolpropane bis(indenyl) acrylate, polycaprolactone modified tris(propylene decylethyl) isocyanurate, polycaprolactone modified two Pentaerythritol penta(indenyl) acrylate, polycaprolactone modified dipentaerythritol hexa(meth) acrylate. The amine acetoacetate (meth) acetoacetate oligo (8) having a butane diol structure contained in the resin composition of the present invention also has an effect of improving the scratch resistance (conservation property) of the cured product. Specific examples may be exemplified by reacting a diol compound with an organic polyisocyanate, followed by addition of a diol compound containing a trans-group (meth) propyl acetoacetate, which can be used in the present invention. Butylene glycol, 3-methylbutanediol, and the like. The city f has various diol compounds of any molecular weight and can be easily obtained, but in the present invention, a molecular weight 5 (10) butanediol compound is particularly preferred. Examples of the organic polyisocyanate which can be used in the present invention include tetramethylene-isocyanate, hexamethylene diisocyanate, and 2,2,4 hexamethylene diisocyanate. , 4,4-trimethylhexamethylene diisocyanine 324097 11 201250386 iso-chain saturated hydrocarbon isocyanate, isophorone (is〇ph〇r〇ne) diisocyanate, norbornane diisocyanate, a cyclic saturated hydrocarbon isocyanate such as dicyclohexyldecane diisocyanate, fluorenylene bis(4-cyclohexyl isocyanate), hydrogenated diphenyl decane diisocyanate, hydrogenated diphenylene diisocyanate or hydrogenated phthalic acid diisocyanate; 4-extended phenyl diisocyanate, 1> 3-phenylenediguanide diisocyanate, p-phenylene diisocyanate, 3,3,-dimethyl-4,4-diisocyanate, 6-isopropyl-hydrazine, An aromatic polyisocyanate such as 3-phenylene diisocyanate or 1'5-naphthalene diisocyanate is preferably a cyclic saturated hydrocarbon isocyanate, and more preferably a tolyl diisocyanate or isophorone diisocyanate. Specific examples of the hydroxyl group-containing (meth) acrylate which can be used in the present invention include, for example, 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (-methyl) acrylate, 1, 4 - Butanediol (decyl) acrylate, polyethylene glycol soap (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl alcohol tris(decyl) acrylate, 2-hydroxyethyl Ε-^ lactone adduct of (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (fluorenyl) acrylate 4, preferably 2-hydroxyethyl (meth) acrylate . The amine phthalate (meth) acrylate vinegar oligomer (8) having a butane diol structure used in the present invention can be used as the above diol compound, hydroxy sulphuric acid vinegar, and a methicone containing a thiol group. Acrylic vinegar is synthesized by a usual method. That is, for example, an alcohol compound and an organic polyisocyanate are reacted by an addition reaction to obtain a reactant (I)', followed by addition of a reactant (丨) to a hydroxyl group-containing (meth) acrylate, thereby obtaining an amine formate B. Ester (meth) acrylate. When synthesizing the reactant (I), for the hydroxy group equivalent of the aforementioned diol, there is 324097

S 12 201250386 The isocyanate group of polyisocyanate is subjected to a general reaction of from 1 to 2.0 equivalents, preferably from 1.3 to 2. The reaction temperature is usually from 60 to 100 °C. The isocyanate group is the end point of the reaction when it is 5.0% by mass or less before the reaction. Further, in order to lower the viscosity at the time of the reaction, a compound which does not participate in the reaction may be added as a diluent. Specifically, a (fluorenyl) acrylate having no hydroxyl group structure can be used as a diluent. In the reaction of the reactant (I) with a hydroxyl group-containing (mercapto) acrylate, the isocyanate group of the reactant (I) is usually equivalent to the hydroxyl group-containing (meth) acrylate acid. 95 to 1. 丨 equivalent reaction. The reaction temperature is usually from 60 to 100 C. The isocyanate group is 0.1% by mass or less before the reaction. Further, in order to promote such a reaction, for example, a dibasic amine such as triethylamine 'nodal mercaptoamine, a dilaurate compound such as dibutyltin dilaurate or dioctyltin dilaurate may be used as a touch. Media, but in the present invention, since the concerns about environmental influences have increased in recent years and the regulations are more stringent, the catalyst containing tin is not used. Further, in order to prevent polymerization in the reaction, for example, hydroquinone (hydrohydrazine), hydroquinone monomethyl ether, or a hydrazine emulsion may be used, and a polymerization inhibitor such as Benzene may be used. 01至重量重量。 The addition amount of the polymerization inhibitor is usually 0.001 to 5% by mass, preferably 0.01 to 1% by weight. Further, in the resin composition of the present invention, the amine oxime (meth) acrylate oligomer (D) having a butanediol structure may be used singly or in combination of plural kinds. The photopolymerization initiator (E) contained in the resin composition of the present invention may, for example, be benzoin, benzoin, benzoin ethyl ether, benzoin 324097 13 201250386 propyl ether, benzoin isobutyl ether and the like benzoin; (acetophenone), 2,2-diethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2- Hydroxy-2-mercapto-phenylpropan-1-one, diethoxy acetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-mercapto-1-[4-(fluorenylthio) Phenyl]-2-N-morpholino propan-1-one, oligomeric [2-hydroxy-2-methyl-l-[4-(1-decylethenyl)phenyl] Acetones such as acetone; 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-chloroindole, 2-pentyl hydrazine, etc.; anthraquinone; 2, 4- 2 Thiophenone ketone, 2-isopropyl β-zegging ketone, 2-gas thiophene 17 ketone, etc.; thioxanthone; acetophenone didecyl ketal, benzyl didecyl ketal Equivalent ketals; diphenyl phenylphenone, 4-phenylmercapto-4'-mercaptodiphenyl sulfide, 4,4'-bismethylaminodiphenyl ketone 2, 4, 6-trimethylphenyl fluorenyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphonium oxide, dipyridyl-( 2, 4, 6-tridecyl-based fluorenyl-based phosphine oxides and the like. Preferred are acetophenones, and more preferred are 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone. Further, in the resin composition of the present invention, the photopolymerization initiator (E) may be used singly or in combination of plural kinds. In the resin composition of the present invention, in consideration of the viscosity, refractive index, adhesion, and the like of the obtained resin composition of the present invention, the component (A), the component (B), the component (C), and the component (D) may be used ( Mercapto) acrylate alone or in combination with two types = used above. The (fluorenyl) acrylate may be a monofunctional (fluorenyl) ruthenium acrylate, a bifunctional (meth) acrylate, or a polyfunctional (fluorenyl) acrylate having three or more (meth) acrylonitrile groups in the molecule. , Polyester (meth)acrylic acid 324097 14 201250386 vinegar 'epoxy (fluorenyl) acrylic acid, etc.:. Examples of the monofunctional (fluorenyl) acrylate include isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and (indenyl) propionate. I- pentyloxyethyl ester, alicyclic (meth) acrylate such as cyclomethacrylate, benzyl (meth) acrylate, ethoxy modified cresol (meth) acrylate Ester, propoxy modified cresol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, morpholine (meth) acrylate, etc. (meth) acrylate having an aromatic ring a heterocyclic (fluorenyl) acrylic acid such as caprolactone (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate Ester, quinone imine (mercapto) acrylate, butanediol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropionate Ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dipropylene (fluorenyl) acrylate (hydroxy) acrylate (meth) acrylate, methyl (meth) acrylate, methyl (meth) acrylate, butyrate, (meth) acrylate Vinegar, tert-butyl (meth) acrylate, octafluoropentyl (mercapto) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, ( Methyl acrylate isooctyl vinegar, 2-ethylhexyl acrylate (meth) acrylate, stearic acid (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate Ester, (meth)acrylic acid lauryl ester, etc. having an alkyl (T-based) acrylate 'ethoxy di" ethylene glycol (methyl) propionate, 2-ethylhexyl carbitol (carbit〇i (meth)acrylic acid g of a polyhydric alcohol such as (meth) acrylate, polyethylene glycol (mercapto) acrylate or polypropylene glycol (methyl) propionate vinegar. 324097 15 201250386 2-functional (fluorenyl) acrylates can be exemplified by: hydropivalaldehyde (hydr〇p丨vaj earth c aldehyde) modified trimethylolpropane di(meth)acrylic acid vinegar, ethoxylated double A di(meth) acrylate, propoxy modified double a (meth) acrylate, ethoxy modified bisphenol F di(meth) acrylate, propoxy modified bisphenol F II (曱-based) acrylic vinegar, ethoxylated bisphenol 5 di(methyl)

Acrylate, propoxy modified bisphenol S di(meth) acrylate, bisphenol A polyethoxy di(indenyl) acrylate, bisphenol A polypropoxy di(meth) acrylate, bisphenol F-polyethoxy di(meth)acrylate, hexahydrophthalic acid di(methyl) acrylate such as (meth) acrylate having an aromatic ring, dipropylene sulfonated isocyanurate, etc. Isocyanate propylene telluride, hydrazine, 4-butanediol di(meth) acrylate, 1>6-hexanediol di(meth) acrylate, 1,9-nonanediol bis(indenyl) acrylate An alicyclic (fluorenyl) acrylate such as a (meth) acrylate having a linear fluorenylene structure, a tricyclodecane decyl decyl acrylate or a dicyclopentanyl diacrylate, and an ethylene glycol Di((meth)acrylic acid of a polyhydric alcohol such as di(meth) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate or polypropylene di(decyl) acrylate Ester and the like. The polyfunctional (meth) acrylate having three or more (meth) acrylonitrile groups in the molecule may be a polyfunctional having an isocyanurate ring such as tris(acryloxyethyl)isocyanurate. (Meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetrakis(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol (meth) acrylate, tripentenol/((mercapto) acrylate, pentaerythritol penta(indenyl) acrylate, trishydroxypropyl propane bis(indenyl) acrylate, two (three) Hydroxyalkyl propane) tetra(methyl) 324097

S 16 201250386 Polyfunctional (meth) acrylate of a polyol such as acrylate. The polyacetate (mercapto) acrylate may, for example, be a reaction product of a polyester diol with (meth)acrylic acid, or a reaction product of the polyester diol diol compound with a dibasic acid or an acid anhydride thereof. Examples of the epoxy group (meth) acrylate include bisphenol A type epoxy resin, double age F type epoxy resin, phenol novolac type epoxy epoxide, and bismuth a propylene oxide plus A reaction product of an epoxy resin such as a glycidyl ether, a first epoxy resin or a bisphenol S-type epoxy resin, and a (meth)acrylic acid. The ratio of use of each component of the resin composition of the present invention is determined in consideration of the refractive index, glass transition temperature (Tg), viscosity, and adhesion, etc., but component (A) + component (B) + component (C) When the component (D) is 100 parts by mass, the content of the component (A) is from 30 to 70 parts by mass, preferably from 40 to 65 parts by mass. The knives (Β) έι are 3 to 5 parts by mass, preferably 1 to 45 parts by mass. The content of the component (C) is from 3 to 20 parts by mass, preferably from 5 to 15 parts by mass. The component (D) content is from 3 to 20 parts by mass, preferably from 5 to 15 parts by mass. The total amount of the component (A) + the component (B) + the component (C) + the component (D) is 100 mass%, and the component (E) is i to 1 part by mass, preferably 3 to 7 parts by mass. In order to improve the convenience in handling, etc., the resin composition of the present invention contains, in addition to the above-mentioned components, a medicinal agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, and the like. Polymerization is prohibited by W antistatic agent. In addition, acrylic polymers, polyester popcoal, ethyl urethane polymer and nitrile rubber may be added as needed. A solvent may also be added, but it is preferably one in which no solvent is added. 324097 17 201250386 The resin composition of the present invention can be prepared by mixing and dissolving each component in accordance with a usual method. For example, in a round bottom flask equipped with a mixing plant and a thermometer, the components are added, and the mixture is stirred at 40 to 8 (rc for 5 to 6 hours). The viscosity of the resin composition of the present invention is produced on a substrate. In the case of the formed optical lens, the viscosity of the shape transfer property and the workability of the workability is preferably 2,000 mPa·s or less as measured by using an E-type viscometer (manufactured by T-Shirt Co., Ltd.). The resin composition of the present invention can be easily hardened by an energy ray. Specific examples of the wire can be exemplified by ultraviolet rays, visible light, infrared rays, xenon rays, 7* rays, laser rays, and the like. In the present invention, ultraviolet rays, laser light rays, visible light rays, or electron beams are preferable. The resin composition of the present invention is irradiated with the aforementioned energy ray according to a usual method. The hardened material of the present invention is obtained. The refractive index of the resin composition of the present invention is usually from 51.51 to 1.59', preferably from 1.53 to 1.57. The refractive index can be measured by an Abbe refractometer ( Model·· DR-M2, ATAG0 shares The optical lens formed on the substrate of the present invention is obtained, for example, by coating and setting the stamper having a shape such as a lenticular lens or a prism lens. a layer of a resin composition, which is followed by a back sheet of a transparent substrate (eg, polymethyl acrylate resin, polybroken acid resin, polystyrene resin, polyester resin, or such polymerization) a film composed of a mixture of substances or the like, or a glass substrate which is easily treated, or the like, followed by 324097

S 201250386 The transparent substrate side is irradiated with an energy ray by a high pressure mercury lamp or the like to cure the resin composition, and then the cured product is peeled off by the stamper. The optical lens film of the present invention comprises a layer which is produced by various manufacturing methods, for example, a stamper having a shape of a lenticular lens, a prism lens or the like, and which is provided with a resin composition, and then a transparent substrate is provided on the layer. a back sheet of a material (for example, a film composed of a polyacrylic resin, a polycarbonate resin, a polystyrene resin, a polyester resin, or a mixture of such polymers) or a glass substrate which is easily treated by a subsequent treatment or the like. Then, the transparent substrate side is irradiated with an energy ray by a high pressure mercury lamp or the like to cure the resin composition, and then the cured product is peeled off from the stamper. (Embodiment) Next, the present invention will be described in more detail by way of examples. The invention is not limited to the following examples. In addition, the unit "parts" represents the parts by mass. The ultraviolet curable resin composition and cured product of the present invention were obtained as shown in the following examples. Further, the evaluation methods and evaluation criteria of the resin composition and the cured film are as follows. U) Viscosity: It was measured at 25t using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.). (2) Refractive index (25. 〇): The refractive index of the cured ultraviolet curable resin layer was measured by an Abbe refractometer (DR-M2: manufactured by ATAG0 Co., Ltd.) (25. 〇. (3) Release property. Indicates the ease with which the hardened resin is released from the mold. 〇···Good release from the mold 324097 19 201250386 △...The release is slightly difficult or there is a peeling sound when it is released. Residual mold (4) type reproducibility: coating/forming an ultraviolet curable resin layer on a substrate, and irradiating l〇〇〇mJ/em2 with a high pressure mercury lamp (10) W/cm, no ozone (〇z〇neiess) The shape of the surface of the ultraviolet curable resin layer which hardened and the surface shape of the mold were observed. 〇...reproducible X...reproducibility

(5) Adhesiveness: The sample used for the evaluation of the reproducibility of the type was evaluated according to the JIS standard. The linear result was evaluated as a one-price result; to 2, 3, 3 to 5 was \. (6) Scratch resistance: A test piece shaped into a crucible shape was formed on the PET substrate by using a mold. The smooth surface of the diffusion film was attached to the test piece, and the image was taken in a vertical direction with the 稜鏡 pattern. The scratch generated when the diffusion film is stretched. The diffusion film is made of commercially available Oiaze® 50%). 〇~No scratches to only slightly scratches X... There are scratches [Example 1]

NEW FRONTIER BPE-10 (manufactured by Daiichi Kogyo Co., Ltd.: bisphenol A polyethoxy diacrylate (HH m = 5 in the general formula (1), n = 5)) 5 parts of NEW FRONTIER PHE (manufactured by Daiichi Kogyo Co., Ltd., phenoxyethyl acrylate), and KAYARAD 0PP-1. 5 (Sakamoto Chemical Co., Ltd.) There are 324097

S 20 201250386 Limited company: o-phenylphenol polyethoxy acrylate) 4 parts, KAREARAD THE-330 (made by Nippon Kayaku Co., Ltd.: trimethylol propyl ethoxylate triacrylate) 1 part, KAYARAD UX-0937 (made by Nippon Kayaku Co., Ltd.: polyether urethane acrylate oligomer) of 5 parts, Irgacure 184 of component (E) (BASF Japan limited stock) Company made: 1-hydroxy-cyclohexyl phenyl ketone) 5 parts, at 6 〇. The resin composition of the present invention is obtained by heating and mixing. The resin composition was irradiated with ultraviolet rays having an irradiation amount of 1000 mJ/cm2 with a high pressure mercury lamp to obtain a cured film, and the refractive index was measured. Further, the resin composition was applied to a ruthenium lens mold at a film thickness of about 50 m, and an easy-to-adhere PET film (Toyobo Cosmoshine A4300, thickness l〇〇//) was attached thereto as a substrate. m), the ultraviolet ray having an irradiation dose of 1000 m J/cm 2 was irradiated thereon with a high pressure mercury lamp, and the ruthenium lens sheet of the present invention was obtained by peeling after hardening. (Evaluation results) Viscosity: 300 mPa · s, refractive index: 1. 557, release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: 〇 [Example 2] Component (A) NEWFRONTIERBPE-10 is 60 parts, ingredient (B) NEW FRONTIER PHE-2 (manufactured by Daiichi Kogyo Co., Ltd.: phenoxydiethoxy acrylate) 1 part, ingredient (C) KAYARADDPCA-60 (Sakamoto Chemical Co., Ltd.: dipentaerythritol polycaprolactone hexaacrylate) 15 parts, component (D) of KAYARAD UX-0937 is 15 parts, component (E) of Darocur 1173 (BASF Japan shares Co., Ltd.: 2-hydroxy-2-324097 201250386 methyl-1-phenyl-propan-1-one) 5 parts, heated and mixed at 60 ° C to obtain the resin composition of the present invention. Further, the refractive index of the obtained resin layer was measured in the same manner as in Example 1. The tantalum lens sheet of the present invention was obtained in the same manner as in Example 1 using the obtained resin composition. (Evaluation result) Viscosity: 800 mPa · s, refractive index: 1.53 release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: 〇 [Example 3] The component (A) NEW FRONTIER BPE-20C First Industrial Pharmaceutical Co., Ltd.: bisphenol A polyethoxy diacrylate (R1=H, R2=H, m=l〇, η=ι〇 in general formula (1)) 30 The new FRONTIER PHE of the ingredients and ingredients is 10 parts, and the same ingredients (Kayara £) opp-i (manufactured by Nippon Kayaku Co., Ltd.: o-phenylphenol monoethoxy acrylate) 3 parts, ingredients (C ) KAYARAD DPCA-120C Nippon Kayaku Co., Ltd.: dipentaerythritol polycaprolactone hexaacrylate) 1 part, component (D) KAYARAD ϋΧ_0937 is 20 parts, component (E) lrgacure 184 is Five parts of 'heated at 60 ° C and mixed to obtain the resin composition of the present invention. Further, the refractive index of the obtained resin layer was measured in the same manner as in Example 1. The tantalum lens sheet of the present invention was obtained in the same manner as in Example 1 using the obtained resin composition. (Evaluation result) Viscosity '850 mPa · S, refractive index: 1. 548, release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: 〇 324097

S 22 201250386 [Example 4] The NEW FRONTIER BPE-10 of the component (A) was 30 parts, the NEW FRONTIER PHE of the component (B) was 5 parts, and the KAYARAD 0PP-1. 5 of the composition (B) was also 45. 5 parts of SR-9035 (manufactured by Sartomer: trihydroxydecylpropane polyethoxy triacrylate), KAYARAD UX-0937 of component (D), 15 parts, Darocur 1173 of component (E) The resin composition of the present invention was obtained by heating and mixing 5 parts at 60 °C. The resin composition had a viscosity (25 ° C) of 500 mPa · s. Further, the refractive index of the obtained resin layer was measured in the same manner as in Example 1. The tantalum lens sheet of the present invention was obtained in the same manner as in Example 1 using the obtained resin composition. (Evaluation results) Viscosity: 500 mPa · S, refractive index: 1. 560, release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: 〇 [Comparative Example 1] According to Patent Document 1 ( In Example 3 of JP-A-2010-126670, the compound of the literature production example 3 (acrylic acid 4 molar addition of bisphenol A diglycidyl ether) was synthesized, and then 90 parts of the compound of Production Example 3 was prepared. KAYARADDPHA (Nippon Chemical Pharmaceutical Co., Ltd.'s dipentaerythritol hexaacrylate) 1 part, Irgacure 184 (manufactured by BASF Japan Co., Ltd.: 1-hydroxy-cyclohexyl phenyl ketone) 2 parts, at 6 (TC The resin composition for comparison was heated while heating. The viscosity (50 ° C) of the resin composition was 9,400 mPa · s. Further, the refractive index of the obtained resin layer was measured in the same manner as in Example 1. 324097 23 201250386 The obtained resin composition was obtained in the same manner as in Example 1. The comparative example had a very high viscosity, so that the workability was poor and the release property was not good, so that it was not suitable for continuous molding. (Evaluation results) Viscosity: 9400mPa · s, refraction ·· 1. 550, release property: X, type reproducibility: 〇, adhesion: 〇, scratch resistance: X [Comparative Example 2] According to Example 1 of Patent Document 2 (Japanese Patent No. 4457960), Further, the amine acetoacetate acrylate of Synthesis Example 1 was synthesized, and the compound of Synthesis Example 1 was 22.5 parts, bis(4-propenyl methoxy ethoxy phenyl) sulfide 20 parts, and phthalic acid phthalic acid. 25 parts of phenyl phenyl ester, 10 parts of benzyl methacrylate, 17.5 parts of tetrahydrofurfuryl acrylate, 5 parts of trishydroxypropyl propane triacrylate, and 5 parts of Irgacure 184, which were obtained by heating (mixing and mixing TC) The resin composition for comparison was measured, and the refractive index of the obtained resin layer was measured in the same manner as in Example 1. Using the obtained resin composition, a ruthenium lens sheet was obtained in the same manner as in Example 1. (Evaluation results) Viscosity : 70 mPa · S, refractive index: 1. 560, detachment: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: X [Comparative Example 3]

Manufactured by NEW FRONTIER BPE-4C First Industrial Pharmaceutical Co., Ltd. of ingredient (A): bisphenol A polyethoxy diacrylate (1 = [1, 匕 = 1, 111 = 2 in the general formula (1) 11=2)) 40 parts, ingredient (B) of NEWFRONTIERPHE 324097 24 201250386 is 5 parts, KAYARAD OPP-l·5 of composition (B) is 40 parts, and KAYARAD THE-330 of ingredient (C) is 10 parts. The KAYARAD UX-0937 of the component (D) is 5 parts, and the Irgacure 184 of the component (E) is 5 parts, and is heated and mixed at 60 ° C to obtain a comparative resin composition. Further, the refractive index of the obtained resin layer was measured in the same manner as in Example 1. Using a obtained resin composition, a ruthenium lens sheet was obtained in the same manner as in Example 1. (Evaluation results) Viscosity: 300 mPa · s, refractive index: 1. 566, release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: X [Comparative Example 4] Component (A) FANCRYL FA-328C manufactured by Hitachi Chemical Co., Ltd.: bisphenol A polyethoxy diacrylate (r1 = h, R2 = H, m = 4, n = 4 in the formula (1)) 30 parts, The ingredient (B) of NEW FRONTIER PHE is 5 parts, the KAYARAD OPP-l. 5 which is also the component (B) is 40 parts, the KAYARAD THE-330 of the component (C) is 20 parts, and the KAYARAD UX- of the component (D) 5 parts for 0937 and 5 parts for ingredient (E) for irgacure 184 at 60. (: The resin composition was compared and heated, and the refractive index of the obtained resin layer was measured in the same manner as in Example 1. Using the obtained resin composition, a ruthenium lens was obtained in the same manner as in Example 1. Diaphragm. (Evaluation results) Viscosity: 200 mPa · s, refractive index: 1. 555, release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: x 324097 25 201250386 [Comparative Example 5 Ingredients (A), NEW FRONTIER BPE-10, 60 parts, ingredient (B), NEW FRONTIER PHE-2C, First Industrial Pharmaceutical Co., Ltd.: phenoxydiethoxy acrylate) 5 parts, ingredients ( C) KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.: pentaerythritol triacrylate) 20 parts, component (D) of KAYARADUX-0937 is 15 parts, component (E) of Darocur 1173 is 5 parts, (6) (TC was heated and mixed to obtain a resin composition for comparison. Further, the refractive index of the obtained resin layer was measured in the same manner as in Example 1. The obtained resin composition was obtained in the same manner as in Example 1. Prism lens diaphragm (evaluation result) Viscosity: 90 0mPa · s, refractive index: 1. 535, release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: X [Comparative Example 6] The composition (A) of NEWFRONTIERBPE-10 is 60份, ingredients (B), NEW FRONTIER PHE-2C, First Industrial Pharmaceutical Co., Ltd.: phenoxydiethoxy acrylate) 10 parts, component (C), KAY ARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) : 15 parts of dipentaerythritol hexa-propyl vinegar vinegar, 15 parts of KAYARAD UX-0937 of component (D), 5 parts of Darocur 1173 of component (E), heated and mixed at 60 ° C, The resin composition used for comparison. Further, the refractive index of the obtained resin layer was measured in the same manner as in Example 1. Using the obtained resin composition, a ruthenium lens sheet was obtained in the same manner as in Example 1 (evaluation result)

324097 26 S 201250386 Viscosity: 900 mPa · s, refractive index: 1. 539, release property: 〇, type reproducibility: 〇, adhesion: 〇, scratch resistance: x From Examples 1 to 4 and Comparative Example 1 As is apparent from the evaluation results of the above-mentioned composition, the resin composition of the present invention having a specific composition is excellent in release property, reproducibility, and adhesion to a substrate film, and is excellent in durability (scratch resistance and scratch resistance). Therefore, it is suitable for an optical lens film formed on a substrate such as a lenticular lens, a prism lens, or a microlens, and it is also possible to suppress shape defects caused by contact with other optical films. (Industrial Applicability) The ultraviolet curable resin composition of the present invention and the cured product thereof are particularly suitable for an optical lens sheet which is mainly formed on a substrate such as a lenticular lens, a prism lens, or a microlens. [Simple diagram description] None [Main component symbol description] None 324097 27

Claims (1)

201250386 VII. Patent application scope: 1. An energy ray-curable resin composition for an optical lens film formed on a substrate, which contains a polyethylene oxide modified by the following formula (1) A-type bis(indenyl) acrylate (A), 30 to 70 parts by mass of a mono(indenyl) acrylate (B) having a diisopropyl ether structure, 3 to 50 parts by mass, and having 3 or more a polyfunctional (meth) acrylate having a propylene fluorenyl group and modified by caprolactone or epoxy bhide, 3 to 2 parts by mass of an amine decyl acrylate having a butane diol structure Oligomer 〇)) '3 to 20 parts by mass, and photopolymerization initiator (E), 1 to 1 part by mass, (wherein R, Rz each independently represent a hydrogen atom or a fluorenyl group, and m and η are repeating numbers and each independently represents a positive number of 5 to 1 Å). The energy ray-curable resin composition according to claim 1, wherein the mono(meth)acrylate fluorene having a diphenyl ether structure is composed of phenoxyethyl acrylate and phenoxy acrylate. Ethoxylate, o-phenylphenol (meth)acrylate, o-phenylphenol mono(ethoxy)acrylate, o-phenylphenol polyethoxylate (meth)acrylate, p-phenylphenol (methyl) Any of a group of acrylates, p-phenylphenol mono(ethoxy)acrylate, and (meth)acrylic acid to phenylphenol polyethoxylate. For example, applying the full-time energy line hardening resin to form 324097 S 1 201250386, wherein the ethyl phthalate acrylate oligomer (D) having a butanediol structure has a molecular weight of 500 to 1000. An amine phthalate acrylate oligomer obtained by reacting a diol compound, a polyisocyanate compound, or a hydroxyl group-containing (meth) acrylate. The energy ray-curable resin composition according to any one of claims 1 to 3, wherein the polyisocyanate compound has a ring structure. 5. The energy ray-curable resin composition according to any one of claims 1 to 4, wherein the viscosity measured at 25 ° C by an E-type viscosity meter is 2000 mPa·s or less. A hardened material obtained by curing an energy ray-curable resin composition according to any one of claims 1 to 5 by energy ray irradiation. An optical lens film having a cured product as described in claim 6 of the patent application. 324097 2 201250386 IV. Designated representative map: (1) The representative representative of the case is: (). (There is no picture in this case) (2) The symbol of the symbol of this representative figure is simple: (none) 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 324097 4