KR20120128550A

KR20120128550A - Energy ray-curable resin composition for optical lens sheet and cured product thereof, and the optical lens sheet

Info

Publication number: KR20120128550A
Application number: KR1020120039096A
Authority: KR
Inventors: 노부히코 나이토우; 준코 이치카와; 노리코 키요야나기
Original assignee: 닛뽄 가야쿠 가부시키가이샤
Priority date: 2011-05-17
Filing date: 2012-04-16
Publication date: 2012-11-27

Abstract

(Problem) The resin composition suitable for the optical lens shape | molded on the base material excellent in mold release property, mold reproducibility, adhesiveness with a board | substrate film, and high durability (scratch resistance and scratch resistance) is provided.
(Solution means) Polyethylene oxide modified bisphenol A type di (meth) acrylate (A) represented by the following general formula (1):

(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, m and n each independently represent an integer of 5 to 10), and a mono (meth) having 30 to 70 parts by mass and a phenyl ether structure. 3-20 parts by mass of polyfunctional (meth) acrylate (C) modified with caprolactone or ethylene oxide, having 3-50 parts by mass of acrylate (B) and three or more (meth) acryloyl groups, and tetra Energy-beam curable resin for optical lens sheets formed on a substrate containing 3-20 parts by mass of a urethane (meth) acrylate oligomer (D) having a methylene glycol structure and 1-10 parts by mass of a photopolymerization initiator (E), respectively. Composition.

Description

Energy ray curable resin composition for optical lens sheets, its cured product, and optical lens sheet {ENERGY RAY-CURABLE RESIN COMPOSITION FOR OPTICAL LENS SHEET AND CURED PRODUCT THEREOF, AND THE OPTICAL LENS SHEET}

The ultraviolet curable resin composition is used for the prism lens sheet used for the backlight of a liquid crystal display device, the optical lens sheet shape | molded on base materials, such as Fresnel lens, lenticular lens, etc. used for projection television etc., a transmissive screen, etc.

These optical lens sheets tend to decrease in number of optical sheets as the demand for cost reduction in recent years increases, and durability (abrasion resistance and scratch resistance) in contact with other optical sheets which have not been directly contacted in the past Etc.) is desired to a high level.

In the patent document 1, although durability was expressed by using the material with small acrylic equivalent as what gave the resin layer itself durability, the resin composition containing the material with small acrylic equivalent has a tendency for strong curl, and it is an optical sheet As not preferred. Moreover, when trying to express durability with a material with a small acrylic equivalent weight, a cured film will become hard and brittle, and especially there existed a problem that a flaw was easily made by contacting with the optical sheet containing an organic or inorganic filler.

In patent document 2, the sum total of repeating number is 0-8, the ethylene oxide modified di (meth) acrylate, the compound which has two aromatic rings, and one (meth) acryloyl group, one aromatic ring, and one ( It is useful as resin for an optical lens by the combination of the compound which has a meta) acryloyl group, the compound which has three or more (meth) acryloyl groups, and specific resins other than the above-mentioned ethylenically unsaturated group containing compound as an arbitrary component. It is proposed. Ethylene oxide modified di (meth) acrylate having a total of 0 to 8 repeats is poor in scratch resistance (scratch resistance) and is not suitable for use when scratch resistance (scratch resistance) is required. This is because, if the alkylene oxide modification is short, it hardens, but at the same time, it breaks down well. In addition, although only the diacrylate of a sulfide frame | skeleton is used in the Example of patent document 2, generally, when using resin containing a sulfur atom, there exists a tendency for a refractive index to rise, but odor becomes strong, It is known that light resistance becomes remarkably bad. Therefore, there exists a problem in use in the recent resin composition for optical lens sheets.

As mentioned above, the resin composition which had the characteristic which is generally required for an optical lens sheet, high light transmittance, mold release property, base material adhesiveness, and high durability was not obtained.

Japanese Laid-Open Patent Publication No. 2010-126670 Japanese Patent Publication No. 4457960

An object of the present invention is to provide a resin composition suitable for an optical lens sheet to be molded on a substrate such as a lenticular lens, a prism lens, a microlens, and excellent light transmittance and mold release property, and high durability (scratch resistance, scratch resistance). It is to provide a cured product.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors discovered that the ultraviolet curable resin composition and its hardened | cured material which have a specific composition solve the said subject, and completed this invention.

That is, the present invention,

(1) 30-70 mass parts of polyethylene oxide modified bisphenol-A di (meth) acrylate (A) represented by following General formula (1), and mono (meth) acrylate (B) which has a phenyl ether structure are 3? Urethane (meth) which has 50 mass parts and 3 or more (meth) acryloyl groups, and has 3-20 mass parts and the tetramethylene glycol structure of the polyfunctional (meth) acrylate (C) modified with caprolactone or ethylene oxide ) Is an energy ray curable resin composition for an optical lens sheet which is molded on a substrate containing 3 to 20 parts by mass of the acrylate oligomer (D) and 1 to 10 parts by mass of the photopolymerization initiator (E):

(In formula, R <_1> , R <_2> is respectively independently a hydrogen atom or a methyl group, m and n are repeat numbers, and each independently represents the integer of 5-10.).

(2) (meth) acrylate (B) which has a phenyl ether structure is phenoxyethyl (meth) acrylate, phenoxypolyethoxy (meth) acrylate, o-phenylphenol (meth) acrylate, o-phenyl Phenol monoethoxy (meth) acrylate, o-phenyl phenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol It is 1 or more selected from the group which consists of polyethoxy (meth) acrylate, The energy-beam curable resin composition as described in (1) characterized by the above-mentioned.

(3) urethane (meth) acrylate oligomers obtained by reacting a urethane (meth) acrylate oligomer (D) having a tetramethylene glycol structure with a diol compound having a molecular weight of 500 to 1000, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate. It is an energy-beam curable resin composition as described in phosphorus (1).

(4) The energy ray-curable resin composition according to (1) to (3) in which the polyisocyanate compound has a ring structure.

(5) The energy-beam curable resin composition as described in any one of (1)-(4) whose viscosity in 25 degreeC measured with the E-type viscosity meter is 2000 mPa * s or less.

(6) It is hardened | cured material obtained by hardening | curing the energy-beam curable resin composition as described in (1)-(5) by irradiation of an energy beam.

(7) It is an optical lens sheet which has a hardened | cured material as described in (6).

Stability is good, and the resin composition of this invention is good in releasability from a metal mold | die, mold reproducibility, and adhesiveness with a base film. Moreover, it is excellent in durability (abrasion resistance and scratch resistance). Therefore, it is especially suitable for the optical lens sheet shape | molded on base materials, such as a lenticular lens, a prism lens, a micro lens.

(Mode for carrying out the invention)

Polyethylene oxide-modified bisphenol-A di (meth) acrylate (A) whose total number of repetitions used in this invention (m + n in the said General formula (1)) is 10-20 is abrasion resistance (scratch resistance of hardened | cured material) ) Has the effect of improving. If the total number of repetitions is other than 10 to 20, it becomes hard but becomes a brittle hardened material. As a specific example, an ethoxy 10 mol modified bisphenol A di (meth) acrylate, an ethoxy 18 mol modified bisphenol A di (meth) acrylate, an ethoxy 20 mol modified bisphenol A di (meth) acrylate, etc. are mentioned, These can be easily obtained as a commercial item. Specifically, Daiichi Kogyo Chemical Co., Ltd. New Frontier BPE-10 (in formula (1), R ₁ = H, R ₂ = H, m = 5, n = 5) and Daiichi Kogyo Co., Ltd.) New frontier BPEM-10 (R ₁ = CH ₃ , R ₂ = CH ₃ , m = 5, n = 5) manufactured by Yaku Corp., New Frontier BPE-20 (Daiichi Kogyo Seiyaku Co., Ltd.) ) R ₁ = H, R ₂ = H, m = 10, n = 20), Hitachi Kasei Co., Ltd. FANCRYL FA-321A (R ₁ = H, R ₂ = H, m = 5, n = 5), Hitachi Kasei Co., Ltd. plate krill FA-3218A (R ₁ = H, R ₂ = H, m = 9, n = 9), Hitachi Kasei Co., Ltd. plate Krill FA-321M (R ₁ = CH ₃ , R ₂ = CH ₃ , m = 5, n = 5), Hitachi Kasei Co., Ltd. plate krill FA-3218M (R ₁ = CH ₃ , R ₂ = CH _{3, m = 9, n =} 9), Shin-Nakamura Kagaku Kogyo manufactured by whether or NK ester _{A-BPE-10 (R 1} = H, R 2 H, m = 5, n = 5), Shin-Nakamura Kagaku Kogyo manufactured by whether or _{R 1 = H, R 2 =} H, m = 10, in the manufacture NK ester A-BPE-20 (formula (1) n = 20), manufactured manufactured by Shin-Nakamura Kagaku Kogyo whether or NK ester _{BPE-500 (R 1 = CH} 3, R 2 = CH 3, m = 5, n = 5), Shin-Nakamura Kagaku Kogyo manufactured by whether or manufacturing NK Ester BPE-900 (R ₁ = CH ₃ , R ₂ = CH ₃ , m = 8, n = 9), Nichiyu Corporation Blemmer PDBLE-450 (R ₁ = CH ₃ , R ₂ = CH ₃ , m = 5, n = 5), Satomer manufactured SR602 (R ₁ = H, R ₂ = H, m = 5, n = 5), Satomer manufactured SR480 (R ₁ = CH ₃ , R ₂ = CH _3, there may be mentioned m = 5, n = 5) , MIWON prepared _{MIRAMER M2100 (R 1 = H,} R 2 = H, m = 5, n = 5) or the like.

The following are mentioned as (meth) acrylate (B) which has a phenyl ether structure used for the resin composition of this invention.

p-cumylphenoxyethylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, ethoxy modified tribromophenyl (meth) acrylate, propoxy modified tribromophenyl (meth) acrylate, phenoxy Cyhydroxypropyl (meth) acrylate, phenoxy polyethylene (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate , Phenoxypolyethoxy (meth) acrylate, nonylphenol (meth) acrylate, ethoxy modified nonylphenol (meth) acrylate, polyethoxy modified nonylphenol (meth) acrylate, o-phenylphenol (meth) Acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylic re Agent, and the like p- phenylphenolato poly ethoxy (meth) acrylate, o- phenylphenol epoxy (meth) acrylate, p- phenylphenol epoxy (meth) acrylate. In particular, phenoxyethyl (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, and o-phenylphenol polyethoxy (meth) acrylate are preferable. The (meth) acrylate which has these phenyl ether structures may be used independently, and can mix and use multiple types.

The polyfunctional (meth) acrylate (C) having three or more (meth) acryloyl groups and modified with caprolactone or ethylene oxide has an effect of improving scratch resistance (scratch resistance) of the cured product. When the thing which is not modified with caprolactone or ethylene oxide is used, although hardened | cured material is hard, it will fall easily. Specific examples of the polyfunctional (meth) acrylate (C) having three or more (meth) acryloyl groups and modified with caprolactone or ethylene oxide include polyethoxy-modified trimethylolpropane tri (meth) acrylate and poly Toxy modified pentaerythritol tetra (meth) acrylate, polyethoxy modified glycerol tri (meth) acrylate, polyethoxy modified dipentaerythritol penta (meth) acrylate, polyethoxy modified dipentaerythritol hexa (meth ) Acrylic acid, polycaprolactone modified trimethylolpropane tri (meth) acrylate, polycaprolactone modified dipentaerythritol penta (meth) acrylate, polycaprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone Modified tris (acryloxyethyl) isocyanurate, polycaprolactone modified tris (acryloxyethyl) isocyanurate, pole On the like-ethoxy-modified tris (acryloxyethyl) isocyanurate. In particular, polyethoxy modified trimethylol propane tri (meth) acrylate, polycaprolactone modified tris (acryloxyethyl) isocyanurate, polycaprolactone modified dipentaerythritol penta (meth) acrylate, and polycaprolactone modified Dipentaerythritol hexa (meth) acrylate is preferred.

The urethane (meth) acrylate oligomer (D) which has the tetramethylene glycol structure contained in the resin composition of this invention also has the effect | action which improves the scratch resistance (scratch resistance) of hardened | cured material. As a specific example, the reactant etc. which made the diol compound and organic polyisocyanate react, and then added the hydroxyl-containing (meth) acrylate are mentioned, for example.

As a diol compound which can be used in this invention, polytetramethylene glycol, 3-methyl tetramethylene glycol, etc. are mentioned, for example. Although the diol compound of arbitrary molecular weight each can be obtained easily as a commercial item, in this invention, the polytetramethylene diol compound of the molecular weight 500-1000 is especially preferable.

Examples of the organic polyisocyanate that can be used in the present invention include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like. Chain saturated hydrocarbon isocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexyl methane diisocyanate, methylenebis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated Cyclic saturated hydrocarbon isocyanates such as toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylene diisocyanate, p-phenylenedi isocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6- Isopropyl-1,3-phenyldiisocyanate, 1,5-naphthal D can include aromatic polyisocyanates, such as an isocyanate, and cyclic saturated hydrocarbon isocyanate is preferably hydrogen, particularly preferably a tolylene diisocyanate or isophorone diisocyanate.

As a specific example of the hydroxyl-containing (meth) acrylate which can be used in this invention, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1, 4- butanediol ( Ε-caprolactone addition of meta) acrylate, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, and 2-hydroxyethyl (meth) acrylate Water, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, etc. are mentioned, 2-hydroxyethyl (meth) acrylate is preferable.

The urethane (meth) acrylate oligomer (D) which has the tetramethylene glycol structure used for this invention is obtained by synthesize | combining by a conventional method using the said diol compound, organic polyisocyanate, and hydroxyl-containing (meth) acrylate. Can be. That is, for example, the reactant (I) is obtained by adding a diol compound and an organic polyisocyanate, and then a urethane (meth) acrylate is obtained by adding a hydroxyl group-containing (meth) acrylate to the reactant (I).

At the time of synthesis | combination of reactant (I), it is preferable to make 1.1-2.0 equivalent of isocyanate groups of organic polyisocyanate normally, and 1.3-2.0 equivalent to 1 equivalent of hydroxyl groups of the said diol. Reaction temperature is 60-100 degreeC normally. When an isocyanate group became 5.0 mass% or less before reaction, let it be a reaction end point.

In addition, in order to lower a viscosity, you may add the compound which does not participate in a reaction as a diluent. Specifically, the (meth) acrylate of the structure which does not have a hydroxyl group can be used as a diluent.

In the reaction between the reactant (I) and the hydroxyl group-containing (meth) acrylate, 0.95 to 1.1 equivalents of the hydroxyl group of the hydroxyl group-containing (meth) acrylate is usually reacted per 1 equivalent of the isocyanate group of the reactant (I). Reaction temperature is 60-100 degreeC normally. When an isocyanate group became 0.1 mass% or less before reaction, let it be a reaction end point. Moreover, in order to accelerate | stimulate these reaction, dilauryl compounds, such as tertiary amines, such as a triethylamine and a benzyl methylamine, dibutyltin dilauryllate, and dioctyl tin dilaurylate, can be used, for example. Although it may be used as a catalyst, in the present invention, a tin-containing catalyst is not used due to the recent increase in environmental considerations and strict regulation. Moreover, in order to prevent superposition | polymerization in reaction, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, p-benzoquinone, can be used, for example. The addition amount of a polymerization inhibitor is 0.001-5 mass% normally with respect to the whole reaction mixture, and it is preferable that it is 0.01-1 mass%. In addition, in the resin composition of this invention, the urethane (meth) acrylate oligomer (D) which has a tetramethylene glycol structure may be used independently, and may mix and use multiple types.

As a photoinitiator (E) contained in the resin composition of this invention, Benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propylether, benzoin isobutyl ether; acetophenone, 2,2- Diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone , 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, oligo [2-hydroxy-2-methyl-1 Acetophenones such as-[4- (1-methylvinyl) phenyl] propanone]; anthraquines such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone Rice field; Thioxanthones such as 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone and 2-chloro thioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone and 4-benzoyl-4'- Benzophenones such as methyl diphenyl sulfide and 4,4'-bismethylaminobenzophenone; Phosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide Oxides; and the like. Preferably, they are acetophenones, More preferably, 2-hydroxy-2- methyl- phenyl propane- 1-one and 1-hydroxy cyclohexyl phenyl ketone are mentioned. In addition, in the resin composition of this invention, a photoinitiator (E) may be used independently and may be used in mixture of multiple types.

Moreover, in consideration of the viscosity, refractive index, adhesiveness, etc. of the resin composition of this invention obtained to the resin composition of this invention, (meth) acryl other than a component (A), a component (B), a component (C), and a component (D) You may use a rate individually or in mixture of 2 or more types. As said (meth) acrylate, monofunctional (meth) acrylate, bifunctional (meth) acrylate, the polyfunctional (meth) acrylate which has three or more (meth) acryloyl groups in a molecule | numerator, polyester (meth) An acrylate, an epoxy (meth) acrylate, etc. can be used.

As monofunctional (meth) acrylate, for example, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acryl Alicyclic (meth) acrylates, such as the rate and cyclohexyl (meth) acrylate, benzyl (meth) acrylate, ethoxy modified cresol (meth) acrylate, propoxy modified cresol (meth) acrylate, neopentyl glycol benzo (Meth) acrylate which has aromatic rings, such as an eight (meth) acrylate and a morpholine (meth) acrylate, a caprolactone (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and a caprolactone modified tetrahydrofur (Meth) acrylate which has heterocycles, such as a furyl (meth) acrylate, the imide (meth) acrylate which has an imide ring structure, butanediol mono (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dipropylene glycol (Meth) acrylate which has hydroxyl groups, such as (meth) acrylate, dimethylaminoethyl (meth) acrylate, butoxyethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , Octafluoropentyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (Meth) acrylate, ethoxydiethylene glycol having alkyl groups such as stearyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, and lauryl (meth) acrylate ( And the like other) acrylate, 2-ethylhexyl carbitol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) (meth) acrylates of polyhydric alcohols, such as acrylate.

As bifunctional (meth) acrylate, hydropivalaldehyde modified trimethylolpropanedi (meth) acrylate, ethoxy modified bisphenol A di (meth) acrylate, propoxy modified bisphenol A di (meth) acrylate, ethoxy modified Bisphenol F di (meth) acrylate, propoxy modified bisphenol F di (meth) acrylate, ethoxy modified bisphenol S di (meth) acrylate, propoxy modified bisphenol S di (meth) acrylate, bisphenol A polyethoxy (Meth) acryl which has aromatic rings, such as a cddi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, and hexahydrophthalic acid di (meth) acrylate Acrylate, 1, 4- butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate of isocyanate, such as a acrylate and diacrylated isocyanurate Alicyclic (meth) s such as (meth) acrylates having a straight chain methylene structure such as 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, and dicyclopentanyl diacrylate Di (meth) acrylates of polyhydric alcohols such as acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and polypropylene di (meth) acrylate Can be mentioned.

As a polyfunctional (meth) acrylate which has three or more (meth) acryloyl groups in a molecule, polyfunctional (meth) acrylate which has isocyanurate rings, such as tris (acryloxyethyl) isocyanurate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylic And polyfunctional (meth) acrylates of polyhydric alcohols such as late, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.

As polyester (meth) acrylate, the reactant of polyester diol which is a reaction product of a diol compound, a dibasic acid or its anhydride, and (meth) acrylic acid, etc. are mentioned.

Examples of the epoxy (meth) acrylates include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, terminal glycidyl ethers of propylene oxide adducts of bisphenol A, fluorene epoxy resins, and bisphenol S type epoxy resins. The reactant of epoxy resins, such as these, and (meth) acrylic acid, etc. are mentioned.

Although the use ratio of each component of the resin composition of this invention is determined in consideration of desired refractive index, glass transition temperature (Tg), a viscosity, adhesiveness, etc., A component (A) + component (B) + component (C) + component When (D) is 100 mass parts, content of a component (A) is 30-70 mass parts, Preferably it is 40-65 mass parts. Content of a component (B) is 3-50 mass parts, Preferably it is 10-45 mass parts. Content of a component (C) is 3-20 mass parts, Preferably it is 5-15 mass parts. Content of a component (D) is 3-20 mass parts, Preferably it is 5-15 mass parts. Component (E) is 1-10 mass parts with respect to 100 mass parts of total amounts of component (A) + component (B) + component (C) + component (D), Preferably it is 3-7 mass parts.

In addition to the above components, the resin composition of the present invention may contain a release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, an antistatic agent, etc. in combination depending on the situation in order to improve convenience in handling. have. Moreover, polymers, such as an acrylic polymer, a polyester elastomer, a urethane polymer, and a nitrile rubber, can also be added as needed. Although a solvent can also be added, it is preferable not to add a solvent.

The resin composition of this invention can be prepared by mixing and melt | dissolving each component in accordance with a conventional method. For example, it can obtain by putting each component in the round bottom flask with a stirring apparatus and a thermometer, and stirring at 40-80 degreeC for 0.5-6 hours.

The viscosity of the resin composition of this invention is a viscosity suitable for the workability of the transferability and workability of the shape at the time of manufacturing the optical lens shape | molded on a base material, and uses E-type viscosity meter (TV-200: Toki Sangyo Co., Ltd. make). The composition whose viscosity measured using is 2000 mPa * s or less at 25 degreeC is preferable.

The resin composition of this invention can be hardened easily by an energy ray. Specific examples of the energy rays include ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and electromagnetic waves such as laser beams, particle rays such as alpha rays, beta rays, and electron beams. In this invention, an ultraviolet-ray, a laser beam, a visible ray, or an electron beam is preferable among these.

According to a conventional method, the hardened | cured material of this invention can be obtained by irradiating the said energy ray to the resin composition of this invention. The refractive index of the resin composition of this invention is 1.51-1.59 normally, Preferably it is 1.53-1.57. The refractive index can be measured with an Abbe refractive index meter (article number: DR-M2, manufactured by Atago Co., Ltd.) and the like.

The optical lens to be molded on the substrate of the present invention is applied, for example, on a stamper having a shape such as a lenticular lens, a prism lens, to form a layer of the resin composition, and a back sheet as a transparent substrate on the layer (eg For example, a film made of a polymethacryl resin, a polycarbonate resin, a polystyrene resin, a polyester resin, a brand product of these polymers, or the like) or a glass substrate subjected to a treatment such as a bismuth adhesive treatment is adhered, and then the After irradiating an energy beam with a high pressure mercury lamp etc. from the transparent base material side, and hardening the said resin composition, it can obtain by peeling a hardened | cured material from the said stamper.

Although the optical lens sheet of this invention includes what is produced by what kind of manufacturing method, For example, it applies to the stamper which has shapes, such as a lenticular lens and a prism lens, to form the layer of the said resin composition, and the transparent base material on the layer A glass substrate subjected to a treatment such as a phosphorous back sheet (for example, a film made of a polymethacryl resin, a polycarbonate resin, a polystyrene resin, a polyester resin, a brand product of these polymers, or the like) or an easy-adhesive treatment is bonded to each other, Subsequently, after irradiating an energy ray with the high pressure mercury lamp etc. from the said transparent base material side, and hardening the said resin composition, it can obtain by peeling hardened | cured material from the said stamper.

[Example]

Next, an Example demonstrates this invention further in detail. This invention is not limited at all by the following example. In addition, numerical unit "part" shows a mass part.

The ultraviolet curable resin composition and hardened | cured material of this invention were obtained with the composition as shown to the following example. In addition, the evaluation method and evaluation criteria for a resin composition and a cured film were performed as follows.

(1) Viscosity: It measured at 25 degreeC using the E-type viscosity meter (TV-200: Toki Sangyo Co., Ltd. make).

(2) Refractive index (25 degreeC): The refractive index (25 degreeC) of the hardened ultraviolet curable resin layer was measured by the Abbe refractometer (DR-M2: The product made by Atago, Inc.).

(3) Release property: The difficulty at the time of releasing cured resin from a metal mold | die is shown.

Good release from mold

△ ‥‥ Sometimes difficult to release or there is peeling sound when releasing

Difficult to mold release or mold marks

(4) Mold reproducibility: The ultraviolet curable resin layer was apply | coated and shape | molded on the base material, and it hardened | cured by irradiating 1000mJ / cm <2> with the high pressure mercury lamp (80W / cm, ozoneless). The surface shape of the hardened ultraviolet curable resin layer and the surface shape of the metal mold | die were observed.

○ ‥‥ Reproducibility is good

× ‥‥ Poor reproducibility

(5) Adhesiveness: In the sample used by the mold reproducibility evaluation, adhesive evaluation was performed according to JISK5600-5-6. The evaluation result set 0-2 to (circle) and 3-5 to x.

(6) Scratch resistance: The prism shape was shaped using a mold on a PET substrate, and a test piece was produced. The mat surface of the diffusion sheet was aligned on the test piece, a weight of 100 g was further placed thereon, and the scratches generated when the diffusion sheet was pulled in the direction perpendicular to the prism pattern were observed. A commercial item (Haze value 50%) was used for the diffusion sheet.

○ ‥‥ No scratches, a few scratches

× ‥‥ There is a scratch

Example One

New Frontier BPE-10 (manufactured by Daiichi Kogyo Chemical Co., Ltd.) as component (A): bisphenol A polyethoxy diacrylate (in formula (1), R ₁ = H, R ₂ = H, m = 5, 40 parts of n = 5)) and 5 parts of New Frontier PHE (made by Daiichi Kogyo Chemical Co., Ltd .: phenoxyethyl acrylate) as a component (B), and KAYARAD OPP-1.5 (Nippon Kaya) as the same component (B) 40 parts of o-phenylphenol polyethoxyacrylates) and 10 parts of KAYARAD THE-330 (made by Nippon Kayaku Co., Ltd .: trimethylolpropane polyethoxytriacrylate) as a component (C) 5 parts of KAYARAD UX-0937 (manufactured by Nippon Kayaku Co., Ltd .: polyether urethane acrylate oligomer) as component (D) and Irgacure 184 (manufactured by BASF Japan Co., Ltd .: 1-hydroxy) as component (E) -Cyclohexyl phenyl ketone) 5 parts, heated to 60 ° C and mixed, the resin composition of the present invention Obtained. This resin composition was irradiated with the ultraviolet-ray of 1000 mJ / cm <2> irradiation amount with the high pressure mercury lamp, the cured film was obtained, and the refractive index was measured.

Further, this resin composition was applied onto the prism lens mold so that the film thickness was about 50 μm, and then the easily-adhesive PET film (Toyobo Cosmoshine A4300, 100 μm thick) was adhered thereon as a base material, and further a high-pressure mercury lamp thereon. Ultraviolet rays with an irradiation amount of 1000 mJ / cm 2 were irradiated, cured, and then peeled to obtain a prism lens sheet of the present invention.

Evaluation results

Viscosity: 300 mPas, Refractive index: 1.557, Release property: ○, Mold reproducibility: ○, Adhesiveness: ○, Scratch resistance: ○

Example 2

60 parts of New Frontier BPE-10 as component (A) and 10 parts of New Frontier PHE-2 (made by Daiichi Kogyo Chemical Co., Ltd .: phenoxy diethoxyacrylate) as component (B) as component (C) 15 parts of KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd .: dipentaerythritol polycaprolactone hexaacrylate), 15 parts of KAYARAD UX-0937 as component (D), Darocur 1173 (BASF) as component (E) Japan-made 2-hydroxy-2-methyl-1-phenyl-propane-1-one) was heated and mixed at 5 parts and 60 degreeC, and the resin composition of this invention was obtained. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

The prism lens sheet of this invention was obtained like Example 1 using the obtained resin composition.

Evaluation results

Viscosity: 800 mPas, refractive index: 1.531, mold release property: ○, mold reproducibility: ○, adhesion: ○, scratch resistance: ○

Example 3

New Frontier BPE-20 (manufactured by Daiichi Kogyo Chemical Co., Ltd .: bisphenol A polyethoxy diacrylate (in formula (1), R ₁ = H, R ₂ = H, m = 10, as a component (A)) 30 parts of n = 10)) and 10 parts of New Frontier PHE as component (B) and KAYARAD OPP-1 (made by Nippon Kayaku Co., Ltd .: o-phenylphenol monoethoxyacrylate) as the same component (B) 30 parts of KAYARAD DPCA-120 (manufactured by Nippon Kayaku Co., Ltd .: dipentaerythritol polycaprolactone hexaacrylate) as component (C), 20 parts of KAYARAD UX-0937 as component (D), Irgacure 184 was heated and mixed at 5 parts and 60 degreeC as a component (E), and the resin composition of this invention was obtained. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

Evaluation results

Viscosity: 850 mPas, Refractive index: 1.548, Release property: ○, Mold reproducibility: ○, Adhesiveness: ○, Scratch resistance: ○

Example 4

30 parts of New Frontier BPE-10 as component (A), 5 parts of New Frontier PHE as component (B), 45 parts of KAYARAD OPP-1.5 as component (B) and SR-9035 as component (C) Toma Preparation: 5 parts of trimethylolpropanepolyethoxytriacrylate), 15 parts of KAYARAD UX-0937 as component (D), and 5 parts of Darocur 1173 as component (E) were heated and mixed to 60 ° C, The resin composition of the invention was obtained. The viscosity (25 degreeC) of this resin composition was 500 mPa * s. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

Evaluation results

Viscosity: 500 mPas, refractive index: 1.560, release property: ○, mold reproducibility: ○, adhesiveness: ○, scratch resistance: ○

Comparative example One

According to Example 3 of Patent Literature 1 (Japanese Laid-Open Patent Publication No. 2010-126670), the compound (4 moles of acrylic acid of bisphenol A diglycidyl ether) of the literature preparation example 3 was synthesized. 90 parts of compounds, 10 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate), 2 parts of Irgacure 184 (manufactured by BASF Japan: 1-hydroxy-cyclohexylphenyl ketone) It heated and mixed at 60 degreeC, and obtained the resin composition for comparison. The viscosity (50 degreeC) of this resin composition was 9400 mPa * s. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

It carried out similarly to Example 1 using the obtained resin composition, and obtained the prism lens sheet. This comparative example is unsuitable for continuous molding because the viscosity is very high, resulting in poor workability and poor releasability.

Evaluation results

Viscosity: 9400 mPas, refractive index: 1.550, release property: ×, mold reproducibility: ○, adhesion: ○, scratch resistance: ×

Comparative example 2

According to Example 1 of Patent Document 2 (Japanese Patent No. 4457960), the urethane acrylate of Synthesis Example 1 was synthesized, and 22.5 parts of the compound of Synthesis Example 1 and bis (4-acryloyloxyethoxyphenyl) 20 parts feed, 25 parts o-phenylphenylacrylate, 10 parts benzyl methacrylate, 17.5 parts tetrahydrofurfuryl acrylate, 5 parts trimethylolpropanetriacrylate, 5 parts Irgacure 184, 60 parts It warmed and mixed at ° C and obtained the resin composition for comparison. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

It carried out similarly to Example 1 using the obtained resin composition, and obtained the prism lens sheet.

Evaluation results

Viscosity: 70 mPas, Refractive index: 1.560, Mold release property: ○, Mold reproducibility: ○, Adhesiveness: ○, Scratch resistance: ×

Comparative example 3

New Frontier BPE-4 (manufactured by Daiichi Kogyo Chemical Co., Ltd .: bisphenol A polyethoxy diacrylate (in General Formula (1), R ₁ = H, R ₂ = H, m = 2, as a component (A)) n = 2)) 40 parts, 5 parts New Frontier PHE as component (B), 40 parts KAYARAD OPP-1.5 as component (B), 10 parts KAYARAD THE-330 as component (C), component ( 5 parts of KAYARAD UX-0937 as D) and 5 parts and 5 parts of Irgacure 184 as a component (E) were heated and mixed, and the resin composition for a comparison was obtained. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

Evaluation results

Viscosity: 300 mPas, Refractive index: 1.566, Release property: ○, Mold reproducibility: ○, Adhesiveness: ○, Scratch resistance: ×

Comparative example 4

As a component (A), Pancryl (FANCRYL) FA-328 (Hitachi Chemical Co., Ltd. make: bisphenol A polyethoxy diacrylate (in general formula (1), R ₁ = H, R ₂ = H, m) = 4, n = 4)), 30 parts of New Frontier PHE as component (B), 40 parts of KAYARAD OPP-1.5 as component (B), 20 parts of KAYARAD THE-330 as component (C) 5 parts of KAYARAD UX-0937 as a component (D) and 5 parts and 5 parts of Irgacure 184 as a component (E) were heated and mixed, and the resin composition for a comparison was obtained. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

Evaluation results

Viscosity: 200 mPas, Refractive index: 1.555, Release property: ○, Mold reproducibility: ○, Adhesiveness: ○, Scratch resistance: ×

Comparative example 5

60 parts of New Frontier BPE-10 as component (A) and 5 parts of New Frontier PHE-2 (made by Daiichi Kogyo Chemical Co., Ltd .: phenoxydiethoxyacrylate) as component (B) as component (C) 20 parts of KAYARAD PET-30 (Nippon Kayaku Co., Ltd .: pentaerythritol triacrylate), 15 parts of KAYARAD UX-0937 as a component (D), 5 parts Darocur 1173 as a component (E), 60 degreeC It heated and mixed with and obtained the resin composition for comparison. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

Evaluation results

Viscosity: 900 mPas, refractive index: 1.535, release property: ○, mold reproducibility: ○, adhesiveness: ○, scratch resistance: ×

Comparative example 6

60 parts of New Frontier BPE-10 as component (A) and 10 parts of New Frontier PHE-2 (made by Daiichi Kogyo Seika Co., Ltd .: phenoxy diethoxyacrylate) as component (B) as component (C) 15 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd .: dipentaerythritol hexaacrylate), 15 parts of KAYARAD UX-0937 as component (D), 5 parts Darocur 1173 as component (E), 60 ° C It heated and mixed and obtained the resin composition for comparison. Moreover, the refractive index of the resin layer obtained by carrying out similarly to Example 1 was measured.

Evaluation results

Viscosity: 900 mPas, refractive index: 1.539, release property: ○, mold reproducibility: ○, adhesion: ○, scratch resistance: ×

As is clear from the evaluation results of Examples 1 to 4 and Comparative Examples 1 to 6, the resin composition of the present invention having a specific composition has good release property, mold reproducibility, and adhesion with a substrate film, and has excellent durability (scratch resistance and scratch resistance). Excellent) Therefore, it is suitable for the optical lens sheet shape | molded on base materials, such as a lenticular lens, a prism lens, a microlens, for example, and can suppress the fault of the shape which arises by contact with another optical sheet.

The ultraviolet curable resin composition of this invention and its hardened | cured material are especially suitable for the optical lens sheet shape | molded mainly on base materials, such as a lenticular lens, a prism lens, a microlens.

Claims

30-50 mass parts of polyethylene oxide modified bisphenol-A di (meth) acrylate (A) represented by following General formula (1), and 3-50 mass parts of mono (meth) acrylate (B) which has a phenyl ether structure , Urethane (meth) acrylate having 3 or more (meth) acryloyl groups and having 3 to 20 parts by mass of a polyfunctional (meth) acrylate (C) modified with caprolactone or ethylene oxide and having a tetramethylene glycol structure Energy-beam curable resin composition for optical lens sheets formed on a base material containing 3-20 mass parts of oligomers (D) and 1-10 mass parts of photoinitiators (E), respectively:

(In formula, R <_1> , R <_2> respectively independently represents a hydrogen atom or a methyl group, m, and n respectively independently represent the integer of 5-10.).

The method of claim 1,
(Meth) acrylate (B) which has a phenyl ether structure is phenoxyethyl (meth) acrylate, phenoxypolyethoxy (meth) acrylate, o-phenylphenol (meth) acrylate, o-phenylphenol mono Methoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy Energy-beam curable resin composition which is 1 or more types chosen from the group which consists of (meth) acrylate.

The method of claim 1,
The urethane (meth) acrylate oligomer (D) having a tetramethylene glycol structure is an urethane (meth) acrylate oligomer obtained by reacting a diol compound having a molecular weight of 500 to 1000 with a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate. Precurable resin composition.

The method according to claim 1, wherein
Energy-beam curable resin composition in which a polyisocyanate compound has a ring structure.

The method according to any one of claims 1 to 3,
Energy-beam curable resin composition whose viscosity in 25 degreeC measured with the E-type viscosity meter is 2000 mPa * s or less.

Hardened | cured material obtained by hardening | curing the energy-beam curable resin composition of any one of Claims 1-3 by irradiation of an energy beam.

The optical lens sheet which has a hardened | cured material of Claim 6.