JP2013028662A - Energy ray-curable resin composition for optical lens sheet and cured product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable for an optical lens which excels in mold releasability, mold reproducibility and adhesion to a substrate film, and is molded on a substrate having high durability (abrasion resistance and scratch resistance).SOLUTION: This energy ray-curable resin composition for a lens sheet includes: biphenyl-typed epoxy (meth)acrylate (A) and/or (meth)acrylate (B) having naphthalene; (meth)acrylate (C) having a phenylphenol structure; a plasticizer (D); and a photopolymerization initiator (E).

Description

  Ultraviolet curable resin compositions include prism lens sheets used in backlights for liquid crystal display devices, optical lens sheets molded on substrates such as Fresnel lenses and lenticular lenses used in projection televisions, and transmissive types. Used for screens.

  These optical lens sheets tend to reduce the number of optical sheets due to the recent increase in cost reduction demand, and durability when contacting with other optical sheets that have not been in direct contact in the conventional liquid crystal display device (Referred to as scratch resistance, scratch resistance, etc.) is demanded at a high level. In addition, there is a strong demand for energy saving, and reduction of the backlight and high performance of the optical sheet are being studied. The optical lens sheet has a feature that the higher the refractive index, the higher the front luminance. If the front brightness is increased, the backlight emission intensity can be reduced, or the number of backlights can be reduced. Also, a device equipped with a liquid crystal display device is often used outdoors, and the liquid crystal display device has high brightness. Therefore, there is a demand for a resin composition having higher refraction (Patent Document 1).

  However, when the refractive index of the resin composition is increased, it is generally necessary to increase the compounding ratio of the resin having a rigid structure, and as a result, the cured resin film becomes hard and brittle. In a touch panel type liquid crystal display device, since pressure is applied to the display, components in the liquid crystal display device may come into contact with each other. Therefore, when the durability of the optical lens sheet is low even at a high refractive index, there is a problem that it is damaged due to contact with other parts.

  Patent Document 2 discusses a technique using a plasticizer as a resin composition for a Fresnel lens, but its refractive index is low. In the bisphenol A skeleton urethane acrylate in the document, it is difficult to increase the refractive index, and the durability is also lowered.

  Moreover, as what gave durability to the resin layer itself, in patent document 3, although durability was expressed by using a material with a small acrylic equivalent, the resin composition containing a material with a small acrylic equivalent is The curl property tends to be strong, and there is a high possibility of contact with other components in the liquid crystal display device due to curling and deformation, which is not preferable as a material for the optical sheet. Further, when the acrylic equivalent is small, the cured film becomes hard and brittle, and particularly, there is a problem that it is easily scratched by contact with an optical sheet containing an organic or inorganic filler.

  In Patent Document 4, although a resin composition for an optical lens sheet containing (meth) acrylate having a binaphthol skeleton is studied as having a high refractive index, the scratch resistance is not sufficient.

  As described above, a resin composition having high durability while having high light transmittance, refractive index, mold releasability, and substrate adhesion, which are generally required for optical lens sheets, is obtained. It was not done.

JP 2010-106046 A Japanese Patent Laid-Open No. 9-40730 JP 2010-126670 A JP 2010-189534 A

  The 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, or a microlens, and has excellent light transmittance, refractive index, mold releasability, and durability. A cured product having high (abrasion resistance, scratch resistance) is provided.

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

That is, the present invention includes (1) a biphenyl type epoxy (meth) acrylate (A) and / or a (meth) acrylate (B) having a naphthalene ring represented by the following general formula (1), and a phenylphenol structure (meta ) Energy ray curable resin composition for optical lens sheet containing acrylate (C), plasticizer (D), and photopolymerization initiator (E),

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

(2) 10 to 60 parts by mass of biphenyl type epoxy (meth) acrylate (A) and / or (meth) acrylate (B) having a naphthalene ring, and 40 to 90 (meth) acrylate (C) having a phenylphenol structure. Energy beam curable resin composition for optical lens sheet according to (1), comprising 1 part by mass of 1 part by mass of plasticizer (D) and 1-10 parts by mass of photopolymerization initiator (E),
(3) The biphenyl type epoxy (meth) acrylate (A) is a compound obtained by reacting a compound represented by the following general formula (2) with an ethylenically unsaturated group-containing monocarboxylic acid. Energy ray curable resin composition for optical lens sheet,

(In the formula, R ₁ represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. X represents an integer of 0 to 4, y represents an average value of 1 to 6 positive numbers. Represent each.)

(4) (Meth) acrylate (C) having a phenylphenol structure is o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenyl It is one or more selected from the group consisting of phenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, and p-phenylphenol polyethoxy (meth) acrylate (1) to (3) Energy beam curable resin composition according to any one of
(5) The energy beam curable resin composition according to any one of (1) to (4), wherein the plasticizer (D) has a polyether chain and / or an aromatic ring,
(6) The energy ray-curable resin composition according to any one of (1) to (4), wherein a viscosity at 25 ° C. measured with an E-type viscometer is 5000 mPa · s or less.
(7) A cured product obtained by curing the energy beam curable resin composition according to any one of (1) to (6),
(8) Hardened | cured material as described in (7) whose refractive index of hardened | cured material is 1.59 or more,
(9) An optical lens sheet having the cured product according to (7) or (8),
About.

  The resin composition of the present invention has good stability, good releasability from a mold, mold reproducibility, and adhesion to a substrate film. Moreover, it is excellent in durability (abrasion resistance, scratch resistance). Therefore, it is particularly suitable for an optical lens sheet molded on a substrate such as a lenticular lens, a prism lens, or a microlens.

  The biphenyl type epoxy (meth) acrylate (A) contained in the resin composition of the present invention is obtained by acrylating a known epoxy resin with an unsaturated carboxylic acid such as acrylic acid or methacrylic acid by a known method. Can be obtained. In the present invention, as a known epoxy resin, NC-3000, NC-3000L, NC-3000H, NC-3000S, NC-3000-FH-75M manufactured by Nippon Kayaku Co., Ltd. is used with unsaturated carboxylic acid. A compound obtained by acrylation can be used, and a compound obtained by reacting a compound represented by the following general formula (2) with an ethylenically unsaturated group-containing monocarboxylic acid is preferable.

(In the formula, R ₁ represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. X represents an integer of 0 to 4, y represents an average value of 1 to 6 positive numbers. Represent each.)

  Moreover, the compound which modified the obtained biphenyl type epoxy (meth) acrylate by carboxylic acid by a well-known method is also used.

  The (meth) acrylate (B) having a naphthalene ring contained in the resin composition of the present invention is obtained by reacting 1,1′-binaphthol and alkylene oxide or alkylene carbonate, followed by (meth) acrylic acid and It can be obtained by dehydration condensation reaction in the presence of an acid catalyst. The (meth) acrylate (B) having a naphthalene ring may be used alone or in combination of two or more. In the present invention, 1,1'-bi-2-naphthol is preferably used as 1,1'-binaphthol, and is available from S & R CHIRAL CHEMICAL. In the reaction of 1,1'-binaphthol and alkylene oxide, 0.5 to 24 mol of alkylene oxide is reacted with 1 mol of 1,1'-binaphthol. In the reaction of 1,1'-binaphthol and alkylene carbonate, 2 to 5 mol of alkylene carbonate is reacted with 1 mol of 1,1'-binaphthol. Alkylene oxide or alkylene carbonate may be used alone or in combination of two or more.

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

  The reaction of 1,1′-binaphthol and alkylene oxide or alkylene carbonate is carried out under an alkali catalyst such as sodium hydroxide or potassium hydroxide at a reaction time of 1 to 48 hours and a reaction temperature of 90 ° C. to 200 ° C. It is. In the reaction of 1,1'-binaphthol and alkylene oxide, 0.01 to 5% by mass of an alkali catalyst is used with respect to 100% by mass of the reaction mixture. In the reaction of 1,1'-binaphthol and alkylene carbonate, 0.01 to 0.5 mol of alkali catalyst is used with respect to 1 mol of 1,1'-binaphthol.

  In the dehydration condensation reaction of a reaction product of 1,1′-binaphthol with alkylene oxide or alkylene carbonate and (meth) acrylic acid, (meth) acrylic acid is 0 with respect to 1 mole of 1,1′-binaphthol. .1 to 10 moles are used. As a reaction solvent in the dehydration condensation reaction, an azeotropic solvent capable of distilling off water generated in the reaction can be used. The azeotropic solvent here has a boiling point of 60 to 130 ° C. and can be easily separated from water, and in particular, non-reactive organic solvents such as benzene, toluene, n-hexane, n-heptane, and cyclohexane. It is desirable to use one kind or a mixture of two or more kinds. The amount used is arbitrary, but is preferably 10 to 70% by mass with respect to the reaction mixture.

  The reaction time in the dehydration condensation reaction may be in the range of 1 to 24 hours, and the reaction temperature may be in the range of 60 to 150 ° C.

  Usually, a commercially available (meth) acrylic acid used as a raw material is already added with a polymerization inhibitor such as p-methoxyphenol, but a polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, Examples include phenothiazine. The amount of its use is 0.01-1 mass% with respect to the reaction mixture.

  The acid catalyst used in the dehydration condensation reaction can be arbitrarily selected from known ones such as sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and the amount used is 1 mole of (meth) acrylic acid. It is 0.01-10 mol% with respect to it, Preferably it is 1-5 mol%.

  The (meth) acrylate (B) having a naphthalene ring used in the resin composition of the present invention is based on 1 mol of 1,1′-binaphthol in consideration of the refractive index and compatibility with other components. A compound obtained by reacting 0.5 to 4 mol of alkylene oxide or a compound obtained by reacting 2 to 4 mol of alkylene carbonate to 1 mol of 1,1′-binaphthol is preferable. The alkylene oxide may be any alkylene oxide having 1 to 4 methylene groups, but ethylene oxide or propylene oxide is preferred. The alkylene carbonate may be any alkylene carbonate having a methylene group of 1 to 4, but ethylene carbonate (ethylene carbonate) or propylene carbonate (propylene carbonate) is preferred.

  The (meth) acrylate (C) having a phenylphenol structure used in the resin composition of the present invention may be used alone or in combination of two or more. Specifically, the following can be mentioned. o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate , P-phenylphenol polyethoxy (meth) acrylate, o-phenylphenol epoxy (meth) acrylate, p-phenylphenol epoxy (meth) acrylate, and the like. In particular, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, and p-phenylphenol polyethoxy (meth) acrylate are preferable.

  The phenylphenol polyethoxy (meth) acrylate is preferably a compound having an average number of repeating ethoxy structure moieties of 1 to 4, and a reaction product of o-phenylphenol, p-phenylphenol and ethylene oxide as raw materials. It can be obtained by reacting (meth) acrylic acid. o-phenylphenol and p-phenylphenol are commercially available products, for example, O-PP and P-PP, both available from Sanko Co., Ltd.). A reaction product of phenylphenol and ethylene oxide can be obtained by a known method, and a commercially available product can also be used. The reaction product of phenylphenol and ethylene oxide is preferably dissolved in the presence of an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid, or a polymerization inhibitor such as hydroquinone or phenothiazine, such as toluene, cyclohexane, n- In the presence of hexane, n-heptane, etc.), phenylphenol polyethoxy (meth) acrylate is obtained by reacting with (meth) acrylic acid, preferably at 70 to 150 ° C. The use ratio of (meth) acrylic acid is 1 to 5 mol, preferably 1.05 to 2 mol, with respect to 1 mol of the reaction product of phenylphenol and ethylene oxide. An esterification catalyst is 0.1-15 mol% with respect to the (meth) acrylic acid to be used, Preferably it is 1-6 mol%.

  The plasticizer (D) is a compound that does not participate in the curing reaction of the resin composition of the present invention, and improves the scratch resistance, mold releasability, substrate adhesion, etc. of the cured product, and is suitable for processing. Any compound may be used as long as it can improve (lower viscosity), reduce low-temperature brittleness, and reduce shrinkage of curing (reduction of substrate curl), but the following compounds can be generally exemplified. For example, phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate , Trimellitic acid esters such as tris (2-ethylhexyl) trimellitate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (2- (2-butoxyethoxy) ethyl) adipate, bis (2-ethylhexyl) azelate, dibutyl sebacate, bis (2-ethylhexyl) sebacate, diethyl succinate Aliphatic dibasic acid ester, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc. Normal phosphoric acid ester, ricinoleic acid ester such as methylacetylricinoleate, polyester such as poly (1,3-butanediol adipate), acetic acid ester such as glyceryl triacetate, sulfonamide such as N-butylbenzenesulfonamide, polyethylene glycol Polyalkylene oxide dibenzoates such as dibenzoate and polypropylene glycol dibenzoate, polypropylene glycol, Polyether modified bisphenols such as those having polyether chains such as reethylene glycol and polytetramethylene glycol, polyalkoxy modified bisphenol A such as polyethoxy modified bisphenol A, polypropoxy modified bisphenol A, polyethoxy modified bisphenol F, polypropoxy modified bisphenol F, etc. Examples thereof include those having an aromatic ring such as F, nitrobiphenyl and phenylphenol, and those having a polycyclic aromatic ring such as naphthalene, phenanthrene and anthracene. Polyethylene glycol dibenzoate and polypropylene glycol dibenzoate are preferable. In addition, in the resin composition of this invention, a plasticizer (D) may be used independently and may be used in mixture of multiple types.

  Examples of the photopolymerization initiator (E) contained in the resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy- 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and the like Acetophenones; Anthraquinones such as luanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; acetophenone dimethyl ketal, benzyl Ketals such as dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, phosphine oxides such as diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, etc. It can be mentioned. Preferred are acetophenones, and more preferred are 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone. 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.

  In addition, the resin composition of the present invention includes (meta) other than the component (A), the component (B), and the component (C) in consideration of the viscosity, refractive index, adhesion, and the like of the resin composition of the present invention to be obtained. ) Acrylate may be used alone or in combination of two or more. As the (meth) acrylate, monofunctional (meth) acrylate, bifunctional (meth) acrylate, polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule, polyester (meth) acrylate, epoxy (Meth) acrylate or the like can be used.

  Examples of monofunctional (meth) acrylates include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate. Such as alicyclic (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate and other (meth) acrylate benzyl (meth) acrylate, ethoxy (Meth) acrylates having aromatic rings such as modified cresol (meth) acrylate, propoxy-modified cresol (meth) acrylate, neopentylglycol benzoate (meth) acrylate, cal (Meth) acrylate having a heterocyclic ring such as sol (poly) ethoxyacrylate, imide (meth) acrylate having an imide ring structure, butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate having a hydroxyl group such as dipropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, butoxyethyl ( (Meth) acrylate, caprolactone (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, stearyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) (Meth) acrylates having an alkyl group such as acrylate, ethoxydiethylene glycol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, polyethylene glycol (meth) acrylate, polyhydric alcohol (meta) such as polypropylene glycol (meth) acrylate ) Acrylate and the like.

  Examples of the bifunctional (meth) acrylate include hydropivalaldehyde-modified trimethylolpropane di (meth) acrylate, ethoxy-modified bisphenol A di (meth) acrylate, propoxy-modified bisphenol A di (meth) acrylate, and 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 di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate , Bisphenol F polyethoxydi (meth) acrylate, hexahydrophthalic acid di (meth) acrylate, binaphthol polyethoxydi (meth) acrylate Acrylate, (meth) acrylates having aromatic rings such as bisphenoxy (poly) polyethoxyfluorene, acrylated isocyanates such as diacrylated isocyanurate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol (Meth) acrylate having a linear methylene structure such as di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, Alicyclic (meth) acrylates such as dicyclopentanyl diacrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene di (meth) And di (meth) acrylate of a polyhydric alcohol such as acrylate.

  Examples of the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule include polyfunctional (meth) acrylates having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane Polyfunctional (meth) acrylates of polyhydric alcohols such as tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate and (poly) ethylene of these polyhydric alcohols Oxide, may be mentioned (poly) propylene oxide or (poly) caprolactone-modified (meth) acrylate.

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

  Epoxy (meth) acrylates other than biphenyl type, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, terminal glycidyl ether of bisphenol A propylene oxide adduct, fluorene epoxy resin, bisphenol S type The reaction material of epoxy resins, such as an epoxy resin, and (meth) acrylic acid etc. can be mentioned.

  The proportion of each component of the resin composition of the present invention is determined in consideration of a desired refractive index, glass transition temperature (Tg), viscosity, adhesion, etc., but component (A) + component (B) + component When (C) is 100 parts by mass, the content of component (A) and / or component (B) is 10 to 60 parts by mass, preferably 15 to 40 parts by mass. Content of a component (C) is 40-90 mass parts, Preferably it is 50-70 mass parts. Component (D) is 1 to 10 parts by mass, preferably 3 to 7 parts by mass, relative to 100 parts by mass of the total amount of component (A) + component (B) + component (C). Component (E) is 1 to 10 parts by mass, preferably 3 to 7 parts by mass with respect to 100 parts by mass as a total of component (A) + component (B) + component (C). Other (meth) acrylate is 0-15 mass parts with respect to 100 mass parts of total amounts of a component (A) + component (B) + component (C).

  In addition to the above components, the resin composition of the present invention includes a release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, an antistatic agent, in order to improve convenience during handling. An agent or the like can be used in combination depending on the situation. Furthermore, polymers such as acrylic polymer, polyester elastomer, urethane polymer and nitrile rubber can be added as necessary. Although a solvent can also be added, what does not add a solvent is preferable.

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

  The viscosity of the resin composition of the present invention is an E-type viscometer (TV-200: Toki) as a viscosity suitable for workability of shape transferability and workability when manufacturing an optical lens molded on a substrate. A composition having a viscosity measured at 25 ° C. of not more than 5000 mPa · s using an industrial company) is preferred.

  The resin composition of the present invention can be easily cured by energy rays. Specific examples of energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in the present invention.

  According to a conventional method, the cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the energy beam. The refractive index of the cured product of the present invention is usually 1.59 or more, preferably 1.59 to 1.62. The refractive index can be measured with an Abbe refractometer (model number: DR-M2, manufactured by Atago Co., Ltd.) or the like.

  The optical lens having the cured product of the present invention is, for example, coated on a stamper having a shape such as a lenticular lens or a prism lens, and provided with a layer of the resin composition of the present invention, and a transparent substrate on the layer. A back sheet (for example, a film made of polymethacrylic resin, polycarbonate resin, polystyrene resin, polyester resin, or a blend of these polymers) or a glass substrate that has been subjected to treatment such as easy adhesion treatment is adhered, and then the transparent substrate After curing the resin composition by irradiating energy rays from a material side with a high-pressure mercury lamp or the like, the cured product can be peeled off from the stamper.

  Next, the present invention will be described in more detail with reference to examples. The present invention is not limited in any way by the following examples. The unit “part” of the numerical value indicates part by mass.

Synthesis Example 1 Synthesis of Binaphthol Polyethoxydiacrylate In a flask equipped with a stirrer, a reflux tube, and a thermometer, 286.3 g (1.0 mol) of 1,1′-bi-2-naphthol and 264 of ethylene carbonate were added. 0.2 g (3.0 mol), 41.5 g (0.3 mol) of potassium carbonate, and 2000 ml of toluene were charged and reacted at 110 ° C. for 12 hours.
After the reaction, the resulting reaction solution was washed with water and 1% NaOH aqueous solution, and then washed with water until the washing water became neutral. The solvent after the water-washed solution was distilled off under reduced pressure using a rotary evaporator to obtain 300.0 g of a 1,1′-bi-2-naphthol ethylene oxide 2 mol reaction product.
Subsequently, in a flask equipped with a stirrer, a reflux tube, a thermometer, and a water separator, 187.2 g (0.5 mol) of ethylene oxide 2 mol reaction product of 1,1′-bi-2-naphthol, acrylic acid 86.5 g (2.4 mol), 0.95 g of paratoluenesulfonic acid, 0.87 g of hydroquinone, 917.4 g of toluene and 393.2 g of cyclohexane were charged, and the produced water was distilled off azeotropically with the solvent at a reaction temperature of 95 to 105 ° C. It was made to react. After the reaction, the solution was neutralized with a 25% NaOH aqueous solution and then washed with 200 g of 15% by mass saline solution three times. The solvent was distilled off under reduced pressure to obtain binaphthol polyethoxydiacrylate.

Synthesis Example 2: Synthesis of epoxy carboxylate compound 144 g NC-3000H (epoxy equivalent 288 g / eq) manufactured by Nippon Kayaku Co., Ltd., which is a biphenyl novolac type epoxy resin as an epoxy resin, acrylic as an ethylenically unsaturated group-containing monocarboxylic acid 36 g of acid (molecular weight 72), 1.5 g of triphenylphosphine as a reaction catalyst and 100 g of propylene glycol monomethyl ether monoacetate as a solvent were added and reacted at 100 ° C. for 24 hours to obtain an epoxy carboxylate compound.
4 g (set acid value 7) of tetrahydrophthalic anhydride as a polybasic acid anhydride is added to the obtained epoxycarboxylate compound, and propylene glycol monomethyl as a solvent is added so that the total amount with the epoxycarboxylate compound is 70% by mass. Ether monoacetate was added, and the mixture was heated at 100 ° C. for 10 hours for addition reaction to obtain a (poly) carboxylic acid compound (actual solid acid value 11).

  The ultraviolet curable resin composition and cured product of the present invention were obtained with the compositions as shown in the following examples. The evaluation method and evaluation criteria for the resin composition and the cured film were as follows.

(1) Viscosity: Viscosity was measured at 25 ° C. using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).

(2) Refractive index (25 ° C.): The refractive index (25 ° C.) of the cured ultraviolet curable resin layer was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

(2) Releasability: Expresses the degree of difficulty when releasing a cured resin from a mold.
○ ···········································································································································

(3) Mold reproducibility: An ultraviolet curable resin layer was applied and molded on a substrate, and cured by irradiation with 1000 mJ / cm ² with a high-pressure mercury lamp (80 W / cm, ozone-less). The surface shape of the cured ultraviolet curable resin layer and the surface shape of the mold were observed.
○ ···· Reproducibility is good × ··· Reproducibility is poor

(4) Adhesiveness: Adhesive evaluation was performed according to JIS K5600-5-6 with the sample used in the mold reproducibility evaluation.
In the evaluation results, 0 to 2 were evaluated as ○, and 3 to 5 as ×.

(5) Scratch resistance: A test piece is prepared by forming a prism shape on a PET substrate using a mold. The mat surface of the diffusion sheet was aligned on the test piece, and a weight of 100 g was placed thereon, and the scratches generated when the diffusion sheet was pulled in the direction perpendicular to the prism pattern were observed. A commercial product (Haze value 25%) was used for the diffusion sheet.
○ ・ ・ ・ ・ No scratch ~ Slightly scratch ×× ・ ・ ・ Strong scratch

Example 1
20 parts of the compound of Synthesis Example 2 as component (A), 75 parts of KAYARAD OPP-1.5 (manufactured by Nippon Kayaku Co., Ltd .: o-phenylphenol polyethoxy acrylate) as component (C), component (D) Benzoflex 9-88 (manufactured by Genovique Specialties Wuhan Youji Chemical: dipropylene glycol dibenzoate) as component E, Irgacure 184 (manufactured by BASF Japan Ltd .: 5 parts of 1-hydroxy-cyclohexyl phenyl ketone) As a component, 5 parts of New Frontier PHE (Daiichi Kogyo Seiyaku Co., Ltd .: phenoxyethyl acrylate) was heated to 60 ° C. and mixed to obtain the resin composition of the present invention. This resin composition was irradiated with 1000 mJ / cm ² of ultraviolet rays with a high-pressure mercury lamp to obtain a cured film, and the refractive index was measured.
Further, this resin composition was applied on a prism lens mold so that the film thickness was about 50 μm, and an easy-adhesion PET film (Toyobo Cosmo Shine A4300, 100 μm thickness) was adhered thereon as a base material. The prism lens sheet of the present invention was obtained by irradiating with an ultraviolet ray of 1000 mJ / cm ^{2 with} a high-pressure mercury lamp from above, curing, and then peeling off.
Evaluation results Viscosity: 700 mPa · s, refractive index: 1.594, releasability: ○, mold reproducibility: ○, adhesion: ○, scratch resistance: ○

Example 2
30 parts of the compound of Synthesis Example 2 as component (A), 65 parts of KAYARAD OPP-1 (manufactured by Nippon Kayaku Co., Ltd .: o-phenylphenol monoethoxy acrylate) as component (C), and new as component (D) 8 parts of Paul BPE-100 (manufactured by Sanyo Chemical Industries, Ltd .: polyethoxy-modified bisphenol A), Darocur 1173 as component E (manufactured by BASF Japan Ltd .: 2-hydroxy-2-methyl-phenylpropan-1-one) And 5 parts of biscoat # 150 (manufactured by Osaka Organic Chemical Industry Co., Ltd .: tetrahydrofurfuryl acrylate) as the other components were heated to 60 ° C. and mixed to obtain the resin composition of the present invention. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
Using the obtained resin composition, a prism lens sheet of the present invention was obtained in the same manner as in Example 1.
Evaluation results Viscosity: 1600 mPa · s, refractive index: 1.603, releasability: ○, mold reproducibility: ○, adhesion: ○, scratch resistance: ○

Example 3
40 parts of the compound of Synthesis Example 2 as component (A), 50 parts of KAYARAD OPP-1.5 as component (C), Sunflex EB-400 (manufactured by Sanyo Chemical Industries, Ltd .: polyethylene glycol as component (D)) 3 parts of dibenzoate), 5 parts of Darocur 1173 as component E, and 10 parts of New Frontier PHE as other components were heated and mixed at 60 ° C. to obtain a resin composition of the present invention. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
Using the obtained resin composition, a prism lens sheet of the present invention was obtained in the same manner as in Example 1.
Evaluation results Viscosity: 4400 mPa · s, refractive index: 1.601, releasability: ○, mold reproducibility: ○, adhesion: ○, scratch resistance: ○

Example 4
20 parts of the compound of Synthesis Example 2 as component (A), 70 parts of KAYARAD OPP-1.5 as component (C), triphenylphosphine (manufactured by Kishida Chemical Co., Ltd .: triphenylphosphine) as component (D) 5 parts, Irgacure 184 as component E, 5 parts New Frontier PHE as other ingredients, 5 parts FA-321A (manufactured by Hitachi Chemical Co., Ltd .: polyethoxy-modified bisphenol A), added to 60 ° C The mixture was warmed to obtain the resin composition of the present invention. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
Using the obtained resin composition, a prism lens sheet of the present invention was obtained in the same manner as in Example 1.
Evaluation results Viscosity: 800 mPa · s, Refractive index: 1.594, Releasability: ○, Mold reproducibility: ○, Adhesion: ○, Scratch resistance: ○

Example 5
20 parts of the compound of Synthesis Example 2 as component (A), 70 parts of KAYARAD OPP-1.5 as component (C), and O-PP (manufactured by Sanko Co., Ltd .: o-phenylphenol) as component (D) 5 parts, 5 parts Irgacure 184 as component E, 5 parts New Frontier PHE as other ingredients, 5 parts KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd .: dipentaerythritol hexaacrylate), heated to 60 ° C., By mixing, a resin composition of the present invention was obtained. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
Using the obtained resin composition, a prism lens sheet of the present invention was obtained in the same manner as in Example 1.
Evaluation results Viscosity: 900 mPa · s, Refractive index: 1.597, Releasability: ○, Mold reproducibility: ○, Adhesion: ○, Scratch resistance: ○

Example 6
15 parts of the compound of Synthesis Example 2 as the component (A), 30 parts of the compound of Synthesis Example 1 as the component (B), 40 parts of KAYARAD OPP-1.5 as the component (C), and Sunflex as the component (D) 10 parts of EB-200 (manufactured by Sanyo Chemical Industries, Ltd .: polyethylene glycol dibenzoate), 5 parts of Irgacure 184 as the component (E), 5 parts of New Frontier PHE as the other components are heated to 60 ° C. and mixed. The resin composition of the present invention was obtained. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
Using the obtained resin composition, a prism lens sheet of the present invention was obtained in the same manner as in Example 1.
Evaluation results Viscosity: 2100 mPa · s, Refractive index: 1.605, Releasability: ○, Mold reproducibility: ○, Adhesion: ○, Scratch resistance: ○

Example 7
30 parts of the compound of Synthesis Example 1 as component (B), 60 parts of KAYARAD OPP-1.5 as component (C), Unisafe PKA-5016 (manufactured by NOF Corporation: polyoxypropoxypoly) as component (D) 8 parts of oxyethoxyallyl butyl ether), 5 parts of Irgacure 184 as component (E), and 10 parts of New Frontier PHE as other components were heated to 60 ° C. and mixed to obtain a resin composition of the present invention. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
Using the obtained resin composition, a prism lens sheet of the present invention was obtained in the same manner as in Example 1.
Evaluation results Viscosity: 300 mPa · s, Refractive index: 1.592, Releasability: ○, Mold reproducibility: ○, Adhesion: ○, Scratch resistance: ○

Comparative Example 1
According to the example of Patent Document 1 (Japanese Patent Laid-Open No. 2010-106046), the fluorene skeleton diacrylate of Synthesis Example 1 of the document was synthesized, and 5 parts of the obtained compound, 85 parts of KAYARAD OPP-1 and 3 parts of Darocur 1173 were synthesized. Part, ACMO (manufactured by Kojin Co., Ltd .: acryloylmorpholine) was heated to 60 ° C. and mixed to obtain a resin composition. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
A prism lens sheet was obtained in the same manner as in Example 1 using the obtained resin composition.
Evaluation results Viscosity: 120 mPa · s, Refractive index: 1.604, Releasability: ○, Mold reproducibility: ○, Adhesion: ○, Scratch resistance: ×

Comparative Example 2
According to the example of Patent Document 2 (Japanese Patent Laid-Open No. 9-40730), the urethane acrylate of Synthesis Example 1 of this document was synthesized, 90 parts of the resulting compound, Aronix M-5700 (manufactured by Toagosei Co., Ltd.): 2-hydroxy-3-phenoxypropyl acrylate) 50 parts, Aronix M-101 (manufactured by Toagosei Co., Ltd .: phenoxydiethylene glycol acrylate) 15 parts, tricresyl phosphate 5 parts, Darocur 1173 2 parts, 60 The mixture was heated to 0 ° C. and mixed to obtain a resin composition. Further, the refractive index of the resin layer obtained in the same manner as in Example 1 was measured.
A prism lens sheet was obtained in the same manner as in Example 1 using the obtained resin composition. Evaluation results Viscosity: 3200 mPa · s, refractive index: 1.555, releasability: ○, mold reproducibility: ○, adhesion: ○, scratch resistance: ○

Comparative Example 3
20 parts of the compound of Synthesis Example 2 as component (A), 75 parts of KAYARAD OPP-1.5 as component (B), 5 parts of Irgacure 184 as component D, 5 parts of New Frontier PHE as other components, 60 The mixture was heated to 0 ° C. and mixed to obtain a resin composition.
A prism lens sheet was obtained in the same manner as in Example 1 using the obtained resin composition.
Evaluation results Viscosity: 700 mPa · s, refractive index: 1.595, releasability: Δ, mold reproducibility: ○, adhesion: ○, scratch resistance: ×

Comparative Example 4
According to Example 1 of Patent Document 4 (Japanese Patent Laid-Open No. 2010-189534), 31 parts of KAYRAD OPP-1, 20 parts of the compound obtained in Synthesis Example 1 in the literature, 3 parts of Irgacure 184, Speedcure TPO (DKSH Japan Co., Ltd.) ): Diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide 0.1 part, KAYARAD R-551 (Nippon Kayaku Co., Ltd .: bisphenol A tetraethoxydiacrylate) 20 parts, KAYARAD R -115 (Nippon Kayaku Co., Ltd .: bisphenol A epoxy diacrylate) 4 parts, Aronix M-315 (Toagosei Co., Ltd .: Tris (2-acryloyloxyethyl) isocyanurate) 18 parts, ACMO ( 7 parts of Kojin Co., Ltd .: acryloylmorpholine), heated to 60 ° C, mixed To obtain a resin composition. Also, to measure the refractive index of the resin layer obtained in the same manner as in Example 1.
A prism lens sheet was obtained in the same manner as in Example 1 using the obtained resin composition.
Evaluation results Viscosity: 900 mPa · s, Refractive index: 1.587, Releasability: ○, Mold reproducibility: ○, Adhesion: ○, Scratch resistance: ×

  As is apparent from the evaluation results of Examples 1 to 7 and Comparative Examples 1 to 4, in the comparative example, the viscosity is very high so that the workability is bad, and the releasability is low, so that it is unsuitable for continuous molding processing. Some performance was insufficient, such as low scratch resistance and low refractive index, and none had the required performance. On the other hand, the resin composition of the present invention has good viscosity, releasability, mold reproducibility and adhesion to a substrate film, is excellent in durability (scratch resistance, scratch resistance), and has a high refractive index. Therefore, for example, it is suitable for an optical lens sheet molded on a substrate such as a lenticular lens, a prism lens, or a microlens, and the shape damage caused by contact with other optical sheets can be suppressed.

  The ultraviolet curable resin composition of the present invention and the cured product thereof are particularly suitable for optical lens sheets that are mainly molded on a substrate such as a lenticular lens, a prism lens, or a microlens.

Claims (9)

Biphenyl type epoxy (meth) acrylate (A) and / or (meth) acrylate (B) having naphthalene represented by the following general formula (1), (meth) acrylate (C) having a phenylphenol structure, plasticizer ( D) and an energy ray curable resin composition for an optical lens sheet containing a photopolymerization initiator (E).

(Wherein R ₁ is the same or different, hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₂ is the same or different hydrocarbon group having 1 to 4 carbon atoms, and m and n are the average number of repetitions) And m + n = 0.4 to 12, respectively.) 10-60 parts by mass of (meth) acrylate (B) having biphenyl type epoxy (meth) acrylate (A) and / or naphthalene, 40-90 parts by mass of (meth) acrylate (C) having phenylphenol structure, plasticity The energy ray-curable resin composition for an optical lens sheet according to claim 1, comprising 1 to 10 parts by mass of the agent (D) and 1 to 10 parts by mass of the photopolymerization initiator (E). The biphenyl type epoxy (meth) acrylate (A) is a compound obtained by reacting a compound represented by the following general formula (2) with an ethylenically unsaturated group-containing monocarboxylic acid. Energy ray curable resin composition for optical lens sheet.

(In the formula, R ₁ represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. X represents an integer of 0 to 4, y represents an average value of 1 to 6 positive numbers. Represent each.) (Meth) acrylate (C) having a phenylphenol structure is o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meta 4) One or more selected from the group consisting of acrylate, p-phenylphenol monoethoxy (meth) acrylate, and p-phenylphenol polyethoxy (meth) acrylate. The energy beam curable resin composition according to one item. The energy beam curable resin composition according to any one of claims 1 to 4, wherein the plasticizer (D) has a polyether chain and / or an aromatic ring. The energy ray curable resin composition according to any one of claims 1 to 5, wherein the viscosity at 25 ° C measured with an E-type viscometer is 5000 mPa · s or less. Hardened | cured material obtained by hardening the energy-beam curable resin composition as described in any one of Claims 1 thru | or 6. The cured product according to claim 7, having a refractive index of 1.59 or more. An optical lens sheet having the cured product according to claim 7 or 8.