JPWO2010137501A1 - Energy ray curable resin composition for optical lens sheet and cured product thereof - Google Patents

Abstract

A resin composition having excellent releasability, mold reproducibility, adhesion to a substrate and light resistance, a high refractive index, a high glass transition point, and a low viscosity is provided. An energy ray-curable resin composition for an optical lens sheet comprising a compound (A) having a carbazolyl group and a photopolymerization initiator (B).

Description

  The present invention relates to an energy beam curable resin composition for an optical lens sheet and a cured product thereof. More specifically, the present invention relates to a resin composition and a cured product particularly suitable for lenses such as a Fresnel lens, a lenticular lens, a prism lens, and a microlens.

  Conventionally, the above-described lens has been molded by a method such as a press method or a cast method (casting method). The former pressing method was poor in productivity because it was manufactured by heating, pressurizing and cooling cycles. Further, the latter casting method has a problem that it takes a long manufacturing time because a monomer is poured into a mold for polymerization, and a manufacturing cost increases because a large number of molds are required. In order to solve such a problem, various proposals have been made for using an ultraviolet curable resin composition (Patent Documents 1 and 2).

  By using these ultraviolet curable resin compositions, a method for producing an optical lens sheet used for a transmission screen or the like has been successful to some extent. However, these conventional cured resin compositions have the drawback of poor adhesion to the substrate and releasability from the mold. If the adhesion is poor, the types of substrates that can be used are limited, making it difficult to obtain the intended optical properties. If the releasability is poor, the resin remains in the mold at the time of mold release and the mold cannot be used. In addition, a resin composition that gives a cured product with good adhesion is likely to have poor mold releasability because of good adhesion to the mold. On the other hand, a resin composition with good mold releasability tends to have poor adhesion. is there. Therefore, it is desired to provide a resin composition that can satisfy both the performance of adhesion to the substrate and the releasability from the mold.

  The composition for lenses used in these optical lens sheets and the like has been demanded to have a high refractive index in accordance with recent high-definition images and thinning of final products. In order to be processed, processed thinner, or continuously processed into a roll-like sheet or film, a low-viscosity one tends to be required. Furthermore, it is also necessary that the fine structure is not easily crushed when the lens sheet is wound up. Further, even when actually used as a product, it is fatal that the lens shape changes due to heat from a light source or the like, and in this case, a high glass transition temperature (Tg) is required.

  Among them, Patent Document 3 proposes a resin composition having both adhesiveness and releasability, but it cannot be said that the viscosity for processing into a finer shape is sufficient. Reference 4 discloses that β-N-carbazolylethyl acrylate is used as a monomer for obtaining a photoconductive resin. However, the performance of β-N-carbazolylethyl acrylate before polymerization is disclosed. And its optical features are not specified. Further, Patent Document 5 proposes a transparent resin composition containing a compound having a carbazolyl group, but the compound is an antioxidant and is not a monomer for an energy ray curable resin, but a cured product. It prevents coloring.

  Patent Document 6 discusses a curable composition containing a compound having a carbazolyl group, but the compound is a polymer having a carbazolyl group as a structural unit, not a monomer.

  In any case, it is difficult to obtain a low-viscosity lens composition used for optical lens sheets having a high refractive index and a fine structure, and having a high Tg point, releasability, and adhesion. What could be done was not obtained.

JP 63-167301 A JP-A 63-199302 Japanese Patent No. 3209554 JP-A-53-116369 JP 2000-143945 A JP 2009-91465 A

  The object of the present invention is a low-viscosity resin composition suitable for the production of lens sheets such as Fresnel lenses, lenticular lenses, prism lenses, and micro lenses, and is excellent in releasability, mold reproducibility, adhesion, and light resistance. It provides a cured product having a high refractive index.

  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 provides (1) an energy ray curable resin composition for an optical lens sheet comprising a compound (A) having a carbazolyl group and a photopolymerization initiator (B),
(2) Compound (C) in which compound (A) having a carbazolyl group is represented by formula (2)

(Wherein R ₁₀ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₁₁ is the same or different hydrocarbon group having 1 to 4 carbon atoms, n is an average number of repetitions, and n = 0 to 4 and optionally having a substituent on the carbazolyl group), the resin composition according to (1),
(3) The resin composition according to (1) or (2), further including a monoacrylate monomer (D) having a phenyl ether group,
(4) Monoacrylate monomer (D) having a phenyl ether group is o-phenylphenol (poly) ethoxy (meth) acrylate, p-phenylphenol (poly) ethoxy (meth) acrylate, o-phenylphenol epoxy (meth) acrylate The resin composition according to any one of (1) to (3), which is at least one selected from the group consisting of p-phenylphenol epoxy (meth) acrylates,
(5) The resin composition according to any one of (1) to (4), further including (meth) acrylate compound (E) other than compound (A) and monoacrylate monomer (D) having a phenyl ether group. object,
(6) A cured product obtained by curing the resin composition according to any one of (1) to (5),
(7) An optical lens sheet using the cured product according to (6),
About.

  The resin composition of the present invention has a low viscosity, and its cured product is excellent in releasability, mold reproducibility, and adhesion to a substrate, and has a high refractive index and good light resistance. Therefore, it is particularly suitable for optical lens sheets such as Fresnel lenses, lenticular lenses, prism lenses, and micro lenses.

  The resin composition of the present invention contains a compound (A) having a carbazolyl group and a photopolymerization initiator (B).

  The compound (A) having a carbazolyl group used in the resin composition of the present invention will be described. The compound (A) having a carbazolyl group is not limited as long as it has a carbazolyl group, and examples thereof include compounds represented by the following general formula (1).

(Wherein R _{1 to} R ₉ are the same or different and are a hydrogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, alkylthio group, amino group, alkylamino group, aryl group, aryloxy group, arylthio group, aryl amino group, a diarylamino group, an alkylaryl group, a heterocyclic group, a polymerizable group, at least one of R ₁ to R ₉ among .R ₂ to R ₉ is a polymerizable group, two adjacent Two substituents may be bonded to each other to form a ring structure, and R _{2 to} R ₉ may further have a substituent.)

  In said general formula (1), as an alkyl group, a C1-C30 thing is preferable, More preferably, it is C1-C15, More preferably, it is C1-C8. Specific examples include methyl, ethyl, t-butyl, cyclohexyl and the like. As an alkenyl group, a C2-C30 thing is preferable, More preferably, it is C2-C15, More preferably, it is C2-C8. Specific examples include vinyl, 1-propenyl, 1-buten-2-yl, cyclohexen-1-yl and the like. The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms. Specific examples include ethynyl and 1-propynyl.

  In said general formula (1), as an alkoxy group, a C2-C30 thing is preferable, More preferably, it is C2-C15, More preferably, it is C2-C8. Specific examples include a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, a 2-ethylhexyloxy group, and the like. As an alkylthio group, a C2-C30 thing is preferable, More preferably, it is C2-C15, More preferably, it is C2-C8. Specific examples include a methylthio group, an ethylthio group, a butylthio group, and an octylthio group. As an alkylamino group, a C2-C30 thing is preferable, More preferably, it is C2-C15, More preferably, it is C2-C8. Specific examples include a methylamino group, an ethylamino group, a butylamino group, a phenoxypropylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a piperidino group, and a morpholino group.

  In said general formula (1), as an aryl group, a C6-C30 thing is preferable, More preferably, it is C6-C15, More preferably, it is C6-C12. Specific examples include phenyl, biphenyl, tolyl, xylyl, naphthyl, pyrenyl and the like.

  In said general formula (1), as an aryloxy group, a C6-C30 thing is preferable, More preferably, it is C6-C15, More preferably, it is C6-C8. Specific examples include a phenoxy group and a tolyloxy group. As an arylthio group, a C6-C30 thing is preferable, More preferably, it is C6-C15, More preferably, it is C6-C8. Specific examples include a phenylthio group. As an arylamino group, a C6-C30 thing is preferable, More preferably, it is C6-C15, More preferably, it is C6-C8. Specifically, an anilino group, a toluidino group, etc. can be mentioned, for example. The diarylamino group preferably has 12 to 30 carbon atoms, more preferably 12 to 20 carbon atoms, and still more preferably 12 to 15 carbon atoms. Specific examples include a diphenylamino group.

In the general formula (1), the alkylarylamino group preferably has 7 to 30 carbon atoms, more preferably 7 to 15 carbon atoms, and still more preferably 7 to 8 carbon atoms. Specific examples include N-methylanilino group and N-ethylanilino group. As a heterocyclic group, a C2-C30 thing is preferable, More preferably, it is C2-C15, More preferably, it is C4-C8. Specific examples include a pyrrole group, a furan group, and a carbazolyl group. These heterocyclic groups may have the above substituents represented by R _{1 to} R ₉ .

In the general formula (1), among R _{2 to} R ₉ , two adjacent substituents are bonded to each other to form a ring structure such as a cyclic hydrocarbon, an aromatic ring, a hetero ring, or a hetero aromatic ring. Also good. Particularly preferred ring structures are aromatic hydrocarbon rings or heteroaromatic rings having a ring skeleton selected from thiophene, furan, pyrrole, selenophene and carbazole.

  In the general formula (1), examples of the polymerizable group include a high strain hydrocarbon group such as a cyclopropane group and a cyclobutane group, a cyclic ether group such as an epoxy group and an oxetane group, an acrylic group, a methacryl group, a vinyl group, A vinyl ether group, a vinyl ester group, etc. are mentioned. The polymerizable group is preferably an acryl group, a methacryl group, a vinyl group, an epoxy group, or an oxetane group, and particularly preferably an acryl group or a methacryl group. The polymerizable group may be directly substituted on the ring structure or may be substituted via a divalent linking group.

Examples of the divalent linking group include an ether group and an alkylene group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. For example, a methylene group (- CH ₂ -), ethylene group (-CH ₂ CH ₂ -), trimethylene group _{(-CH 2 CH 2 CH 2 -} . that), and the like), an arylene group (preferably having 6 to 30 carbon atoms, more preferably It has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. Examples thereof include a phenylene group (—C ₆ H ₄ —) and a naphthylene group (—C ₁₀ H ₆ —).), An oxyalkylene group ( preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, oxymethylene group (-OCH ₂ -), an oxyethylene group (-OCH ₂ CH ₂ -) ,Such . Cited), oxyarylene group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example oxy-phenylene group (-OC ₆ H ₄ -), An oxynaphthylene group (—OC ₁₀ H ₆ —) and the like), an oxycarbonyl group (—COO—), an iminocarbonyl group (—CONH—), a ureylene group (—NHCONH—) and the like. These divalent linking groups may be further substituted with the above substituents. Further, in the present invention, the divalent linking group has a structure in which the same kind of divalent linking group (for example, ethylene oxide group) is repeatedly bonded. Or you may have a structure which couple | bonded two or more.

The compound represented by the general formula (1) can be synthesized by a known method. First, Aza-Cope rearrangement reaction of arylhydrazine and cyclohexanone derivative, followed by synthesis by dehydroaromatization, synthesis by denitrogenation cyclization of biphenyl-2-azide, reduction of 2-nitrobiphenyl by triethyl phosphite A carbazole derivative can be obtained by synthesis or the like by an efficient cyclization reaction. The raw material carbazole derivative can be used as a commercially available aryl hydrazine having a substituent corresponding to R _1, and is available, for example, from Aldrich or NJR Aromatics GmdH. The obtained carbazole derivative is reacted with, for example, alkylene oxide or alkylene carbonate, and subjected to dehydration condensation reaction in the presence of (meth) acrylic acid and an acid catalyst, or reacted with epichlorohydrin, and then (meth) acrylic acid. The compound represented by the general formula (1) can be obtained by reacting, but is not limited thereto.

A compound in which the heterocyclic group is a carbazolyl group can be synthesized by a known method described in WO2005 / 014398 and J.Org.Chem.2009, 74, p.4490-4498, and can also be obtained from the market. .

  As the compound (A) having a carbazolyl group used in the resin composition of the present invention, at least one of the substituents is a polymerizable group, and at least one of the substituents is a polymerizable group and is substituted. In the present invention, at least one of the groups is a carbazolyl group which may have a substituent. Among the compounds represented by the general formula (1), which is the compound (A) having such a carbazolyl group, the following general formula (2)

(Wherein R ₁₀ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₁₁ is the same or different hydrocarbon group having 1 to 4 carbon atoms, n is an average number of repetitions, and n = 0 to 4 (which may have a substituent on the carbazolyl group), and the following general formula (3):

The compound (C2) represented by the formula (wherein R ₁₀ and R ₁₁ and n are the same as those in the general formula (2)) is more preferable.

The compound (C) represented by the general formula (2) can be obtained by reacting carbazole with alkylene oxide or alkylene carbonate, followed by dehydration condensation reaction in the presence of (meth) acrylic acid and an acid catalyst. . In the reaction between carbazole and alkylene oxide, 1 to 8 mol of alkylene oxide is reacted with 1 mol of carbazole. In the reaction of carbazole and alkylene carbonate, 1 to 3 mol of alkylene carbonate is reacted with 1 mol of carbazole. Alkylene oxide or alkylene carbonate may be used alone or in combination of two or more. When used alone, R ₁₁ is all the same, and when used in a mixture of two or more, R ₁₁ can be arbitrarily different.

The compound (C2) represented by the general formula (3) is reacted with 3,3′-bi [9H-carbazole] and an alkylene oxide or an alkylene carbonate, and subsequently, in the presence of (meth) acrylic acid and an acid catalyst. It can be obtained by dehydrating condensation reaction. In the reaction between carbazole and alkylene oxide, 2 to 16 mol of alkylene oxide is reacted with 1 mol of 3,3′-bi [9H-carbazole]. In the reaction of 3,3′-bi [9H-carbazole] with alkylene carbonate, 2 to 6 mol of alkylene carbonate is reacted with 1 mol of 3,3′-bi [9H-carbazole]. Alkylene oxide or alkylene carbonate may be used alone or in combination of two or more. When used alone, R ₁₁ is all the same, and when used in a mixture of two or more, R ₁₁ can be arbitrarily different.

  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), propylene carbonate (propylene carbonate), and butylene carbonate (butylene carbonate).

  The reaction of carbazole or 3,3′-bi [9H-carbazole] with alkylene oxide or alkylene carbonate is carried out under an alkali catalyst such as sodium hydroxide or potassium hydroxide for a reaction time of 1 to 48 hours and a reaction temperature of 90 ° C. to 200 ° C. Performed between ° C. In the reaction of carbazole or 3,3′-bi [9H-carbazole] with 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 carbazole or 3,3′-bi [9H-carbazole] with alkylene carbonate, 0.01 to 1.0 mol of carbazole or 3,3′-bi [9H-carbazole] is used per 1 mol of carbazole or 3,3′-bi [9H-carbazole]. An alkali catalyst is used.

  In the dehydration condensation reaction of a reaction product of carbazole or 3,3′-bi [9H-carbazole] with alkylene oxide or alkylene carbonate and (meth) acrylic acid, (meth) acrylic acid is carbazole or 3,3′-bi [ 9H-carbazole] is used in an amount of 0.1 to 20 moles per mole. 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 1 to 24 hours, and the reaction temperature may be in the range of 60 to 150 ° C, but it is preferably performed at 75 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization.

  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 compound (C) that can be used in the resin composition of the present invention is a compound obtained by reacting 1 to 2 mol of alkylene oxide with 1 mol of carbazole in consideration of the refractive index and compatibility with other components. In addition, a compound obtained by reacting (meth) acrylic acid with a compound obtained by reacting 1 to 2 moles of alkylene carbonate with 1 mole of carbazole 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 compound (C2) that can be used in the resin composition of the present invention is 2 to 2 moles of 3,3′-bi [9H-carbazole] in consideration of the refractive index and compatibility with other components. (Meth) acrylic acid is reacted with a compound obtained by reacting 4 mol of alkylene oxide or a compound obtained by reacting 2 to 4 mol of alkylene carbonate with 1 mol of 3,3′-bi [9H-carbazole]. The compound obtained is preferred. 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.

  Specific examples (A-1) to (A-11) of the compound represented by the general formula (2), the specific example (A-12) of the compound represented by the general formula (1), and the general formula Although the specific example (A-13) of a compound represented by (3) is given, this invention is not limited to these.

  Examples of the photopolymerization initiator (B) 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 phenyl ketone, 2 -Acetophenones such as methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] Class: 2-Echi Anthraquinones such as anthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; acetophenone dimethyl ketal; Ketals such as benzyldimethyl 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 oxide such as diphenyl- (2,4,6-trimethylbenzoyl) -phosphine oxide Mention may be made of the earth and the like. Preferred are acetophenones, and more preferred are 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone. In the resin composition of the present invention, the photopolymerization initiator (B) may be used singly or as a mixture of a plurality of types, but 2,4,6-trimethylbenzoyldiphenylphosphine oxide It is preferable to use at least one phosphine oxide such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and diphenyl- (2,4,6-trimethylbenzoyl) -phosphine oxide.

  The monoacrylate monomer (D) having a phenyl ether group that can be used in the present invention will be described.

  Examples of the monoacrylate monomer (D) having a phenyl ether group include phenoxyethyl (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, and tribromophenyloxyethyl (meth). Examples include acrylate, phenylthioethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, and phenylphenol epoxy (meth) acrylate. Phenylphenol (poly) ethoxy (meth) acrylate and phenylphenol epoxy (meth) acrylate are preferred, among which o-phenylphenol (poly) ethoxy (meth) acrylate, p Phenylphenol (poly) ethoxy (meth) acrylate, o- phenylphenol epoxy (meth) acrylate, p- phenylphenol epoxy (meth) acrylate. In the present invention, the monoacrylate monomer (D) may be used alone or in combination of two or more.

  The phenylphenol (poly) ethoxy (meth) acrylate is preferably a compound having an average number of repeating ethoxy structure moieties of 1 to 3, and a reaction product of phenylphenol and ethylene oxide as a raw material (meth) It can be obtained by reacting acrylic acid. As for phenylphenol, o-phenylphenol which is an ortho form and p-phenylphenol which is a para form can be obtained by using commercially available products (for example, O-PP and P-PP, both Sanko Can be obtained). 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 phenylphenol epoxy (meth) acrylate is obtained by reacting the above phenylphenol with epihalohydrin in the presence of an alkali metal hydroxide, and reacting an epoxy resin as a reaction product with acrylic acid.

  As the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used, and among them, epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 2-20 mol normally with respect to 1 mol of phenylphenol, Preferably it is 3-15 mol.

  Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and a solid substance or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are distilled off continuously under reduced pressure or normal pressure, followed by liquid separation to remove the water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.1-10.0 mol normally with respect to 1 mol of said phenylphenol, Preferably it is 0.3-5.0 mol, More preferably, it is 0.8-3.0. Is a mole.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. When a quaternary ammonium salt is used, the amount used is usually 0.1 to 20 g, preferably 0.2 to 15 g, per 1 mol of the phenylphenol.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as aliphatic alcohols such as methanol, ethanol and isopropyl alcohol, dimethylsulfone, dimethylsulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the usage-amount is 1-50 mass% normally with respect to the usage-amount of epihalohydrin, Preferably it is 2-30 mass%. Moreover, when using an aprotic polar solvent, it is 3-100 mass% normally with respect to the usage-amount of epihalohydrin, Preferably it is 5-80 mass%.

  The reaction temperature is usually 30-100 ° C, preferably 35-90 ° C. The reaction time is usually 0.2 to 10 hours, preferably 0.5 to 8 hours. In the presence of an alkali metal hydroxide, epihalohydrin and the like are removed under heating and reduced pressure after washing the reaction solution of phenylphenol and epihalohydrin with or without washing with water. Furthermore, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.5 mol, preferably 0.05 to 0.3 mol, relative to 1 mol of phenylphenol used. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the desired epoxy resin. An epoxy resin that can be used without special purification is obtained by a method represented by such a formulation.

  Phenylphenol epoxy (meth) acrylate is obtained by reacting the aforementioned epoxy resin with (meth) acrylic acid. (Meth) acrylic acid is preferably reacted in an amount of 0.8 to 1.1 equivalents, more preferably 0.9 to 1.05 equivalents, based on an epoxy equivalent of 1 of the epoxy resin.

  The reaction can be carried out without a solvent, but if necessary, a solvent having no alcoholic hydroxyl group, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic carbonization such as benzene, toluene, xylene and tetramethylbenzene Hydrogens, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl Cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether monoacetate, glue Esters such as dialkyl oxalate, dialkyl succinate and dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and alcoholic hydroxyl groups. Various monomers not included alone or mixed, for example, acryloylmorpholine, terminal acrylate ester of 2-phenylphenol ethylene oxide adduct (for example, Nippon Kayaku Co., Ltd. KAYARAD OPP-1, OPP-2), Polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate Relate, di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxybivalate (for example, Nippon Kayaku Co., Ltd. KAYARAD HX-220, HX-620 etc.), pentaerythritol tetra (meth) acrylate, di The reaction can be performed in poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, or the like, which is a reaction product of pentaerythritol and ε-caprolactone. Some of the components (D) and (E) that can be used in the present invention are contained in the various monomers, but when the components (D) and (E) are used as the various monomers, they are obtained by reaction. Can be used in the present invention with or without purification.

  During the reaction, it is preferable to use a catalyst in order to promote the reaction. When the catalyst is used, the amount of the catalyst used is 0.1 to 10% by mass with respect to the reaction product. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Examples of the catalyst used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like. Can be mentioned.

  Further, a thermal polymerization inhibitor may be used, and examples of the thermal polymerization inhibitor include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, and diphenylpicryl. Examples include hydrazine and diphenylamine. When a thermal polymerization inhibitor is used, it is preferably used in an amount of about 0.1 to 10% by mass with respect to the reaction product. The reaction is terminated at an appropriate time when the acid value of the sample is 5 mg · KOH / g or less, preferably 3 mg · KOH / g or less.

  Furthermore, in addition to the compound (A) represented by the general formula (1) and the monoacrylate monomer (D) having a phenyl ether group, the viscosity and adhesion of the obtained resin composition of the present invention, Considering the glass transition temperature (Tg), the hardness of the cured product, etc., the (meth) acrylate compound (E) other than the component (A) and the component (D) may be used alone or in combination of two or more. Good. Examples of the (meth) acrylate compound (E) include (meth) acrylate monomers and (meth) acrylate oligomers.

  Examples of the (meth) acrylate monomer include a monofunctional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a trifunctional or higher polyfunctional (meth) acrylate monomer.

  Examples of the monofunctional (meth) acrylate monomer include acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, and tetrahydrofurfuryl. (Meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. be able to.

  Examples of the bifunctional (meth) acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and tricyclodecanedi. Methanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate hydroxybivarin Examples include di (meth) acrylates of ε-caprolactone adducts of acid neopentyl glycol (for example, Nippon Kayaku Co., Ltd. KAYARAD HX-220, HX-620, etc.).

  Examples of the trifunctional or higher polyfunctional (meth) acrylate monomer include tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include pentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. it can.

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

  Examples of the urethane (meth) acrylate include diol compounds (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6- Hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane Diol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxydiol Or a diol compound and a reaction product of a dibasic acid or an anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid, or an anhydride thereof) And organic polyisocyanates (for example, chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane Diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate Cyclic saturated hydrocarbon isocyanates such as hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylene isocyanate, 6 -Aromatic polyisocyanates such as isopropyl-1,3-phenyl diisocyanate and 1,5-naphthalene diisocyanate), followed by addition of a hydroxyl group-containing (meth) acrylate. Moreover, the compound etc. which made the said organic polyisocyanate and the hydroxyl-containing (meth) acrylate react are mentioned.

  Epoxy (meth) acrylates include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, terminal glycidyl ether of bisphenol A propylene oxide adduct, and fluorene epoxy resin and (meth) Examples include a reaction product with acrylic acid.

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

  Among them, the (meth) acrylate compound (E) that can be used in the resin composition of the present invention is preferably a compound having a bisphenol A skeleton in consideration of the refractive index, such as bisphenol A polyethoxydi (meth) acrylate and bisphenol A poly. (Meth) acrylate monomers such as propoxy di (meth) acrylate, urethane (meth) acrylate oligomers having a bisphenol A skeleton (diol compounds such as bisphenol A polyethoxydiol and bisphenol A polypropoxydiol, or these diol compounds and dibasic compounds A compound obtained by reacting a polyester diol, which is a reaction product with an acid or an anhydride thereof, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate), an ester having a bisphenol A skeleton. Xyl (meth) acrylate oligomer (bisphenol A type epoxy resin, epoxy resin such as terminal glycidyl ether of bisphenol A propylene oxide adduct and a reaction product of (meth) acrylic acid), 9,10-dihydro-9- Reaction of phosphine oxide compound obtained from oxa-10-phosphaphenanthrene-10-oxide, di (meth) acrylate having binaphthol skeleton, (meth) acrylate having fluorene skeleton, or phenylphenol epoxy acrylate and aromatic organic polyisocyanate The urethane acrylate etc. which were made to mention are mentioned.

  In consideration of the adhesiveness and viscosity of the cured product, monofunctional or bifunctional (meth) acrylate monomers are suitable as the (meth) acrylate compound (E), and among them, acryloylmorpholine, tetrahydrofurfuryl (meth). Acrylate, phenoxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like are preferable.

  In consideration of the glass transition temperature (Tg) of the cured product, the (meth) acrylate compound (E) includes tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trifunctional or higher functional (meth) acrylate monomers such as dipentaerythritol penta (meth) acrylate and trimethylolpropane tri (meth) acrylate are preferred.

  The proportion of each component of the resin composition of the present invention is determined in consideration of the desired refractive index, glass transition temperature, viscosity, adhesion, etc., but component (A) + component (D) + component (E) Is 100 parts by mass, the content of component (A) is 2 to 100 parts by mass, preferably 5 to 100 parts by mass. Content of a component (D) is 0-85 mass parts, Preferably it is 0-75 mass parts. Content of a component (E) is 0-60 mass parts, Preferably it is 0-50 mass parts. Component (B) is usually used in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, based on 100 parts by weight of the total amount of component (A) + component (D) + component (E). It is.

  In addition to the above components, the energy ray curable resin composition of the present invention includes a mold release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, and a polymerization prohibition in order to improve convenience during handling. An agent, an antistatic agent, an ultraviolet absorber and the like can be used in combination depending on the situation. Furthermore, polymers such as acrylic polymer, polyester elastomer, urethane polymer and nitrile rubber, inorganic or organic light diffusing filler, and the like can be added as necessary. Although the resin composition of the present invention can be obtained by adding a solvent as necessary, in the present invention, it is preferable not to add a solvent.

  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 4,000 mPa · s at 25 ° C. measured using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.) as a viscosity suitable for producing optical lens sheets. Compositions that are s or less are preferred.

  A cured product obtained by curing the resin composition of the present invention by irradiating energy rays such as ultraviolet rays according to a conventional method is also included in the present invention. The cured product is obtained by applying the resin composition of the present invention on a stamper having a shape of, for example, a Fresnel lens, a lenticular lens, or a prism lens to form a layer of the resin composition, and a hard transparent substrate on the layer. A back sheet (for example, a substrate or film made of polymethacrylic resin, polycarbonate resin, polystyrene resin, polyester resin, or a blend of these polymers) is adhered, and then ultraviolet light is emitted from the hard transparent substrate side by a high-pressure mercury lamp or the like. After the resin composition is cured by irradiation, the cured product can be peeled off from the stamper. Moreover, it can also carry out by a continuous process as these applications.

  In this manner, an optical lens having a high refractive index (25 ° C.) and an optical lens portion such as a Fresnel lens, a lenticular lens, a prism lens, and a microlens having a high releasability, mold reproducibility, adhesion, and light resistance. Sheets can be obtained and these are also included in the present invention. The refractive index can be measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

  As described above, the resin composition of the present invention is useful for optical lens sheets. Applications other than those for optical lens sheets include various coating agents and adhesives.

  Next, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited at all by the following examples. In the examples, “part” means “part by mass”.

Synthesis example 1
Synthesis of Compound (A) In an autoclave, 167.2 g (1.0 mol) of carbazole, 114.5 g of toluene and 0.5 g of potassium hydroxide were charged, and after nitrogen substitution, 48.5 g (1.1 mol) ) Was added dropwise in the range of 120 ° C. to 140 ° C. and a reaction pressure of 0.2 MPa or less, and reacted for 6 hours. After the reaction, unreacted ethylene oxide and toluene were distilled off under reduced pressure to obtain 211.3 g of N- (2-hydroxyethyl) carbazole.
Subsequently, in a flask equipped with a stirrer, a reflux tube, a thermometer, and a water separator, 105.6 g (0.5 mol) of N- (2-hydroxyethyl) carbazole and 54.1 g of acrylic acid (0 .7 mol), 1.44 g of paratoluenesulfonic acid, 0.54 g of hydroquinone, 517.6 g of toluene and 221.8 g of cyclohexane, respectively, and azeotropically distills off the produced water 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 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 130.0 g of N- (2-acryloyloxyethyl) carbazole represented by the following formula (C-1) as a pale yellow solid.

The physical properties of the compound (A) are shown below.
Liquid refractive index (D line, 25 ° C.) 1.61
¹ H-NMR (CDCl ₃ , 300 MHz)
4.48-4.60 ppm = 4H, 5.70-5.80 ppm = 1H, 5.90-6.05 ppm = 1H, 6.20-6.30 ppm = 1H, 7.10-7.55 ppm = 6H, 8.05-8.15 ppm = 2H

Synthesis example 2
Synthesis of Compound (E) Synthesis was performed according to Synthesis Example 2 and Example 2 of International Publication 2008/136262. 181 g of p-phenylphenol (manufactured by P-PP Sanko Co., Ltd.), 394 g of epichlorohydrin, and 80 g of methanol were charged and dissolved in a flask equipped with a thermometer, a cooler, and a stirrer while performing nitrogen gas purge. The mixture was further heated to 70 ° C., 44 g of flaky sodium hydroxide was added in portions over 90 minutes, and then reacted at 70 ° C. for 60 minutes. After completion of the reaction, washing was performed twice with 200 g of water to remove the generated salt and the like, and then the mixture was stirred for 3 hours with stirring under reduced pressure (˜70 ° C., −0.08 MPa to −0.09 MPa). Epichlorohydrin and the like were distilled off. To the residue, 480 g of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 12 g of a 10% by weight sodium hydroxide aqueous solution was added and reacted for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was subjected to methyl isobutyl ketone under reduced pressure using a rotary evaporator. Etc. was distilled off to obtain 227 g of the desired epoxy resin (e-1). The obtained epoxy resin (e-1) had an epoxy equivalent of 242 g / eq. It was white crystalline at room temperature.
Next, 145.2 g (0.6 eq.) Of the obtained epoxy resin (e-1) as a thermal polymerization inhibitor was placed in a 1 L flask equipped with a stirrer and a reflux tube, and 2,6-di-tert- 0.57 g of butyl-p-cresol, 43.3 g (0.6 eq.) Of acrylic acid, 0.57 g of triphenylphosphine as a reaction catalyst were charged, reacted at 98 ° C. for 30 hours, and the acid value was measured. The first reaction was completed at 2 mg · KOH / g.
After completion of the first reaction, the reaction temperature was set to 40 ° C., 232.0 g of o-phenylphenol monoethoxy acrylate was added as a reaction diluent, and the mixture was stirred and mixed. Next, 0.070 g of dibutyltin dilaurate was added as a urethane reaction catalyst, 43.6 g (0.5 eq.) Of 2,4-tolylene diisocyanate was added, the reaction temperature was raised to 60 ° C., and the reaction was allowed to proceed for 24 hours. %). At this time, NCO (%) was 0.00%, and the reaction was terminated. The product was 460 g, and an o-phenylphenol monoethoxy acrylate mixture containing 50% by mass of urethane acrylate as the compound (E) was obtained.

Synthesis example 3
Synthesis of Compound (E) In a dry container, 139.3 parts of 2,4-tolylene diisocyanate, 0.05 parts of di-n-butyltin dilaurate and 0.16 parts of methoquinone were added and the temperature was raised to 40 ° C. , Stirred. To this, 185.6 parts of 2-hydroxyethyl acrylate was added dropwise over 1 hour while confirming the exotherm, and reacted at 80 ° C. for 1 to 2 hours. The isocyanate value after the reaction was 0.1 or less, indicating that the reaction was almost quantitatively completed, and urethane acrylate as compound (E) was obtained.

Synthesis example 4
Synthesis of Compound (E) Synthesis was performed according to Synthesis Example 1 of JP2008-94987. A 2L 4-neck flask equipped with a stirrer, thermometer, condenser water separator, etc., and then 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (trade names: BPEF, JEF Chemical Co., Ltd.) )) Is prepared in an amount of 400.0 g, acrylic acid is 161.0 g, toluene is 600 ml, p-toluenesulfonic acid is 45.6 g, and hydroquinone is 4.6 g. went. The reaction time was 5 hours, the reaction temperature was 103 to 120 ° C., and the amount of distilled water by dehydration reaction was 38 g. Next, after cooling the reaction solution, the reaction solution was diluted with 1500 ml of toluene, neutralized by adding 200 g of a 20% by weight aqueous sodium hydroxide solution, washed with 500 g of a 15% by weight aqueous sodium chloride solution, and further toluene was distilled off. By leaving, 458.2g of bifunctional acrylate which is a compound (E) was obtained.

  The resin composition and cured product of the present invention were obtained with the composition as shown in the following examples (the numerical value indicates part by mass). 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) Releasability: Expresses the degree of difficulty when releasing a cured resin from a mold.
○ ······························································································································· Mold reproducibility: 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) Adhesion: A test piece was prepared by applying a resin composition on a substrate to a film thickness of about 50 μm and then irradiating it with a high-pressure mercury lamp (80 W / cm, ozone-less) at 1000 mJ / cm ^2. The adhesion was evaluated according to JIS K5600-5-6.
In the evaluation results, 0 to 2 were evaluated as ○, and 3 to 5 as ×.

(5) 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.).
(6) Glass transition temperature (Tg): Tg point of the cured ultraviolet curable resin layer was measured with a viscoelasticity measurement system (DMS-6000: manufactured by Seiko Denshi Kogyo Co., Ltd.) in a tensile mode at a frequency of 1 Hz.
(7) Light resistance: A test piece was prepared by applying a resin composition on a substrate to a film thickness of about 80 μm and then irradiating it with a high-pressure mercury lamp (80 W / cm, ozone-less) at 600 mJ / cm ² . . Next, after performing a light resistance test for 4 hours under conditions of 60 ° C. and 60% RH with EYE SUPER UV TESTER SUV-W11 (manufactured by Iwasaki Electric), the state of the film was visually evaluated.
○ ··· Slightly yellowing, but good appearance with no problems in appearance and transparency × ····· State of great appearance change such as coloring and cracking of resin layer

Example 1
20 parts of the compound obtained in Synthesis Example 1 as component (A), 31 parts of o-phenylphenol monoethoxy acrylate as component (D), and 3 parts of Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) as component (B) Parts, 0.1 parts of diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 20 parts of KAYARAD R-551 (Nippon Kayaku: bisphenol A polyethoxydiacrylate) as component (E), KAYARAD 4 parts of R-115 (Nippon Kayaku: bisphenol A epoxy acrylate), 18 parts of tris (2-acryloyloxyethyl) isocyanurate, 7 parts of acryloylmorpholine, heated to 60 ° C. and mixed to prepare the present invention A resin composition was obtained. The viscosity of this resin composition was 690 mPa · s. Moreover, the refractive index (25 ° C.) of the 200 μm-thick UV curable resin layer obtained by curing this resin composition by irradiation with 600 mJ / cm ² with a high-pressure mercury lamp (80 w / cm, ozone-less) is 1.589. The glass transition temperature (Tg) was 82 ° C.
Further, this resin composition was applied onto a prism lens mold so that the film thickness was 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 from above by being cured by irradiating with an ultraviolet ray of 600 mJ / cm ^{2 with} a high-pressure mercury lamp and then curing.
Evaluation results: releasability: ○, mold reproducibility: ○, adhesion: ○.

Example 2
In Example 1, 52 parts of o-phenylphenol monoethoxyacrylate as component (D), 3 parts of 2-hydroxy-2-methyl-1-phenylpropan-1-one as component (B), and as component (E) 10 parts of the compound obtained in Synthesis Example 3, 13 parts of acryloylmorpholine, 5 parts of tetrahydrofurfuryl acrylate, heated to 60 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 150 mPa · s. The resin layer obtained in the same manner as in Example 1 had a refractive index (25 ° C.) of 1.599 and a glass transition temperature (Tg) of 59 ° C.
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: releasability: ○, mold reproducibility: ○, adhesion: ○, light resistance: ○.

Example 3
In Example 1, 65 parts of the compound obtained in Synthesis Example 1 as component (A), 3 parts of Irgacure 184 as component (B), 0 of diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide .1 part, 25 parts of phenoxyethyl acrylate as component (D), 10 parts of KAYARAD DPHA (manufactured by Nippon Kayaku: dipentaerythritol hexaacrylate) as component (E), heated to 60 ° C. and mixed, An inventive resin composition was obtained. The viscosity of this resin composition was 340 mPa · s. The resin layer obtained in the same manner as in Example 1 had a refractive index (25 ° C.) of 1.622 and a glass transition temperature (Tg) of 69 ° C.
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: releasability: ○, mold reproducibility: ○, adhesion: ○.

Example 4
In Example 1, 10 parts of the compound obtained in Synthesis Example 1 as component (A), 59 parts of o-phenylphenol monoethoxyacrylate as component (D), 8 parts of phenoxyethyl acrylate, and Irga as component (B) 5 parts of Cure 184, 0.1 part of diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 3 parts of KAYARAD DPHA as component (E), 30 parts of the mixture obtained in Synthesis Example 2 5 parts of the compound obtained in Example 3 and 3 parts of 1,4-butanediol diacrylate were heated to 60 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 510 mPa · s. The resin layer obtained in the same manner as in Example 1 had a refractive index (25 ° C.) of 1.604 and a glass transition temperature (Tg) of 52 ° C.
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: releasability: ○, mold reproducibility: ○, adhesion: ○.

Example 5
In Example 1, 55 parts of the compound obtained in Synthesis Example 1 as component (A), 7 parts of o-phenylphenol monoethoxyacrylate as component (D), 25 parts of phenoxyethyl acrylate, and Irga as component (B) 3 parts of Cure 184, 0.1 part of diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 10 parts of KAYARAD DPHA as component (E), 10 parts of the compound obtained in Synthesis Example 4 The resin composition of the present invention was obtained by heating to ℃ and mixing. The viscosity of this resin composition was 465 mPa · s. The resin layer obtained in the same manner as in Example 1 had a refractive index (25 ° C.) of 1.618 and a glass transition temperature (Tg) of 71 ° C.
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: releasability: ○, mold reproducibility: ○, adhesion: ○.

Comparative Example 1
According to Example 1 of Patent Document 1 (Japanese Patent Laid-Open No. 63-167301), 70 parts Aronics M-315 (tris (2-acryloyloxyethyl) isocyanurate), 30 parts tetrahydrofurfuryl acrylate, 1 as a photopolymerization initiator 3 parts of-(4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one was heated to 60 ° C. and mixed to obtain a comparative resin composition. The viscosity of this resin composition was 134 mPa · s. The refractive index (25 ° C.) of the resin layer obtained in the same manner as in Example 1 was 1.520.
From this result, the composition of Comparative Example 1 has a lower refractive index than the composition of the present invention, and is not suitable for the production of the lenses of the present invention.

Comparative Example 2
According to Example 1 of Patent Document 3 (Japanese Patent No. 3209554), urethane acrylate of Synthesis Example 1 of this document (neopentyl glycol and polyester diol of adipic acid, ethylene glycol, tolylene diisocyanate and 2-hydroxyethyl acrylate reaction product) And 30 parts of the urethane acrylate, 15 parts of the o-phenylphenol diethoxyacrylate, and 45 parts of KAYARAD R-551. Then, 10 parts of tribromophenyl acrylate and 3 parts of Irgacure 184 were heated and mixed at 60 ° C. to obtain a comparative resin composition. The viscosity of this resin composition was 4420 mPa · s. Further, the refractive index (25 ° C.) of the resin layer obtained in the same manner as in Example 1 was 1.574.
From this result, the composition of Comparative Example 2 has a higher viscosity than the composition of the present invention, and is unsuitable for fine processing and continuous processing of roll-shaped sheets and films.

Comparative Example 3
Without using component (A), 51 parts o-phenylphenol monoethoxyacrylate as component (D), 3 parts Irgacure 184 as component (B), diphenyl- (2,4,6-trimethylbenzoyl) phosphine 0.1 parts of oxide, 20 parts of KAYARAD R-551 as component (E), 4 parts of KAYARAD R-115, 18 parts of tris (2-acryloyloxyethyl) isocyanurate, 7 parts of acryloylmorpholine, 60 ° C. The mixture was heated and mixed to obtain a comparative resin composition. The viscosity of this resin composition was 409 mPa · s. The resin layer obtained in the same manner as in Example 1 had a refractive index (25 ° C.) of 1.581 and a glass transition temperature (Tg) of 71 ° C.
A comparative prism lens sheet was obtained in the same manner as in Example 1 using the obtained resin composition.
From this result, the composition of Comparative Example 3 has a lower refractive index than the composition of the present invention, and is not suitable for the production of the lenses of the present invention.
Evaluation results: releasability: ○, mold reproducibility: ○, adhesion: ○, light resistance: ○.

Table 1 summarizes the evaluation results.

  As is clear from the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 3, the resin composition of the present invention has a low viscosity, and the cured product of the present invention has a high refractive index, releasability, and mold reproduction. And excellent adhesion to the substrate. For this reason, it is suitable for an optical lens sheet having a fine structure, for example, a Fresnel lens, a lenticular lens, a prism lens, a microlens and the like. In particular, since it has a high refractive index, it is suitable for high-luminance products, and it is suitable for manufacturing that requires fine processing and processes that require continuous processing.

  The ultraviolet curable resin composition and the cured product thereof according to the present invention are particularly suitable mainly for optical lens sheets such as Fresnel lenses, lenticular lenses, prism lenses, and micro lenses.

Claims (7)

An energy ray-curable resin composition for an optical lens sheet, comprising a compound (A) having a carbazolyl group and a photopolymerization initiator (B). The compound (C) having the carbazolyl group is represented by the general formula (2)

(Wherein R ₁₀ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ₁₁ is the same or different hydrocarbon group having 1 to 4 carbon atoms, n is an average number of repetitions, and n = 0 to The resin composition according to claim 1, which is 4 and may have a substituent on the carbazolyl group. The resin composition according to claim 1 or 2, further comprising a monoacrylate monomer (D) having a phenyl ether group. Monoacrylate monomer (D) having a phenyl ether group is o-phenylphenol (poly) ethoxy (meth) acrylate, p-phenylphenol (poly) ethoxy (meth) acrylate, o-phenylphenol epoxy (meth) acrylate, p- The resin composition according to any one of claims 1 to 3, wherein the resin composition is one or more selected from the group consisting of phenylphenol epoxy (meth) acrylates. The resin composition according to any one of claims 1 to 4, further comprising a (meth) acrylate compound (E) other than the compound (A) having a carbazolyl group and the monoacrylate monomer (D) having a phenyl ether group. Hardened | cured material obtained by hardening | curing the resin composition as described in any one of Claims 1 thru | or 5. An optical lens sheet using the cured product according to claim 6.