JP2011037943A - Curable resin composition, cured article thereof, and plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a (meth)acrylate resin having a high refractive index in a cured article as an organic optical material and being also excellent in heat-resistance and moisture-resistance in the cured article, a curable resin composition, its cured article, and a plastic lens. <P>SOLUTION: The curable resin composition includes a polymerizable compound (A) having a bi-naphthalene skeleton and a radical polymerizable unsaturated bond, zirconia particles (B) having a primary particle diameter of 10-100 nm, and a radical polymerization initiator (C). The curable resin composition is cured by heating or irradiation with an active energy ray. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is cured by irradiation with active energy rays or heating, and after curing, a cured product having a high refractive index and high heat resistance and high moisture resistance. The present invention relates to a curable resin composition suitable for a coating agent, an antireflection film, an eyeglass lens, an optical component such as an optical fiber, an optical waveguide, a hologram, and other plastic lenses such as a prism lens, a Fresnel lens, and a lenticular lens, and a cured product thereof.

  In recent years, resin materials have been widely used for optical parts such as optical overcoat agents, hard coat agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, and holograms because of their excellent processing and productivity. Therefore, a resin material having a high refractive index is demanded from the viewpoint of miniaturization and thinning of optical components, or adjustment of antireflection properties.

  Conventionally, an acrylate resin having a fluorene skeleton has been known as an optical material having a high refractive index that meets such requirements. For example, a bifunctional compound in which an acryloyl group is bonded to a fluorene skeleton via an alkyleneoxy group (see below) Patent Literature 1, Patent Literature 2, and Patent Literature 3), and compounds obtained by reacting diglycidyl ether containing a fluorene skeleton with acrylic acid or methacrylic acid (see Patent Literature 4 below) are known.

  However, when the acrylate resin having a fluorene skeleton described above is used alone as a polymerizable component, the refractive index of the cured product becomes high, but the acrylate resin itself is solid or has a high value of 3000 Pa · S or more at room temperature. Since it is a viscous liquid, it is necessary to use a large amount of a diluent having a low refractive index, so that the refractive index of the resulting cured product eventually becomes low. In addition, the cured product of the acrylate resin having a fluorene skeleton is inferior in heat resistance and high moisture resistance, and inferior in the long-term reliability of the optical material.

A polyester resin having a binaphthol skeleton is known as an optical material having a high refractive index (see Patent Document 5 below).
However, since the polyester resin having such a binaphthol skeleton has a high weight average molecular weight (Mw) of 10,000 to 100,000 and is a solid thermoplastic resin at room temperature, it is applied to the use of active energy rays or thermosetting resins. In addition, it was inferior in solvent resistance, heat resistance and high moisture resistance, and the long-term reliability of the optical material was low.

Japanese Patent No. 3130555 JP 2007-84815 A International Publication Number WO2005 / 033061 Japanese Patent Laid-Open No. 03-106918 JP 2002-332345 A

  Therefore, the problem to be solved by the present invention is to provide a curable resin composition having a high refractive index in a cured product and excellent in heat resistance and moisture resistance of the cured product, and a cured product having such performance. There is.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymerizable compound having a binaphthalene skeleton and a radical polymerizable unsaturated bond can be obtained as a cured product having a high refractive index, and the polymerizable compound. By combining with fine particles of a specific inorganic compound, the refractive index of the cured product is further increased, and the cured product has been found to have excellent heat resistance and moisture resistance, and the present invention has been completed.

That is, the present invention includes a polymerizable compound (A) having a binaphthalene skeleton and a radical polymerizable unsaturated bond, zirconia particles (B) having a primary particle size of 10 to 100 nm, and a radical polymerization initiator (C). The present invention relates to a curable resin composition.
The present invention further relates to a cured product obtained by curing the curable resin composition by irradiation with active energy rays or heating.
The present invention further relates to a plastic lens obtained by molding and curing the curable resin composition.

  According to the present invention, a curable resin composition having a high refractive index in a cured product as an organic optical material while having a low viscosity, and excellent in heat resistance and moisture resistance of the cured product, and curing having such performance Can provide things.

  Therefore, the (meth) acrylate resin of the present invention can be widely applied to optical parts such as optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, hologram, prism lens, In particular, it can be preferably applied to plastic lenses such as spectacle lenses and prism lenses.

  The polymerizable compound (A) used in the present invention is characterized by being a polymerizable compound (A) having a binaphthalene skeleton and a radical polymerizable unsaturated bond. Since it has such a binaphthalene skeleton, heat resistance and moisture resistance are good, and the organic material is a material having an extremely high refractive index of 1.60 or more.

  Examples of the binaphthalene skeleton include a 1,1′-binaphthalene skeleton, a 1,2′-binaphthalene skeleton, a 2,2′-binaphthalene skeleton, a 4,4′-binaphthalene skeleton, and the like. From the viewpoint, a 1,1′-binaphthalene skeleton is preferable.

  The polymerizable compound (A) used in the present invention is, for example, a polymer having a structure obtained by reacting an epoxy resin (a1) having a binaphthalene skeleton with a radically polymerizable unsaturated double bond-containing monocarboxylic acid (x1). Compound (vinyl ester resin) (a2) and the like.

  Here, as the epoxy resin (a1) having a binaphthalene skeleton, for example, an epoxy resin obtained by reacting a binaphthol with an epihalohydrin, or an epoxy resin obtained by further reacting the binaphthol with the epoxy resin Is mentioned.

  Examples of the binaphthols include 1,1′-bi-2-naphthol and 4,4′-bi-1-naphthol. Among them, 1,1′-bi-2-naphthol is preferable because a curable resin composition having a high refractive index of the obtained cured product can be obtained.

  As the 1,1′-bi-2-naphthol, specifically, the following structural formula (1)

（式中、Ｘ^１〜Ｘ^１２は、各々独立的に水素原子、ハロゲン原子、炭素原子数１〜１０の炭化水素基、又は炭素原子数１〜１０のアルコキシ基を表す。）で表されるものが挙げられる。

(Wherein, X ^{1 to} X ¹² each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms). Things.

Among these, X ^{1 to} X ¹² in the above general formula (1) are each independently a hydrogen atom or carbon from the viewpoint of compatibility of both refractive index and viscosity, difficulty in synthesis, and cost. An alkyl group having 1 to 3 atoms is preferable, and all of them are particularly preferably hydrogen atoms.

  Examples of the epihalohydrins include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like, and epichlorohydrin is preferable in view of availability and economy.

  In the present invention, an epoxy resin obtained by reacting 1,1′-bi-2-naphthol and epihalohydrin among the epoxy resins (a1) is particularly preferable from the viewpoint of heat resistance of the cured product and adhesion to the substrate. .

  The epoxy resin (a1) has an epoxy equivalent of 200 to 500 g / eq. Is preferable from the point that the flexibility of the cured product and the sensitivity to light irradiation are good, and particularly 200 to 300 g / eq. It is preferable that it is the range of these.

  On the other hand, examples of the radical polymerizable unsaturated double bond-containing monocarboxylic acid (x1) to be reacted with the epoxy resin (a1) include (meth) acrylic acid such as acrylic acid and methacrylic acid; acrylic acid chloride and methacrylic acid. (Meth) acrylate halogens such as chloride; alkyl (meth) acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate. Of these, halogens (meth) acrylates cause by-products such as hydrochloric acid during reaction to cause corrosion problems in the reaction kettle, and when alkyl (meth) acrylates are used, by-product alcohol is removed. (Meth) acrylic acid is preferred because it is necessary to carry out a dealcoholization treatment.

  The reaction ratio between the epoxy resin (a1) and the radically polymerizable unsaturated double bond-containing monocarboxylic acid (x1) is not particularly limited, but acrylic acid is equivalent to one epoxy group equivalent of the epoxy resin. It is preferable that the carboxyl group is in a range of 0.4 to 1, 1 equivalent, and in particular, a range of 0.8 to 1.0 mol is preferable in that a resin excellent in photocurability and storage stability is obtained. .

Among the epoxy resins (a1), an epoxy resin obtained by reacting 1,1′-bi-2-naphthol and epihalohydrins, or further reacting with 1,1′-bi-2-naphthol. When the epoxy resin obtained is used and (meth) acrylic acid is used as the radical polymerizable unsaturated double bond-containing monocarboxylic acid (x1), the resulting polymerizable compound (a2) is specifically: Includes those represented by the following general formula (2). (In the formula, n represents the average number of repeats and is in the range of 0 to 10, R ¹ represents a hydrogen atom or an alkyl group which may have a substituent, and R ² represents a hydrogen atom or a methyl group. .)

  Examples of these include the following structural formula (2-1) or (2-2). (In the formula, n is 0 to 10.)

  The polymerizable compound (A) used in the present invention has a viscosity at 25 ° C. of 3000 Pa · s or less, good fluidity and wide application range for various uses, and low refractive index used for viscosity adjustment. It is preferable because the amount of diluent used as a substance can be reduced. In particular, the range of 1000 to 100 Pa · s is preferable from the viewpoint that this effect becomes remarkable.

  As described above, the polymerizable compound (A) has a high refractive index per se, specifically, a refractive index of 1.55 or higher, and a refractive index of 1.60 or higher depending on the selection of the molecular structure. It becomes the material which has.

  The zirconia particles (B) used in the present invention have a primary average particle diameter of 10 to 100 nm. The zirconia particles (B) used in the present invention may be particles having a primary particle size or a bond particle size. The nanoparticles are preferably not bound. In the present invention, the primary particle diameter is a particle diameter measured by a transmission electron microscope (TEM).

  The zirconia particles (B) used in the present invention are used as a dispersion, and the average dispersed particle diameter is preferably 10 to 50 nm because a cured product having a high refractive index and excellent transparency can be obtained. Furthermore, it is more preferable that the thickness is 10 to 30 nm because a cured product having better transparency can be obtained. As the zirconia fine particles (B) used in the present invention, a commercially available zirconia dispersion, for example, a product marketed under the product name Nalco OOSSOO8 from Nalco Chemical Company of Naperville, Illinois, USA, or Boole AG in Switzerland A product commercially available from Buhler AG Uzwi as the trade name “Buhler zirconia Z-WO sol” can be used.

  Alternatively, a commercially available zirconia powder, for example, a product marketed as a product name “UEP Zirconium Oxide” or “RC-100 Zirconium Oxide” from Daiichi Rare Element Chemical Co., Ltd., is dispersed in a dispersion medium using a disperser. It can also be used as a dispersion.

  As the disperser, for example, a homogenizer, a sand mill, an ultrasonic disperser, a ball mill, a bead mill, a triple roll, a pressure kneader, a bead mill and the like can be used. Among these, use of a bead mill that can be dispersed by a wet method using beads of 15 to 100 μm is more preferable because zirconia can be dispersed to the vicinity of the primary particles.

  Examples of such a bead mill include a star mill manufactured by Ashizawa Finetech Co., Ltd., a pico mill manufactured by Asada Iron Works Co., Ltd., and an ultra apex mill manufactured by Kotobuki Industries Co., Ltd.

  Examples of the dispersion medium include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; dimethylformamide, Amides such as N, N-dimethylacetoacetamide and N-methylpyrrolidone can be used.

  The surface of the zirconia particles (B) used in the present invention may be modified or not modified. Moreover, when using the zirconia particle | grains which are not modifying the surface as a zirconia particle, it is set as the composition which the dispersion stability of the zirconia microparticles | fine-particles improved by adding a dispersing agent and a dispersing aid in the curable composition of this invention. be able to.

  For example, a nonionic dispersant can be suitably used as the dispersant. Preferably, it is a phosphoric ester nonionic dispersant having a polyoxyethylene alkyl structure.

  As the dispersion aid, for example, one or more selected from methyl acetoacetate, acetylacetone, and N, N-dimethylacetoacetamide can be suitably used. Since methyl acetoacetate is a mutagenic substance, acetylacetone and N, N-dimethylacetoacetamide are particularly preferable.

  Since the content rate of the said zirconia particle (B) in the curable composition of this invention has a high refractive index and a transparent hardened | cured material is obtained, it is 10-70 on the basis of the mass of the formation component of hardened | cured material. % By mass is preferable, and 20 to 60% by mass is more preferable.

  As the zirconia particles (B) used in the present invention, those having a modified particle surface are preferably used. By modifying the surface, for example, hydrophilic zirconia particles can be hydrophobized and the dispersibility in the polymerizable compound (A) can be enhanced. As the surface modifier, for example, silane compounds such as alkoxysilane, chlorosilane, alkylalkoxysilane, alkylchlorosilane, and siloxane can be preferably used.

The alkoxysilane, chlorosilane, alkylalkoxysilane, and alkylchlorosilane are compounds represented by the structural formula SiX _m Y _4-m , and each of the X group and the Y group includes one or more of those shown below. Those are preferred.

X group includes vinyl group, allyl group, 3-glycidoxypropyl group, 2- (3,4 epoxycyclohexyl) ethyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group, styryl group, 3- Aminopropyl group, N-2 (aminoethyl) 3-aminopropyl group, N-phenyl-3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, alkyl group represented by C _n H _{2n + 1} Among them, those in which n is in the range of 1 to 20, phenyl groups and the like are mentioned.

Examples of the Y group include chlorine, a hydroxy group, an alkoxy group represented by C _n H _{2n + 1} O, wherein n is in the range of 1 to 20, an acetoxy group, and the like.

  As the alkoxysilane or chlorosilane, a silane coupling agent is particularly preferable. For example, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxy Examples include silane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

  Examples of the alkylchlorosilane include methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, trimethylchlorosilane, and triethylchlorosilane.

  Siloxane is preferably a modified silicone or a silicone resin. The modified silicone is an epoxy-modified silicone, an epoxy / polyether-modified silicone, an alcohol-modified silicone, a methacryl-modified silicone, a methacrylate-modified silicone, a phenol-modified silicone, a methylstyryl-modified silicone, an acrylic. Examples include modified silicone, mercapto-modified silicone, amino-modified silicone, and methyl hydrogen silicone.

  Examples of the method for modifying the surface of the zirconia particles using the surface modifier include a wet method and a dry method. The wet method is a method for modifying the surface of the zirconia fine particles by introducing and mixing the surface modifier and the zirconia fine particles in a solvent (for example, the above-described dispersion medium). The dry method is a method of modifying the surface of the zirconia fine particles by introducing the surface modifier and the dried zirconia fine particles into a dry mixer such as a mixer and mixing them. Further, commercially available products of surface-modified zirconia particles can be used as they are. Furthermore, the particles (B) used in the present invention may have a polymerizable unsaturated bond such as a (meth) acryloyl group on the surface thereof.

  Examples of the radical polymerization initiator (C) used in the present invention include a photopolymerization initiator and a thermal polymerization initiator. Specific examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, 2-methylbenzoin, benzophenone, Michler's ketone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, benzoylbenzoic acid, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthiophenyl)]-2-morpholino) propane-1, 2-chlorothioxanthone, 2,4 -Diethylthioki Cantonal, 2,4-diisopropyl thioxanthone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like.

  These photopolymerization initiators can be used alone or as a mixture of two or more. The amount used is preferably such that the photopolymerization initiator is 0.01 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound (A), particularly preferably 0.01 to 20 parts by mass or less. It is.

  These photopolymerization initiators can be used in combination with a photopolymerization accelerator such as amines. Examples include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and the like. The use ratio of these photopolymerization accelerators is in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of the photopolymerization initiator, the polymerization rate is fast, and the refractive index of the cured product is high. This is preferable.

  Next, as the thermal polymerization initiator, a known peroxide-based initiator or azobis-based initiator can be used. Specifically, as the peroxide initiator, ketone peroxide initiators such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexane ketone peroxide, acetylacetone peroxide, isobutyl peroxide, Diacyl peroxide initiators such as m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, α-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, 2,4,4 -Hydroperoxides such as trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide Id initiator, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumylper Dialkyl peroxide initiators such as oxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-di- (t-butylperoxy) butane, 4,4- Peroxyketal initiators such as di-t-butylperoxyvaleric acid-n-butyl ester, 2,4,4-trimethylpentylperoxyphenoxyacetate, α-cumylperoxyneodecanoate, t-butylper Alkyl perester initiators such as oxybenzoate and di-t-butylperoxytrimethylodipate, di-t-methoxybutyl -Peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, percarbonate-based initiators such as bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, other acetylcyclohexylsulfonylperoxydi Examples thereof include carbonates, t-butylperoxyallyl carbonate and the like. Specific examples of the azobis initiator include 1,1′-azobiscyclohexane-1-carbonitrile and 2,2′-azobis. -(2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (methylisobutyrate), α, α ' -Azobis- (isobutyronitrile), 4,4'-azobis- (4- Cyanovaleric acid) and the like.

  These thermal polymerization initiators can be used alone or in a mixture of two or more. The amount of use is such that the thermal polymerization initiator is in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound (A), the polymerization rate is high, and the cured product This is preferable from the viewpoint of increasing the refractive index.

  Additives such as a diluent, a silane coupling agent, a polymerization inhibitor, and a leveling agent can be added to the curable resin composition of the present invention in order to further improve the performance without changing the original characteristics.

  As the diluent, for example, a low-viscosity organic compound, so-called organic solvent can be used. Examples of the organic solvent include methyl ethyl ketone, carbitol acetate, butyl cellosolve acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and solvent naphtha.

  Among diluents, a reactive diluent is more preferable because the curable resin composition can be cured without volatilizing the diluent. Examples of the reactive diluent include a radical polymerizable monomer. Examples of the radical polymerizable monomer include (meth) acrylate monomers such as monofunctional (meth) acrylate monomers, bifunctional (meth) acrylate monomers, and trifunctional or higher polyfunctional (meth) acrylate monomers; styrene, methyl Examples thereof include vinyl monomers such as styrene, halogenated styrene and divinylbenzene.

  Here, 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 tetrahydro. Furfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) ) Acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Acrylate, and phenyl phenol polyethoxy (meth) acrylate.

  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. Examples include methanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. be able to.

  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, Pentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of hydroxypentylglycolate neopentyl glycol, trimethylolpropane tri (meth) acrylate, trimethylolpropane poly Examples thereof include ethoxytri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.

  Among these, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meta) are particularly effective as a reactive diluent in the curable resin composition because of the effect of reducing the viscosity of the composition and maintaining a high refractive index of the cured product. ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Monofunctional or bifunctional (meth) acrylate monomers such as dicyclopentenyloxyethyl (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, and divinylbenzene are preferable, and phenoxyethyl (meth) acrylate is particularly preferable. Phenylphenol polyethoxy (meth) acrylate, and preferably from the standpoint of refractive index increases in the cured product with those selected from the group consisting of divinylbenzene has excellent dilution capability, and more preferably phenyl polyalkoxy (meth) acrylate.

  Examples of the phenylphenol polyalkoxy (meth) acrylate include the following general formula (3):

（式中、Ｒ_１は水素原子又はメチル基であり、ｎの平均値は１〜５である。）で表される化合物等が挙げられる。

(Wherein, R ₁ is a hydrogen atom or a methyl group, and the average value of n is 1 to 5).

  The compound represented by the general formula (3) reacts, for example, a reaction product of P-phenylphenol or O-phenylphenol with an alkylene oxide such as ethylene oxide or propylene oxide, and (meth) acrylic acid. Can be obtained.

Among the phenylphenol polyalkoxy (meth) acrylates, phenylphenol polyethoxy (meth) acrylate [in the general formula (3), R ₁ is a hydrogen atom] is preferable.

  Among the phenylphenol polyalkoxy (meth) acrylates, O-phenylphenol polyalkoxy (meth) acrylate is preferable, and O-phenylphenol polyethoxy (meth) acrylate is more preferable. As O-phenylphenol polyethoxy (meth) acrylate, for example, a compound represented by the following general formula (3-1)

（式中、ｎの平均値は１〜５である。）等が挙げられる。

(Wherein the average value of n is 1 to 5).

  Moreover, as said reactive diluent, following General formula (4)

(Wherein R ₁ and R ₂ are each a hydrogen atom or an alkyl group, X is a hydrogen atom or a hydroxyl group, and m and n are each 0 to 5). An acrylate monomer can also be preferably used.

As said alkyl group of R < ₁ >, R < ₂ >, a C1-C4 linear or branched alkyl group is preferable, for example.

Among these, R ₁ and R ₂ are each more preferably a hydrogen atom or a methyl group.

  As for m and n in the said General formula (4), 1-3 are respectively preferable. Moreover, 0-4 are preferable on the average of m and n, and 2-4 are more preferable.

  Further, among the general formula (4), the following formula (4-1)

で表される化合物、または、式（４−２）

Or a compound represented by formula (4-2)

で表される化合物がより好ましい。

The compound represented by these is more preferable.

  In the present invention, when a reactive diluent is used, the amount used thereof can sufficiently exhibit the effect of reducing the viscosity of the curable composition of the present invention and can maintain the refractive index of the cured product at a high level. To [polymerizable compound (A) / reactive diluent] is preferably used at a ratio of 90/10 to 30/70, and more preferably at a ratio of 80/20 to 40/60.

  Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.

  Examples of the polymerization inhibitor include hydroquinone monomethyl ether, methyl hydroquinone, t-butylcatechol, p-benzoquinone, 2,5-t-butyl-hydroquinone, phenothiazine and the like. Examples of the leveling agent include “Modaflow” manufactured by Monsanto.

  The method of curing the curable resin composition of the present invention described in detail is that the curable resin composition is applied or molded to a substrate according to the purpose and application, and then irradiated with active energy rays or heated. The method of doing is mentioned.

Here, when it hardens | cures by irradiation of an active energy ray, an electron beam, an ultraviolet-ray, visible light etc. are mentioned as this active energy ray. When an electron beam is used as the active energy beam, a Cochloft Walton type accelerator, a bandegraph type electron accelerator, a resonant transformer type accelerator, an insulated core transformer type, a dynamitron type, a linear filament type, a high frequency type, etc. The curable resin composition of the present invention can be cured using a generator. When ultraviolet rays are used as the active energy ray, they can be cured by irradiation with a mercury lamp such as an ultra-high pressure mercury lamp, a high pressure mercury lamp or a low pressure mercury lamp, a xenon lamp, a carbon arc, a metal height lamp or the like. In this case, the exposure amount of ultraviolet rays is preferably in the range of 0.1 to 1000 mJ / cm ² .

  On the other hand, when cured by heating, it can be cured by heating to a temperature range of 60 to 250 ° C.

  Since the curable resin composition of the present invention described in detail above has performances such as high refractive index, high heat resistance, and high moisture resistance, plastic lenses such as spectacle lenses, digital camera lenses, Fresnel lenses, and prism lenses. It can be applied to various optical materials such as optical overcoat agent, hard coat agent, antireflection film, optical fiber, optical waveguide, hologram, prism lens, LED sealing material, solar cell coating material and the like.

  Among these, it can be preferably applied to a plastic lens because of its high refractive index in the cured product and excellent heat resistance and moisture resistance of the cured product, and is particularly useful as a prism lens for a liquid crystal substrate.

  Here, the prism lens for a liquid crystal substrate has a plurality of fine prism-shaped portions on one side of a sheet-like molded body, and usually has a prism surface on the back side (light source side) of the liquid crystal display element and on the element side. Further, the sheet-like lens is used so that the light guide sheet is arranged on the back surface thereof, or the prism lens is a sheet-like lens having a function of the light guide sheet.

  Here, the prism portion of the prism lens preferably has a prism apex angle θ in the range of 70 to 110 ° from the viewpoint of excellent light-collecting properties and improved luminance, particularly in the range of 75 to 100 °. In particular, the range of 80 to 95 ° is particularly preferable.

  The pitch of the prisms is preferably 100 μm or less, and particularly preferably in the range of 70 μm or less from the viewpoint of preventing the occurrence of moire patterns on the screen and further improving the definition of the screen. Further, the height of the unevenness of the prism is determined by the value of the prism apex angle θ and the prism pitch, but is preferably in the range of 50 μm or less. Further, the sheet thickness of the prism lens is preferably thick from the viewpoint of strength, but optically thin is preferable in order to suppress the absorption of light, and it is in the range of 50 μm to 1000 μm from the viewpoint of these balances. preferable.

  In order to produce the prism lens described above from the curable resin composition of the present invention, for example, the curable resin composition is applied to a molding die such as a mold or a resin die on which a prism pattern is formed, Examples include a method of smoothing the surface and volatilizing an organic solvent as necessary, and then overlaying a transparent substrate and irradiating and curing an active energy ray.

  Here, as long as the transparent base material is highly transparent, a material having a thickness of 3 mm or less is preferable in consideration of the transparency of the active energy ray, the handleability, and the like. Examples of the material for the transparent substrate include acrylic resins, polycarbonate resins, polyester resins, polystyrene resins, fluorine resins, polyimide resins, synthetic resins such as a mixture of these polymers, and glass.

  The prism sheet formed on the transparent base material thus obtained can be used as it is, but the transparent base material may be peeled off and used as a single prism portion. When using with the prism part formed on a transparent substrate, it is important from the viewpoint of weather resistance and durability that the interface is adequately bonded. It is preferable to perform the treatment.

  On the other hand, when the transparent substrate is used after being peeled off, it is preferable that the transparent substrate can be peeled relatively easily, and the surface of the transparent substrate is preferably subjected to a surface treatment with silicone or a fluorine-based release agent.

  In the following, embodiments of the present invention will be described in more detail with reference to synthesis examples, but the present invention is not limited thereto. In the examples, “part” and “%” are all based on mass unless otherwise specified. The melt viscosity and softening point measurement at 150 ° C., NMR, and MS spectrum were measured under the following conditions.

1) Viscosity: Measured at 25 ° C. using an E-type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.).
2) ¹³ C-NMR: NMR “GSX270” manufactured by JEOL Ltd.
3) FD-MS: double convergence mass spectrometer “AX505H (FD505H)” manufactured by JEOL Ltd.

Synthesis Example 1 (Synthesis of polymerizable compound (A))
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas while 143 g of 1,1′-bi-2-naphthol (1 equivalent of hydroxyl group) and 463 g of epichlorohydrin (5.0 g). Mol), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Subsequently, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin. The epoxy equivalent of the obtained epoxy resin was 225 g / eq, and the softening point was 60 ° C.

225 parts of the obtained epoxy resin and 72 parts of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1: 1) were reacted to obtain 297 parts of a resin. The resin had a structure represented by the structural formula (2-1) because a peak of M ⁺ = 543 and M ⁺ = 885 corresponding to the theoretical structure of n = 1 and n = 2 was obtained in the mass spectrum. It was confirmed that this was an epoxy acrylate resin of interest. This is abbreviated as a polymerizable compound (A1).

Synthesis example 2 (same as above)
While a nitrogen gas purge was applied to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 143 g of 1,1′-bi-2-naphthol (1 equivalent of hydroxyl group) and 185 g of epichlorohydrin (2.0 Mol), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Subsequently, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin. The epoxy equivalent of the obtained epoxy resin was 270 g / eq, and the softening point was 74 degreeC.

270 parts of the obtained epoxy resin and 72 parts of methallylic acid (the number of epoxy groups: the number of total carboxyl groups = 1: 1) were reacted to obtain 342 parts of a resin. The resin had a structure represented by the structural formula (2-2) because peaks of M ⁺ = 571 and M ⁺ = 913 corresponding to the theoretical structure of n = 1 and n = 2 were obtained in the mass spectrum. It was confirmed that this was an epoxy acrylate resin of interest. This is abbreviated as a polymerizable compound (A2).

Reference Example 1 [Production of dispersion of zirconia particles (B)]
Zirconium oxide powder (trade name: RC-100, manufactured by Daiichi Rare Element Chemical Co., Ltd., primary particle size 10 nm) 27 g, phosphate ester dispersant (trade name: Disper BYK106, manufactured by Big Chemie) 1.35 g Then, 270 g of toluene was mixed, and ultrasonic dispersion was applied for 10 minutes with stirring to coarsely disperse, thereby obtaining a mixed solution.

  The obtained liquid mixture was disperse | distributed with Kotobuki Industries Co., Ltd. ultra apex mill UAM-015. For dispersion, 400 g of stabilized zirconia beads having an average particle size of 0.03 mm (manufactured by high frequency thermal smelting) were used as media, the filling rate in the vessel volume of the beads mill was 64% by volume, and the rotor peripheral speed of the beads mill. Is 10 m / s, the circulation flow rate of the slurry supply pump is 10 L / hour, and β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane (trade name: KBM-303, Shin-Etsu Chemical) from 30 to 120 minutes immediately after the start of the dispersion treatment. 1.35 g (manufactured by Kogyo Co., Ltd.) was added to the raw slurry tank at a constant rate. Then, after 180 minutes from the start of the dispersion treatment, the dispersion treatment was terminated and the dispersion was recovered. The obtained dispersion was concentrated to obtain a dispersion of zirconia particles having a dry weight ratio at 150 ° C. of 50%. This is a dispersion of zirconia particles (B1). When this dispersion was diluted with toluene so that the content of zirconium oxide was 0.1%, the median diameter was measured using a particle size distribution analyzer LB-550 manufactured by Horiba, Ltd., 40 nm.

Reference example 2 (same as above)
Zirconium oxide powder (trade name: RC-100, manufactured by Daiichi Rare Element Chemical Co., Ltd., primary particle size 10 nm) 27 g, phosphate ester dispersant (trade name: Disper BYK106, manufactured by Big Chemie) 1.35 g Then, 270 g of toluene was mixed, and ultrasonic dispersion was applied for 10 minutes with stirring to coarsely disperse, thereby obtaining a mixed solution.

  The obtained liquid mixture was disperse | distributed with Kotobuki Industries Co., Ltd. ultra apex mill UAM-015. For dispersion, 400 g of stabilized zirconia beads having an average particle size of 0.03 mm (manufactured by high frequency thermal smelting) were used as media, the filling rate in the vessel volume of the beads mill was 64% by volume, and the rotor peripheral speed of the beads mill. Is 10 m / s, the circulation flow rate of the slurry supply pump is 10 L / hour, and β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane (trade name: KBM-303, Shin-Etsu Chemical) from 30 to 120 minutes immediately after the start of the dispersion treatment. 1.35 g (manufactured by Kogyo Co., Ltd.) was added to the raw slurry tank at a constant rate. Then, after 180 minutes from the start of the dispersion treatment, the dispersion treatment was terminated and the dispersion was recovered. 20 g of “Light Acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd. was added to 200 g of the obtained dispersion and concentrated under reduced pressure to obtain a dispersion of zirconia particles having a dry weight ratio at 150 ° C. of 50%. This is a dispersion of zirconia particles (B2). When this dispersion was diluted with toluene so that the content of zirconium oxide was 0.1%, the median diameter was measured using a particle size distribution analyzer LB-550 manufactured by Horiba, Ltd., 40 nm.

Examples 1-6 and Examples 8-9
A varnish-like composition was prepared according to the formulation shown in Table 1 below. Next, the composition was applied to a glass plate using a bar coater (No. 20), dried at 120 ° C. for 5 minutes, and then irradiated with a high pressure mercury lamp of 120 W / cm ^{2 in} an air atmosphere at an irradiation dose of 500 mJ / cm ² . And cured film was obtained. The cured film was evaluated for solvent resistance, heat resistance, and moisture resistance according to the following methods.

[Solvent resistance]
Using a cured coating film prepared on a glass plate, this film was rubbed 50 times with a cotton swab (manufactured by Johnson) containing methyl ethyl ketone, and the change of the coating film was visually observed. Evaluation was judged as follows.
Evaluation ○: No change ×: Change such as cloudiness or peeling

[Heat-resistant]
Using a cured coating film prepared on a glass plate, this film was placed in a dryer at 125 ° C. and held for 150 hours. The change of the coating film after holding was visually observed. Evaluation was judged as follows.
Evaluation ○: No change △: Change in hue only, no change in shape ×: Change in hue and shape

[Moisture resistance]
Using a cured coating film prepared on a glass plate, this film was placed in a constant temperature and humidity chamber at 85 ° C. and a humidity of 85% and held for 300 hours. The change of the coating film after holding was visually observed. Evaluation was judged as follows.
Evaluation ○: No change △: Change in hue only, no change in shape ×: Change in hue and shape

  Moreover, the cured film A and the board | substrate B with a cured film were manufactured by the following method using each composition, and the refractive index, transparency, and adhesiveness of cured | curing material were evaluated. Furthermore, the release property from a metal mold | die was evaluated by the following method using this composition. The results are shown in Table 1.

[Production of cured film A]
The composition prepared in accordance with the composition shown in Table 1 below is poured onto a chrome-plated metal plate so as to have a predetermined thickness, dried at 120 ° C. for 5 minutes, and then a transparent surface untreated PET film is bonded together with a pressure roll. After adjusting the thickness, UV light of 500 mJ / cm ² is irradiated from the transparent substrate side with a high-pressure mercury lamp to be cured, and the cured film (hereinafter referred to as “cured film A”) from the metal plate and the transparent substrate. ) Was taken out.

[Manufacture of substrate B with cured film]
The composition prepared in accordance with the composition shown in Table 1 below is poured onto a chrome-plated metal plate so as to have a predetermined thickness, dried at 120 ° C. for 5 minutes, and then a transparent surface adhesion-treated PET film is bonded together with a pressure roll. After adjusting the thickness, UV light of 500 mJ / cm ² is irradiated from the transparent base material side with a high-pressure mercury lamp to be cured, only the metal plate is peeled off, and a substrate with a cured film (hereinafter referred to as “substrate B with cured film B”). For short).

[Hardened material refractive index]
The cured film A was brought into close contact with the prism of an Abbe refractometer with 1-bromonaphthalene, and the refractive index (D-line of 589.3 mm) was measured at 25 ° C.

[transparency]
Using the cured film A, the light transmittance in a wavelength region of 400 to 900 nm was measured. A film having a transmittance of 85% or more in all regions was marked with ◯, and a light transmittance less than that was marked with ×.

[Adhesion]
Using the substrate B with a cured film, the adhesion between the base material and the cured film layer was measured in accordance with JIS K5400.

[Releasability]
Pour onto chrome-plated prism mold to a predetermined thickness, dry at 120 ° C for 5 minutes, paste a transparent surface adhesion PET film, adjust the thickness with a pressure roll, 500 mJ with a high-pressure mercury lamp After curing by irradiating with / cm 2 of ultraviolet rays from the transparent substrate side, when the mold was released from the mold, “O” indicates that the composition does not remain in the mold, and “X” indicates the remaining.

Example 7 and Comparative Examples 1-2
A varnish-like composition was prepared according to the formulation shown in Table 1 below. Next, the composition was applied to a glass plate using a bar coater (No. 20). Next, it irradiated with the irradiation amount of 500 mJ / cm < ² > using the 120 W / cm < ² > high pressure mercury lamp in air atmosphere, and obtained the cured coating film. Using this cured coating film, the solvent resistance, heat resistance, and moisture resistance were evaluated in the same manner as in Example 1.

  Moreover, the cured film A and the board | substrate B with a cured film were manufactured by the following method using each composition, and the refractive index, transparency, and adhesiveness of cured | curing material were evaluated similarly to Example 1. FIG. Further, the releasability from the mold was evaluated by the following method. The results are shown in Table 1.

[Production of cured film A]
The composition prepared according to the composition shown in Table 5 below was placed between a chrome-plated metal plate and a transparent untreated PET film, the thickness was adjusted, and UV light of 500 mJ / cm2 was applied to the transparent substrate side with a high-pressure mercury lamp. After being irradiated and cured, a cured film (hereinafter abbreviated as “cured film A”) was taken out from the metal plate and the transparent substrate.

[Manufacture of substrate B with cured film]
The composition prepared according to the composition shown in Table 5 below was placed between a chromium-plated metal plate and a transparent surface adhesion-treated PET film, the thickness was adjusted, and a UV light of 500 mJ / cm2 was applied to the transparent substrate with a high-pressure mercury lamp. After being irradiated and cured from the side, only the metal plate was peeled off to obtain a substrate with a cured film (hereinafter abbreviated as “substrate B with cured film”).

[Releasability]
The composition adjusted according to the composition shown in Table 5 below was placed between the chrome-plated prism mold and the transparent surface adhesion-treated PET film, the thickness was adjusted, and UV light of 500 mJ / cm ² was made transparent with a high-pressure mercury lamp. After being cured by irradiation from the material side, when the mold was released from the mold, the one in which the composition did not remain in the mold was marked with ◯, and the remaining one was marked with x.

Footnotes in Table 1 EA-0200: Structural formula below

で表されるフルオレン型アクリレート（大阪ガスケミカル社製「オグゾールＥＡ−０２００」）。
フェノキシエチルアクリレート」：共栄社化学（株）製「ライトアクリレートＰＯ−Ａ」
ＯＰＰＥＡ：ｏ−フェニルフェノールエチレンオキサイド変性アクリレート（東亞合成(株)製「アロニックスＴＯ−１４６３」。エチレンオキサイドの平均付加モル数１） 光開始剤：１−ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャルティ・ケミカルズ製「イルガキュアー１８４」）。

A fluorene-type acrylate represented by the formula (“Ogsol EA-0200” manufactured by Osaka Gas Chemical Company).
“Phenoxyethyl acrylate”: “Light acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd.
OPPEA: o-phenylphenol ethylene oxide modified acrylate (“Aronix TO-1463” manufactured by Toagosei Co., Ltd., average added mole number of ethylene oxide 1) Photoinitiator: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals) “Irgacure 184”).

  In Comparative Example 2, since the viscosity of the varnish exceeded the measurement upper limit of the viscometer, it could not be measured (measurement impossible). In addition, physical properties other than the releasability of the cured product evaluation are that the cured coating film cannot be peeled off from the glass plate or the chrome-plated metal plate during the production of the cured coating film, the cured film A and the substrate B with the cured film, Since a cured film was not obtained, evaluation was not possible.

Claims (10)

A curable resin comprising a polymerizable compound (A) having a binaphthalene skeleton and a radical polymerizable unsaturated bond, zirconia particles (B) having a primary particle size of 10 to 100 nm, and a radical polymerization initiator (C). Composition. A structure obtained by reacting the polymerizable compound (A) with an epoxy resin (a1) having a 1,1′-binaphthalene skeleton and a radically polymerizable unsaturated double bond-containing monocarboxylic acid (x1). The curable resin composition according to claim 1, which is a polymerizable compound (a2). The curable resin composition according to claim 2, wherein the epoxy resin having a 1,1'-binaphthalene skeleton is obtained by reacting 1,1'-bi-2-naphthol and epihalohydrin. The epoxy resin having the 1,1'-binaphthalene skeleton has an epoxy equivalent of 200 to 500 g / eq. The curable resin composition according to claim 2 or 3, wherein The curable resin composition according to claim 1, wherein the zirconia particles (B) are zirconia particles having a primary particle diameter of 10 to 50 nm. Furthermore, the curable resin composition of any one of Claims 1-5 containing a reactive diluent. The reactive diluent is represented by the following general formula (4)

(Wherein R ₁ and R ₂ are each a hydrogen atom or an alkyl group, X is a hydrogen atom or a hydroxyl group, and m and n are each 0 to 5). The curable resin composition according to claim 6, which is an acrylate monomer. The said polymerization initiator (C) is a photoinitiator, The curable resin composition as described in any one of Claims 1-6. Hardened | cured material formed by hardening | curing the curable resin composition of Claims 1-8 by active energy ray irradiation or a heating. A plastic lens obtained by molding and curing the curable resin composition according to claim 1.