JP2010060890A - Active energy ray-curable resin composition for optical article and cured product - Google Patents

Abstract

（式中、Ｒ₁はＨ又はＣＨ₃であり、ｎの平均値は１〜５の数である。）
【選択図】 なしPROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition for optical articles having excellent curability and mold reproducibility, and having a high refractive index of the obtained cured product and excellent environmental stability, and a cured product excellent in environmental stability. A monomer (A) having a polymerizable unsaturated double bond containing a compound represented by the following formula (1) and one polymerizable unsaturated double bond per molecule. A polymer having a structure obtained by polymerizing two monomers having a main skeleton, the weight average molecular weight of which is 2,000 to 100,000, and contains a polymerizable unsaturated double bond in the polymer structure A polymer (B) and a photopolymerization initiator (C), and the monomer (A) and the polymer (B) in a weight ratio [(A) / (B)] of 97 An active energy ray-curable resin composition for optical articles, which is contained in a range of / 3 to 55/45.
[Chemical 1]

(In the formula, R ₁ is H or CH ₃ , and the average value of n is a number of 1 to 5.)
[Selection figure] None

Description

  The present invention relates to an active energy ray-curable resin composition for optical articles used for cast polymerization applying a curing reaction by irradiation with active energy rays and a cured product thereof. More specifically, the present invention relates to an active energy ray-curable resin composition for optical articles used for the manufacture of an article provided with a resin layer made of a cured resin having a required shape on a support using a matrix and a cured product thereof. .

  The technology applying the curing reaction by active energy ray irradiation is widely applied to paints, resist materials, printing inks, adhesives and the like. In the past, applied technology with a film thickness of about several μm was common, but nowadays, the active energy ray curable resin composition can be applied without solvent and the curing reaction occurs instantaneously by irradiation. Taking advantage of the above, processing and coating techniques for creating a specific shape with a film thickness of several tens of μm or more are attracting attention, and stereolithography and light casting polymerization have been put to practical use. The stereolithography method is a method in which, for example, a liquid active energy ray curable resin composition is cured one by one with an ultraviolet laser or the like, and a cured layer is overlaid with a thickness of about 0.05 to 0.2 mm. The stereolithography method can produce an article having a free-form surface or a complicated structure, which has been difficult with the conventional cutting method, but has problems such as lack of smoothness of the obtained article and time-consuming production of the article.

  In contrast to such an optical modeling method, the light casting polymerization method is, for example, filling (batch injection) an active energy ray-curable resin composition into a mother mold with a fine shape, and interposing it in the mother mold. In this method, the resin composition is cured by ultraviolet rays or the like, and a master replica can be precisely produced in large quantities.

  The above-mentioned light casting polymerization method is an optical sheet with a shape having a fine and complex uneven surface shape made of a resin cured material on a plastic substrate (for example, a prism lens sheet or a Fresnel lens) as equipment becomes smaller and lighter. Sheet, etc.), lenses, prisms, and other plastic articles and optical articles. The active energy ray-curable resin composition used when producing plastic articles and optical articles by this light casting polymerization method is required to have excellent curability, and the cured product to be produced is subjected to high temperature and high humidity. Excellent environmental stability and mold reproducibility (the property that the fine shape copied from the mold is not chipped or deformed when the cured product is peeled off from the matrix). As an active energy ray-curable resin composition for optical articles, which has excellent curability and environmental stability and mold reproducibility of the resulting cured product, for example, an activity containing epoxy (meth) acrylate or urethane (meth) acrylate Many energy ray curable resin compositions have been reported. Specifically, for example, it contains a polymer component such as bisphenol A type epoxy (meth) acrylate, monofunctional (meth) acrylate, bifunctional (meth) acrylate, and an acrylic resin having a weight average molecular weight of 95,000. In addition, an ionizing radiation curable resin composition for Fresnel lenses having a refractive index after curing of 1.55 or more is known (for example, see Patent Document 1).

  However, in the ionizing radiation curable resin composition for Fresnel lens described in Patent Document 1, the polymer component is not bonded to a crosslinked structure caused by a curing reaction. Therefore, when there is much content of a polymer component, sclerosis | hardenability will worsen. In addition, the obtained cured product has problems such as gradually becoming turbid at high temperatures, and environmental stability is not sufficient.

  In addition, as a composition that can be used for stereolithography, for example, a polymer obtained by reaction of a (meth) acrylic polymer having a plurality of carboxyl groups in the molecule and a polymerizable unsaturated epoxy compound, and / or Or a polymer obtained by the reaction of a (meth) acrylic polymer having a plurality of epoxy groups in the molecule and a polymerizable unsaturated acid compound, and selected from the group consisting of Zn, Sn, and Zr A (meth) acrylic polymer having a polymerizable double bond and a polymerizable monomer obtained by using the compound containing at least one element as a catalyst for promoting the introduction of the polymerizable double bond A photosensitive resin composition comprising a (meth) acrylic syrup and a photopolymerization initiator is also disclosed (see, for example, Patent Document 2).

  However, even if the photosensitive composition used in the stereolithography described in Patent Document 2 is applied to the light casting polymerization method to obtain a cured product such as an optical article, the fine shape applied to the matrix Is difficult to reproduce on the surface of the cured product (the mold reproducibility is not good).

Japanese Patent Laid-Open No. 11-240926 JP 2000-159828 A

  An object of the present invention is to provide an active energy ray-curable resin composition for an optical article that is excellent in curability and mold reproducibility, has a high refractive index of the cured product, and is excellent in environmental stability, and environmental stability. The object is to provide an excellent cured product.

As a result of intensive investigations to solve the above problems, the present inventors have found the following findings.
(1) An active energy ray-curable resin composition having good curability and environmental stability of a cured product obtained by introducing a polymerizable unsaturated double bond into a polymer such as a (meth) acrylic polymer. Is obtained.

  (2) As a monomer having a polymerizable unsaturated double bond such as monofunctional (meth) acrylate or bifunctional (meth) acrylate, P-phenylphenol, O-phenylphenol and ethylene oxide or A cured product having a high refractive index can be obtained by using a monomer containing a compound having a polymerizable unsaturated double bond obtained by reacting a reaction product with propylene oxide and (meth) acrylic acid.

  (3) A monomer having a polymerizable unsaturated double bond and a polymer are in a weight ratio [polymer: monomer having a polymerizable unsaturated double bond] of 97/3 to 55/45. By containing it in such a range, an active energy ray-curable resin composition having excellent mold reproducibility is obtained.

  (4) Mold reproducibility is obtained by polymerizing a monomer having one polymerizable unsaturated double bond as the polymer used in (1), and has a weight average molecular weight of 2,000 to 100,000. It is further excellent by using a polymerizable unsaturated double bond-containing (meth) acrylic polymer.

  (5) The other polymerizable monomer used together with the (meth) acrylic polymer having the polymerizable double bond is not limited to bisphenol A type epoxy (meth) acrylate as in the cited reference 1. Any monomer having a polymerizable unsaturated double bond may be used. Therefore, the range of design is expanded.

(6) The active energy ray-curable resin composition is suitable for cast polymerization applications, and particularly suitable for cast polymerization applications used when manufacturing optical articles typified by optical sheets such as prism lens sheets. .
The present invention has been completed based on the above findings.

  That is, the present invention has a monomer (A) having a polymerizable unsaturated double bond containing a compound represented by the following formula (1) and one polymerizable unsaturated double bond per molecule. A polymer having a structure obtained by polymerizing monomers as a main skeleton, having a weight average molecular weight of 2,000 to 100,000, and further comprising a polymerizable unsaturated double in the polymer structure. A polymer (B) containing a bond and a photopolymerization initiator (C), and the monomer (A) and the polymer (B) are in a weight ratio [(A) / (B) In the present invention, an active energy ray-curable resin composition for optical articles is provided, which is contained in a range of 97/3 to 55/45.

（式中、Ｒ₁はＨ又はＣＨ₃であり、ｎの平均値は１〜５の数である。）

(In the formula, R ₁ is H or CH ₃ , and the average value of n is a number of 1 to 5.)

  The present invention also provides a cured product obtained by curing the active energy ray-curable resin composition for optical articles.

  The active energy ray-curable resin composition for optical articles of the present invention is excellent in curability and mold reproducibility. Moreover, the cured product of the active energy ray-curable resin composition for optical articles of the present invention is excellent in environmental stability and also has good adhesion to other plastic substrates. Therefore, the active energy ray-curable resin composition for an optical article of the present invention is suitable for producing an optical article having a fine surface shape such as a Fresnel lens, a prism lens lenticular lens, and an array lens.

  The monomer (A) having a polymerizable unsaturated double bond used in the present invention is a monomer having a polymerizable unsaturated double bond containing the compound represented by the above formula (1). As specific examples of the compound represented by the formula (1), for example, P-phenylphenol or a reaction product of O-phenylphenol and ethylene oxide or propylene oxide and (meth) acrylic acid are reacted. Can be obtained. A reaction product of P-phenylphenol or O-phenylphenol and ethylene oxide or propylene oxide can be easily obtained from the market. For example, Sanyo Chemical Co., Ltd. New Pole OPE-20 (1 mol of O-phenylphenol reacted with 2 mol of ethylene oxide) New Pole OPE-40 (O-phenyl) 1 mole of phenol and 4 moles of ethylene oxide reacted). The reaction of P-phenylphenol or O-phenylphenol with a reaction product of ethylene oxide or propylene oxide and (meth) acrylic acid is carried out by esterification of P-toluenesulfonic acid or sulfuric acid by a known method. The reaction is preferably performed in the presence of a catalyst and a polymerization inhibitor such as hydroquinone and phenothiazine, preferably in the presence of solvents (for example, toluene, benzene, cyclohexane, n-hexane, n-heptane, etc.) at a temperature of 70 to 150 ° C. Can be obtained. The proportion of (meth) acrylic acid used is 1 to 5 mol, preferably 1.05 to 1 mol of a reaction product of P-phenylphenol or O-phenylphenol and ethylene oxide or propylene oxide. 2 moles. The esterification catalyst is present in a concentration of 0.1 to 15 mol%, preferably 1 to 6 mol%, based on the (meth) acrylic acid used.

  The monomer (A) having a polymerizable unsaturated double bond used in the present invention contains 10 to 80% by weight of the compound represented by the above formula (1) based on the weight of the monomer (A). What contains is preferable, and what contains 20 to 60 weight% is more preferable.

  The monomer (A) used in the present invention can contain a monomer other than the compound represented by the above formula (1) within a range not impairing the effects of the present invention. Specifically, for example, a polymerizable monomer having an aromatic ring other than the compound represented by the above formula (1), a polymerizable monomer having a cyclic aliphatic structure, and a polymerizable monomer having a heterocyclic structure Body, a styrene compound, a polymerizable monomer having a linear aliphatic structure, and the like.

  Examples of the polymerizable monomer having an aromatic ring include (meth) acrylic acid esters having an aromatic ring. Examples of (meth) acrylic acid esters having an aromatic ring include benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate. 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-phenyl-2- (4-acryloyloxyphenyl) propane, 2-phenyl-2- (4-acryloyloxyalkoxyphenyl) propane, 2,4,6 -Trichlorophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6-trichlorobenzyl (meth) acrylate, 2,4,6-tribromobenzyl (meth) acrylate, 2 , 4,6-tric Borophenoxyethyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, o-phenylphenol (poly) ethoxy (meth) acrylate, p-phenylphenol (poly) ethoxy (meth) acrylate;

A monomer containing an alkylene oxide adduct structure of bisphenol A, specifically, for example, a bifunctional (meth) acrylate represented by the following general formula (2)

(式中、Ｒ１、Ｒ２はそれぞれ独立して水素原子又はメチル基を表す。ｍ１、ｍ２はそれぞれ繰り返し単位数を示す整数であり、ｍ１とｍ２との合計は平均値で１〜２０である。)；

(In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group. M1 and m2 are each an integer indicating the number of repeating units, and the sum of m1 and m2 is 1 to 20 on average. );

Ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of halogenated bisphenol F, propylene oxide adduct of halogenated bisphenol F, etc. (meth) acrylic acid ester to alkylene oxide adduct of bisphenol F A monomer having a bonded bisphenol F alkylene oxide adduct structure;

Ethylene oxide adduct of bisphenol S, propylene oxide adduct of bisphenol S, ethylene oxide adduct of halogenated bisphenol S, propylene oxide adduct of halogenated bisphenol S, etc. (meth) acrylic acid ester to alkylene oxide adduct of bisphenol S A monomer having an alkylene oxide adduct structure of bound bisphenol S;

2,2'-di (hydroxypropoxyphenyl) propane and their halides, 2,2'-di (hydroxyethoxyphenyl) propane and their halides with (meth) acrylic acid ester-linked;

Bis [4- (meth) acryloyloxyphenyl] -sulfide, bis [4- (meth) acryloyloxyethoxyphenyl] -sulfide, bis [4- (meth) acryloyloxypentaethoxyphenyl] -sulfide, bis [4- ( (Meth) acryloyloxyethoxy-3-phenylphenyl] -sulfide, bis [4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl] -sulfide, bis (4- (meth) acryloyloxyethoxyphenyl) sulfone;

Bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, partially halogen-substituted bisphenol A-type epoxy resin, partially halogen-substituted bisphenol F-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, and mixtures thereof Bisphenol type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate obtained by reaction of one or more epoxy resins selected from the group with (meth) acrylic acid , Epoxy (meth) acrylate of naphthalene skeleton or a mixture thereof;

Urethane (meth) acrylate obtained by reaction of polyol and organic polyisocyanate having a cyclic structure and hydroxyl group-containing (meth) acrylate, urethane obtained by reaction of diol having cyclic structure, organic polyisocyanate and hydroxyl group-containing (meth) acrylate ( Examples thereof include (meth) acrylate, urethane (meth) acrylate obtained by a reaction of an organic polyisocyanate having a cyclic structure and a hydroxyl group-containing (meth) acrylate.

  Examples of the polymerizable monomer having a cycloaliphatic structure include (meth) acrylic acid esters having a cycloaliphatic group. Examples of (meth) acrylic acid esters having a cycloaliphatic group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and tetrahydroflurane. Examples include furyl (meth) acrylate, glycidyl cyclocarbonate (meth) acrylate, and tricyclodecane dimethylol di (meth) acrylate.

  Examples of the styrene compound include styrene, α-methylstyrene, chlorostyrene, and the like.

  Examples of the heterocyclic compound include N-vinylpyrrolidone, N-vinylcaprolactone, acryloylformoline;

To compounds having a hydroxyl group such as tris (2-hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate, and a hydroxyl group-containing compound obtained by ring-opening addition of 1 to 20 moles of alkylene oxide or ε-caprolactone to (meth) Examples include compounds having an isocyanuric acid structure in which acrylic acid is ester-bonded.

  Examples of the polymerizable monomer having a linear aliphatic structure include (meth) acrylic acid esters having an alkyl group. Examples of (meth) acrylic acid esters having an alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate. , Heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms such as stearyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate; hydroxyethyl (meth) acrylate, (meta ) Hydroxypropyl acrylate, glycerol (meth) acrylate, lactone modification (Meth) acrylate, hydroxypropyl (meth) polyethylene glycol acrylate, acrylic acid esters having a (meth) hydroxyalkyl group, such as acrylic acid polypropylene glycol.

  The following polymerizable monomers can also be exemplified as the monomer (A) having a polymerizable unsaturated double bond used in the present invention. For example, glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3 , 4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β- Polymerizable unsaturated double bonds such as methyl glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4-epoxycyclohexyl, vinylcyclohexene oxide and epoxy groups A polymerizable monomer having:

(Meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid and ester bonds such as lactone modified products thereof An unsaturated monocarboxylic acid having a polymerizable monomer having a polymerizable unsaturated double bond and a carboxyl group such as maleic acid;

Unsaturated dicarboxylic esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;

Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene; diene compounds such as butadiene, isoprene, piperylene and dimethylbutadiene; vinyl halides and vinylidene halides such as vinyl chloride and vinyl bromide; methyl vinyl ketone Unsaturated vinyls such as butyl vinyl ketone; vinyl esters such as vinyl acetate and vinyl butyrate; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl cyanides such as acrylonitrile, methacrylonitrile and vinylidene cyanide; acrylamide and Its alkyd substituted amides; N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide;

Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyl trifluorovinyl ether, pentafluoroethyltri (Per) fluoroalkyl perfluorovinyl ethers having a (per) fluoroalkyl group such as fluorovinyl ether or heptafluoropropyl trifluorovinyl ether having 1 to 18 carbon atoms; 2,2,2-trifluoroethyl (meth) acrylate; 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-he Fluorine-containing ethylenic compounds such as (per) fluoroalkyl (meth) acrylates having a (per) fluoroalkyl group of 1 to 18 carbon atoms such as tadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Unsaturated monomers;

(16) Silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylamino N, N-dialkylaminoalkyl (meth) acrylates such as propyl (meth) acrylate;

Phosphoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate, di [(meth) acryloyloxy Ethyl] phosphate, tri [(meth) acryloyloxyethyl] phosphate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,

Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4 -Butylene glycol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (Meth) acrylate, di (meth) acrylate of a compound obtained by adding caprolactone to neopentyl glycol hydroxypivalate, neopentyl glycol adipate di (meth) acrylate,

(Meth) acrylic to compounds having 3 or more hydroxyl groups such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolmethane, and a hydroxyl group-containing compound in which 1 to 20 mol of alkylene oxide is added thereto. Examples include compounds in which three or more molecules of acid are ester-bonded.

  As the monomer (A) used in the present invention, (meth) acrylic acid esters having an aromatic ring are used because it becomes an active energy ray-curable resin composition for optical articles from which a cured product having excellent environmental stability is obtained. The monomer to contain is preferable.

  In addition, the monomer (A) used in the present invention has an alkylene oxide chain because it becomes an active energy ray-curable resin composition for optical articles from which a cured product having excellent shape restoration properties of the obtained cured product is obtained. Monomers are preferred.

  Furthermore, as the monomer (A) used in the present invention, a monomer having an aromatic ring and an alkylene oxide chain is preferable because the obtained cured product is excellent in environmental stability and excellent in shape restoration properties. A monomer containing an alkylene oxide adduct structure of bisphenol A is more preferable.

  Among monomers containing an alkylene oxide adduct structure of bisphenol A, a monomer containing a bifunctional (meth) acrylate represented by the general formula (2) is more preferable.

  Examples of the bifunctional (meth) acrylate represented by the general formula (2) include an average added mole number of ethylene oxide [average value of the total of m1 and m2 in the general formula (1)] of 1 to 20 The di (meth) acrylate of ethylene oxide-modified bisphenol A and the average added mole number of propylene oxide [average value of the sum of m1 and m2 in the general formula (1)] of 1 to 20 Dimeth of ethylene oxide / propylene oxide modified bisphenol A having an average added mole number of (meth) acrylate, ethylene oxide and propylene oxide [average value of sum of m1 and m2 in the general formula (1)] of 1 to 20 And (meth) acrylate.

  R1 in the bifunctional (meth) acrylate represented by the general formula (2) is preferably a hydrogen atom because it becomes an active energy ray-curable resin composition for optical articles from which a cured product having excellent shape restoring properties can be obtained. In addition, R1 in the bifunctional (meth) acrylate represented by the general formula (1) has a good adhesion and an active energy ray-curable resin composition for optical articles from which a cured product excellent in environmental stability is obtained. Therefore, a methyl group is preferable.

    R2 in the bifunctional (meth) acrylate represented by the general formula (2) is preferably a hydrogen atom because it becomes an active energy ray-curable resin composition for optical articles having good curability.

  Active energy ray curable type for optical articles in which a cured product having an excellent shape restoring property of 6 to 14 is obtained as the average value of the total of m1 and m2 in the bifunctional (meth) acrylate represented by the general formula (2). Since it becomes a resin composition, it is preferable.

  As a commercial item of the bifunctional (meth) acrylate represented by the general formula (2), for example, Aronix M-210, M-211B [above, manufactured by Toagosei Co., Ltd.], light acrylate BP-4EA, BP-4PA, light ester BP-2EM [above, manufactured by Kyoeisha Chemical Co., Ltd.], NK ester A-BPE-4, BPE-100, BPE-200, NK ester BPE-500 [above, Shin Nakamura Chemical Industrial Co., Ltd.], Kayarad R-55 [above, Nippon Kayaku Co., Ltd.], Beam Set 750 [Arakawa Chemical Industries, Ltd.], SR-348, SR-349, SR-601, SR- 602, SR-480 [above, manufactured by Kayaku Sartomer Co., Ltd.], New Frontier BPE-4, BPP-4, BPE-10, BPE-20, BPEM-10 [above, Daiichi Kogyo Seiyaku Co., Ltd. ) Made] Biscote # 700 [Osaka Organic Chemical Industry Co., Ltd.], Photomer 4028, Photomer 4025 (above, Cognis Co., Ltd.), Evecril 150, 1150, BPA (EO3) DMA (above, Daicel UCB Co., Ltd.), FANCLIL FA-321M (manufactured by Hitachi Chemical Co., Ltd.), BLEMMER ADBE-200, PDBE-200, ADBP series, PDBP series, ADBEP series, PDBEP series, PDBE-450, 43PDBPE-800B [Now, manufactured by Nippon Oil & Fats Co., Ltd.].

  Furthermore, in the present invention, as the monomer (A) having a polymerizable unsaturated double bond, the compound represented by the formula (1) is 10 to 80 weights based on the weight of the monomer (A). The active energy ray for optical articles according to claim 1, further comprising 5 to 50% by weight of bifunctional (meth) acrylate represented by the formula (2) based on the weight of the monomer (A). A curable resin composition is preferred.

  Moreover, there exists an effect of improving the brittleness of hardened | cured material by using as a monomer (A) using the (meth) acrylic acid ester compound of the aliphatic polyhydric alcohol which has an alkylene oxide structure and has two or more hydroxyl groups. . Examples of (meth) acrylic acid ester compounds of aliphatic polyhydric alcohols having an alkylene oxide structure and two or more hydroxyl groups include, for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Polyethylene glycol di (meth) acrylates such as di (meth) acrylate and heptaethylene glycol di (meth) acrylate; dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate , Di (meth) acrylates of polypropylene glycol such as heptapropylene glycol di (meth) acrylate;

(Meth) acrylic acid is added to a compound having 3 or more hydroxyl groups such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and a hydroxyl group-containing compound obtained by adding 1 to 20 mol of alkylene oxide to tetramethylolmethane. Examples thereof include compounds having an ester bond over a molecule.

  The polymer (B) used in the present invention is a polymer having a main skeleton having a structure obtained by polymerizing a monomer having one polymerizable unsaturated double bond per molecule, and its weight average molecular weight. Is from 2,000 to 100,000, and further contains a polymerizable unsaturated double bond in the polymer structure (side chain). Only when such a polymer is used, becomes an active energy ray-curable resin composition for cast polymerization which is excellent in curability, and the resulting cured product also has good environmental stability. In addition, there is an advantage that workability such as not involving air bubbles when the active energy ray-curable resin composition for casting polymerization of the present invention is poured into a matrix is good. As a weight average molecular weight of the polymer (B) used by this invention, 3,000-50,000 are preferable, 3000-30000 are more preferable, 3000-20000 are still more preferable, 3000-10000 are especially preferable. The weight average molecular weight of the polymer (B) is appropriately selected within the range of 2,000 to 100,000 depending on the thickness of the cured layer having a fine shape to be formed and the purpose and conditions of forming the cured layer having a fine shape. be able to.

  As the polymer (B) used in the present invention, for example, a (meth) acrylic polymer can be preferably used. Examples of the (meth) acrylic polymer include the following (meth) acrylic polymers.

  Polymer (B1): a polymer obtained by reacting a (meth) acrylic polymer (b1) having an epoxy group with a monomer (d) having an unsaturated double bond and a carboxyl group.

  Polymer (B2): A polymer obtained by reacting a (meth) acrylic polymer (b2) having a carboxyl group with a monomer (e) having an unsaturated double bond and an epoxy group.

  The (meth) acrylic polymer used in the present invention is a polymer obtained by reacting a (meth) acrylic polymer having an epoxy group with a monomer having an unsaturated double bond and a carboxyl group. The containing (meth) acrylic polymer is preferable.

  The (meth) acrylic polymer (b1) used for the preparation of the polymer (B1) is, for example, a polymerizable monomer having an unsaturated double bond and an epoxy group, and another polymerizable monomer as required. Obtained by copolymerization reaction with the body.

  Examples of the polymerizable monomer having an unsaturated double bond and an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, and glycidyl α-n-propyl (meth) acrylate. , Glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxy Pentyl, α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3, 4-epoxycyclohexyl, vinylcyclohexene oxide and the like can be mentioned. These may be used alone or in combination of two or more.

  The (meth) acrylic polymer (b2) used for the preparation of the polymer (B2) is, for example, a polymerizable monomer having an unsaturated double bond and a carboxyl group and, if necessary, other polymerizable monomers. Obtained by copolymerization reaction with the body.

  Examples of the polymerizable monomer having an unsaturated double bond and a carboxyl group include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid. Examples include 2-acryloyloxyethyl hexahydrophthalic acid and unsaturated monocarboxylic acids having an ester bond such as modified lactones thereof; maleic acid and the like. These may be used alone or in combination of two or more.

  Examples of other polymerizable unsaturated monomers that are copolymerized as necessary when preparing the (meth) acrylic polymer (b1) or the (meth) acrylic polymer (b2) include the following polymerizable monomers: Examples include a polymer.

  (1) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, hepsyl (meth) acrylate, (meth) acrylic acid Octyl, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms, such as docosyl (meth) acrylate;

(2) (meth) having an alicyclic alkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acrylic esters;

(3) Benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters having an aromatic ring such as hydroxy-3-phenoxypropyl;

(4) Hydroxyethyl (meth) acrylate; hydroxypropyl (meth) acrylate, glycerol (meth) acrylate; lactone-modified hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene (meth) acrylate Acrylic acid esters having a hydroxyalkyl group such as (meth) acrylic acid ester having a polyalkylene glycol group such as glycol;

(5) Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;

(6) Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene;

(7) Diene compounds such as butadiene, isoprene, piperylene, dimethylbutadiene;

(8) Vinyl halides and vinylidene halides such as vinyl chloride and vinyl bromide;

(9) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;

(10) Vinyl esters such as vinyl acetate and vinyl butyrate;

(11) Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;

(12) Vinyl cyanides such as acrylonitrile, methacrylonitrile, vinylidene cyanide;

(13) Acrylamide and its alkyd-substituted amides;

(14) N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

(15) Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyltrifluorovinyl ether, penta (Per) fluoroalkyl perfluorovinyl ethers having a (per) fluoroalkyl group of 1 to 18 carbon atoms such as fluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; 2,2,2-trifluoroethyl (meta ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, Fluorine-containing such as (per) fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in the (per) fluoroalkyl group such as H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Ethylenically unsaturated monomers;

(16) Silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane;

(17) N, N-dialkylaminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate Is mentioned.

  Other polymerizable unsaturated monomers used when preparing these (meth) acrylic polymers (b1) and (meth) acrylic polymers (b2) may be used alone or in combination of two kinds. You may use the above together.

  The (meth) acrylic polymers (b1) and (b2) can be obtained by polymerization (copolymerization) using a known and commonly used method, and the copolymerization form is not particularly limited. It can be produced by addition polymerization in the presence of a catalyst (polymerization initiator), and any of a random copolymer, a block copolymer, a graft copolymer and the like may be used. As the copolymerization method, a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method can be used.

  Here, as typical solvents that can be used for solution polymerization, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl- ketone solvents such as n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holon;

Ether solvents such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran;

Ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl Examples include ether solvents such as ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and ethyl-3-ethoxypropionate.

  As the catalyst, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), Azo compounds such as 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) ) Organic peroxides such as cyclohexane, t-amylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, and hydrogen peroxide.

  When using a peroxide as a catalyst, it is good also as a redox type initiator using a peroxide with a reducing agent.

  The polymer (B1) which is an example of the (meth) acrylic polymer is, as described above, the (meth) acrylic polymer (b1) having an epoxy group and the monomer having an unsaturated double bond and a carboxyl group ( react with d). Examples of the monomer (d) having an unsaturated double bond and a carboxyl group include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalate. Examples include acids, 2-acryloyloxyethyl hexahydrophthalic acid, and unsaturated monocarboxylic acids having an ester bond such as lactone-modified products thereof; maleic acid and the like. These may be used alone or in combination of two or more.

  The polymer (B2) which is an example of the (meth) acrylic polymer is, as described above, a (meth) acrylic polymer (b2) having a carboxyl group and a monomer having an unsaturated double bond and an epoxy group ( obtained by reacting with e). Examples of the monomer (e) having an unsaturated double bond and an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, α-n-butyl (meth) acrylate glycidyl, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl , Α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4 -Epoxycyclohexyl, vinylcyclohexene oxide and the like. These may be used alone or in combination of two or more.

  Reaction of the (meth) acrylic polymer (b1) having an epoxy group with a monomer (d) having an unsaturated double bond and a carboxyl group, or a (meth) acrylic polymer having a carboxyl group (b2) ) And the monomer (e) having an unsaturated double bond and an epoxy group can be carried out, for example, by the method described in Patent Document 2. The following method can also be used.

  Method 1: The (meth) acrylic polymer (b1) was obtained by polymerizing by a solution polymerization method and then once removed, and the monomer (d) having an unsaturated double bond and a carboxyl group was added to the reaction system. In addition to react.

  Method 2: (meth) acrylic polymer (b2) obtained by polymerizing by a solution polymerization method and then once solvent-removed, and a monomer (e) having an unsaturated double bond and an epoxy group is added and reacted. How to make.

  When the (meth) acrylic polymer is produced in the method 1 or 2, the (b1) or (b2) is redissolved in the compound corresponding to the monomer (A), and the unsaturated double bond and What is obtained by reacting with the monomer (d) having a carboxyl group and the monomer (e) having an unsaturated double bond and an epoxy group is a mixture of the polymer (B) and the monomer (A). Become a solution. By obtaining such a mixed solution, the manufacturing process of the active energy ray-curable resin composition for optical articles of the present invention can be simplified. In this case as well, the ring-opening addition reaction as described in Patent Document 2 can be carried out using a catalyst, and if necessary, in the presence of a polymerization inhibitor, for example, at a reaction temperature of 60 to 150 ° C.

  The polymer (B) used in the present invention is a polymer having a main skeleton having a structure obtained by polymerizing a monomer having one polymerizable unsaturated double bond per molecule. You may use together the monomer which has two or more polymerizable unsaturated double bonds in the range which does not impair an effect.

In the present invention, the weight average molecular weight was measured using a gel permeation chromatograph (GPC) under the following conditions.
Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H _XL- H manufactured by Tosoh Corporation
+ Tosoh Corporation TSKgel G5000H _XL
+ Tosoh Corporation TSKgel G4000H _XL
+ Manufactured by Tosoh Corporation TSKgel G3000H _XL
+ Tosoh Corporation TSKgel G2000H _XL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 1.0 ml / min Standard; polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

  The double bond equivalent of the polymer (B) used in the present invention, that is, the molecular weight per unsaturated double bond is preferably in the range of 200 to 10,000 because excellent curability can be expressed, More preferably, it is in the range of 200 to 6,000, more preferably in the range of 300 to 2000, and particularly preferably in the range of 400 to 1000.

  The active energy ray-curable resin composition for optical articles of the present invention comprises a monomer (A) and a polymer (B) in a weight ratio [(A) / (B)] of 97/3 to 55/45. It contains in the range which becomes. By blending the monomer (A) and the (meth) acrylic polymer (B) at such a weight ratio, an active energy ray-curable resin composition for optical articles excellent in mold reproducibility can be obtained for the first time. . In addition, workability when performing cast polymerization is improved. The active energy ray-curable resin composition for optical articles of the present invention comprises a monomer (A) and a polymer (B) in a weight ratio [(A) / (B)] of 97/3 to 60 / The composition contained in the range of 40 is more preferred, and the composition contained in the range of 90/10 to 70/30 is more preferred.

  Examples of the photopolymerization initiator (C) used in the present invention include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4 Benzophenones such as 4,4'-dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Xanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; thioxanthones; acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;

Α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl -1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- -Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, Benzyldimethylketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl- 4-dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine 2,4-bis-trichloromethyl-6- (4-eth C) Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazine anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloro Anthraquinone etc. are mentioned.

  The said photoinitiator (C) can also be used individually or in combination of 2 or more types. The amount used is not particularly limited, but in order to maintain good sensitivity and prevent precipitation of crystals, physical properties of the coating film, etc., to 100 parts by weight of the active energy ray-curable resin composition for optical articles of the present invention. 0.05 to 20 parts by weight is preferably used, and 0.1 to 10 parts by weight is particularly preferable.

  Examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one selected from the group of one or more types , Particularly preferred since high curability optical article for radiation-curable resin composition.

  Examples of the commercially available photopolymerization initiator (C) include Irgacure-184, 149, 261, 369, 500, 651, 754, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2850, 2959, 4043, Darocur-1173 (manufactured by Ciba Specialty Chemicals), Lucirin TPO (manufactured by BASF), KAYACURE-DETX, MBP, DMBI, EPA OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFER Co. LTD), TRIGONALP1 (manufactured by AKZO Co. LTD), SANDORY 1000 (manufactured by SANDOZ Co. LTD), DEAP (APJOHN Co .LTD), QUANTACURE-PD O, ITX, EPD (manufactured by WARD BLEKINSOP Co. LTD), and the like.

  Furthermore, in the active energy ray-curable resin composition for optical articles of the present invention, various photosensitizers can be used in combination with the photopolymerization initiator (C). Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

  In the manufacture of an article using the active energy ray-curable resin composition for optical articles of the present invention, active energy rays such as ultraviolet rays are often irradiated through the transparent substrate surface serving as a support. Therefore, the photopolymerization initiator is preferably an initiator having a light-absorbing ability in the long wavelength region, and for example, a photopolymerization initiator that exhibits the photoinitiating ability in the range of 360 to 450 nm is preferable.

  The active energy ray-curable resin composition for optical articles of the present invention is used in combination with a resin (G) other than the (meth) acrylic polymer (B) for the purpose of improving viscosity and adhesion to a transparent substrate. be able to.

  Examples of the other resin (G) include acrylic resins such as methyl methacrylate resin and methyl methacrylate copolymer; polystyrene, methyl methacrylate-styrene copolymer; polyester resin; polyurethane resin; polybutadiene and butadiene-acrylonitrile series. Examples thereof include polybutadiene resins such as copolymers; epoxy resins such as bisphenol type epoxy resins, phenoxy resins and novolac type epoxy resins.

  The viscosity of the active energy ray-curable resin composition for optical articles of the present invention is 25 ° C. so that the matrix can be uniformly applied to the matrix and the matrix having a fine structure can be replicated. It is preferably in the range of 100 to 30000 mPa · s, and particularly preferably 150 to 20000 mPa · s. Even if the viscosity is outside the above range, it can be used by adjusting the viscosity by controlling the temperature of the resin composition.

  The acid value of the active energy ray-curable resin composition for optical articles of the present invention (the number of milligrams of potassium hydroxide required to neutralize the acid content present in 1 g of the sample based on the prescribed method) is 5 0.0 mg KOH / g or less is preferable because it becomes an active energy ray-curable resin composition for optical articles from which a cured product excellent in environmental stability is obtained, and 0 mg KOH / g to 3.0 mg KOH / g is particularly preferable.

  The active energy ray-curable resin composition for an optical article of the present invention is added with an ultraviolet absorber as required, for example, when further light resistance is required for the cured resin molding layer formed on the substrate. be able to. In addition, when improving coating properties, coating suitability and mold release properties, antioxidants, silicon additives, fluorine additives, rheology control agents, defoamers, mold release agents It is also possible to add silane coupling agents, antistatic agents, antifogging agents, colorants and the like.

  Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Triazine derivatives such as 2,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like.

  Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants.

  Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl. Examples thereof include polyorganosiloxanes having an alkyl group and a phenyl group, such as a polysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer.

  The amount of the various additives as described above is sufficient to exert the effect and does not inhibit the ultraviolet curing, so that 100 parts by weight of the active energy ray-curable resin composition for optical articles, Each is preferably in the range of 0.01 to 10 parts by weight.

  The active energy ray-curable resin composition for optical articles of the present invention may contain a solvent as necessary, but the active energy ray-curable type for optical articles is less likely to contaminate the working environment if the solvent content is lower. It is preferable because a resin composition is obtained. Specifically, the solvent content in the active energy ray-curable resin composition for optical articles of the present invention is preferably 1% by weight or less.

  The active energy ray-curable resin composition for optical articles of the present invention is a material suitable for various articles having a structure in which a molded resin layer made of a cured resin on a film-like, sheet-like or plate-like transparent substrate is provided. is there. Especially, when using for manufacture of articles | goods which require transparency, such as a lens, in the hardened | cured material of thickness 200 +/- 25micrometer, the light transmittance of the wavelength range of 400-900 nm is 80% or more, Preferably it is 85% or more. It is preferable to use each resin composition component in combination.

  The cured product of the present invention is obtained by curing the active energy ray-curable resin composition for optical articles of the present invention. The cured product has a hardness that does not deform when the pressure applied to the resin-cured layer with a fine shape is small, and is not too rigid even if deformation occurs when a strong pressure is applied temporarily. The elastic modulus at 25 ° C. is preferably 1500 MPa or less, more preferably 50 to 1000 MPa, in order to obtain a hardness that can be restored to the shape under use conditions.

  As a method for producing the cured product of the present invention, the active energy ray-curable resin composition for optical articles of the present invention is filled on a matrix having a required fine shape, and then the filled resin composition. A plastic substrate is pressed and laminated so that air does not enter the object, and the resin composition is cured by irradiating active energy rays such as ultraviolet rays from the plastic substrate side, and then separated from the matrix. For example, a molding method. Further, for example, after the resin composition is continuously filled in a roll-shaped matrix, the plastic substrate is continuously adhered onto the filled resin composition so that air is not mixed, and the plastic substrate side And a continuous production method in which the resin composition is cured by irradiating active energy rays such as ultraviolet rays and then released from a roll-shaped matrix.

  Examples of the film-like, sheet-like, and plate-like transparent substrates that can be used for this include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), triacetyl cellulose, polycarbonate resin, and methyl methacrylate. Examples thereof include acrylic resins such as copolymers, styrene resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, vinyl chloride resins, and polymethacrylimide resins. Moreover, although it is not a plastic base material, inorganic base materials, such as a glass base material, can also be used similarly.

  The active energy ray for curing the active energy ray-curable resin composition for optical articles of the present invention means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, for example, visible light. , Ultraviolet rays, electromagnetic waves such as X-rays, or charged particle beams such as electron beams. Of these, visible light and ultraviolet light are frequently used in practice. In the case of ultraviolet rays, a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a black light lamp, or a metal halide lamp can be used.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. All parts and percentages in the examples are by weight unless otherwise specified.

Synthesis Example 1 [Synthesis of Compound Represented by Formula (1)]
258 g of the compound represented by formula (3)

(Sanyo Chemical Co., Ltd., reaction product of 1 mol of O-phenylphenol and 2 mol of ethylene oxide, product name, new-pole OPE-20, OH value 217.5), 86.5 g of acrylic acid, toluene 300 g, 21 g of sulfuric acid and 5 g of hydroquinone were charged, heated, and the produced water was distilled together with the solvent, condensed, and cooled to produce 18 parts of water in a separator, and the reaction mixture was cooled. The reaction temperature was 130-140 ° C. The reaction mixture was dissolved in 500 parts of toluene, neutralized with a 20% aqueous NaOH solution, and then washed 3 times with 100 g of a 20% aqueous NaCl solution. The solvent was distilled off under reduced pressure to obtain 303 g of Compound (B) (Liquid). The viscosity (25 ° C.) was 204 CPS, and the refractive index (23 ° C.) was 1.567. This is abbreviated as OPPEA.

Synthesis Example 2 [Synthesis of monomer having unsaturated double bond and cyclic structure]
A flask equipped with a thermometer, a stirrer, and a condenser was charged with 300 g of phenoxyethyl acrylate, 214 g of xylylene diisocyanate and 0.2 g of dibutyltin diacetate, and the temperature was raised to 70 ° C. while stirring. 417 g of bisphenol A ethylene oxide adduct (OH value = 230 KOH-mg / g) was added and reacted for 1 hour while paying attention to heat generation. The reaction was carried out for 5 hours, after which 69 g of hydroxyethyl acrylate was added, and the reaction was further carried out for 5 hours. It was confirmed that the absorption of the isocyanate group disappeared by an infrared absorption spectrum, and a phenoxyethyl acrylate solution of urethane acrylate (A-1), which is a monomer having an unsaturated double bond and a cyclic structure, was obtained. The weight average molecular weight of urethane acrylate (A-1) by gel permeation chromatography (GPC) was 2200. The content of urethane acrylate (A-1) in the phenoxyethyl acrylate solution was 70%.

Synthesis Example 3 [Synthesis of (meth) acrylic polymer (B)]
Into a four flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas inlet, 150 g of xylene was charged and heated to 130 ° C. with stirring in a nitrogen atmosphere, and then 30 g of methyl methacrylate and ethyl acrylate A mixed solution of 63 g, 7 g of glycidyl methacrylate and 5 g of t-butylperoxy-2-ethylhexanoate was added dropwise over 6 hours. After the completion of dropping, the mixture was kept at 130 ° C. for 2 hours, 0.5 g of t-butylperoxy-2-ethylhexanoate was added, and the mixture was further reacted at the same temperature for 4 hours. Next, the obtained resin solution was gradually heated under reduced pressure to raise the temperature, and xylene was distilled off under reduced pressure. Next, the atmosphere was changed to an atmosphere with an oxygen concentration of 7% (nitrogen: air = 2: 1 mixture), and 44 g of phenoxyethyl acrylate was added to obtain a homogeneous solution. 3 g and 0.02 g of hydroquinone monomethyl ether were added, heated to 120 ° C. and reacted for 5 hours, and a phenoxyethyl acrylate solution of a (meth) acrylic polymer (B-1) having an unsaturated double bond in the molecule Got. The weight average molecular weight by gel permeation chromatography (GPC) of the (meth) acrylic polymer (B-1) was 7200. The content of the (meth) acrylic polymer (B-1) in the phenoxyethyl acrylate solution was 70%. The unsaturated double bond equivalent in the (meth) acrylic polymer (B-1) was 2100. The xylene content in the phenoxyethyl acrylate solution was measured by gas chromatography, and the xylene content was 1% by weight or less.

Synthesis example 4 (same as above)
A four flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet was charged with 150 g of xylene, heated to 130 ° C. with stirring in a nitrogen atmosphere, and then 60 g of methyl methacrylate and n methacrylate. -A mixed solution of 10 g of butyl, 30 g of glycidyl methacrylate and 5 g of t-butylperoxy-2-ethylhexanoate was added dropwise over 6 hours. After the completion of dropping, the mixture was kept at 130 ° C. for 2 hours, 0.5 g of t-butylperoxy-2-ethylhexanoate was added, and the mixture was further reacted at the same temperature for 4 hours. Next, the obtained resin solution was gradually heated under reduced pressure to raise the temperature, and xylene was distilled off under reduced pressure. Next, the atmosphere was changed to an atmosphere having an oxygen concentration of 7% (nitrogen: air = 2: 1 mixture), and 50 g of tripropylene glycol diacrylate was added to obtain a uniform solution. 3 g and 0.02 g of hydroquinone monomethyl ether were added, the temperature was raised to 120 ° C., the reaction was carried out for 5 hours, and the tripropylene glycol di (meth) acrylic polymer (B-2) having an unsaturated double bond in the molecule. An acrylate solution was obtained. The weight average molecular weight by GPC of the (meth) acrylic polymer (B-2) was 6500. The content of the (meth) acrylic polymer (B-2) in the tripropylene glycol diacrylate solution was 70%. The unsaturated double bond equivalent in the (meth) acrylic polymer (B-2) was 520. When the xylene content in the tripropylene glycol diacrylate solution was measured in the same manner as in Synthesis Example 2, the xylene content was 1% by weight or less.

Synthesis example 5 (same as above)
A four flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet was charged with 150 g of xylene, heated to 130 ° C. with stirring in a nitrogen atmosphere, and then 60 g of methyl methacrylate and n methacrylate. A mixed solution of 25 g of butyl, 15 g of methacrylic acid and 5 g of t-butylperoxy-2-ethylhexanoate was added dropwise over 6 hours. After the completion of the dropwise addition, the mixture was kept at 130 ° C. for 2 hours, 0.5 g of t-butylperoxy-2-ethylhexanoate was added, and the mixture was further reacted at the same temperature for 4 hours. Next, xylene was distilled off under reduced pressure while gradually heating the obtained resin solution under reduced pressure. Next, the atmosphere was changed to an atmosphere with an oxygen concentration of 7% (nitrogen: air = 2: 1 mixture), and after adding 53 g of tripropylene glycol diacrylate to obtain a uniform solution, 24 g of glycidyl methacrylate, triphenylphosphine 0 .3 g and 0.02 g of hydroquinone monomethyl ether, heated to 120 ° C. and reacted for 5 hours, tripropylene glycol of (meth) acrylic polymer (B-3) having an unsaturated double bond in the molecule A diacrylate solution was obtained. The weight average molecular weight by GPC of the (meth) acrylic polymer (B-3) was 11500. The content of the (meth) acrylic polymer (B-3) in the tripropylene glycol diacrylate solution was 70%. Moreover, the unsaturated double bond equivalent in the (meth) acrylic polymer (B-3) was 730. When the xylene content in the tripropylene glycol diacrylate solution was measured in the same manner as in Synthesis Example 2, the xylene content was 1% by weight or less.

Example 1
An active energy ray-curable resin composition 1 for optical articles was prepared according to the formulation shown in Table 1. While measuring the viscosity of the obtained active energy ray-curable resin composition 1 for optical articles, using the composition 1, a cured product with shape (L), a cured resin film (F), and a smooth cured product (S). Manufactured. Evaluation concerning each article was performed as follows. The results are shown in Table 3.

  About the hardened | cured material (L) with a shape, the cast workability | operativity at the time of manufacture was evaluated, the mold reproducibility of the obtained hardened | cured material, and the refractive index of hardened | cured material were evaluated.

  The cured resin film (F) was evaluated for transparency and environmental stability.

  About smooth hardened | cured material (S), shape recovery property and light resistance were evaluated.

  A method for measuring the viscosity of the composition 1, a method for producing a cured product with shape (L), a cured resin film (F), a smooth cured product (S), and an evaluation method for each article are shown below.

(1) A method for measuring the viscosity of the active energy ray-curable resin composition 1 for optical articles.
Using an E-type rotational viscometer, the viscosity at 25 ° C. (mPa · s) was measured.

(2-1) A method for producing a shaped cured product (L).
The viscosity of the resin composition was adjusted to 5000 mPa · s or less by heating as necessary. A composite metal matrix obtained by superimposing a chrome-plated metal matrix having a chevron shape with a width of 120 μm and a height of 100 μm and a transparent substrate (a transparent and easy-adhesive treated PET film) on the composition after adjustment. After filling (casting) the gap between the transparent substrate and the transparent substrate, UV light of 800 mJ / cm 2 is irradiated from the PET film side with an ultra-high pressure mercury lamp, and then cured. It peeled from the type | mold and produced the hardened | cured material (L) with the shape by which the shape of the metal mother die was transcribe | transferred.

(2-2) Casting workability evaluation method.
Filling the active energy ray-curable resin composition with good resin rollability into the matrix when the resin composition is placed between the metal matrix and the PET film during the preparation of the shaped cured product (L) Evaluation was made as ◎ with good workability, and x with poor resin workability to the matrix and poor filling workability.

(2-3) Evaluation method of mold reproducibility.
The appearance of the shaped cured product (L) after peeling from the metal matrix was visually observed and evaluated according to the following criteria.
A: A uniform surface shape was obtained.
X: The resin did not reach the metal matrix details, or cracks / chips or missing shapes were observed.

(2-4) Measuring method of refractive index.
The refractive index of the cured resin was measured using a prism coupler refractometer model 2010 manufactured by METRICON.

(3-1) A method for producing a cured resin film (F).
The viscosity of the resin composition was adjusted to 5000 mPa · s or less by heating as necessary. The prepared composition is applied onto a glass plate with an applicator, cured by irradiating with 800 mJ / cm 2 of ultraviolet light with an ultra-high pressure mercury lamp in a nitrogen atmosphere, and then the active energy ray curable resin layer is peeled off from the glass plate. A cured resin film (F) having a smooth surface with a thickness of 160 ± 25 μm was produced.

(3-2) Method for evaluating transparency The light transmittance in the wavelength region of 400 to 900 nm is measured by a spectrophotometer, and the one showing a transmittance of 85% or more in all regions is marked with ◎, and the transmittance is less than that Was marked with x.

(3-3) Environmental stability evaluation method (environmental stability 1)
The cured resin film (F) was left in an environment of a temperature of 85 ° C. and a relative humidity of 95% for 240 hours. Subsequently, the haze value was measured using a direct reading haze computer [HGM-2DP manufactured by Suga Test Instruments Co., Ltd.].

(3-4) Environmental stability evaluation method (environmental stability 2)
The cured resin film (F) was left in an environment at a temperature of 120 ° C. for 240 hours. Next, using a Nippon Denshoku color difference meter (ZE2000), the degree of yellowing (ΔYI) before and after heating is calculated from the XYZ values, and the numerical value indicating the difference is less than 3 when ◎, 3-7 Was marked with ◯, and the case of 7 or more was marked with ×.

(4-1) A method for producing a smooth cured product (S).
After filling (casting) the active energy ray-curable resin composition 1 for an optical article into the gap between the acrylic resin plate and the chrome-plated metal plate, UV light of 800 mJ / cm2 is applied to the acrylic resin plate side by an ultra-high pressure mercury lamp. And cured by irradiation. The acrylic resin plate was peeled from the metal plate together with the cured active energy ray curable resin layer, and a smooth cured product (S) having a cured resin layer having a smooth surface of 200 ± 25 μm in thickness on a plastic substrate was produced.

(4-2) Shape Restorability Evaluation Method Applying a universal hardness test using an ultra-micro hardness meter (manufactured by Fisher Instruments Co., Ltd., H-100), the following (i) to (v) The shape restoration property was evaluated according to the procedure. As the indenter, a ball indenter made of tungsten carbide having a radius R of 0.2 mmφ was used.
(I) At 40 ° C., the load is increased in 10 seconds until the penetration depth (= deformation amount) becomes 15 to 20 μm.
(Ii) This compressive load value is maintained for 60 seconds.
(Iii) Reduce to load value 0.4 mN (= test machine minimum load) in 4 seconds.
(Iv) Maintain the load value of 0.4 mN for 60 seconds to recover the penetration depth.
(V) The above (i) to (iv) are repeated three times to obtain the average value of the restoration rate.
The case where the average depth of penetration that was recovered was less than 3 μm was evaluated as ◎: the case where it was 3 μm or more and less than 5 μm, Δ if it was 5 μm or more and less than 8 μm, and × if it was 8 μm or more.

Examples 2-5 and Comparative Examples 1-2
The active energy ray-curable resin compositions 2 to 5 for optical articles and the active energy ray-curable resin composition 1 'for optical articles for comparison were used in the same manner as in Example 1 except for the formulations shown in Tables 1 and 2. ˜2 ′ was prepared. Evaluation similar to Example 1 was performed. The results are shown in Table 3.

<Footnotes in Tables 1 and 2>
(A-2): Diacrylate of ethylene oxide-modified bisphenol A in which R1 and R2 are hydrogen atoms and the average value of m1 + m2 is 10 in the general formula (1).
(A-3): Diacrylate of ethylene oxide-modified bisphenol A in which R1 and R2 are hydrogen atoms and the average value of m1 + m2 is 4 in the general formula (1) (A-4): bisphenol A type epoxy resin (epoxy equivalent 640 g) / Eq) and an epoxy acrylate obtained by reacting acrylic acid.
(A-5): Phenoxyethyl acrylate.
(A-6): Reaction product of phenylglycidyl ether and acrylic acid.
(A-7): Acryloylmorpholine.
(C-1): 1-hydroxycyclohexyl phenyl ketone.
(C-2): 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPGDA): tripropylene glycol diacrylate.
(HDDA): 1,6-hexanediol diacrylate.
(MMA): Methyl methacrylate
(TMP-EO3-TA): A triacrylate of polyhydric alcohol obtained by adding an average of 3 moles of ethylene oxide to trimethylolpropane.
(PMMA-1): polymethyl methacrylate having a weight average molecular weight of 9000 (PMMA-2 :) polymethyl methacrylate having a weight average molecular weight of 80000

  The acrylic polymer (B) synthesized in Synthesis Examples 2 to 4 is in a state (solution) dissolved in a monomer having a polymerizable unsaturated double bond (for example, phenoxyethyl acrylate in Synthesis Example 2). . In Tables 1 and 2, the acrylic polymer (B) and the monomer having a polymerizable unsaturated double bond in this solution are described separately. For example, in Table 1, 15 parts by weight of phenoxyethyl acrylate and 35 parts by weight of polymer (B-1) are used. This is because the content of the polymer (B) in the solution of the polymer (B) synthesized in Synthesis Example 2 is 70% by weight, and when 50 parts by weight of this solution is used, as shown in Table 1. 35 parts by weight of the polymer (B-1) and 15 parts by weight of phenoxyethyl acrylate are used.

Claims (12)

A monomer (A) having a polymerizable unsaturated double bond containing a compound represented by the following formula (1) and a monomer having one polymerizable unsaturated double bond per molecule are polymerized. A polymer having a structure obtained as a main skeleton, having a weight average molecular weight of 2,000 to 100,000, and further containing a polymerizable unsaturated double bond in the polymer structure (B) and a photopolymerization initiator (C), and the monomer (A) and the polymer (B) are in a weight ratio [(A) / (B)] of 97/3. An active energy ray-curable resin composition for optical articles, which is contained in a range of ˜55 / 45.

(In the formula, R ₁ is H or CH ₃ , and the average value of n is a number of 1 to 5.) The active energy ray-curable resin composition for an optical article according to claim 1, wherein the polymer (B) contains a (meth) acrylic polymer having a weight average molecular weight of 3,000 to 50,000. 2. The optical article activity according to claim 1, wherein the monomer (A) and the polymer (B) are contained in a weight ratio [(A) / (B) of 97/3 to 60/40]. Energy ray curable resin composition. The (meth) acrylic polymer includes a polymer obtained by reacting a (meth) acrylic polymer having an epoxy group with a monomer having a polymerizable unsaturated double bond and a carboxyl group. The active energy ray-curable resin composition for optical articles according to claim 2. The active energy ray-curable resin composition for optical articles according to claim 1, wherein the monomer (A) having a polymerizable unsaturated double bond further contains a monomer having an aromatic ring. The active energy ray-curable resin composition for an optical article according to claim 5, wherein the monomer containing an aromatic ring is a monomer having an aromatic ring and an alkylene oxide chain. The active energy ray-curable resin composition for an optical article according to claim 6, wherein the monomer having an aromatic ring and an alkylene oxide chain is a bifunctional (meth) acrylate represented by the following general formula (2).

(In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group. M1 and m2 are each an integer indicating the number of repeating units, and the sum of m1 and m2 is 1 to 20 on average. ) The active energy ray-curable resin composition for an optical article according to claim 7, wherein the sum of m1 and m2 in the general formula (2) is 6 to 14 on average. The active energy ray-curable resin composition for an optical article according to any one of claims 1 to 8, wherein the acid value is 3.0 mgKOH / g or less. The monomer (A) having a polymerizable unsaturated double bond contains 10 to 80% by weight of the compound represented by the formula (1) based on the weight of the monomer (A), and the formula ( 2. The active energy ray-curable resin composition for an optical article according to claim 1, comprising 5 to 50% by weight of the bifunctional (meth) acrylate represented by 2) based on the weight of the monomer (A). The active energy ray curable resin composition for optical articles according to claim 1, wherein the solvent content in the active energy ray curable resin composition is 1% by weight or less. Hardened | cured material formed by hardening | curing the active energy ray hardening-type resin composition for optical articles of any one of Claims 1-10.