JP2000281725A - UV curable resin composition for optical lens and optical element using the same - Google Patents

Abstract

[PROBLEMS] To use a conventional optical element made of an ultraviolet-curable resin composition for an optical lens in a high-temperature and high-humidity environment, the surface absorption dimension of the cured resin layer is high, and the surface shape dimensional accuracy is extremely poor. There is a disadvantage that a clear image cannot be obtained. The present invention is obtained by reacting an epoxy acrylate having a saturated cyclic structure (A) and / or an epoxy acrylate having a saturated cyclic structure with a polyisocyanate and a compound having a polymerizable unsaturated group and a hydroxyl group at a terminal. Disclosed is an ultraviolet curable resin composition for an optical lens containing a radical curable compound (B), wherein a cured product of the composition has a low water absorption and an excellent surface dimensional accuracy even under high temperature and high humidity. Bring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable resin composition for an optical lens used for an optical element having a structure in which a molded layer made of a cured resin is provided on a substrate, such as a video camera, a still camera, a microscope, and the like. The present invention relates to an object and an optical element using the same.

[0002]

2. Description of the Related Art As optical devices have become smaller and lighter and have higher performance, optical elements having fine and complicated uneven surface shapes, lenses having ultra-high precision flat or aspheric surface shapes,
The need for prisms and mirrors is increasing.

In general, such an optical element is required to withstand long-term use in a heat cycle test in which a temperature change from a high temperature to a low temperature or a moisture resistance test in which the optical element is left in a high-temperature and high-humidity atmosphere. The refractive index, transmittance, and the adhesive strength between the base material and the resin layer do not change for a long time, and durability such that cracks are not required is required. As an optical element that meets such requirements, a specific urethane-modified polyester is used. Curing by curing an active energy ray-curable resin composition containing a (meth) acrylate oligomer, a trifunctional (meth) acrylate, and a monofunctional (meth) acrylate on a base material such as glass using active energy rays such as ultraviolet rays. An optical element provided with a resin layer is known (JP-A-62-258401).

[0004]

However, although the optical elements of the prior art have been improved in terms of durability, they are still insufficient to withstand long-term use. In particular, when an optical element made of a conventional ultraviolet-curable resin composition for an optical lens is used in a high-temperature and high-humidity environment, there is a disadvantage that the water absorption of the cured resin layer is high and the surface shape accuracy is extremely poor. Therefore, in order to obtain an optical element that can be used for a long time in a high-temperature and high-humidity environment, the appearance of an ultraviolet-curable resin composition for an optical lens having a low water absorption and an optical element using the same are desired. In view of the above problems, an object of the present invention is to provide a UV-curable resin composition for optical lenses having a low water absorption and an optical element using the same.

[0005]

In view of such circumstances, the present inventors have conducted intensive studies and as a result, have found that a composition containing a compound having a specific chemical structure can achieve the above object, and completed the present invention. I came to.

That is, the present invention is described in each claim as claims and is as follows.

(1) An ultraviolet curable resin composition for an optical lens, comprising an epoxy acrylate (A) having a saturated cyclic structure.

(2) A radical curable compound (saturated) obtained by the reaction of an epoxy acrylate (A) having a saturated cyclic structure, a polyisocyanate (a1), and a compound (a2) having a polymerizable unsaturated group and a hydroxyl group at a terminal. A resin composition for an optical lens, comprising: an epoxy acrylate-modified urethane acrylate having a cyclic structure) (B).

(3) The main skeleton of the acrylate resin (A) having a saturated cyclic structure according to the above (1) or (2) has a hydrogenated bisphenol and / or a hydrogenated phenol novolak resin skeleton. An ultraviolet curable resin composition for an optical lens, which is a compound.

(4) A polymerizable monomer (C) is contained in addition to the epoxy acrylate (A) having a saturated cyclic structure and / or the epoxy acrylate-modified urethane acrylate (B) having a saturated cyclic structure. UV curable resin composition for optical lenses.

(5) The resin composition for an optical lens according to the above (4), wherein the polymerizable monomer (C) is a polymerizable monomer (c1) having a saturated cyclic structure.

(6) The ultraviolet curable resin composition for an optical lens according to the above (5), wherein the polymerizable monomer (C) is a monofunctional monomer (c2) having a saturated cyclic structure.

(7) In addition to the epoxy acrylate (A) having a saturated cyclic structure and / or the epoxy acrylate modified urethane acrylate (B) having a saturated cyclic structure and the polymerizable monomer (C), a polymerizable linear oligomer (D) An ultraviolet-curable resin composition for an optical lens, comprising:

(8) 1-hydroxycyclohexylphenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) as photoinitiator (E) Phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- The resin composition for an optical lens according to any one of the above (1) to (7), comprising one or more photoinitiator systems selected from the group of trimethylpentylphosphine oxide. .

(9) Any one of the above (1) to (8), wherein the water absorption of the cured product is 2% or less, preferably 1% or less.
4. The resin composition for an optical lens according to any one of the above.

(10) A resin layer obtained by curing the resin composition for an optical lens according to any one of (1) to (9) is provided in a desired shape on the surface of the substrate. An optical element, characterized in that:

(11) The optical element according to (10), wherein the substrate is a glass lens.

(12) The optical element according to the above (10), wherein the substrate is a plastic lens.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Typical and best modes for carrying out the present invention will be specifically shown in the following embodiments. The outline and various constituent elements that can be selected in carrying out the present invention are described. Will be described below.

The UV-curable resin composition for an optical lens of the present invention will be described in detail. When a compound having a saturated cyclic structure (A) is used as a starting material, the epoxy acrylate (A) having a saturated cyclic structure used in the present invention is glycidyl-etherified with epichlorohydrin or glycidol, and is added to a terminal such as acrylic acid or methacrylic acid. It is obtained by reacting a compound having a polymerizable unsaturated group and a carboxyl group. When a substance having a phenolic hydroxyl group is used as a starting material, after glycidyl etherification with epichlorohydrin, hydrogenation is performed to form a saturated cyclic structure, and then a polymerizable unsaturated group and a carboxyl group are added to the terminal of acrylic acid, methacrylic acid, or the like. It is obtained by reacting a compound having a group. Here, the saturated cyclic structure is a cycloalkyl structure such as cyclopentane, cyclohexane, cyclooctane, benzene, naphthalene, anthracene, pentalene, indene, azulene, heptalene, biphenylene, indacene, acenaphthylene, fluorene, phenanthrene, fluoranthene, acephenanthane. Rylene, aceanthrylene, triphenylene, chrysene, pyrene,
Hydrogenated cyclic structures obtained by hydrogenating (hydrogenating) aromatic rings such as naphthacene, picene, perylene, pentaphene, pentacene, bisphenol A, bisphenol F, bisphenol S, phenol novolak resin, tricyclodecane,
Bicycloheptane, norbornane, dicyclopentane,
Polycyclic structures such as pinane and bornane, spiro [3.4] octane, 2,4,8,10-tetraoxaspiro [5,5]
Spiro ring structures such as undecane, oxolane, thiolane,
Heterocyclic structures such as sirolan, dioxane, thioisatin, thiazole, oxathiazine, dithiazine, furan, thiophene, pyrrole, oxazole, imidazole, pyran, pyridine, pyrrolinepiperidine, piperazine, morpholine, indole, quinoline, xanthene,
It has a hydrogenated heterocyclic structure in which unsaturated groups such as carbazole, acridine, indoline, and chroman are hydrogenated.

Among them, those using a phenolic hydroxyl group as a starting material are preferred because they have a good glycidyl etherification yield, can improve the purity of epoxy acrylate, and particularly improve the curability of the resin composition for optical lenses.

The radical polymerizable compound (B) used in the present invention is a compound (a2) having the above-mentioned epoxy acrylate (A) having a saturated cyclic structure, a polyisocyanate (a1), and a polymerizable unsaturated group and a hydroxyl group at the terminal. ). As the polyisocyanate (a1),
Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate,
p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1, Polyisocyanates such as 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, and trimethylhexamethylene diisocyanate are used.

Among these, non-aromatic polyisocyanates are particularly preferable because high curability can be obtained.
Further, the polyisocyanates (a) used in the present invention
1) Other than the above, 3
A dimer is also used. This diisocyanate trimer is a compound having an isocyanuric acid skeleton obtained by trimerizing diisocyanate and three isocyanate groups,
The three diisocyanates used as monomers may be of different types or of the same type.

Of these, trimers of diisocyanate containing at least one monomer of diisocyanate having a cyclic structure such as an alicyclic ring are particularly preferable in terms of increasing the glass transition temperature.

Next, as the compound (a2) having a polymerizable unsaturated group and a hydroxyl group at its terminal, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid,
Pentaerythritol tri (meth) acrylate, 3-
Acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-
Hydroxy-1- (meth) acryloxy-3- (meth)
Acryloxypropane, glycerin di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyε-caprolactone mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε-
Caprolactone mono (meth) acrylate and the like. Further, as (d3), an isocyanuric acid derivative having a polymerizable unsaturated group and a hydroxyl group at a terminal is also useful. As the isocyanuric acid derivative, for example, γ-butyrolactone, γ-valerolactone, δ-
Valerolactone, ε-caprolactone, D-glucono-
Lactones such as 1,4-lactone, 1,10-phenanthrene carboractone, 4-pentene-5-olide and 12-dodecanolide, or alkyl ether oxides such as ethylene oxide and propylene oxide, and cyclic ethers such as tetrahydrofuran are added to form A compound obtained by reacting a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid or (meth) acrylic acid ester by dehydration condensation or transesterification in an equivalent ratio that leaves 1 mol or more of the hydroxyl group is usually used.

The polymerizable monomer (C) of the present invention further comprises
In addition to the epoxy acrylate (A) having a saturated cyclic structure and / or the epoxy acrylate-modified urethane acrylate (B) having a saturated cyclic structure, it is usually used for the purpose of lowering the viscosity. Examples of the polymerizable monomer (C) include compounds having a structure in which (meth) acrylic acid is bonded to a compound containing an amino group or a hydroxyl group by an esterification reaction, and examples thereof include methoxyethylene glycol (meth) acrylate and methoxypolyethylene glycol ( (Meth) acrylate, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, nonylphenoxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, phenoxyethyl (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, β- (meth) acryloyloxypropyl hydrogen phthalate, β- (Meth) acryloyloxypropyl hydrogen succinate, butoxy polyethylene glycol (meth) acrylate, alkyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid,
3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
2-hydroxy-1- (meth) acryloxy-3- (meth) acryloxypropane, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyε-caprolactone mono (meth) acrylate, dialkylaminoethyl ( Meth) acrylate, glycidyl (meth) acrylate,
Mono [2- (meth) acryloyloxyethyl] acid phosphate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4,4 -Hexafluorobutyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecanyloxy Ethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, morpholine (meth) acrylate, and monofunctional polymerizable monomers such as N-vinylpyrrolidone, N-vinylpyridine, and N-vinylcaprolactam; , 2-dimethyl- - hydroxy-propyl-2,2
Di (meth) -dimethyl-3-hydroxypropionate
Acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,
4-butanediol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate of neopentyl glycol hydroxypivalate, di (meth) acrylate of ethylene oxide adduct of bisphenol A, Di (meth) acrylate of propylene oxide adduct of bisphenol A, di (meth) acrylate of 2,2′-di (hydroxypropoxyphenyl) propane, di (meth) of 2,2′-di (hydroxyethoxyphenyl) propane Bifunctional polymerizable monomers such as acrylate, di (meth) acrylate of tricyclodecane dimethylol, and (meth) acrylic acid adduct of 2,2'-di (glycidyloxyphenyl) propane; for example, trimethylolpropane Li (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, Tris (2-
Hydroxy (ethyl) isocyanurate tri (meth) acrylate, tris (hydroxypropyl) isocyanurate tri (meth) acrylate, trimellitic acid tri (meth) acrylate, and triallyl trimellitic acid, triallyl isocyanurate There are functional polymerizable monomers. Among them, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, isobornyl (meth) acrylate, N-vinyl −
Polymerizable monomers having a saturated cyclic structure, such as 2-pyrrolidone, N-vinylpyridine, morpholine (meth) acrylate, and N-vinylcaprolactone, are preferable because they have low viscosity, do not lower the water absorption, and do not reduce toughness.

The polymerizable linear oligomer (D) of the present invention is a compound having a molecular weight of 500 or more and having a polymerizable unsaturated group such as a vinyl group, an acryl group or a methacryl group at a terminal.
This polymerizable linear oligomer (D) is a polyol (d)
Urethane acrylate synthesized from 1), polyisocyanate (d2), and compound (d3) containing a polymerizable unsaturated group and a hydroxyl group at a terminal is preferable. Examples of the polyol (d1) include polyester polyols obtained by polycondensation of polybasic acids and polyhydric alcohols, polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone, γ-valerolactone, ethylene oxide, Examples thereof include polymers of alkyl ethers such as propylene oxide and butylene oxide, polymers of cyclic ethers such as tetrahydrofuran and alkyl-substituted tetrahydrofuran, and polyether polyols which are copolymers of two or more of these. Among these, urethane acrylate using a polyol having a molecular weight of 400 to 5,000 is preferable, and urethane acrylate using a polyol having a molecular weight of 600 to 3,000 has high curability, and a resin composition for an optical lens having a low viscosity is obtained. Is particularly preferred. The polyisocyanate (d2) includes tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 5-naphthalenediisocyanate, tolidine diisocyanate, p
-Phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1.3 Polyisocyanates such as 2,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, and trimethylhexamethylene diisocyanate are used.

Among these, non-aromatic polyisocyanates are particularly preferred because high curability can be obtained.
Furthermore, the polyisocyanates (d) used in the present invention
2) In addition to the above, 3
A dimer is also used. This diisocyanate trimer is a compound having an isocyanuric acid skeleton obtained by trimerizing diisocyanate and three isocyanate groups,
The three diisocyanates used as monomers may be of different types or of the same type.

Among these, a trimer of diisocyanate containing at least one monomer having diisocyanate having a cyclic structure such as an alicyclic ring is particularly preferable for increasing the glass transition temperature.

Next, as the compound (d3) having a polymerizable unsaturated group and a hydroxyl group at the terminal, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- Phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid,
Pentaerythritol tri (meth) acrylate, 3-
Acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-
Hydroxy-1- (meth) acryloxy-3- (meth)
Acryloxypropane, glycerin di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyε-caprolactone mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε-
Caprolactone mono (meth) acrylate and the like. Further, as (d3), an isocyanuric acid derivative having a polymerizable unsaturated group and a hydroxyl group at a terminal is also useful. As the isocyanuric acid derivative, for example, γ-butyrolactone, γ-valerolactone, δ-
Valerolactone, ε-caprolactone, D-glucono-
Lactones such as 1,4-lactone, 1,10-phenanthrene carboractone, 4-pentene-5-olide and 12-dodecanolide, or alkyl ether oxides such as ethylene oxide and propylene oxide, and cyclic ethers such as tetrahydrofuran are added to form A compound obtained by reacting a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid or (meth) acrylic acid ester by dehydration condensation or transesterification in an equivalent ratio that leaves 1 mol or more of the hydroxyl group is usually used.

When the ultraviolet curable resin composition for an optical lens of the present invention is cured by ultraviolet rays, a photopolymerization initiator and the like may be used in addition to the components (A), (B), (C) and (D). It is necessary to add the photosensitizer (E). Examples of the photosensitizer (E) include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, benzyldimethylketal, benzophenone and benzophenone derivatives, alkyl benzoylbenzoate, and bis (4-dialkylamino). Phenyl) ketone, benzyl and benzyl derivatives, benzoin and benzoin derivatives, benzoin alkyl ether,
-Hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenoylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl 2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like. Among these, 1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenoylphosphine oxide, 2-methyl-1-
[4- (Methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1-
One or a mixture of two or more selected from the group of (4-morpholinophenyl) -butanone-1 is particularly preferable as the photosensitizer (E) because of its high curability.

Next, the content of each compound in the ultraviolet curable composition for an optical lens of the present invention will be described. Epoxy acrylate (A) having the above-mentioned saturated cyclic structure and / or
Alternatively, the urethane-modified epoxy acrylate having a saturated cyclic structure (B) may be an epoxy acrylate having a saturated cyclic structure (A) and / or a urethane-modified epoxy acrylate having a saturated cyclic structure (B), a polymerization monomer (C), and a polymer. 5 to 100% by weight based on the total of 100% by weight of the linear oligomer (D). Above all, 10 to 80% by weight is preferred from the viewpoint that the viscosity is low, the moldability is excellent, and the cured product is tough.

The polymerizable monomer (C) is added for the purpose of lowering the viscosity of the ultraviolet ray curable composition for an optical lens of the present invention, and includes an epoxy acrylate (A) having a saturated cyclic structure and / or The urethane-modified epoxy acrylate (B) having a saturated cyclic structure is contained in an amount of 5 to 70% by weight based on a total of 100% by weight of the polymerizable monomer (C) and the polymerizable linear oligomer (D). Above all, 10 to 60% by weight is preferable from the viewpoint of low viscosity, excellent moldability and toughness of the cured product.

The radical-curable compound (D) is not essential for the ultraviolet-curable composition for an optical lens of the present invention, but is added for the purpose of imparting toughness, and has a saturated cyclic structure. Epoxy acrylate having (A)
And / or 0% in a total of 100% by weight of the urethane-modified epoxy acrylate having a saturated cyclic structure (B), the polymerizable monomer (C) and the radical-curable compound (D).
Up to 60% by weight is contained. Especially, it is preferable to contain it in the upper limit of 0 to 40% by weight from the viewpoint that the cured product is excellent in toughness.

The photosensitizer (E) is added to cure the resin composition for an optical lens of the present invention with ultraviolet rays, and usually contains an epoxy acrylate (A) having a saturated cyclic structure and / or , A urethane-modified epoxy acrylate having a saturated cyclic structure (B), a polymerizable monomer (C) and a polymerizable linear oligomer (D) in total of 10
0.2 to 10% by weight based on 0% by weight. Among them, 0.5 to 7% by weight is preferable from the viewpoint of increasing curability.

Further, in addition to the above (A), (B), (C), (D) and (E), the ultraviolet curable composition for an optical lens of the present invention may further comprise a polymerization inhibitor such as hydroquinone or methoquinone. , Hindered phenol-based antioxidants, hindered amine-based yellowing inhibitors, phosphate ester-based decolorizing agents,
Antifoaming agents such as silicone oil, release agents, leveling agents,
A coloring dye or the like may be added.

Next, an optical element using the ultraviolet curable resin composition for an optical lens of the present invention will be described in detail. Examples of the substrate used in the present invention include, for example, glass, ceramic, metal, plastic, mineral crystals, and the like, which are flat or preformed. As a method for producing the optical element of the present invention, for example, the ultraviolet curable resin composition for an optical lens of the present invention is placed on a mold of a material having a desired shape, such as glass, ceramic, metal, plastic, or mineral crystal. After the constant-rate pouring, the above-mentioned base material is stacked through an appropriate gap, and the ultraviolet-curable resin composition for an optical lens is held so that no bubbles or voids are formed in the gap formed by the base material and the mold, the ultraviolet light is applied to the resin. After the resin composition is cured by irradiating it with a dose necessary for curing the resin composition, the resin composition is released. Of course, a method in which the ultraviolet-curable resin composition for an optical lens of the present invention is dropped on a substrate and a mold is stacked thereon may be used. Alternatively, a method of applying the ultraviolet-curable resin composition for an optical lens of the present invention on a substrate by spin coating or the like without using a mold and curing the composition may be employed.

When the resin composition is cured by using ultraviolet rays, either the mold or the substrate is made of glass, quartz,
It is necessary to use a transparent substance such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate and poly 4-methyl-1-pente. Further, the surface of the substrate is treated with an oxidizing agent such as a silane coupling agent, a titanate coupling agent, nitric acid, or an alkali to improve the adhesion between the substrate and the ultraviolet-curable resin composition for an optical lens of the present invention. A method or a method of treating a mold with a mold release agent to facilitate demolding may be employed.

Further, titanium oxide, zirconium oxide, and the like are formed on the surface of the cured resin of the optical element obtained by the above method.
An oxide or a fluoride of a metal such as silicon oxide, aluminum oxide, or magnesium fluoride may be vacuum-deposited under heating or non-heating conditions to provide an antireflection film.

When ultraviolet light is used, a metal halide lamp, a high-pressure mercury lamp, a black light, or the like is used as the ultraviolet light source.

[0041]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples and Production Examples, but the present invention is not limited thereto. All parts and percentages in the examples are on a weight basis.

(Production Example 1) 163 parts of acrylic acid was added to 376 parts of hydrogenated bisphenol A type epoxy resin (epoxy equivalent: 213 g / eq) in a flask equipped with a stirrer, a thermometer, and a reflux condenser. C. for 8 hours to obtain an epoxy acrylate having a saturated cyclic structure (A-
1) was obtained.

(Production Example 2) A flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 222 parts of isophorone diisocyanate, and the temperature was raised to 70 ° C. while stirring, and ε-
Hydroxyl-containing acrylate compound obtained by opening caprolactone with hydroxyethyl acrylate (having a hydroxyl value of 16
336 parts of 7 mg-KOH / g) was added dropwise over 1 hour to obtain an intermediate compound I-1.

Next, 163 parts of acrylic acid was added to 376 parts of a hydrogenated bisphenol A type epoxy resin (epoxy equivalent: 213 g / eq) in a flask equipped with a stirrer, a thermometer, and a reflux condenser. The reaction was performed for 8 hours. 558 parts of the intermediate compound I-1 was added thereto and reacted at 80 ° C. for 5 hours to obtain a radical curable compound (B-1) having a saturated cyclic structure.

(Production Example 3) Isophorone diisocyanate was added to a flask equipped with a stirrer, a thermometer, and a reflux condenser.
22 parts were charged, the temperature was raised to 70 ° C. with stirring, and 336 parts of hydroxyethyl acrylate was added dropwise over 1 hour to obtain an intermediate compound I-2.

Next, 144 parts of acrylic acid was added to 376 parts of a hydrogenated bisphenol A type epoxy resin (epoxy equivalent: 213 g / eq) in a flask equipped with a stirrer, a thermometer, and a reflux condenser. The reaction was performed for 8 hours. 279 parts of the intermediate compound I-2 was added thereto and reacted at 80 ° C. for 5 hours to obtain a radical curable compound (B-2) having a saturated cyclic structure.

(Production Example 4) Isophorone diisocyanate 4 was placed in a flask equipped with a stirrer, thermometer and reflux condenser.
44 parts were charged, the temperature was raised to 70 ° C., and polypropylene glycol (hydroxyl value 112 mg-KOH / g) was added to 1000 parts.
Was added. After reacting at 70 ° C. for 5 hours, 232 parts of hydroxyethyl acrylate was added and the reaction was further conducted for 5 hours to obtain a polymerizable linear oligomer (D-1).

(Production Example 5) Isophorone diisocyanate 4 was placed in a flask equipped with a stirrer, thermometer and reflux condenser.
44 parts were charged, and the temperature was raised to 70 ° C., and 10 parts of polytetramethylene glycol (hydroxyl value: 112 mg-KOH / g) was added.
00 parts were added. After reacting at 70 ° C. for 5 hours, 232 parts of hydroxyethyl acrylate was added, and further
The reaction was performed for a time to obtain a polymerizable linear oligomer (D-2).

(Production Example 6) Tolylene diisocyanate 34 was placed in a flask equipped with a stirrer, thermometer and reflux condenser.
8 parts were charged, the temperature was raised to 70 ° C., and 1000 parts of polycaprolactone (hydroxyl value 115 mg-KOH / g) was added. After reacting at 70 ° C. for 5 hours, 232 parts of hydroxyethyl acrylate was added and the reaction was further conducted for 5 hours to obtain a radical curable compound (X).

Examples 1 to 6 and Comparative Example 1 Epoxy acrylate having a saturated cyclic structure synthesized in Production Examples 1 to 6 (A-1) and urethane-modified epoxy acrylate having a saturated cyclic structure (B-1) to (B-1) B-
2) Radical curable compound, polymerizable monomer (C-1)
~ (C-2), radical curable compounds (D-1) ~ (D
-2), the radical-curable compound (X), and the photosensitizers (E-1) to (E-2) were blended in the proportions shown in Table 1, mixed uniformly, and then mixed with a 10-micron cartridge filter. Filtration was performed to obtain an ultraviolet curable resin composition for an optical lens of the present invention and a comparative example.

Next, the viscosity of the resin composition for an optical lens shown in Table 1 and the rigidity, water absorption and lens evaluation of the cured product were evaluated by the methods described below. Viscosity: 25 ° C using a Brookfield rotational viscometer
Was measured. Preparation of a cured product sheet: Each of the ultraviolet curable resin compositions for an optical lens shown in Table 1 was applied to a clean and smooth glass plate using an applicator, and the mixture was irradiated under a nitrogen atmosphere using a conveyor-type ultraviolet irradiation device of a metal halide lamp. 1000mJ
Irradiated with ultraviolet light at / cm 2 to form a cured sheet.

Preparation of a sheet for measuring the rigidity: A sheet of the above cured product was prepared by using a super dumbbell (JIS) manufactured by Dumbbell Co., Ltd.
(No. 7113 No. 2 dumbbell) to form a measurement sheet, and the rigidity was measured. At this time, the thickness of the sheet of the cured product was in the range of 0.10 to 0.20 mm. However, at the time of measurement, in order to prevent the measurement sheet from slipping with the chuck, the four right, left, upper and lower portions outside the interval between the marked lines (25 mm) are 0.3 mm thick, 20 mm vertically and horizontally, and an adhesive (Toa Gosei Chemical Co., Ltd.) (Aron Alpha) and used as a grip.

Rigidity: The distance between the air chucks of the tensile tester was set to 25 mm, the grip of the measurement sheet was set in accordance with the distance between the chucks, and the measurement sample was pulled at a speed of 1 mm / min and stretched by 2.5%. Was measured, and the rigidity was calculated by the following equation. The number of measurements was three, and the average value is shown in Table 1. Rigidity = Stress at elongation of 2.5% / 0.025

Preparation of Water Absorption Measurement Sheet: A sheet of the above cured product was cut into 5 cm × 5 cm and used as a measurement sheet, and the water absorption was measured. At this time, the thickness of the sheet of the cured product was in the range of 0.10 to 0.20 mm. Water absorption: The water absorption measurement sheet was immersed in pure water at 23 ° C. for 24 hours, and the weight increase was expressed in%.

Preparation of optical element: thickness 2 mm, diameter 10 m
m in a concave portion of a glass substrate made of BK7 polished into a spherical shape,
A 2% by weight methanol solution of γ-methacryloxypropyltrimethoxysilane is applied by spraying,
After drying for 0 minutes, a silane-treated glass substrate was obtained.

Next, the base material was held on a tray, and 0.3 g of each of the above compositions was dropped on the silane-treated surface of the base material. Each composition was fixed at a distance of 0.1 mm from the material and held between the substrate and the mold. Next, the composition was cured by irradiating ultraviolet rays of 800 mJ / cm2 from the substrate side with a metal halide lamp, and then demolded to obtain an aspheric lens.

The lenses obtained in Examples 1 and 2 and Comparative Example 1 were made of zirconium oxide and magnesium fluoride to a thickness of about O.D. An antireflection film of 5 microns was formed on the surface of the cured product of the composition by a vapor deposition method. Each lens was subjected to a moisture resistance test in which the lens was left for 600 hours in an atmosphere at 60 ° C. and a relative humidity of 95% by weight, and the state of the lens between the substrate and the cured resin layer and the state of the cured resin layer surface after the test were observed. The results are shown in Table 1. However, the state of the surface of the cured resin layer was evaluated as x when wrinkles and cracks occurred and when there was a dimensional difference of 2 μm or more from the reference surface of the mold surface, and ○ for others.

[0058]

[Table 1]

(Explanation of Examples in the Table) The polymerizable monomer (C) and the photosensitizer (E) in the table are described below. C-1: isobornyl acrylate C-2: dicyclopentenyloxyethyl methacrylate C-3: tris (2-hydroxyethyl) isocyanurate triacrylate E-1: 1-hydroxycyclohexyl phenyl ketone E-2: 2,4 , 6-Trimethylbenzoindiphenylphosphine oxide

[0060]

As described above, when the ultraviolet curable resin composition for an optical lens of the present invention is used, a molded layer of a cured resin free from surface deformation, wrinkles and cracks can be obtained even in a moisture resistance test. Further, it is possible to provide an optical element having a highly accurate surface shape such as a flat surface, a spherical surface, an aspherical surface, and a complicated uneven shape, and having high durability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04 F term (Reference) 4J011 QA13 QA22 QA23 QA24 QB20 QB24 SA64 SA83 SA84 UA01 WA07 4J027 AB01 AC03 AC04 AE01 AE02 AE03 AE05 AG01 AG03 AG04 AG07 AG09 AG10 AG12 AG23 AG24 AG25 AG27 AG28 AJ08 BA07 BA08 BA09 BA11 BA13 BA15 BA16 BA19 BA20 BA21 BA23 BA24 BA26 BA28 BA29 CB10 CC05 CD04 4J100 AL08P AL08Q AL08R AL08R03 BA10 BA39Q BA39S BB01R BC01P BC43R BC54P CA05 CA06 JA32 JA33

Claims (12)

[Claims] 1. An ultraviolet curable resin composition for an optical lens, comprising an epoxy acrylate (A) having a saturated cyclic structure. 2. A radical-curable compound (saturated cyclic compound) obtained by reacting an epoxy acrylate (A) having a saturated cyclic structure, a polyisocyanate (a1), and a compound (a2) having a polymerizable unsaturated group and a hydroxyl group at a terminal. Epoxy acrylate modified urethane acrylate having a structure)
A resin composition for an optical lens, comprising (B). 3. The optical system according to claim 1, wherein the main skeleton of the acrylate resin (A) having a saturated cyclic structure is a compound having a hydrogenated bisphenol and / or a hydrogenated phenol novolak resin skeleton. UV curable resin composition for lenses. 4. An optic comprising a polymerizable monomer (C) in addition to an epoxy acrylate (A) having a saturated cyclic structure and / or an epoxy acrylate-modified urethane acrylate (B) having a saturated cyclic structure. UV curable resin composition for lenses. 5. The resin composition for an optical lens according to claim 4, wherein the polymerizable monomer (C) is a polymerizable monomer (c1) having a saturated cyclic structure. 6. The ultraviolet curable resin composition for an optical lens according to claim 5, wherein the polymerizable monomer (C) is a monofunctional monomer (c2) having a saturated cyclic structure. 7. A polymerizable linear oligomer (D) in addition to an epoxy acrylate (A) having a saturated cyclic structure and / or an epoxy acrylate-modified urethane acrylate (B) having a saturated cyclic structure and a polymerizable monomer (C). An ultraviolet-curable resin composition for an optical lens, comprising: 8. Photoinitiator (E): 1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-
[4- (Methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl The resin composition for an optical lens according to any one of claims 1 to 7, comprising one or more photoinitiator systems selected from the group of phosphine oxides. 9. The resin composition for an optical lens according to claim 1, wherein the water absorption of the cured product is 2% or less, preferably 1% or less. 10. A resin layer obtained by curing the resin composition for an optical lens according to claim 1 is provided on a surface of a substrate in a desired shape. Optical element. 11. The substrate according to claim 10, wherein the substrate is a glass lens.
The optical element as described in the above. 12. The optical element according to claim 10, wherein the substrate is a plastic lens.