JPH11158229A - Composition for spectacle lens and spectacle lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve transparency, heat resistance, chemical resistance, initial coloring, weathering resistance, surface hardness and impact resistance by employing a sulfur-containing urethane-vinyl compound, a (meth)acrylate compound and a radical polymerization initiator. SOLUTION: A sulfur-containing urethane-vinyl compound in an amount of 10-70 pts.wt. obtained by a reaction of an aromatic vinyl compound of formula I (wherein R<1> is a 1-4C hydrocarbon group) containing a hydroxyl group and a sulfur atom with an isocyanate compound, 10-60 pts.wt. di(meth)acrylate compound of formula II (wherein R<2> is H or CH3 ; R<3> and R<4> are each a hydrocarbon group; X is Cl, Br or I; (m) and (n) are each 1-5 and (p) is 0-4) and 10-50 pts.wt. (meth)acrylate compound having a (meth)acryloyl group are blended with 0.005-5 pts.wt, relative to 100 pts.wt. total of the above three compounds, at least one radical polymerization initiator selected from an actinic radiation sensitive and a heat sensitive radical polymerization initiators.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention rapidly cures upon irradiation with active energy rays, has good transparency, heat resistance, chemical resistance, initial coloring properties, and weather resistance, and has excellent surface hardness and impact resistance. The present invention relates to a spectacle lens composition suitable as a material for a high refractive index spectacle lens and a spectacle lens using the same.

[0002]

2. Description of the Related Art Plastic eyeglass lenses have been rapidly spreading in recent years because they are lighter and harder to break than glass eyeglass lenses, can be dyed, and are easy to perform precision molding. Since heat resistance and chemical resistance are required for spectacle lenses, thermosetting plastics typified by radical polymerization cured products of diethylene glycol bisallyl carbonate are not thermoplastic polymers obtained by radical polymerization of methyl methacrylate, styrene, etc. Is mainly used.

[0003] However, this thermosetting plastic has various characteristics such as excellent impact resistance and dyeability, light weight, and good workability such as cutting and polishing properties. However, the crown glass (refractive index n _D =
Compared to 1.52), the refractive index is as low as n _D = 1.50, and it is necessary to increase the center thickness, the edge thickness, and the curvature of the lens in order to obtain optical characteristics equivalent to those of a crown glass lens. It became thick and it was not possible to obtain a thinner and lighter spectacle lens.

[0004]

Accordingly, as a resin for a lens giving a high refractive index, an aromatic (meth) acrylate compound having a bromine atom introduced therein disclosed in JP-A-57-28117 is used. Materials obtained by radical polymerization and materials obtained by the reaction of a polyol compound containing a sulfur atom and a polyisocyanate compound as disclosed in JP-A-60-217229,
Further, a material obtained by a reaction between a vinyl compound containing a sulfur atom and a polyisocyanate compound as disclosed in JP-A-1-197514 has been proposed.

However, although spectacle lenses obtained from these materials can achieve a certain degree of improvement in the refractive index, they are still insufficient for the required refractive index and have various requirements such as heat resistance and impact resistance. There is a problem that the performance balance is insufficient. In addition, as a molding method of a spectacle lens using these materials, a mold thermal polymerization method is generally used, and there is also a problem in productivity.

SUMMARY OF THE INVENTION It is an object of the present invention to provide high-refractive-index spectacles which are required for spectacle lenses, have good transparency, heat resistance, chemical resistance, initial coloring property, and weather resistance, and have excellent surface hardness and impact resistance. It is an object of the present invention to provide a spectacle lens composition capable of manufacturing lenses for eyeglasses with high productivity, and a spectacle lens obtained from the composition.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on eyeglass lens materials, and as a result, used a radical polymerizable composition containing a specific sulfur-containing urethane-vinyl compound, and converted this into other specific components. It has been found that the above object can be achieved by combining with the above, and the present invention has been completed.

That is, the composition for eyeglass lenses of the present invention comprises an aromatic vinyl compound (A-1) containing a hydroxyl group and a sulfur atom represented by the general formula (1) and an isocyanate compound (A-2). A sulfur-containing urethane-vinyl compound (A) obtained by the reaction,

[0009]

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(In the formula, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms.) (Meth) acrylate compound (B) having at least one methacryloyl group or acryloyl group in the molecule
And an active energy ray-sensitive radical polymerization initiator (C-
1) and a radical polymerization initiator (C) comprising at least one kind of a heat-sensitive radical polymerization initiator (C-2), wherein the component (A) is 10 to 70 parts by weight and the component (B) is 3
0 to 90 parts by weight, the component (C) is 0.005 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), and the component (B) is represented by the general formula (2) )) And the sulfur-containing di (meth) acrylate compound (B-1)
10 to 10 parts by weight of the total amount of component and component (B)
It is characterized in that it is contained in a range of 60 parts by weight.

[0011]

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(Wherein R ² represents H or —CH ₃ ,
³ and R ⁴ are the same or different hydrocarbon groups having 1 to 4 carbon atoms, X is Cl, Br or I, m and n are integers of 1 to 5, p is 0 to 4 Indicates an integer. In addition, the composition for eyeglass lenses of the present invention comprises a mixture of 2- (4-vinylbenzylthio) ethanol and 2- (3-vinylbenzylthio) ethanol, 2- (4-vinylbenzylthio) isopropanol and A mixture of-(3-vinylbenzylthio) isopropanol, 2- (4-
An aromatic vinyl compound (A-1) containing at least one hydroxyl group and a sulfur atom selected from a mixture of vinylbenzylthio) butanol and 2- (3-vinylbenzylthio) butanol, and an isocyanate compound (A- 2) to 10 to 70 parts by weight of a sulfur-containing urethane-vinyl compound (A) obtained by reacting p-bis (β-
10 to 60 parts by weight of a sulfur-containing di (meth) acrylate compound (B-1) comprising at least one of (meth) acryloyloxyethylthio) xylylene and m-bis (β- (meth) acryloyloxyethylthio) xylylene; A (meth) acrylate compound (B) consisting of 10 to 50 parts by weight of a (meth) acrylate compound (B-2) other than the (B-1) component having at least one methacryloyl group or acryloyl group in the molecule; 0.1 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B).
005 to 5 parts by weight of a radical polymerization initiator (C) comprising at least one of an active energy ray-sensitive radical polymerization initiator (C-1) and a heat-sensitive radical polymerization initiator (C-2). It is characterized by the following.

Further, the spectacle lens of the present invention comprises the above-mentioned composition for a spectacle lens obtained by adding an active energy ray and / or
Or, it is obtained by polymerization and curing with heat, and has a refractive index of 1.58
The above is the feature. In addition, (meth) acrylate described in this specification means methacrylate and / or acrylate, and (meth) acryloyl group means methacryloyl group and / or acryloyl group. Further, the active energy ray described in this specification means an ultraviolet ray, a visible light ray, and the like.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The composition for a spectacle lens of the present invention comprises:
It comprises a sulfur-containing urethane-vinyl compound (A), a (meth) acrylate compound (B) having at least one methacryloyl group or acryloyl group in a molecule, and a radical polymerization initiator (C). is there. In the present invention, the sulfur-containing urethane-vinyl compound (A) has the following general formula (1)

[0015]

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(Wherein R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms), an aromatic vinyl compound (A-1) containing a hydroxyl group and a sulfur atom, and an isocyanate compound (A- It is a component obtained by reacting 2), and gives a high refractive index, impact resistance, heat resistance, surface hardness and chemical resistance to the obtained spectacle lens. The spectacle lens composition of the present invention comprises an aromatic vinyl compound (A-1) containing a hydroxyl group and a sulfur atom represented by the general formula (1).
And a sulfur-containing urethane-vinyl compound (A) obtained by preliminarily urethanizing the isocyanate compound (A-2). By using the sulfur-containing urethane-vinyl compound (A) obtained by previously reacting the component (A-1) and the component (A-2), the composition has good physical properties even in the case of curing by active energy rays. A spectacle lens can be obtained with high productivity.
On the other hand, when the composition for eyeglass lenses is cured by irradiation with active energy rays, (A) may be used instead of the component (A) of the present invention.
When a monomer composition is prepared by blending the component -1) and the component (A-2), and the composition is to be cured by irradiation with an active energy ray, curing does not proceed until the gelled state. In addition, desired physical properties such as surface hardness, heat resistance, impact resistance, and chemical resistance required for eyeglass lenses cannot be imparted.

Specific examples of the component (A-1) represented by the general formula (1) include, for example, the following general formulas (3) to (3).
(5)

[0018]

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2- (4-vinylbenzylthio) ethanol

[0020]

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2- (4-vinylbenzylthio) isopropanol

[0022]

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Compounds represented by 2- (4-vinylbenzylthio) butanol, meta isomers of the compounds represented by formulas (3) to (5), and the like may be used. They can be used in combination. Especially,
In order to obtain a spectacle lens having a high refractive index, the general formula (3)
2- (4-vinylbenzylthio) ethanol, 2- (3-vinylbenzylthio) ethanol or a mixture thereof is preferable.

In the present invention, the isocyanate compound (A-2) used for obtaining the component (A) means a compound having one or more isocyanate groups in a molecule, and is a monoisocyanate compound, a polyisocyanate compound, Alternatively, a polyisocyanate-modified compound obtained by reacting a polyisocyanate compound with a polyol, a polyester-based or polycarbonate-based diol, and the like can be given. These can be used alone or in combination of two or more.

Among these (A-2) components, specific examples of the monoisocyanate compound include, for example, isocyanatoethyl (meth) acrylate and (meth) acryloyl isocyanate. Specific examples of the polyisocyanate compound include For example, 1,6-hexamethylene diisocyanate, tris (isocyanatohexyl) isocyanurate, 1,4-tetramethylene diisocyanate, 2,2,4, -trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, bis (4 4'-isocyanatocyclohexyl) methane, bis (4,4'-isocyanatocyclohexyl) propane, 1,3-bis (isocyanatomethyl) cyclohexane, m-xylylene diisocyanate, p-xy Diisocyanate, m-trimethylxylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, bis (4,4'-isocyanatophenyl) methane, naphthalene diisocyanate, etc. Is mentioned.

Among these, isocyanatoethyl (meth) acrylate, m-xylylene diisocyanate,
m-tetramethylxylylene diisocyanate, isophorone diisocyanate, tris (isocyanatohexyl) isocyanurate, bis (4,4′-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, or bis (4 4'-Isocyanatophenyl) methane is particularly preferred.

Specific examples of the polyol used for synthesizing the polyisocyanate-modified compound include ethylene glycol, propylene glycol, butylene glycol,
Neopentyl glycol, ethylene oxide adduct or propylene oxide adduct of bisphenol A, ethylene oxide adduct or propylene oxide adduct of bisphenol S, ethylene oxide adduct or propylene oxide adduct of diphenyl disulfide, and polyester diol Specific examples thereof include those obtained from an esterification reaction of a dicarboxylic acid such as adipic acid, phthalic acid, terephthalic acid, and isophthalic acid with glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, and neopentyl glycol. Diols and the like, specific examples of polycarbonate diols, such as diphenyl carbonate, diethyl carbonate, or ethylene carbonate And Boneto acids, hexamethylene-based carbonate diol of 1,6-hexanediol as a raw material can be cited.

As a method for obtaining the component (A) of the present invention, a urethanation reaction with the component (A-1) is carried out (A-2).
When an isocyanate compound having one or more isocyanate groups in the molecule is used as a component, for example, (A) is used in the presence of a tin-based catalyst such as di-n-butyltin dilaurate.
-1) The compounding ratio such that the hydroxyl group of the component and the isocyanate group of the component (A-2) are almost equimolar,
Heating may be performed for several hours in the range of 40 to 100 ° C, preferably 60 to 80 ° C. The reaction product obtained by this method tends to have a high viscosity, and is preferably diluted appropriately with a low-viscosity (meth) acrylate compound during or after the reaction.

When the component (A) is synthesized using a polyisocyanate-modified compound having two or more isocyanate groups in the molecule as the component (A-2), for example, a polyisocyanate compound, a polyol, A polyester-based or polycarbonate-based diol is heated and reacted in the presence of a tin-based catalyst such as di-n-butyltin dilaurate to synthesize a polyisocyanate-modified compound, and then the component (A-1) is further added. Thus, (A-
1) The hydroxyl group of the component can be reacted.

In the present invention, the content of the component (A) is
When the total amount of the component (A) and the component (B) is 100 parts by weight, the amount is in the range of 10 to 70 parts by weight, particularly 20 to 60 parts by weight.
A range of parts by weight is preferred. By setting the content of the component (A) to 10 parts by weight or more, it is possible to impart sufficient high refractive index, impact resistance, surface hardness, heat resistance, and chemical resistance to the obtained spectacle lens. When the amount is not more than 10 parts by weight, the viscosity of the composition for spectacle lenses of the present invention is low, the injection workability is good, and the curability by active energy rays is good.

As the component (B) of the present invention, the (meth) acrylate compound having at least one methacryloyl group or acryloyl group in the molecule is a sulfur-containing di (meth) acrylate represented by the general formula (2): Compound (B-1) having at least one methacryloyl group or acryloyl group in the other molecule (meth)
Contains acrylate compound (B-2). This (B-
The component 1) is a component that imparts a high refractive index, heat resistance, surface hardness, and chemical resistance to the obtained spectacle lens, and at the same time, reduces the viscosity of the highly viscous component (A) to improve the injection workability. Used for the purpose of improving. Also, (B-2)
The component is used for improving physical properties such as injection workability, curability by irradiation with active energy rays or heat, and impact resistance of the obtained spectacle lens, and has a low viscosity (B-
2) It is also used for the purpose of diluting the component (A) having a high viscosity by selecting and using the component.

Specific examples of the component (B-1) used in the present invention include, for example, p-bis (β- (meth) acryloyloxyethylthio) xylylene, m-bis (β-
(Meth) acryloyloxyethylthio) xylylene,
p-bis (β- (meth) acryloyloxyisopropylthio) xylylene, m-bis (β- (meth) acryloyloxyisopropylthio) xylylene, p-bis (β- (meth) acryloyloxybutylthio) xylylene, m- Bis (β- (meth) acryloyloxybutylthio) xylylene, α, α′-bis (β- (meth) acryloyloxyethylthio) -2,3,5,6-tetrachloro-p-xylylene and the like. These can be used alone or in combination of two or more. Among these, from the viewpoint that a composition having a particularly low viscosity can be obtained and a spectacle lens having a higher refractive index can be obtained, p-bis (β-
(Meth) acryloyloxyethylthio) xylylene,
m-Bis (β- (meth) acryloyloxyethylthio) xylylene is more preferred.

Further, specific examples of the component (B-2) include:
For example, bis (4- (meth) acryloyloxyethoxyphenyl) methane, bis (4- (meth) acryloyloxydiethoxyphenyl) methane, 2,2-bis (4
-(Meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4-
(Meth) acryloyloxypentaethoxyphenyl)
Propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4
-(Meth) acryloyloxydipropoxyphenyl)
Propane, 2,2-bis (4- (meth) acryloyloxypentapropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxy-3,5
-Dibromophenyl) propane, 2,2-bis (4-
(Meth) acryloyloxydiethoxy-3,5-dibromophenylpropane, 2,2-bis (4- (meth) acryloyloxypentaethoxy-3,5-dibromophenyl) propane, bis (4- (meth) acryloyloxy Ethoxyphenyl) sulfone, bis (4- (meth) acryloyloxydiethoxyphenyl) sulfone, bis (4- (meth) acryloylthiophenyl) sulfide, bis (4- (meth) acryloyloxyethylthiophenyl) sulfide, bis ( 4- (meth) acryloyloxycyclohexyl) methane, bis (4-
(Meth) acryloyloxyethoxycyclohexyl)
Methane, bis (4- (meth) acryloyloxycyclohexyl) propane, bis (4- (meth) acryloyloxyethoxycyclohexyl) propane, bis (4-
(Meth) acryloyloxydiethoxycyclohexyl) propane, dicyclopentanedi (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate.

Polyethylene glycol (n = 4 to 15)
Di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (n = 4
15) di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polybutylene glycol (n = 2 to 15) di (meth) acrylate, neopentyl glycol di (meth) acrylate, neohydroxypivalate Pentyl glycol ester di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate ,
Pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate,
Dipentaerythritol penta (meth) acrylate.

Methyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, 3-phenoxy-2- Hydroxypropyl (meth) acrylate, phenyl-di (oxyethyl)-(meth) acrylate, phenyl-di (2-methyloxyethyl)-(meth) acrylate,
Phenyl tri (2-ethyloxyethyl)-(meth) acrylate, phenoxybutyl (meth) acrylate,
Phenyl-di (oxybutyl)-(meth) acrylate, phenyl-tri (oxybutyl)-(meth) acrylate, 2-phenylphenyl (meth) acrylate,
2-phenylphenoxyethyl (meth) acrylate,
4-phenylphenoxyethyl (meth) acrylate,
2-phenylphenyl-2-methyloxyethyl (meth) acrylate, 4-phenylphenyl-2-methyloxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, 3- (4-phenylphenyl) -2-hydroxypropyl (meth) acrylate.

1-naphthyl (meth) acrylate, 2-
Naphthyl (meth) acrylate, 1-naphthyloxyethyl (meth) acrylate, 2-naphthyloxyethyl (meth) acrylate, 1-naphthyl-di (oxyethyl)-(meth) acrylate, 2-phenyl-2- (4
-(Meth) acryloyloxyethoxyphenyl) propane, 2-bromophenyl (meth) acrylate, 4-
Bromophenyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,4,6
-Tribromophenoxyethyl (meth) acrylate,
Phenylthioethyl (meth) acrylate, phenylthioethoxyethyl (meth) acrylate, benzylthioethyl (meth) acrylate, 4-chlorobenzylthioethyl (meth) acrylate, 2-chlorobenzylthioethyl (meth) acrylate, p- ( β- (meth) acryloyloxyethylthio)-(β-hydroxyethylthio) -xylylene, m- (β- (meth) acryloyloxyethylthio)-(β-hydroxyethylthio)-
Compounds such as xylylene are exemplified.

Further, a urethane (meth) acrylate compound obtained by reacting xylylene diisocyanate with hydroxypropyl (meth) acrylate or hydroxyethyl (meth) acrylate, isophorone diisocyanate and hydroxypropyl (meth) acrylate or hydroxyethyl (meth) acrylate Epoxy di (meth) acrylate compound obtained by reacting bisphenol A diglycidyl ether with (meth) acrylic acid, such as urethane di (meth) acrylate compound obtained by reacting with tetrabromobisphenol A diglycidyl ether and (meth) acrylic acid And an epoxy di (meth) acrylate compound reacted with These compounds are 1
Species or a mixture of two or more can be used.

In the present invention, the content of the component (B) including the components (B-1) and (B-2) is based on 100 parts by weight of the total amount of the components (A) and (B). Case 3
It is in the range of 0 to 90 parts by weight, particularly preferably in the range of 40 to 80 parts by weight. By setting the content of the component (B) to 30 parts by weight or more, curability upon irradiation with active energy rays is improved, and a spectacle lens having sufficient surface hardness, heat resistance, and chemical resistance is obtained. When the content is 90 parts by weight or less, a spectacle lens having a sufficiently high refractive index and impact resistance can be obtained. At this time, the content of the component (B-1) is 10 times the total amount of the components (A) and (B).
It is in the range of 10 to 60 parts by weight in 0 parts by weight,
The range is preferably from 50 to 50 parts by weight. (B-1) Component 10
When the amount is at least part by weight, the viscosity of the composition for eyeglass lenses of the present invention can be reduced, and the injection workability is good. Further, since the curability upon irradiation with active energy rays is improved, a spectacle lens having a sufficiently high refractive index, surface hardness, heat resistance, and chemical resistance can be obtained. (B-1)
When the component is used in an amount of more than 60 parts by weight, the impact resistance of the obtained spectacle lens is reduced, but this can be prevented by setting the amount to 60 parts by weight or less.

In the present invention, the component (A), the component (B-
When the total amount of component (1) and component (B-2) is 100 parts by weight, component (A) is 10 to 70 parts by weight (preferably 20 to 60 parts by weight) and component (B-1) is 10 parts by weight. ６０60 parts by weight (preferably 20 to 50 parts by weight) and the component (B-2) may be contained in a proportion of 10 to 50 parts by weight (preferably 20 to 40 parts by weight). When the content of the component (B-2) is 1
By adjusting the amount to 0 parts by weight or more, the workability for injecting the composition for spectacle lenses of the present invention and the curability by irradiation with active energy rays or heat are improved, or the physical properties such as impact resistance of the obtained spectacle lenses are improved. can do. Also,
By setting the content to 50 parts by weight or less, it is possible to prevent a decrease in the refractive index and heat resistance of the obtained spectacle lens.

In the eyeglass lens composition of the present invention,
In order to improve the heat resistance, surface hardness, dyeability and chemical resistance of the spectacle lens, and to adjust the radical polymerizability of the composition for a spectacle lens of the present invention, as a component (D),
Other vinyl compounds that can be copolymerized with the component (A) or the component (B) can also be used. Specific examples of the component (D) that can be used in the present invention include, for example, styrene,
Chlorostyrene, bromostyrene, dibromostyrene,
Examples thereof include vinyl compounds such as divinylbenzene, cyclohexanedimethanol divinyl ether, and triethylene glycol divinyl ether; and (meth) allyl compounds such as diethylene glycol bisallyl carbonate, diallyl phthalate, and diallyl biphenylate. One of these monomers may be used alone, or two or more thereof may be used as a mixture.

In the present invention, when the component (D) is used, it is used in an amount of not more than 30 parts by weight, especially not more than 15 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). It is preferred to use. By using the component (D) in a content of 30 parts by weight or less, the curability of active energy ray irradiation can be improved, and the obtained spectacle lens has sufficient heat resistance, surface hardness, dyeability and chemical resistance. Can be provided.

The composition for an eyeglass lens of the present invention containing the above components (A) and (B) is cured and molded by an active energy ray, heat or a combination of an active energy ray and heat. To form a spectacle lens. In this case, the radical polymerization initiator (C) is used in the spectacle lens composition of the present invention in order to impart curability and various properties required for the spectacle lens. Examples of the radical polymerization initiator (C) include an active energy ray-sensitive radical polymerization initiator (C-1) and a heat-sensitive radical polymerization initiator (C-2), and these may be used alone or in combination. Can be. In particular, the composition for a spectacle lens of the present invention comprises an active energy ray-sensitive radical polymerization initiator (C-1) and a heat-sensitive radical polymerization initiator (C-2) in view of productivity of the spectacle lens and the like. It is preferable to use them in combination.

As the component (C-1) used in the present invention, those which generate radical species in response to ultraviolet rays having a wavelength of 200 to 400 nm are preferred. (C-
Specific examples of 1) component include, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, benzyl, benzophenone, p-methoxybenzophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, methyl Phenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-
Carbonyl compounds such as methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide;
4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-
Acylphosphine oxides such as 2,4,4-trimethylpentylphosphine oxide and the like can be mentioned. These components (C-1) can be used alone or in a mixture of two or more. Among these,
Considering the compatibility with the composition for spectacle lenses of the present invention,
Benzophenone, benzoin isopropyl ether, methylphenylglyoxylate, 1-hydroxycyclohexylphenyl ketone, benzyldimethyl ketal,
2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferred.

In the present invention, the content of the component (C-1) is preferably in the range of 0.005 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). And particularly preferably in the range of 0.02 to 2 parts by weight.
By setting the content of the component (C-1) to 0.005 parts by weight or more, the composition for an eyeglass lens of the present invention can sufficiently impart curability. The deep curability of the composition for spectacle lenses of the present invention can be improved, and the obtained spectacle lenses can be prevented from being colored.

As the heat-sensitive radical polymerization initiator which is the component (C-2) of the present invention, an organic peroxide or an azo compound can be used. Specific examples of the component (C-2) include, for example, benzoyl peroxide, octanoyl peroxide, diisopropyl peroxy percarbonate,
Bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisobutyrate, t
Organic peroxides such as -butylperoxy-2-ethylhexanoate; 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2 ' And azo compounds such as -azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (2-methylbutyronitrile).

In the present invention, the content of the component (C-2) is preferably 5 parts by weight or less, more preferably 0.02 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). The preferred range is from 2 to 2 parts by weight. By setting the content of the component (C-2) to 0.02 parts by weight or more, the curability of the spectacle lens composition of the present invention can be improved, and the heat resistance of the obtained spectacle lens can be imparted. can do. By setting the content of the component (C-2) to 5 parts by weight or less, it is possible to obtain a spectacle lens having satisfactory colorless and transparent properties and sufficient impact resistance. When the component (C-1) and the component (C-2) are used in combination in the composition for an eyeglass lens of the present invention, the components (A) and (B) are used in a total amount of both components. It is preferably used in the range of 0.005 to 5 parts by weight, particularly preferably in the range of 0.02 to 2 parts by weight, based on 100 parts by weight in total.

In the present invention, additives such as an amine stabilizer, a phenolic antioxidant and a phosphite antioxidant (for the purpose of suppressing coloring of the spectacle lens at the time of molding and improving weather resistance). E) can be contained. Specific examples of the amine stabilizer phenolic antioxidant and the phosphite ester antioxidant include, for example, bis (2,
2,6,6, -tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) sebacate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3, Condensate with 9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol, 4-
Hindered amine compounds such as methoxy-2,2,6,6-tetramethylpiperidine and 4-methoxy-1,2,2,6,6-pentamethylpiperidine; 1- [2
-[3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] -2,2,6,6-tetramethylpiperidine, hindered phenol compounds such as 2,6-di-t-butyl-4-methylphenol, triphenyl phosphite, triethyl phosphite, tridecyl phosphite Examples include phosphite compounds such as phyte. One of these compounds may be used alone,
Two or more kinds may be used in combination.

In the present invention, the content of these additives (E) is preferably in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
This means that by using the component (E) at a content of 0.01 part by weight or more, the coloring of the spectacle lens at the time of molding by irradiation with active energy rays is suppressed, and the weather resistance of the obtained spectacle lens is improved. This is because Also,
By using the component (E) in a content of 5 parts by weight or less, it is possible to prevent poor curability and poor lens moldability of the composition for an eyeglass lens of the present invention. In addition to the above components (A) to (E), the composition for eyeglass lenses of the present invention may further include an ultraviolet absorber, a bluing agent, a pigment, an anti-settling agent, an antifoaming agent, an antistatic agent, an anti-fogging agent Various additives may be added as needed.

In order to obtain a spectacle lens from the composition for a spectacle lens of the present invention, first, the curable composition is prepared, and this is made of two molds made of glass, plastic, or metal whose inner surfaces are mirror-polished in advance. And a matrix formed of a gasket made of an ethylene-vinyl acetate copolymer or the like, followed by heating and / or irradiation with active energy rays to perform cross-linking polymerization and curing of a three-dimensional structure, The cured product may be taken out of the process.

The curing method, curing time and the like at this time may be appropriately selected depending on the selected resin composition. As a method for curing the composition for spectacle lenses of the present invention, for example, when curing with active energy rays efficient in terms of labor saving and productivity, the composition for spectacle lenses of the present invention is injected into the mold. Irradiating an active energy ray having a wavelength of 100 to 600 nm in a range of 1 to 100 J / cm ² using a high-pressure mercury lamp, a metal halide lamp, a halogen lamp, or the like from one or both sides thereof, The composition may be polymerized and cured. At this time, the atmosphere for irradiating the active energy ray may be air or an inert gas such as nitrogen or argon. Also,
After the injection of the composition for an eyeglass lens of the present invention is gelled and immobilized with an active energy ray irradiation amount of 0.5 to 10 J / cm ² , the composition is heated in a hot air oven at 80 to 150 ° C. or 70 ° C. An eyeglass lens can also be obtained by a two-step curing method using an active energy ray and heat, in which the composition is left in hot water at １００100 ° C. for 1 to 5 hours to complete the polymerization.

The matrix used to obtain the spectacle lens from the spectacle lens composition of the present invention is selected from a mold of the same kind of material such as glass and glass, or a glass, plastic, or metal. In addition to a mold in which different materials are combined and a thermoplastic resin such as the above-described ethylene-vinyl acetate copolymer, a polyester resin adhesive tape or the like fixed using a gasket can be used.

The spectacle lens obtained by using the spectacle lens composition of the present invention may have, if necessary, an antireflection property, a high hardness, an abrasion resistance, a chemical resistance, an antifogging property on one or both sides. It is possible to impart a surface polishing property and an antistatic property, or perform a chemical treatment such as a hard coat treatment, a non-reflection coat treatment, a dyeing treatment, a light control treatment, or a physical treatment.

[0053]

The present invention will be described below in more detail with reference to examples and comparative examples. The symbols of the monomers used in the examples are as follows. SUV1: sulfur-containing urethane obtained by reacting 2.05 mol of a mixture of 2- (4-vinylbenzylthio) ethanol and 2- (3-vinylbenzylthio) ethanol with 1 mol of m-xylylene diisocyanate -Vinyl compound SUV2: sulfur-containing compound obtained by reacting 1.05 mol of a mixture of 2- (4-vinylbenzylthio) ethanol and 2- (3-vinylbenzylthio) ethanol with 1 mol of isocyanatoethyl methacrylate Urethane-vinyl compound BMCX: p-bis (β-methacryloyloxyethylthio) xylylene BZM: benzyl methacrylate BP2EA: 2,2-bis (4-acryloyloxydiethoxyphenyl) propane BPMA: 2-phenyl-2- (4- Methacryloyloxyethoxyphenyl) pro BPEA: 2-phenyl-2- (4-acryloyloxyethoxyphenyl) propane UM1: urethane dimethacrylate POA obtained by reacting 2.05 mol of 2-hydroxypropyl methacrylate with 1 mol of m-xylylene diisocyanate : Phenoxyethyl acrylate DVB: divinylbenzene TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide MPG: methylphenylglyoxylate TBB: t-butyl peroxy-isobutyrate TBEH: t-butyl peroxy-2-ethyl Hexanoate IPP: diisopropyl peroxydicarbonate CR39: diethylene glycol bisallyl carbonate HETS: 2- (4-vinylbenzylthio) ethanol XDI: m Xylylene diisocyanate ETOP: triethyl phosphite DPPC: bis (1,2,2,6,6-pentamethyl-4-puperidyl) sebacate LA63: 1,2,3,4-butanetetracarboxylic acid and 1,2,2 6,6, -Pentamethyl-4-piperidinol and β, β, β ', β'-tetramethyl-3,9-
Condensate with (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol (ADK STAB LA-63P manufactured by Asahi Denka Kogyo KK) HFTMP: 1- [2- [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2.
6,6-Tetramethylpiperidine The evaluation in this example was performed by the following method.

Visible light transmittance (%): A flat plate having a thickness of 2 mm was measured according to ASTM D-1003. Refractive index: 2 mm thick flat plate, width 10 mm, length 20 m
m, and the refractive index of a D line at 589.3 nm was measured at 20 ° C. using an Abbe refractometer. Surface hardness: The Rockwell hardness (L scale) of a flat plate having a thickness of 4 mm was measured according to JIS K7202. Heat resistance (Tg, ° C): Tg of a flat plate having a thickness of 2 mm under a load of 10 g was measured by TMA measurement. Impact resistance (g): Center height 1.5m from 127cm height
m, the maximum weight of a steel ball that does not destroy the spectacle lens when a steel ball of various weights is dropped on the center of the spectacle lens having a power of minus 6.0 degrees. Chemical resistance: The surface of the spectacle lens was wiped with a gauze containing acetone and toluene, and the change was examined. ○: No change. ×: The surface is whitened.

Initial colorability: Yellowness (YI value) of a 4 mm-thick flat plate immediately after curing was measured according to JIS K7103. …: YI value is less than 3.0 ×: YI value is 3.0 or more Weather resistance: JISD0205 using a flat plate having a thickness of 4 mm
According to 0, the accelerated weather resistance test was performed. Twenty-four hours after the start of the test, the yellowness (YI value) was measured according to JIS K7103. …: YI value after test increased by less than 1.0 from YI value before test ×: YI value after test increased by 1.0 or more than YI value before test Injection workability: matrix of eyeglass lens composition The workability of the injection into the sample was evaluated. …: Viscosity is appropriate and injection is easy. ×: High viscosity makes injection difficult and injection distortion occurs. Productivity: Indicates the time required to cure the lens.

Example 1 <Synthesis of urethane-vinyl compound: SUV1> 2-liter 4-neck round bottom flask equipped with a stirrer and a condenser was charged with
(4-vinylbenzylthio) ethanol and 2- (3
398 g of a mixture of -vinylbenzylthio) ethanol
(2.05 mol), di-n-butyltin dilaurate 0.1.
30 g, and hydroquinone monomethyl ether 0.1 g.
Then, while maintaining the internal temperature at 60 ° C., 188 g (1 mol) of m-xylylene diisocyanate (trade name: Takenate 500, manufactured by Takeda Pharmaceutical Co., Ltd.) was added dropwise over 3 hours. Thereafter, the internal temperature was raised to 80 ° C,
For 5 hours to synthesize a sulfur-containing urethane-vinyl compound (hereinafter, referred to as SUV1). Tracking the reaction is based on IR
The isocyanate absorption (2200
cm ^-1 ) was confirmed to have disappeared. SUV1 obtained
Was a colorless transparent viscous liquid.

<Preparation of Casting Composition, Preparation of Lens and Plate> 40 g of SUV1, 35 g of BMCX, BP2
15 g EMA, 10 g BZM, 0.5 ETOP
g, DPPC 0.5g, TPO 0.05g, TBB
0.1 g was added and mixed, and stirred well at room temperature.
The pressure was reduced to kPa and degassing was performed for 10 minutes. This composition was prepared by facing two circular flat glass plates having a diameter of 70 mm, the inner surfaces of which were mirror-finished in advance, and surrounding them with a polyester tape having an adhesive layer on one surface and having an inner thickness of 2 mm and 4 mm. Plastic flat mold and diameter 70m
m, a center thickness of 1.5 mm, and a power of minus 6.0 degrees were combined to prepare an eyeglass lens mold surrounded by a polyester tape and injected into these three kinds of molds. Then
30 J / cm from both sides of the matrix using a 2 kW high-pressure mercury lamp
^The composition was cured by irradiating it with ultraviolet light. Thereafter, the cured product was released from the mold and heated at 130 ° C. for 1 hour to obtain a plastic flat plate and an eyeglass lens. Table 2 shows the evaluation results of the plastic flat plate and the spectacle lens thus obtained.

Example 2 2- (4-vinylbenzylthio) ethanol and 2- (4-vinylbenzylthio) ethanol
Mixture 204 of (3-vinylbenzylthio) ethanol
g (1.05 mol) and 155 g (1 mol) of isocyanatoethyl methacrylate were used in the same manner as in Example 1 to synthesize a sulfur-containing urethane-vinyl compound (SUV2). Then, a plastic flat plate and a spectacle lens were manufactured in the same manner as in Example 1 except that the components (A) to (E) shown in Table 1 were used. Table 2 shows the evaluation results.

Examples 3 and 4 Plastic flat plates and spectacle lenses were manufactured in the same manner as in Example 1 except that the components (A) to (E) shown in Table 1 were used. Table 2 shows the evaluation results.

Examples 5 and 6 Following the first step of irradiating ultraviolet rays using the components (A) to (E) shown in Table 1 (irradiation energy is shown in Table 1),
The second step of heat treatment with a hot air dryer (Table 1 shows the heating temperature,
And a heating time), a plastic flat plate and a spectacle lens were manufactured in the same manner as in Example 1.
Table 2 shows the evaluation results.

Comparative Example 1 Diethylene glycol bisallyl carbonate (PPG
100 g of diisopropyl peroxydicarbonate (trade name: Parloyl IPP, manufactured by NOF Corporation) and 3 g of diisopropyl peroxy dicarbonate (manufactured by NOF CORPORATION), and after stirring well, the same matrix as used in Example 1 was mixed. And maintained at 45 ° C. for 10 hours, at 60 ° C. for 3 hours, at 80 ° C. for 3 hours, and at 90 ° C. for 6 hours for molding. Thereafter, the cured product was released from the matrix, heated at 120 ° C. for 1 hour and annealed to obtain a plastic flat plate and an eyeglass lens. Table 2 shows the evaluation results.

Comparative Examples 2 to 5 Plastic flat plates and spectacle lenses were manufactured in the same manner as in Example 1 except that the components (A) to (E) shown in Table 1 were used. Table 2 shows the evaluation results.

Comparative Example 6 2- (4-vinylbenzylthio) ethanol and 2- (4-vinylbenzylthio) ethanol
27 g of a mixture of (3-vinylbenzylthio) ethanol
A plastic flat plate and a spectacle lens were produced in the same manner as in Example 1 except that SUV1 and 13 g of m-xylene diisocyanate were used instead of SUV1. Table 2 shows the evaluation results.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

EFFECT OF THE INVENTION Using the composition for spectacle lenses of the present invention,
For example, by curing by irradiation with active energy rays, transparency, heat resistance, chemical resistance, initial coloring property, good weather resistance, and excellent surface hardness and impact resistance, a refractive index of 1.58 or more High refractive index spectacle lenses can be obtained with high productivity.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25/14 C08L 25/14 33/14 33/14 G02B 1/04 G02B 1/04 G02C 7/02 G02C 7/02 // B29K 81: 00

Claims (6)

[Claims] An aromatic vinyl compound having a hydroxyl group and a sulfur atom represented by the general formula (1) (A-1)
And a sulfur-containing urethane-vinyl compound (A) obtained by reacting an isocyanate compound (A-2) with: (Wherein, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms.) (Meth) acrylate compound (B) having at least one methacryloyl group or acryloyl group in the molecule
And an active energy ray-sensitive radical polymerization initiator (C-
1) and a radical polymerization initiator (C) comprising at least one kind of a heat-sensitive radical polymerization initiator (C-2), wherein the component (A) is 10 to 70 parts by weight and the component (B) is 3
0 to 90 parts by weight, the component (C) is 0.005 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), and the component (B) is represented by the general formula (2) )) And the sulfur-containing di (meth) acrylate compound (B-1)
10 to 6 in 100 parts by weight of the total amount of the component and the component (B)
A composition for spectacle lenses, characterized in that it is contained in an amount of 0 parts by weight. Embedded image (Wherein, R ² represents H or —CH ₃ , and R ³ and R ⁴ represent a hydrocarbon group having 1 to 4 carbon atoms which may be the same or different,
X represents Cl, Br or I, m and n represent an integer of 1 to 5, and p represents an integer of 0 to 4. ) 2. A mixture of 2- (4-vinylbenzylthio) ethanol and 2- (3-vinylbenzylthio) ethanol, 2- (4-vinylbenzylthio) isopropanol and 2- (3-vinylbenzylthio) An aromatic vinyl compound containing at least one hydroxyl group and a sulfur atom selected from a mixture of isopropanol, 2- (4-vinylbenzylthio) butanol and a mixture of 2- (3-vinylbenzylthio) butanol (A −
1) and a sulfur-containing urethane-vinyl compound (A) obtained by reacting the isocyanate compound (A-2) with 10 to 7
Sulfur-containing di (meth) acrylate compound comprising 0 parts by weight and at least one of p-bis (β- (meth) acryloyloxyethylthio) xylylene and m-bis (β- (meth) acryloyloxyethylthio) xylylene (B-1) 10 to 60 parts by weight and 10 to 50 parts by weight of a (meth) acrylate compound (B-2) other than the component (B-1) having at least one methacryloyl group or acryloyl group in the molecule. 0.005 to 5 parts by weight of an active energy ray-sensitive radical polymerization initiator (C-1) based on 100 parts by weight of the total amount of the (meth) acrylate compound (B) and the components (A) and (B) And a radical polymerization initiator (C) comprising at least one kind of a heat-sensitive radical polymerization initiator (C-2). Composition. 3. The isocyanate compound (A-2) used for obtaining the component (A) is isocyanatoethyl (meth) acrylate, m-xylylene diisocyanate,
m-tetramethylxylylene diisocyanate, isophorone diisocyanate, tris (isocyanatohexyl) isocyanurate, bis (4,4′-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, or bis (4 3. The composition for an eyeglass lens according to claim 1, wherein the composition is 4'-isocyanatophenyl) methane. 4. A vinyl compound (D) copolymerizable with the component (A) or the component (B), the component (A) and the vinyl compound (B).
The spectacle lens composition according to claim 1, wherein the composition is contained in an amount of 0 to 30 parts by weight based on 100 parts by weight of the total amount of the components. 5. An additive (E) comprising at least one of an amine-based stabilizer, a phenol-based or phosphite-based antioxidant is added to 100 parts by weight of the total amount of the components (A) and (B). The composition for eyeglass lenses according to claim 4, wherein the composition is contained in an amount of 0.01 to 5 parts by weight. 6. A spectacle lens having a refractive index of 1.58 or more, obtained by polymerizing and curing the composition according to claim 1 or 2 with active energy rays and / or heat.