JPH1036509A - New high refractive index lens material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high refractive index, a high Abbe number, and a high heat resistance, having a refractive index of 1.58 to 1.64, improved adhesion to a mold during casting polymerization, and a high heat resistance. It is an object to provide a lens material having the following. SOLUTION: (a) A composition comprising a specific meth (acrylate) acrylate compound is more than 5% by weight and 70% by weight or less,
(B) a specific composition containing divinylbenzene of 15% by weight or more and less than 35% by weight, (c) a composition comprising a specific mercapto compound of 15% by weight or more and 60% by weight or less,
(D) a compound having one or more epoxy groups (a)
0.01 to 100 parts by weight in total of (b) and (c)
20 parts by weight, obtained by polymerizing a mixed composition comprising
Lens material and its manufacturing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lens material having a high refractive index, a high Abbe number and a high heat resistance suitable for use in spectacle lenses and the like, and having improved adhesion to a mold during casting polymerization. And a method for manufacturing a lens material using the same.

[0002]

2. Description of the Related Art In recent years, plastic lenses have been used more rapidly than glass lenses because they are lighter and tougher than conventional glass lenses. An important performance for lens materials is that both the refractive index and Abbe number are high. The former enables the lens to be thinner, and the latter reduces chromatic aberration. In addition, heat resistance and strength are important properties from the viewpoint of workability, durability, and safety. As for the heat resistance, specifically, in consideration of a post-processing step, a severe environment at the time of use, etc., for example, 70 ° C. or more is required by a Vicat softening point measurement method.
A plastic lens generally has one unsaturated bond such as (a) a meth (a) acryloyl group, an aromatic vinyl group, or an allyl group.
A method of polymerizing and curing an unsaturated compound having at least two
(A) a method of copolymerizing and curing the unsaturated compound used in (a) and a polymercapto compound having two or more mercapto groups, (c) a polymercap compound used in (b) and a polymer having two or more isocyanate groups A typical method is a method of condensation polymerization and curing of an isocyanate compound.
In the method (c), the reaction between the polymercapto compound and the polyisocyanate compound was slow, and the curing polymerization required two days or more, and the economic disadvantage was inevitable. Furthermore, many of the polyisocyanate compounds are highly toxic and pose a problem from the viewpoint of safety. The method of polymerizing the unsaturated compound (a) is a useful method because the curing polymerization rate is high and toxicity is not so much a problem, but an aliphatic unsaturated compound having a meth (a) acryloyl group, an allyl group or the like is used. The refractive index is 1.5
In the case of an aromatic vinyl group compound, the refractive index is 1.
Although about 6 is possible, the Abbe number is 30 or less, which is not practical. The method of copolymerizing and curing the unsaturated compound and the polymercapto compound in (b) has a high curing polymerization rate, and can be said to be an effective technique. However, allyl compounds and polymercapto compounds, or allyl compounds and meth (a) acryl groups, which are found in JP-A-56-11601, JP-B-2-35645 and JP-A-59-87126, are disclosed. In the method of curing and copolymerizing the polymercapto compound, the curing polymerization did not proceed sufficiently, and the heat resistance was insufficient. Also, JP-A-63-23403
No. 2, JP-B-2-283731 discloses a method of copolymerizing a meth (acrylic) acrylic compound and a polymercapto compound, which basically has an aliphatic structure and lacks a refractive index. Further, JP-A-63-309509 and JP-A-2-283731 disclose methods of curing and copolymerizing divinylbenzene with a meth (acrylic) compound and a polymercapto compound. The cryl compound has only two meta (a) acryloyl groups in one molecule, which also has insufficient heat resistance. Further, when a divinylbenzene or a meth (acrylic) acrylic compound is cured and polymerized with a polymercapto compound, a technique showing that it is possible to use divinylbenzene and a meth (acrylic) acrylic compound in combination is disclosed in 6
JP-A-3-238132, JP-A-1-182314, JP-A-1-197528, JP-A-1-315
No. 701, JP-A-2-251533 and the like, but the amounts of divinylbenzene and meth (acrylic) acrylic compound are not known, and at least the high refractive index, the high Abbe number and the high The three heat-resistant persons are not satisfied at the same time. JP-A-4-351612 and JP-A-7-26089 disclose a technique for producing an optical material by curing and copolymerizing a divinylbenzene or meth (a) acryloyl compound with a polymercapto compound in a specific composition. However, the former cannot obtain a high refractive index, and the latter cannot obtain a high Abbe number. Further, among the above-mentioned known techniques, for example, Japanese Patent Application Laid-Open No. 4-351612 using pentaerythritol tetrakis (β-thiopropionate) having an electron withdrawing group such as an ester group as a polymercapto compound is disclosed. Techniques do not achieve high refractive indices and Abbe numbers. Also,
In the method (b), even if an attempt is made to produce a lens material by cast polymerization, the affinity of the glass surface, which is the material of the mold, with the material is insufficient, so that the lens material is completely cured and polymerized before the lens material is completely cured. Peeled off, uneven surface,
Only a lens with poor appearance due to adhesion of sink marks, air bubbles, dust and the like was obtained, and it was not a method that could withstand practical use. That is, the refractive index and Abbe number of the lens material obtained by the conventional method (b) are inferior to those of the method (c), and a level at least equal to or higher than that of the method (c) is desired. Was rare. That is, a lens material having a high refractive index of 1.58 to 1.64 and an Abbe number equal to or higher than that of the thiourethane lens material of the method (c) has been desired. Furthermore, in the case of a lens material obtained by the conventional method (b), when a high refractive index of 1.58 or more and a high Abbe number are simultaneously realized, only a material having low heat resistance due to insufficiently advanced curing polymerization can be obtained. In addition, even if an attempt is made to produce a lens material by casting polymerization, the lens material will be peeled off from the mold surface before it is completely cured and polymerized due to a lack of affinity between the glass surface of the mold and the material. Only a lens with poor appearance was obtained, and it was not a method that could withstand practical use.

[0003]

The problem to be solved by the present invention is that a meth (a) acryloyl group,
Even if an attempt is made to obtain a lens material by a method of copolymerizing an unsaturated compound having two or more unsaturated bonds such as an aromatic vinyl group and an allyl group and a polymercapto compound having two or more mercapto groups, a sufficiently high refractive index, Abbe number and heat resistance were not obtained at the same time, and peeling occurred during casting polymerization due to poor adhesion, so that only a lens material having poor appearance was obtained.

[0004]

The object of the present invention is to provide (a)
It is composed of one or more meth (a) acrylate compounds having two or more and six or less acryloyl groups and / or methacryloyl groups in one molecule, and has an average of two or more and six or less per molecule in the composition. 5% by weight of a composition having an acryloyl group and / or a methacryloyl group
(B) divinylbenzene and a mono-unsaturated compound having one aromatic vinyl group, acryloyl group or methacryloyl group in one molecule, and divinylbenzene with respect to a total of 100% by weight of both. (C) having two or more mercapto groups in one molecule, wherein the composition is 40% by weight or more and less than 15% by weight and less than 35% by weight;
In addition, a composition comprising at least one aliphatic polymercapto compound having no electron withdrawing group in the molecule and having a sulfur content of 35% by weight or more in the composition is used in an amount of 15% by weight to 60% by weight.
% By weight, (d) one or more epoxy compounds selected from the group of compounds having one or more epoxy groups in an amount of 0.01 to 0.01 parts by weight based on a total of 100 parts by weight of (a), (b) and (c). 20 parts by weight, and (a), (b),
The ratio of the total number of moles of all aromatic vinyl groups and all meth (a) acryloyl groups to the total number of moles of all mercapto groups in the mixed composition consisting of the total of each composition of (c) (total aromatic vinyl group and The refractive index is 1.58 to 1.64, obtained by polymerizing a mixed composition in which the total number of moles of all meth (a) acryloyl groups / the number of moles of all mercapto groups is 1.3 to 7. The present invention has been achieved by a lens material having improved adhesion to a mold during casting polymerization, having a high refractive index, a high Abbe number, and a high heat resistance, and a manufacturing method thereof.

[0005] The lens material of the present invention has a refractive index of 1.58.
Is 1.64 and the Abbe number is 3 when the refractive index is 1.58.
When the refractive index is 7 or more and the refractive index is 1.6, the Abbe number is 36 or more. When the refractive index is 1.64, the Abbe number is 32 or more.

[0006] The meth (a) acrylate compound constituting the composition (a) of the present invention is a generic term for a compound having 2 to 6 acryloyl groups and / or methacryloyl groups in one molecule. Specifically, it has an ester structure of dihydric to hexahydric alcohol and acrylic acid or methacrylic acid. Specific examples include ethylene glycol dimeth (a) acrylate, diethylene glycol dimeth (a) acrylate, triethylene glycol dimeth (a) acrylate, polyethylene glycol dimeth (a) acrylate, and 1,3-butylene glycol dimeth (a). ) Acrylates, 1,6-hexanediol dimeth (a) acrylate, neopentyl glycol dimeth (a) acrylate, polypropylene glycol dimeth (a) acrylate, 2-hydroxy-1,3-dimeth (a) acryloxypropane , 2,2-bis [4- (meth (a) acryloxyethoxy) phenyl] propane, 2,
2-bis [4- (meta (a) cryloxy diethoxy)
Phenyl] propane, 2,2-bis [4- (meta (a)
Dimeth (a) acrylates such as acryloxy / polyethoxy) phenyl] propane; trimetha (a) acrylates such as trimethylolpropane trimeth (a) acrylate and pentaerythritol trimethacrylate; tetrameta such as pentaerythritol tetrameth (a) acrylate (A) acrylates; pentameth (a) acrylates such as pentameth (a) acrylate of bis (2,2,2-trimethylolethyl) ether; bis (2,2,2-
Hexameta (a) acrylates such as hexamethyl (a) acrylate of trimethylolethyl) ether and the like can be mentioned. Examples of these hydroxy compounds having an inner hydroxyl group are 2-hydroxy-1,3-dimeth (a) acryloxypropane, pentaerythritol trimethacrylate, and pentameth (a) of bis (2,2,2-trimethylolethyl) ether. Acrylate and the like,
It is not limited to this. [However, the meth (acrylate) acrylate in the present specification means methacrylate or acrylate.] In order to achieve the object of the present invention, (a) the meth (acrylate) compound used in the composition includes (meth) a) It is necessary that the composition has an average of 2 or more and 6 or less acryloyl groups and / or methacryloyl groups per molecule in the composition.
Not less than 6 and not more than 6. If the acryloyl group and / or methacryloyl group is less than this, the heat resistance of the lens material of the present invention becomes insufficient. If it is too large, the toughness of the material will be insufficient. It goes without saying that this may be effected by a single compound or by two or more compounds. As an embodiment of the composition (a), one of the above-mentioned dimeth (a) acrylates, trimeta (a) acrylates, tetrameth (a) acrylates, pentameth (a) acrylates and hexameth (a) acrylates may be used. ４4 kinds of acryloyl groups and / or methacryloyl groups are blended and used in an average of 2 or more and 6 or less in one molecule. As a preferred embodiment of the composition (a), the above-mentioned 1 to 4 di-hexameth (a) acrylates are used in an average of 3 to 6 acryloyl groups and / or methacryloyl groups per molecule. It is blended and used in the composition as follows. The hydroxymeth (a) acrylate having a hydroxyl group in the composition (a) is not necessarily an essential component. However, in order to enhance the effect of preventing the composition from being peeled off at the time of casting polymerization, the composition preferably has a hydroxyl group content of 5 to 5. 95 mol%, more preferably 5 to 50 mol% is used. (A) If the content of the hydroxy meth (a) acrylate having a hydroxyl group in the composition is lower than this value, peeling may be observed during casting polymerization, and the hydroxy meth (a) acrylate having a hydroxyl group may be observed. The higher the content, the higher the water absorption of the lens material, so if these values are exceeded,
The surface deformation of the lens due to water absorption occurs, which impairs the merchantability, which is not preferable.

[0007] The divinylbenzene constituting the composition (b) of the present invention means paradivinylbenzene, metadivinylbenzene, and a mixture of both. Preferred specific examples of the monounsaturated compound having one aromatic vinyl group, acryloyl group or methacryloyl group in one molecule, which is another component constituting the composition (b) of the present invention, are styrene, α- Aromatic vinyl compounds such as methylstyrene, methylvinylbenzene, ethylvinylbenzene, α-chlorostyrene, chlorovinylbenzene, vinylbenzyl chloride, vinylbenzylthioethanol; methyl meth (a) acrylate, n-butyl meth (a) acrylate, n -Hexyl meth (a) acrylate, cyclohexyl meth (a) acrylate, 2-ethylhexyl meth (a) acrylate, methoxydiethylene glycol meth (a) acrylate, methoxypolyethylene glycol meth (a) acrylate, 3-chloro-2-hydroxypropyl meth ( A ) Monometh (a) acrylates such as acrylate, stearyl meth (a) acrylate, lauryl meth (a) acrylate, phenyl meth (a) acrylate;
-Hydroxyethyl meth (A) acrylate, 2-hydroxypropyl meth (A) acrylate, 3-hydroxypropyl meth (A) acrylate, 3-phenoxy-2-hydroxypropyl meth (A) acrylate, 4-hydroxybutyl meth (A) ) Monometh (a) acrylates having a hydroxy group such as acrylate.
Preferred among these are aromatic vinyl compounds such as styrene, α-methylstyrene, methylvinylbenzene, ethylvinylbenzene, α-chlorostyrene, chlorovinylbenzene, vinylbenzyl chloride, and vinylbenzylthioethanol, The preferred ones are
Styrene, α-methylstyrene, methylvinylbenzene, ethylvinylbenzene, and most preferred is ethylvinylbenzene. Divinylbenzene accounts for at least 40% by weight of the composition (b), but preferably at least 50% by weight, more preferably at least 80% by weight, most preferably at least 95% by weight.

The composition (c) of the present invention has two or more mercapto groups in one molecule and does not have an electron-withdrawing group such as an ester group, a carboxyl group and a cyano group in the molecule. Specific examples of the aliphatic polymercapto compound of at least one kind include 1,2-dimercaptoethane and 1,3-dimercaptoethane.
Dimercaptopropane, 1,4-dimercaptobutane,
Linear dimercaptan compounds such as 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide and 1,2-bis (2-mercaptoethylthio) ethane; 2
-Mercaptomethyl-1,3-dimercaptopropane,
2-mercaptomethyl-1,4-dimercaptobutane,
2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (Mercaptomethyl) branched aliphatic polymercaptan compound such as methane; 1,4-dimercaptocyclohexane, 1,3-
Dimercaptocyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2- Aliphatic cyclic dimercaptan compounds such as mercaptoethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane and 2,5-bis (2-mercaptoethyl) -1-thiane; be able to. In order to achieve the object of the present invention, (c) the composition has a sulfur content of 3
5% by weight is required, but is preferably at least 50% by weight, most preferably at least 55% by weight. If the sulfur content is lower than this, the refractive index, Abbe number and heat resistance of the present invention cannot be simultaneously satisfied. It goes without saying that this may be effected by a single compound or by two or more polymercapto compounds.

The compound (d) of the present invention having one or more epoxy groups is more specifically an aliphatic or aromatic organic compound having one or more epoxy groups. Specific examples of epoxy compounds include epoxy compounds having an unsaturated group such as vinylphenyl glycidyl ether, vinylbenzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether; hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol Phenolic epoxy compounds produced by condensation of polyhalophenol compounds such as sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, and novolak resin with epihalohydrin; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol , Propylene glycol, dipropylene glycol, polypropylene Glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerine,
Trimethylolpropane trimethacrylate, pentaerythritol, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A · ethylene oxide adduct, bisphenol A · Alcohol epoxy compounds produced by condensation of a polyhydric alcohol compound such as propylene oxide adduct and epihalohydrin; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydro Phthalic acid, hexahydrophthalic acid, heptic acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid,
Glycidyl ester epoxy compounds produced by condensation of polyhalocarboxylic acid compounds such as naphthalene dicarboxylic acid and diphenyl dicarboxylic acid with epihalohydrin; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis-
(3-aminopropyl) ether, 1,2-bis- (3
-Aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2'-dimethylpropane, 1,
2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1 , 4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine Amine, m- or p-xylylenediamine, 1,5-
Alternatively, primary diamines such as 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2- (4,4'-diaminodiphenyl) propane, N, N'-dimethyl Ethylenediamine, N, N'-dimethyl-1,2-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N, N'-dimethyl -1,3-diaminobutane,
N, N′-dimethyl-1,4-diaminobutane, N,
N'-dimethyl-1,5-diaminopentane, N, N '
-Dimethyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'-diethyl-1,2-diaminopropane, N, N ' -Diethyl-1,3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane,
N, N′-diethyl-1,4-diaminobutane, N,
N'-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-
Dimethylpiperazine, homopiperazine, 1,1-di-
(4-piperidyl) -methane, 1,2-di- (4-piperidyl) -ethane, 1,3-di- (4-piperidyl)-
Amine-based epoxy compounds produced by condensation of a secondary diamine such as propane and 1,4-di- (4-piperidyl) -butane with epihalohydrin; 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinyl Cyclihexane dioxide, 2-
Alicyclic epoxy compounds such as (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) adipate; cyclopentadiene epoxide, epoxidation Epoxy compounds produced by epoxidation of unsaturated compounds such as soybean oil, epoxidized polybutadiene and vinylcyclohexene epoxide; urethane epoxy compounds produced from the above-mentioned polyhydric alcohols, phenol compounds and diisocyanates and glycidol, etc. Can be. Of these, epoxy compounds having an unsaturated group such as vinyl phenyl glycidyl ether, vinyl benzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether are preferred because high heat resistance is maintained, and glycidyl methacrylate, glycidyl Acrylates are most preferred because of their high polymerization rate and high heat resistance.

The lens material of the present invention is obtained by mixing the above compositions (a), (b), (c), and (d) to form a mixed composition and then curing and polymerizing the mixture. Contains each of the compositions (a), (b), (c), and (d) as essential components,
(A) is more than 5% by weight and 70% by weight or less;
% To less than 35% by weight, (c) 15% to 6% by weight
0% by weight or less, but preferably, (a) is more than 15% by weight and 65% by weight or less, and (b) is 15% by weight or more and 3% by weight or more.
5% by weight or less, and (c) 20% by weight or more and 50% by weight or less. (D) The epoxy compound, which is a composition part,
0.01 to 20 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of (a), (b) and (c) use.
When the compositions (a), (b) and (c) do not simultaneously satisfy the scope of the present invention, the high refractive index, which is the gist of the present invention,
High Abbe number and high heat resistance cannot be satisfied at the same time. (C) Even when the sulfur content in the composition does not satisfy the range of the present invention, the high refractive index, high Abbe number and high heat resistance, which are the gist of the present invention, cannot be satisfied at the same time. Further, when the composition (d) is more than the range of the present invention, the refractive index and the heat resistance decrease, and the object of the present invention cannot be achieved. (D) When the composition is less than the range of the present invention, peeling during casting polymerization, which is one of the objects of the present invention, is not prevented. Further, the ratio of the total number of moles of all aromatic vinyl groups and all meth (a) acryloyl groups to the number of moles of all mercapto groups in the mixed composition (the total number of total aromatic vinyl groups and all meth (a) acryloyl groups) (Mol number / mol number of all mercapto groups) must satisfy 1.3 to 7.
If the lens material of the present invention lacks at least one of the compositions, the heat resistance will decrease, and the desired refractive index and Abbe number will not be achieved. When the ratio of the total number of moles of all aromatic vinyl groups and all meth (a) acryloyl groups in the mixed composition to the number of moles of all mercapto groups is less than 1.3, heat resistance is insufficient,
When it is larger than 7, not only the desired refractive index and Abbe number of the material are not achieved, but also the toughness is reduced. That is,
By simultaneously satisfying the conditions of each composition described above and this condition, the refractive index is 1.58 to 1.64, the Abbe number and the heat resistance are high, which were not achieved by the conventional method (b). A lens material in which peeling during mold polymerization is prevented can be obtained.

The optical material of the present invention is obtained by mixing the above compositions (a), (b), (c), and (d) at a mixing ratio satisfying the above-mentioned predetermined conditions to form a mixed composition, followed by polymerization. It is cured and produced. Examples of the polymerization accelerator include radical polymerization initiators, amines, quaternary ammonium salts, complexes of amines with borane and boron trifluoride, phosphines, and the like. At least 2
Although a combination of species and the like can be mentioned, the use of a radical polymerization initiator is a preferable method.

The radical polymerization initiator is not particularly limited as long as it generates a radical by heating or ultraviolet rays or electron beams. Examples thereof include acetylcyclohexylsulfonyl peroxide, isobutyl peroxide, cumyl peroxy neodecanoate, and diisopropyl peroxy. Dicarbonate, diallylperoxydicarbonate, di-n-propylperoxydicarbonate, dimyristylperoxydicarbonate, cumylperoxyneohexanoate, di (2-ethoxyethyl) peroxydicarbonate, di (methoxyisopropyl) ) Peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, ter-hexylperoxyneodecanate, di (3-methyl-3-methoxybutol) peroxydicarbonate DOO, ter-butyl peroxyneodecanoate, ter-hexyl peroxyneodecanoate hexanoate, ter-butyl peroxy hexanoate, 2,4-dichlorobenzoyl peroxide, te
r-hexylperoxypivalate, ter-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
Cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide, ter-butyl peroxy (2-ethylhexanoate), m-toluoyl peroxide, benzoyl peroxide,
ter-butylperoxyisobutyrate, 1,1-bis (ter-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (ter-butylperoxy) cyclohexane, ter-butylperoxy Maleic acid, ter-butylperoxylaurate, ter-butylperoxy-3,5,5-trimethylhexanoate, cyclohexanone peroxide, ter-butylperoxyallyl carbonate, t
er-butyl peroxyisopropyl carbonate,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,2-bis (ter-butylperoxy) octane, ter-butylperoxyacetate,
2,2-bis (ter-butylperoxy) butane, t
er-butylperoxybenzoate, n-butyl-
4,4-bis (ter-butylperoxy) valerate, di-ter-butylperoxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (ter-butylperoxy) ) Hexane, α, α'-bis (ter-butylperoxy-m-isopropyl) benzene, ter-
Butyl cumyl peroxide, di-ter-butyl peroxide, 2,5-dimethyl-2,5-di (ter-
Peroxides such as butylperoxy) hexine-3; diisopropylbenzene hydroperoxide, p
-Mentane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, ter-butyl hydroperoxide and the like Hydroperoxides: 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1 -[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valero Known thermal polymerization catalyst azo compounds such tolyl, benzoin, benzoin monomethyl ether, benzoin isopropyl ether,
Acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2-hydroxy-4-methoxybenzophenone, benzyldimethylketal, 2,2-diethoxyacetophenone,
Carbonyl compounds such as -hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, tetramethylthiuranium monosulfide, tetramethylthiuranium Known photopolymerization catalysts such as sulfur compounds such as disulfide; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, preferred are peroxides, hydroperoxides, and azo compounds,
More preferred are peroxides and azo compounds, and the most preferred are 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
2,2′-azobis (2-methylbutyronitrile),
1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-
An azo compound such as 2,4-dimethyl-valeronitrile. These can all be mixed and used.

As amines, for example, ethylamine,
n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine,
Laurylamine, mystyrilamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol,
3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine,
Primary amines such as aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine and furfurylamine; ethylenediamine, 1,2-diaminopropane, 1,3- Diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino Octane, dimethylaminopropylamine, diethylaminopropylamine, bis- (3-aminopropyl)
Ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,
2'-dimethylpropane, aminoethylethanolamine, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1, 4-bisaminoethylcyclohexane, 1,3- or 1,4-
Bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2
-Or 4-aminoethylpiperidine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-
Aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, menthanediamine, 1,4-
Bisaminopropylpiperazine, o-, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, 2,4-toluenediamine, m-aminobenzylamine, 4-chloro-o-phenylene Diamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m- or p-xylylenediamine, 1,5- or
2,6-naphthalenediamine, benzidine, 4,4'-
Bis (o-toluidine), dianisidine, 4,4'-diaminodiphenylmethane, 2,2- (4,4'-diaminodiphenyl) propane, 4,4'-diaminodiphenylether, 4,4'-thiodianiline, 4,4 '-Diaminodiphenyl sulfone, 4,4'-diaminoditolyl sulfone, methylenebis (o-chloroaniline),
3,9-bis (3-aminopropyl) 2,4,8,10
-Tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, Primary polyamines such as N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diaminophenyl) sulfone Diethylamine, dipropylamine, di-n-
Butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octylamine, di (2-
Ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4
-Picoline, 2,4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine and the like N, N'-dimethylethylenediamine, N, N'-dimethyl-1,2-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1, 2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane,
N, N′-dimethyl-1,4-diaminobutane, N,
N'-dimethyl-1,5-diaminopentane, N, N '
-Dimethyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'-diethyl-1,2-diaminopropane, N, N ' -Diethyl-1,3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane,
N, N′-diethyl-1,4-diaminobutane, N,
N'-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-
Dimethylpiperazine, homopiperazine, 1,1-di-
(4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- (4-piperidyl) butane, tetramethylguanidine, etc. Secondary polyamines; trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine,
Tri-n-butylamine, tri-iso-butylamine, tri-sec-butylamine, tri-pentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine , Tri-dodecylamine, tri-laurylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N,
N-dimethylcyclohexylamine, N-methyldicyclohexylamine, triethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N -Dimethylaminomethylphenol, 2- (N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-
Tertiary amines such as diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1,3,2-dioxabornane; tetramethylethylenediamine, pyrazine, N, N'-dimethylpiperazine, N,
N'-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ', N'-
Tetramethyl-1,3-butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N- Tertiary polyamines such as dimethylaminomethyl) phenol and heptamethylisobiguanide; imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N -Butylimidazole, 2-butylimidazole, N-undecylimidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-methylimid Sol, N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis -(2-ethyl-4-methylimidazolyl) methane,
Various imidazoles such as adducts of alkyl imidazole and isocyanuric acid, and condensates of alkyl imidazole and formaldehyde; 1,8-diazabicyclo (5,4
0) Undecene-7,1,5-diazabicyclo (4,
Amidines such as (3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; and amine compounds represented by the above.
These may be used alone or in combination of two or more.

Examples of the quaternary ammonium salts include the quaternary ammonium salts of the above-mentioned amines with halogens, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid and the like. These may be used alone or in combination of two or more.

Examples of the complex of amines with borane and boron trifluoride include the above-mentioned complexes of amines with borane and boron trifluoride.

The phosphines include, for example, trimethylphosphine, triethylphosphine, tri-is
Phosphins such as o-propylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, dimethylphenylphosphine, diethylphenylphosphine, ethyldiphenylphosphine, chlorodiphenylphosphine, etc. These may be used alone or as a mixture of two or more.

Radical polymerization initiators, amines, quaternary ammonium salts, complexes of amines with borane and boron trifluoride, phosphines, and the like, and at least two of them used in combination in an amount of Since it varies depending on the components of the product and the curing method, it is not generally determined, but usually 0.01% by weight to 5.0% by weight based on the total amount of the composition.
%, Preferably in the range of 0.1% to 2.0% by weight.

Further, in the production of the lens material of the present invention, it is of course possible to further improve the practicality of the obtained material by adding known additives such as an antioxidant and an ultraviolet absorber. It is also possible to add a known external and / or internal release agent to improve the releasability of the obtained cured material from the mold. The internal release agent referred to herein is a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, a phosphate, an acidic phosphate, an alkali metal salt of an acidic phosphate, or a metal of a higher fatty acid. Examples include salts, higher fatty acid esters, paraffin, wax, higher fatty acid amides, higher fatty acid alcohols, polysiloxanes, and aliphatic amine ethylene oxide adducts. Further, by adding a known polymerization modifier and adjusting the polymerization rate at the time of curing, the lens properties can be made more suitable. Here, the known polymerization modifiers include mercaptans, α-methylstyrene, dimers of α-methylstyrene, and the like. Preferably, a dimer of α-methylstyrene or the like is used.

The lens material of the present invention comprises a composition (a),
A mixed composition comprising (b), (c) and (d), and if desired, a radical polymerization initiator, a composition (a),
Radical-polymerizable monomers other than those used in (c),
Further, after mixing a release agent, a stabilizer and the like, the mixture is polymerized and cured as described below to obtain an optical material such as a lens. That is, the raw material after mixing is poured into a glass or metal mold, and the polymerization and curing reaction is advanced by heating and / or irradiation of ultraviolet rays or electron beams, and then the mold is removed from the mold. Curing time is 0.05-10
0 hours, usually 3 to 48 hours in the case of heat polymerization, and a curing temperature of -10 to 160 ° C, usually -10 to 140
° C. Further, if necessary, a surface treatment such as hard coating, antireflection, imparting anti-fogging property can be performed.

The method for producing the optical material of the present invention will be described in more detail below. As described above, the optical material of the present invention comprises compositions (a), (b), and
After mixing (c), (d) and the auxiliary materials, the mixture is injected and cured in a mold, and the mixture is produced. The mixed composition composed of the main components is a meth (a) acrylate compound, Divinylbenzene, monounsaturated compound, polymercapto compound and epoxy compound are mixed in separate containers to prepare compositions (a), (b), (c) and (d), and then mixed again to obtain a final mixed composition These compounds may be mixed together in the same container at once, or a mixed composition, or an intermediate method. A radically polymerizable monomer used as desired;
The radical polymerization initiator, furthermore, the release agent, the stabilizer, etc., may be mixed under stirring simultaneously in the same container, or the respective raw materials may be added and mixed step by step. You may mix again in the same container. In mixing, the set temperature, the mixing time, etc. may be basically the conditions under which each component is sufficiently mixed, but an excessive temperature and time may cause an undesirable reaction between each raw material and the additive, and furthermore, It is not suitable because the viscosity increases and the casting operation becomes difficult. The mixing temperature should be in the range of about -30C to 100C, the preferred temperature range is -20C to 50C, more preferably -10C to 30C. The mixing time is about 1 minute to 5 hours, preferably about 5 minutes to 2 hours, and more preferably about 5 minutes to 30 minutes. Performing a degassing operation under reduced pressure before, during or after mixing of the raw materials and additives is a preferable method from the viewpoint of preventing the formation of bubbles during the subsequent medium-sized polymerization curing. At this time, the degree of pressure reduction is from about 0.1 mmHg to 700 mmHg, preferably from 10 mmHg to 300 mmHg. Further, it is preferable to remove impurities and the like by filtering them with a microfilter or the like at the time of injection into the mold, from the viewpoint of further improving the quality of the optical material of the present invention.

The production of the optical material of the present invention is carried out by injecting a mixture of the raw materials and additives adjusted as described above into a mold and then polymerizing and curing the mixture.
In the case of heat polymerization, the curing time is 0.05 to 100 hours,
In the case of heat polymerization, it is usually from 3 to 48 hours, and the curing temperature is from -10 to 160C, usually from -10 to 140C. More specifically, preferred heat cure temperatures and times are from 20 to 140 ° C. for 6 to 48 hours. The curing temperature may be a constant temperature, a rising temperature, a falling temperature, or a combination of a constant temperature and a rising temperature, or a combination of a constant temperature, a rising temperature, and a falling temperature. It doesn't matter. Preferred is a combination of constant temperature and elevated and decreased temperatures. After curing,
Annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the distortion of the optical material of the present invention.

[0022]

According to the lens material of the present invention and the method for producing the same, a lens material having a high refractive index of 1.58 to 1.64, a high Abbe number, excellent heat resistance and peeling during casting polymerization is obtained. Thus, it was possible to produce from a safe raw material under a relatively short polymerization condition.

[0023]

The present invention will be described in more detail with reference to the following examples. The physical properties of the optical material of the present invention were measured under the following method conditions. The refractive index and Abbe number were evaluated by Abbe refractometer, and the heat resistance was evaluated by Vicat softening point temperature. The softening point was defined as the temperature at which the needle penetrated 0.1 mm at a load of 5 kg and a heating rate of 1 ° C./min. Regarding the evaluation of peeling, ◎ indicates that no streaks were observed on the surface of the molded body, は indicates that extremely thin streaks were observed on the surface of the molded body, and x indicates that the surface was clear. Was taken. Regarding the evaluation of water absorption, a -6D lens having a center thickness of 1.0 mm was immersed in water at 25 ° C for 24 hours, and ◎ indicates that the lens surface was not deformed, and ○ indicates that the lens surface was slightly deformed. In the case where it was seen, the symbol x indicates that the lens surface was deformed. The abbreviations in the examples are as follows. Pentaerythritol tetraacrylate: TMMTA Trimethylolpropane trimethacrylate: TMPT dipentaerythritol hexaacrylate: DPEHA Pentaerythritol triacrylate: TMM3A 2-hydroxy-1,3-dimethacryloxypropane: GDM divinylbenzene: DVB ethylvinylbenzene: EVB bis (2-mercaptoethyl) sulfide: BMES 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane: BMEMP 2- (2-mercaptoethylthio) -1,3-dimercaptopropane: MEMP 2,5 -Bis (mercaptomethyl) -1,4-dithiane: BMDT glycidyl methacrylate: GMA

Example 1 (a) As a composition, 51 parts by weight of a mixture of TMMTA (the number of acryloyl groups in the molecule 4: 77% by weight) and TMM3A (the number of acryloyl groups in the molecule 3 and the number of hydroxyl groups 1: 23% by weight) b) A mixture of DVB and EVB (D
30 parts by weight (96% by weight as VB) and 0.5 part by weight of GMA as the composition (d) were mixed at 25 ° C. for 1 hour to form a uniform solution. Thereafter, as a composition (c), 19 parts by weight of BMES (sulfur content in the C composition: 62.3% by weight) was added,
Further, 0.3 part by weight of 1,1′-azobis (cyclohexane-1-carbonitrile) was added as an initiator to make the mixture uniform, and degassed and mixed under reduced pressure of about 10 mmHg.
The obtained mixture is poured into a mold (composed of a glass mold and a gasket) adjusted to have a center thickness of 1 mm, and the temperature is increased linearly from 50 ° C to 120 ° C over 18 hours. At 120 ° C. for 2 hours for polymerization and curing. The refractive index, Abbe number, and Vicat softening point temperature of the obtained lens material were measured and are shown in Table 1. (A) the proportion of meth (a) acrylate having a hydroxyl group in the composition, the average number of meth (a) acryloyl groups per molecule, and (c)
The sulfur content in the composition, the ratio of the total number of moles of all vinyl groups and all meth (a) acryloyl groups to the number of moles of all mercapto groups in the mixed composition (total of all vinyl groups and all meth (a) acryloyl groups) (Moles / moles of all mercapto groups) are also shown in Table 1. No peeling during polymerization, surface condition,
The water absorption, refractive index, Abbe number, and heat resistance were all excellent. Examples 2 to 3, 5 to 9 and 12 to 15 Example 1 was changed to the raw materials and compositions shown in Table 1, and this was repeated to obtain lens materials having various compositions. The results are shown in Table 1. (A), (b), (c), (d) in the mixed composition
Each composition of the composition, (a) the proportion of meth (a) acrylate having a hydroxyl group in the composition, and 1 of the meth (a) acryloyl group
The average number per molecule, (c) the sulfur content in the composition, the ratio of the total number of moles of all vinyl groups and all meth (a) acryloyl groups to the number of moles of all mercapto groups (all vinyl groups and Under the condition that the total number of moles of all meth (a) acryloyl groups / the number of moles of all mercapto groups) simultaneously satisfies a specific range, there is no peeling during polymerization, and water absorption, surface state, refractive index, Abbe number, heat resistance Both sexes were excellent. Example 4 (a) 45 parts by weight of a mixture of TMMTA (number of acryloyl groups in the molecule: 77% by weight) and TMM3A (number of acryloyl groups in the molecule, number of hydroxyl groups: 1: 23% by weight) as the composition (b) Mixture of DVB and EVB (D
96 parts by weight as VB) 25 parts by weight, (d) 0.5 parts by weight of GMA as a composition, 0.1 parts by weight of 2,6-di-tert-butyl-4-methylphenol as an antioxidant, ultraviolet absorber As 2- (2-hydroxy-5-t
er-octylphenyl) benzotriazole 0.1
The parts by weight were mixed at 25 ° C. for 1 hour to obtain a homogeneous solution. Thereafter, 30 parts by weight of BMES (sulfur content in the C composition: 62.3% by weight) was added as the composition (c), and 1,1′-azobis (cyclohexane-1-carbonitrile) was added as an initiator at 0%. 3 parts by weight to make the mixture uniform and 10 m
After degassing and mixing under reduced pressure of about mHg, the obtained mixture was poured into a mold (constituted of a glass mold and a gasket) adjusted to have a center thickness of 1 mm,
After linearly raising the temperature from 50 ° C. to 120 ° C. over 18 hours, it was kept at 120 ° C. for 2 hours to carry out polymerization and curing. The refractive index, Abbe number, and Vicat softening point temperature of the obtained lens material were measured and are shown in Table 1. Further, (a) the proportion of meth (a) acrylate having a hydroxyl group in the composition, the average number of meth (a) acryloyl groups per molecule, (c) the sulfur content in the composition, and the total content in the mixed composition. Vinyl group and all meta (A)
Table 1 also shows the ratio of the total number of moles of acryloyl groups to the number of moles of all mercapto groups (total number of moles of all vinyl groups and all meth (a) acryloyl groups / number of moles of all mercapto groups). There was no peeling during polymerization, and the surface state, water absorption, refractive index, Abbe number, and heat resistance were all excellent. Example 10 (a) As a composition, 45 parts by weight of a mixture of TMMTA (number of acryloyl groups in the molecule: 4: 77% by weight) and TMM3A (number of acryloyl groups in the molecule, number of hydroxyl groups: 1: 23% by weight), (b) Composition Mixture of DVB and EVB (D
25 parts by weight of 96% by weight as VB), 25 parts by weight of (d) the composition, 10 parts by weight of GMA, and 0.02 parts by weight of a mixed sodium salt of mono- and diester phosphates of tetraethylene glycol dodecyl ether as an internal mold release agent at 25 ° C. 1
The mixture was mixed for a time to obtain a homogeneous solution. Thereafter, 30 parts by weight of BMES (sulfur content in the C composition: 62.3% by weight) was added as the composition (c), and 1,1′-azobis (cyclohexane-1-carbonitrile) was added as an initiator at 0%. After adding 0.3 parts by weight to make the mixture uniform, degassing and mixing under reduced pressure of about 10 mmHg, the resulting mixture was adjusted to have a center thickness of 1 mm (consisting of a glass mold and a gasket). After the temperature was linearly raised from 50 ° C. to 120 ° C. over 18 hours, the mixture was kept at 120 ° C. for 2 hours to cure by polymerization. The refractive index, Abbe number, and Vicat softening point temperature of the obtained lens material were measured and are shown in Table 1.
Further, (a) the proportion of meth (a) acrylate having a hydroxyl group in the composition, the average number of meth (a) acryloyl groups per molecule, (c) the sulfur content in the composition, and the total content in the mixed composition. The ratio of the total number of moles of vinyl groups and all meth (a) acryloyl groups to the number of moles of all mercapto groups (the total number of moles of all vinyl groups and all meth (a) acryloyl groups / the number of moles of all mercapto groups) is simultaneously displayed. 1 is shown. There was no peeling during polymerization, and the water absorption, surface state, refractive index, Abbe number, and heat resistance were all excellent. Example 11 (a) As a composition, 45 parts by weight of a mixture of TMMTA (number of acryloyl groups in the molecule 4: 77% by weight) and TMM3A (number of acryloyl groups in the molecule 3, number of hydroxyl groups 1: 23% by weight), (b) Composition Mixture of DVB and EVB (D
25 parts by weight (96% by weight as VB) and 1 part by weight of GMA as the composition (d) were mixed at 25 ° C. for 1 hour to form a homogeneous solution. Thereafter, as a composition (c), 30 parts by weight of BMES (sulfur content in the C component: 62.3% by weight) was added, and 2-hydroxy-4-methoxybenzophenone and t
-Butyl peroxy neodecanoate mixed composition 1
After adding 0.3 parts by weight and 0.1 parts by weight with respect to 00 parts by weight, respectively, the mixture was made uniform, degassed and mixed under reduced pressure of about 10 mmHg, and the resulting mixture was adjusted so that the center thickness became 1 mm. The mold was injected into a mold (composed of a glass mold and a gasket), and irradiated with a 1 kW high-pressure mercury lamp at a distance of 30 cm from both sides of the mold for 10 minutes to polymerize and cure. After demolding, annealing was performed at 120 ° C. for 1 hour. The refractive index, Abbe number, and Vicat softening point temperature of the obtained lens material were measured and are shown in Table 1. Also, (a) the proportion of meth (a) acrylate having a hydroxyl group in the composition, the average number of meth (a) acryloyl groups per molecule, (c) the sulfur content in the composition, and the total content in the mixed composition. The ratio of the total number of moles of vinyl groups and all meth (a) acryloyl groups to the number of moles of all mercapto groups (total number of moles of all vinyl groups and all meth (a) acryloyl groups / number of moles of all mercapto groups) is also shown at the same time. 1 is shown. The molded article did not peel off during polymerization, and was excellent in surface state, water absorption, refractive index, Abbe number, and heat resistance.

Comparative Example 1 The same operation as in Example 1 was performed without using the composition (d). The results are shown in Table 1. (D) Since the composition was not used, peeling occurred during polymerization, and the surface condition of the lens was poor. Comparative Example 2 The same operation as in Example 3 was performed without using the composition (d). The results are shown in Table 1. (D) Since the composition was not used, peeling occurred during polymerization, and the surface condition of the lens was poor. Comparative Example 3 The same operation as in Example 12 was performed without using the composition (d). The results are shown in Table 1. (D) Since the composition was not used, peeling occurred during polymerization, and the surface condition of the lens was poor. Comparative Example 4 The same operation as in Example 3 was performed, except that GMA was used as the composition (d).
The test was performed using 30 parts by weight of GMA instead of 0.5 part by weight. The results are shown in Table 1. (D) Since the amount of the composition used exceeded the upper limit of the present invention, the heat resistance was low and the high refractive index which is the gist of the present invention was not exhibited. Comparative Example 5 The same operation as in Example 12 was performed, except that GMA was used as the composition (d).
The test was performed using 30 parts by weight of GMA instead of 0.5 part by weight. The results are shown in Table 1. (D) Since the amount of the composition used exceeded the upper limit of the present invention, the heat resistance was low and the high refractive index which is the gist of the present invention was not exhibited. Comparative Example 6 The same operation as in Example 15 was performed without using the composition (d). The results are shown in Table 1. (D) Since the composition was not used, peeling occurred during polymerization, and the surface condition of the lens was poor.

[0026]

[Table 1]

[Table 2]

[Table 3]

Claims (6)

[Claims] (A) one or more meth (a) acrylate compounds having two or more and six or less acryloyl groups and / or methacryloyl groups in one molecule,
A composition having an average of 2 or more and 6 or less acryloyl groups and / or methacryloyl groups per molecule in the composition is more than 5% by weight and 70% by weight or less. (B) Divinylbenzene and fragrance in one molecule Group vinyl group,
A composition comprising a monounsaturated compound having one acryloyl group or methacryloyl group and having divinylbenzene in an amount of 40% by weight or more based on a total of 100% by weight of 15% to 35% by weight (c) 1 molecule A composition comprising one or more aliphatic polymercapto compounds having two or more mercapto groups in the molecule and having no electron withdrawing group in the molecule, and having a sulfur content of 35% by weight or more in the composition. (D) one or more epoxy compounds selected from the group of compounds having one or more epoxy groups by (a), (b),
A wholly aromatic vinyl in a mixed composition comprising 0.01 to 20 parts by weight based on 100 parts by weight of the total of (c), and comprising the total of each of the compositions of (a), (b) and (c); Ratio of the total number of moles of all the groups and all the meta (a) acryloyl groups to the number of moles of all the mercapto groups (total aromatic vinyl groups and all meta (a)
Total number of moles of acryloyl group / number of moles of all mercapto groups)
Is obtained by polymerizing a mixed composition having 1.3 to 7.
A lens material having a high refractive index, a high Abbe number, and a high heat resistance, having a refractive index of 1.58 to 1.64 and having improved adhesion to a mold during casting polymerization. 2. The composition (a) comprises one or more meth (acrylate) compounds having at least 2 and at most 6 acryloyl groups and / or methacryloyl groups per molecule, and these compounds 2. The lens material according to claim 1, wherein a composition in which 5 mol% to 95 mol% of the above is a hydroxymeth (a) acrylate compound having a hydroxyl group is used in an amount of more than 5% by weight and 70% by weight or less. 3. The composition (a) comprises one or more meth (acrylic) acrylate compounds having at least 2 and at most 6 acryloyl groups and / or methacryloyl groups per molecule, and these compounds The lens material according to claim 1, wherein a composition in which 5 mol% to 50 mol% of the above is a hydroxymeth (a) acrylate compound having a hydroxyl group is used in an amount of more than 5% by weight and 70% by weight or less. 4. The composition (a) comprises one or more meth (acrylate) compounds having at least 2 and at most 6 acryloyl groups and / or methacryloyl groups per molecule, and these compounds A composition in which 5 mol% to 50 mol% of a hydroxy meth (a) acrylate compound having a hydroxyl group is used in an amount of more than 5% by weight and 70% by weight or less,
The lens material according to claim 1, further comprising 0.01 to 5 parts by weight of the composition (d). 5. A method for producing the lens according to claim 1, wherein the composition according to claim 4 is polymerized under heating in the presence of a radical polymerization initiator. 6. A method for producing the lens according to claim 1, wherein the composition according to claim 4 is polymerized under light irradiation in the presence of a photopolymerization initiator.