JPH11279957A - Dyeing of resin having high refractive index and resin dyed thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dyed high refractive index resin having the good balance of an Abbe number with a sufficiently high refractive index and suitable for optical materials, etc., by immersing a resin comprising a sulfur-containing compound in a solution containing a polar inorganic compound, etc., and subsequently dyeing the resin. SOLUTION: This method for dyeing a resin having a high refractive index comprises immersing the resin in a solution containing a polar inorganic compound and/or a polar organic compound (for example, hydrochloric acid or acetic acid) and subsequently dyeing the resin. The resin is obtained by polymerizing and curing a compound, such as bis(β-epithiopropyl) sulfide, having one or more structures of the formula [R<1> is a 1-10C hydrocarbon; R<2> -R<4> are each H or a 1-10C hydrocarbon; Y is O or S; (n) is 0 or 1] in the molecule or a composition containing the compound. A dyed optical material is preferably produced by the dyeing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing optical materials such as plastic lenses, prisms, optical fibers, information recording substrates and filters, and more particularly to a method for producing plastic lenses for spectacles.

[0002]

2. Description of the Related Art Plastic materials are widely used in various optical materials, especially for spectacle lenses in recent years, because they are lightweight, rich in toughness and easy to dye. Optical materials, especially
In addition to the low specific gravity, the performance required for the spectacle lens is a high refractive index and a high Abbe number as optical performance, and high heat resistance and high strength as physical performance. The high refractive index enables the lens to be thinner, the high Abbe number reduces the chromatic aberration of the lens, and the high heat resistance and the high strength are important from the viewpoints of ease of secondary processing and safety and the like. A material having a high refractive index in the prior art is a thermosetting optical material having a thiourethane structure obtained by a reaction between a polythiol compound and a polyisocyanate compound (Japanese Patent Publication No. 4-584).
89, JP-A-5-148340). Furthermore, a technique of polymerizing an epoxy resin or an epithio resin with a compound having two or more functionalities to obtain a lens,
It is proposed in JP-A-1-98615, JP-A-3-81320, and International Publication WO8910575.
However, it goes without saying that a higher refractive index is desirable. On the other hand, another important performance required for the optical material is that the chromatic aberration is small. Since the chromatic aberration becomes better as the Abbe number increases, a material having a high Abbe number is desired. That is, simultaneous realization of a high refractive index and a high Abbe number is also desired. However, in general, the Abbe number tends to decrease with an increase in the refractive index, and in the case of a plastic material made from a compound of the prior art, the Abbe number is about 50 to 55 when the refractive index is 1.50 to 1.55. The limit is about 40 for a refractive index of 1.60 and about 31 for a refractive index of 1.66, and when trying to forcibly achieve a refractive index of 1.70, the Abbe number is about 30 or less, which can withstand practical use. Was not. In order to solve this problem, the present inventors have a refractive index of 1.7 having a small thickness and a low chromatic aberration.
A novel sulfur-containing compound having an epithio structure capable of producing an optical material having an Abbe number of 35 or more has been found, and a patent application has been filed earlier (Japanese Patent Application No. Hei 8-2144631, Japanese Patent Application No. Hei 8
-5797). However, the optical material according to the present invention has poor dyeing properties, and improvement is strongly desired. For this reason, a technique for improving the dyeability of an optical material by polymerizing and curing a composition comprising the sulfur-containing compound and a compound having a polar group was found (Japanese Patent Application No. 9-333120). However, according to the present technology, when a high dyeing property is intended, a large amount of a component other than the compound having an epithio structure must be added, resulting in a remarkable decrease in the refractive index. In order to realize a post-light transmittance of 25%, the refractive index had to be about 1.65. In addition, conventional dyeing techniques use aromatic compounds,
Improvements such as the use of various carriers such as phenolic compounds, alcohols, carboxylic acids, and the same esters, as well as various surfactants, cannot provide a sufficient improvement effect. It has been desired to develop a novel dyeing technique for a high refractive index optical material obtained by polymerizing a compound having an epithio structure and a composition containing the compound, which has a balance between the compound and the Abbe number.

[0003]

The problem to be solved by the present invention is to develop a method for dyeing a resin obtained by polymerizing and curing a sulfur-containing compound having an epithio structure or a composition containing the compound. An object of the present invention is to obtain a dyed high-refractive-index resin having a sufficiently high refractive index and a balance between Abbe number, which cannot be achieved by the technique.

[0004]

The object of the present invention is achieved by polymerizing and curing a compound having at least one structure represented by the following formula (1) in one molecule or a composition containing the compound. This problem has been solved by a dyeing method characterized by immersing a resin in a liquid containing a polar inorganic and / or organic compound, and then dyeing the resin, and an optical material dyed by this method.

Embedded image (Wherein, R ¹ is a hydrocarbon having 1 to 10 carbon atoms, R ² , R ³
, R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents S or O, and n represents 0 or 1. )

In order to exhibit a high refractive index and a high Abbe number, which are one of the main points of the present invention, and a good balance between both, R ¹ in the formula (1) is preferably methylene or ethylene, and 1) R ² , R ³ and R ⁴ in the formula are preferably hydrogen or a methyl group. More preferably R
¹ is methylene and R ² , R ³ and R ⁴ are hydrogen. The compound having one or more structures represented by the formula (1) in one molecule of the present invention includes all organic compounds satisfying this condition, and preferably the compound represented by the formula (1) It is a compound having 3 or more, more preferably 2 or more. Specific examples of the compound having one structure represented by the formula (1) in one molecule are as follows. (A) Organic compound having one or more epithio groups (B) Organic compound having one or more epithioalkyloxy groups (C) Organic compound having one or more epithioalkylthio groups (A) and (B) , (C) have a main skeleton of a chain, an aliphatic ring, an aromatic compound, a heterocyclic compound containing nitrogen, oxygen, and sulfur atoms, and include an epithio group, an epithioalkyloxy group, Alkylthio groups may be simultaneously present in one molecule. Further, these compounds may contain a bond such as a sulfide, ether, sulfone, ketone, ester, amide, or urethane in the molecule.

A preferred specific example of the organic compound having one or more epithio groups in the above (A) is a compound in which one or more epoxy groups of an epoxy group (not a glycidyl group) are substituted with an epithio group. An example can be given. Taking a more specific example method, the following can be given as typical examples. Organic compound having a linear aliphatic skeleton: 1,1-bis (epithioethyl) methane, 1- (epithioethyl) -1-
(Β-epithiopropyl) methane, 1,1-bis (β-
Epithiopropyl) methane, 1- (epithioethyl)-
1- (β-epithiopropyl) ethane, 1,2-bis (β-epithiopropyl) ethane, 1- (epithioethyl) -3- (β-epithiopropyl) butane, 1,3-
Bis (β-epithiopropyl) propane, 1- (epithioethyl) -4- (β-epithiopropyl) pentane,
1,4-bis (β-epithiopropyl) butane, 1-
(Epithioethyl) -5- (β-epithiopropyl) hexane, 1- (epithioethyl) -2- (γ-epithiobutylthio) ethane, 1- (epithioethyl) -2-
[2- (γ-epithiobutylthio) ethylthio] ethane, 1,1,1-tris (β-epithiopropyl) propane, 1,3-bis (β-epithiopropyl) -1-
(Β-epithiopropyl) -2-thiapropane, 1,5
-Bis (β-epithiopropyl) -2,4-bis (β-
Epithiopropyl) -3-thiapentane, compounds having an aliphatic cyclic skeleton: 1,3 and 1,4-
Bis (epithioethyl) cyclohexane, 1,3 and 1,4-bis (β-epithiopropyl) cyclohexane, bis [4- (epithioethyl) cyclohexyl] methane, bis [4- (β-epithiopropyl) cyclohexyl] methane, 2,2-bis [4- (epithioethyl)
Cyclohexyl] propane, 2,2-bis [4- (β-
Epithiopropyl) cyclohexyl] propane, bis [4- (β-epithiopropyl) cyclohexyl] sulfide, bis [4- (epithioethyl) cyclohexyl] sulfide, 2,5-bis (epithioethyl)-
1,4-dithiane, 2,5-bis (β-epithiopropyl) -1,4-dithiane, 4-epithioethyl-1,2
-Cyclohexene sulfide, 4-epoxy-1,2-
Cyclohexene sulfide Compounds having an aromatic skeleton: 1,3 and 1,4-bis (epithioethyl) benzene, 1,3 and 1,4-bis (β-epithiopropyl) benzene, bis [4- (epithioethyl) phenyl] Methane, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4
-(Epithioethyl) phenyl] propane, 2,2-bis [4- (β-epithiopropyl) phenyl] propane, bis [4- (epithioethyl) phenyl] sulfide, bis [4- (β-epithiopropyl) phenyl Sulfide, bis [4- (epithioethyl) phenyl] sulfone, bis [4- (β-epithiopropyl) phenyl] sulfone, 4,4′-bis (epithioethyl) biphenyl and the like, 4,4′-bis (β- Epithiopropyl)
Biphenyl and the like, and compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also exemplified.

Preferred specific examples of the organic compound (B) having one or more epithioalkyloxy groups include an epoxy compound derived from epihalohydrin in which one or more glycidyl groups are replaced with an epithioalkyloxy group (thioglycidyl group). A typical example is a compound substituted with: Specific examples of the epoxy compound include condensation of a polyphenol compound such as hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, and a novolak resin with epihalohydrin. Phenolic epoxy compounds produced; 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, glycerin, trimethylolpropane trimethacrylate, pentaerythritol, 1,3- And polyhydric alcohol compounds such as 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A · ethylene oxide adduct, bisphenol A · propylene oxide adduct, and epihalohydrin Alcoholic epoxy compounds produced by condensation; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, Hexahydroterephthalic acid, hetonic 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 or 1,4-di- (4-piperidyl) -butane with epihalohydrin;
Urethane epoxy compounds produced from phenol compounds, diisocyanates, glycidol and the like can be mentioned. If you take a more specific example method,
The following can be given as typical examples. Organic compound having a linear aliphatic skeleton: bis (β-epithiopropyloxy) ether bis (β-epithiopropyloxy) methane, 1,2-
Bis (β-epithiopropyloxy) ethane, 1,3-
Bis (β-epithiopropyloxy) propane, 1,2
-Bis (β-epithiopropyloxy) propane, 1-
(Β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) propane, 1,4-bis (β-
Epithiopropyloxy) butane, 1,3-bis (β-
Epithiopropyloxy) butane, 1- (β-epithiopropyloxy) -3- (β-epithiopropyloxymethyl) butane, 1,5-bis (β-epithiopropyloxy) pentane, 1- (β -Epithiopropyloxy) -4- (β-epithiopropyloxymethyl) pentane, 1,6-bis (β-epithiopropyloxy) hexane, 1- (β-epithiopropyloxy) -5-
(Β-epithiopropyloxymethyl) hexane, 1-
(Β-epithiopropyloxy) -2-[(2-β-epithiopropyloxyethyl) oxy] ethane, 1-
(Β-epithiopropyloxy) -2-[[2- (2-
chain organic compounds such as β-epithiopropyloxyethyl) oxyethyl] oxy] ethane and the like; tetrakis (β-epithiopropyloxymethyl) methane;
1,1-tris (β-epithiopropyloxymethyl)
Propane, 1,5-bis (β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) -3
-Thiapentane, 1,5-bis (β-epithiopropyloxy) -2,4-bis (β-epithiopropyloxymethyl) -3-thiapentane, 1- (β-epithiopropyloxy) -2,2 -Bis (β-epithiopropyloxymethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3-thiahexane, 8-
Bis (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy)-
4,5 bis (β-epithiopropyloxymethyl)-
3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,4-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-
Bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiopropyloxymethyl) -3,6-
Dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,9-bis (β
-Epithiopropyloxy) -5- (β-epithiopropyloxymethyl) -5-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,7-dithianonane, 1,10-bis (β -Epithiopropyloxy)-
5,6-bis [(2-β-epithiopropyloxyethyl) oxy] -3,6,9-trithiadecane, 1,11
-Bis (β-epithiopropyloxy) -4,8-bis (β-epithiopropyloxymethyl) -3,6,9-
Trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane,
1,11-bis (β-epithiopropyloxy) -5
7-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,6,9-trithiaundecane, 1,1
1-bis (β-epithiopropyloxy) -4,7-bis (β-epithiopropyloxymethyl) -3,6,9
-Compounds having an aliphatic cyclic skeleton such as trithiaundecane: 1,3 and 1,4-
Bis (β-epithiopropyloxy) cyclohexane,
1,3 and 1,4-bis (β-epithiopropyloxymethyl) cyclohexane, bis [4- (β-epithiopropyloxy) cyclohexyl] methane, 2,2-
Bis [4- (β-epithiopropyloxy) cyclohexyl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide, 2,5-bis (β
Compounds having an aromatic skeleton, such as -epithiopropyloxymethyl) -1,4-dithiane and 2,5-bis (β-epithiopropyloxyethyloxymethyl) -1,4-dithiane: 1, 3, and 1 , 4-Bis (β-epithiopropyloxy) benzene, 1,3 and 1,4-bis (β-epithiopropyloxymethyl)
Benzene, bis [4- (β-epithiopropyloxy)
Phenyl] methane, 2,2-bis [4- (β-epithiopropyloxy) phenyl] propane, bis [4- (β
-Epithiopropyloxy) phenyl] sulfide, bis [4-([beta] -epithiopropyloxy) phenyl] sulfone, 4,4'-bis ([beta] -epithiopropyloxy) biphenyl and the epithio group of these compounds A compound in which at least one of the hydrogens of the above is substituted with a methyl group is also an example.

A preferred specific example of the organic compound (C) having one or more epithioalkylthio groups is a compound having a mercapto group and an epoxyalkylthio group of an epoxy compound derived from epihalohydrin (specifically, β
-Epoxypropylthio group) can be exemplified by a compound in which one or more are substituted with an epithioalkylthio group. If a more specific example method is used, the following can be given as typical examples. Organic compounds having a linear aliphatic skeleton: bis (β-epithiopropylthio) sulfide, bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3- Bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2
-(Β-epithiopropylthiomethyl) propane, 1,
4-bis (β-epithiopropylthio) butane, 1,3
-Bis (β-epithiopropylthio) butane, 1- (β
-Epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β -Epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (Β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- (β-epithiopropylthio) -2-[[2- (2-β-epi Thiopropylthioethyl) thioethyl] thio] ethanetetrakis (β
-Epithiopropylthiomethyl) methane, 1,1,1-
Tris (β-epithiopropylthiomethyl) propane,
1,5-bis (β-epithiopropylthio) -2- (β
-Epithiopropylthiomethyl) -3-thiapentane,
1,5-bis (β-epithiopropylthio) -2,4-
Bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropylthio) -2,2-
Bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-
Thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,
6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-
Epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane,
8-bis (β-epithiopropylthio) -2,4,5-
Tris (β-epithiopropylthiomethyl) -3,6-
Dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10
-Bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio]-
3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11 -Bis (β-epithiopropylthio)-
5,7-bis (β-epithiopropylthiomethyl)-
3,6,9-trithiaundecane, 1,11-bis (β
-Epithiopropylthio) -5,7-[(2-β-epithiopropylthioethyl) thiomethyl] -3,6,9-
Trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane Ester group and epithioalkylthio group A chain compound having the following formula: tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthio) acetylmethyl] propane, tetra [2- (Β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) acetylmethyl] propane, etc. Compounds having an aliphatic cyclic skeleton: 1,3 and 1,4-
Bis (β-epithiopropylthio) cyclohexane,
1,3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyl) Thio) cyclohexyl]
Propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-
Bis (β-epithiopropylthioethylthiomethyl)-
Compounds having an aromatic skeleton such as 1,4-dithiane: 1,3 and 1,4-bis (β-epithiopropylthio) benzene, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) Benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl Phenyl] sulfide, bis [4-
(Β-epithiopropylthio) phenyl] sulfone,
Specific examples thereof include 4,4′-bis (β-epithiopropylthio) biphenyl and the like, and compounds in which at least one hydrogen of the β-epithiopropyl group of these compounds is substituted with a methyl group.

Further, organic compounds having an unsaturated group are also included in the above (A) to (C). Preferred examples thereof include vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate. , Thioglycidyl acrylate,
Allylthioglycidyl ether and the like can be mentioned.

Other specific examples of the compound having one epithio group include compounds such as ethylene sulfide, propylene sulfide and thioglycidol, and thiol of monocarboxylic acid such as acetic acid, propionic acid and benzoic acid. And thioglycidyl ethers such as glycidyl esters, methylthioglycidyl ether, ethylthioglycidyl ether, propylthioglycidyl ether, and butylthioglycidyl ether.

Of the above, more preferred are (B) organic compounds having at least one epithioalkyloxy group and (C) organic compounds having at least one epithioalkylthio group, which are specific examples described above. Particularly, particularly preferred is (C) an organic compound having one or more epithioalkylthio groups. Specific examples of particularly preferable ones are bis (β-epithiopropyl) sulfide and linear, branched compounds, aliphatic cyclic and aromatic compounds having two or more β-epithiopropylthio groups which are the specific examples described above. It is. The most preferred of these is bis (β-epithiopropyl) sulfide.

The curing catalyst used for producing an optical material in the present invention includes amines, phosphines, and quaternary amines.
Quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids,
Lewis acids, organic acids, silicic acids, tetrafluoroboric acids and the like can be mentioned. Specific examples include (1) ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, Laurylamine, mystyrylamine, 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, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine, furfurylamine, etc. Primary amines: 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, 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-amino Methylpiperidine, 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-phenylenediamine, 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'-diaminodiphenyl ether, 4,
4'-thiodianiline, 4,4'-diaminodiphenylsulfone, 4,4'-diaminoditolylsulfone, 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, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4 Primary polyamines such as -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,
Secondary amines such as 4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole and morpholine; 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-
Secondary polyamines such as piperidyl) butane and tetramethylguanidine; 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, dicyclohexylethylamine, cyclohexyldiethylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N-diethylethanol Amine, N, N-dimethylethanolamine, N-ethyldiethanolamine, 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-diethylaniline, pyridine, quinoline, N-methylmorpholine, N
Tertiary amines such as -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,
Tertiary polyamines such as N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethylaminomethyl) phenol and heptamethylisobiguanide; imidazole, N-methylimidazole;
2-methylimidazole, 4-methylimidazole,
N-ethylimidazole, 2-ethylimidazole, 4
-Ethylimidazole, N-butylimidazole, 2-
Butyl imidazole, N-undecyl imidazole, 2
-Undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-
Methyl imidazole, 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 alkylimidazole and isocyanuric acid, and condensates of alkylimidazole and formaldehyde; Amidines such as 1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; amine compounds represented by the above. (2) Complexes of the amines of (1) with borane and boron trifluoride. (3) trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-
Butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine , Tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, tris (4-methylphenyl)
Phosphines such as phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, and chlorodiphenylphosphine; (4) tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride,
Tetraethylammonium bromide, tetraethylammonium acetate, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide,
Tetra-n-butylammonium iodide, tetra-
n-butylammonium acetate, tetra-n-butylammonium borohydride, tetra-n-butylammonium hexafluorophosphite, tetra-n
-Butylammonium hydrogensulfite, tetra-n-butylammonium tetrafluoroborate, tetra-n-butylammonium tetraphenylborate, tetra-n-butylammonium paratoluenesulfonate, tetra-n-hexylammonium chloride, tetra-n -Hexyl ammonium bromide, tetra-n-hexylammonium acetate,
Tetra-n-octylammonium chloride, tetra-n-octylammonium bromide, tetra-n-
Octyl ammonium acetate, trimethyl-n-octyl ammonium chloride, trimethyl benzyl ammonium chloride, trimethyl benzyl ammonium bromide, triethyl-n-octyl ammonium chloride, triethyl benzyl ammonium chloride, triethyl benzyl ammonium bromide, tri-n-butyl-n-octyl ammonium Chloride,
Tri-n-butylbenzylammonium fluoride,
Tri-n-butylbenzylammonium chloride, tri-n-butylbenzylammonium bromide, tri-n-butylbenzylammonium iodide, methyltriphenylammonium chloride, methyltriphenylammonium bromide, ethyltriphenylammonium chloride, ethyltriphenylammonium Bromide, n-butyltriphenylammonium chloride, n-butyltriphenylammonium bromide, 1-methylpyridinium bromide, 1-ethylpyridinium bromide, 1-n-butylpyridinium bromide, 1-n-hexylpyridinium bromide,
1-n-octylpyridinium bromide, 1-n-dodecylpyridinium bromide, 1-n-phenylpyridinium bromide, 1-methylpicolinium bromide, 1-ethylpicolinium bromide, 1-n-butylpicolinium bromide, 1-n -Hexylpicolinium bromide, 1-n-octylpicolinium bromide, 1-n-dodecylpicolinium bromide, 1-
quaternary ammonium salts such as n-phenylpicolinium bromide; (5) tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide,
Tetra-n-butylphosphonium chloride, tetra-
n-butylphosphonium bromide, tetra-n-butylphosphonium iodide, tetra-n-hexylphosphonium bromide, tetra-n-octylphosphonium bromide, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, Ethyltriphenylphosphonium iodide, n-butyltriphenylphosphonium bromide, n-butyltriphenylphosphonium iodide, n-hexyltriphenylphosphonium bromide, n-octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetrakishydroxymethylphosphonium chloride , Tetrakishydroxymethylphosphonium bromide, tetrakis Hydroxyethyl phosphonium chloride, phosphonium salts such as tetrakis hydroxybutyl phosphonium chloride. (6) trimethylsulfonium bromide, triethylsulfonium bromide, tri-n-butylsulfonium chloride, tri-n-butylsulfonium bromide, tri-n-butylsulfonium iodide, tri-
n-butylsulfonium tetrafluoroborate, tri-n-hexylsulfonium bromide, tri-n-
Sulfonium salts such as octylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium bromide, and triphenylsulfonium iodide. (7) Iodonium salts such as diphenyliodonium chloride, diphenyliodonium bromide, and diphenyliodonium iodide. (8) Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid and half esters thereof. (9) Lewis acids represented by boron trifluoride etherate of boron trifluoride. (10) Organic acids and their half esters. (11) Silicic acid, tetrafluoroboric acid. And so on. Among these, amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, and secondary iodonium salts are preferred because the cured product is less colored. These may be used alone or in combination of two or more.

The composition of the present invention may be a compound having one or more functional groups capable of reacting with the epithio group in the formula (1), or one or more of these functional groups and another functional group capable of homopolymerization. And a compound having at least one functional group capable of homopolymerization, and a compound having one functional group capable of reacting with an epithio group and capable of homopolymerization. You can also. (1)
Examples of the compound having two or more functional groups capable of reacting with the epithio group in the formula include an epoxy compound and a polycarboxylic anhydride. On the other hand, compounds having at least one functional group capable of reacting with an epithio group and at least one other functional group capable of being homopolymerized include epoxy having an unsaturated group such as methacryl, acryl, allyl, vinyl and aromatic vinyl. Compounds, carboxylic anhydrides and the like. Examples of the compound having at least one functional group capable of being homopolymerized include methacryl,
Compounds having an unsaturated group such as acryl, allyl, vinyl, aromatic vinyl and the like can be mentioned. Specific examples of the compound having two or more functional groups capable of reacting with the epithio group are shown below.

As specific examples of the epoxy compound, those mentioned in the section of the compound having an epithiooxy group can be given as specific examples.

Specific examples of the polyhydric carboxylic acid anhydrides include those mentioned above as the raw materials to be reacted with epihalohydrin described in the above-mentioned epoxy compound.

The following are representative specific examples of compounds having at least one functional group capable of reacting with an epithio group and at least one other functional group capable of homopolymerization. Examples of the epoxy compound having an unsaturated group include vinylphenyl glycidyl ether, vinylbenzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether.

Specific examples of the compound having one or more homopolymerizable functional groups include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate. ,
Triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate,
1,3-butylene glycol dimethacrylate, 1,6
-Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 2,2-bis [4- (acryloxyethoxy) Phenyl) propane,
2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4-
(Methacryloxydiethoxy) phenyl] propane,
2,2-bis [4- (acryloxy-polyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate Pentaerythritol tetramethacrylate, bis (2,2,2-trimethylolethyl) ether hexaacrylate, bis (2,2,2-trimethylolethyl) ether hexamethacrylate, etc.
Compounds having an ester structure of alcohol and methacrylic acid having a valency or higher; allyl compounds such as allyl sulfide, diallyl phthalate, and diethylene glycol bisallyl carbonate; vinyl compounds such as acrolein, acrylonitrile, and vinyl sulfide; styrene, α
And aromatic vinyl compounds such as methylstyrene, methylvinylbenzene, ethylvinylbenzene, α-chlorostyrene, chlorovinylbenzene, vinylbenzyl chloride, paradivinylbenzene, and metadivinylbenzene.

Preferred specific examples of the compound having one functional group capable of reacting with the epithio group and capable of homopolymerization include a compound having one epoxy group. More specifically, ethylene oxide, propylene oxide, monoepoxy compounds such as glycidol, acetic acid, propionic acid, glycidyl esters of monocarboxylic acids such as benzoic acid, methyl glycidyl ether,
Glycidyl ethers such as ethyl glycidyl ether, propyl glycidyl ether and butyl glycidyl ether;

A compound having two or more functional groups capable of reacting with the epithio group in the formula (1) of the composition of the present invention, or
These compounds having one or more functional groups and another compound having one or more homopolymerizable functional groups can be produced by curing polymerization in the presence of a curing polymerization catalyst. As the curing catalyst, the above-mentioned amines, phosphines, acids and the like are used. As a specific example, the above-mentioned ones are used here, but the amount used must be an amount that simultaneously satisfies the relations of the above-mentioned equations (3) to (5).

Further, when a compound having an unsaturated group is used, it is preferable to use a radical polymerization initiator as a polymerization accelerator. The radical polymerization initiator is not particularly limited as long as it generates a radical by heating or ultraviolet light or an electron beam. For example, cumyl peroxy neodecanoate, diisopropyl peroxy dicarbonate, diallyl peroxy dicarbonate, di-n- Propyl peroxy dicarbonate, dimyristyl peroxy dicarbonate, cumyl peroxy neohexanoate, ter-hexyl peroxy neodecanoate,
ter-butyl peroxy neodecanoate, ter-
Hexylperoxyneohexanoate, ter-butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide,
Peroxides such as dicumyl peroxide and di-tert-butyl peroxide; hydroperoxides such as cumene hydroperoxide and ter-butyl hydroperoxide; 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-valeronitrile 2,2′-azobis (2-methylpropane), 2,2′-azobis A known thermal polymerization catalyst such as an azo compound such as (2,4,4-trimethylpentane);
Known photopolymerization catalysts such as benzophenone and benzoin benzoin methyl ether are exemplified. Of these, preferred are peroxides, hydroperoxides and azo compounds, more preferred are peroxides and azo compounds, and 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-2,4-dimethyl-valeronitrile, 2,2′-azobis (2-methylpropane) 2,
2'-azobis, (2,4,4-trimethylpentane)
And the like. These can all be mixed and used. The radical polymerization initiator does not correspond to the catalyst of the production method of the present invention, and the blending amount does not need to satisfy the above-mentioned relationship. Further, it is not generally determined because it varies depending on the components of the composition and the curing method, but it is usually 0.01 wt% to 5.0 wt%, preferably 0.1 wt% to 2.0 wt% based on the total amount of the composition. % Range.

In the method for producing an optical material according to the present invention, it is of course possible to further improve the practicality of the obtained material by adding a known additive such as an antioxidant. Further, the optical material of the present invention tends to peel off from the mold during the polymerization, and in some cases, using or adding a known external and / or internal adhesiveness improving agent to improve the adhesion between the obtained cured material and the mold. It needs to be improved. Examples of the internal adhesion improver referred to herein include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
-Refers to a silane compound such as mercaptopropyltrimethoxysilane and the like, and can be used in an amount of 0.0001 to 5 parts by weight based on 100 parts by weight of the composition of the present invention. The composition of the present invention uses a compound having at least one SH group as an antioxidant component alone or in combination with a known antioxidant in order to impart good oxidation resistance to a material after good curing. Is also possible. Examples of the compound having one or more SH groups include mercaptans, thiophenols, and mercaptans and thiophenols having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl, and allyl. Can be More specifically, as mercaptans, methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, allyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n -Tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, tert-nonyl mercaptan, tert-dodecyl mercaptan, benzyl mercaptan, 4-chlorobenzyl mercaptan, methyl thioglycolate, Ethyl thioglycolate, n-butyl thioglycolate, n-octyl thioglycolate, methyl (3- Lecaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3-mercaptopropionate), n-butyl (3-mercaptopropionate), 2-ethylhexyl (3-ercapto) Monomercaptans such as propionate) and n-octyl (3-mercaptopropionate); methanedithiol;
1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane, 1,5-dimercapto-3-oxapentane, 1,
8-dimercapto-3,6-dioxaoctane, 2,2
-Dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, -(2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-
Mercaptopropane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butane Diol bis (2-mercaptoacetate), 1,4-butanediol bis (3
-Mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate),
Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,
3-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4-bis (mercaptomethyl)
Cyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl)-
1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, 2,5-bis (2-mercaptoethyl)- 1-thiane, 1,4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) ether, 2,2-bis ( 4-mercaptophenyl) propane, bis (4-mercaptomethylphenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4-mercaptomethylphenyl) propane, 2,5-dimercapto-1,3 And polymercaptans such as 3,4-thiadiazole and 3,4-thiophedithiol. As thiophenols, thiophenol, 4-
Thiophenols such as tert-butylthiophenol, 2-methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, and 1,4-dimercaptobenzene I can give it. Further, mercaptans and thiophenols having an unsaturated group are specifically shown below. Examples of the mercaptans having an unsaturated group include allyl mercaptan, 2-vinylbenzyl mercaptan, 3-vinylbenzyl mercaptan, 4-vinylbenzyl mercaptan and the like. Examples of the thiophenol having an unsaturated group include 2-vinylthiophenol, 3-vinylthiophenol, and 4-vinylthiophenol. These may be used alone or as a mixture of two or more types.
0.001 to 40 parts by weight can be used for 00 parts by weight.

It is also possible to use a compound having at least one active hydrogen other than an SH group for the purpose of improving the performance such as dyeability and strength. The term "active hydrogen" used herein means, for example, hydrogen of a hydroxyl group, a carboxyl group, an amide group, and 1,2-diketone, 1,3-dicarboxylic acid and its ester, and 3-ketocarboxylic acid and its ester.
Compounds having at least one active hydrogen per molecule include alcohols, phenols, mercapto alcohols, hydroxythiophenols, carboxylic acids, mercaptocarboxylic acids, hydroxycarboxylic acids, amides, and the like. , 3-Diketones, 1,3-dicarboxylic acids and esters thereof, 3-ketocarboxylic acids and esters thereof, and alcohols having unsaturated groups such as vinyl, aromatic vinyl, methacryl, acryl, and allyl, and phenol , Mercapto alcohols, hydroxythiophenols, carboxylic acids, mercaptocarboxylic acids, hydroxycarboxylic acids, amides,
Examples thereof include 1,3-diketones, 1,3-dicarboxylic acid and esters thereof, and 3-ketocarboxylic acid and esters thereof. More specifically, the alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Isobutyl alcohol, sec-butyl alcohol, t
tert-butyl alcohol, n-pentyl alcohol,
Isopentyl alcohol, n-hexyl alcohol, n
-Heptyl alcohol, n-octyl alcohol, n-
Monovalent such as nonyl alcohol, n-decyl alcohol, n-dodecyl alcohol, cyclopentanol, cyclohexanol, 2-methylthioethanol, 2-ethylthioethanol, 2- (n-dodecylthio) ethanol, n-dodecyl hydroxyethyl sulfoxide Alcohols: ethylene glycol, propylene glycol, 1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, polypropylene glycol, glycerol, penta Erythritol monomethacrylate, pentaerythritol monoacrylate,
Pentaerythritol dimethacrylate, pentaerythritol diacrylate, 2,5-dimethyl-3-hexyne-2,5-diol, 2,5-dimethylhexane-
Polyhydric alcohols such as 2,5-diol, trimethylolpropane, pentaerythritol, hydrogenated bisphenol A, 2-hydroxyethyl isocyanurate, and 2-hydroxyethyl cyanurate; and the like. Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol, hydroquinone, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, bisphenol A, bisphenol F, bisphenol Z and the like. Phenols and the like can be mentioned. As mercapto alcohols,
2-mercaptoethanol, 3-mercaptopropanol, 2-mercaptopropanol, 2-hydroxypropylmercaptan, 2-phenyl-2-mercaptoethanol, 2-phenyl-2-hydroxyethylmercaptan, 3-mercapto-1,2-propane Diol, 2
-Mercapto-1,3-propanediol, 2,3-dimercaptopropanol, 1,3-dimercapto-2-
Examples thereof include propanol, 2,2-dimethylpropane-1,3-dithiol, and glyceryl dithioglycolate. As hydroxythiophenols,
2-hydroxythiophenol, 3-hydroxythiophenol, 4-hydroxythiophenol and the like can be mentioned. As carboxylic acids, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, methyl mercaptopropionate, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, cyclohexanecarboxylic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid,
Examples include phthalic acid, isophthalic acid, terephthalic acid, thiodipropionic acid, dithiodipropionic acid, and the like. Examples of mercaptocarboxylic acids include thioglycolic acid, 2-thiopropionic acid, 3-thiopropionic acid, thiolactic acid, mercaptosuccinic acid, thiomalic acid, N- (2
-Mercaptopropionyl) glycine, 2-mercaptobenzoic acid, 2-mercaptonicotinic acid, 3,3-dithioisobutyric acid, dithioglycolic acid, dithiopropionic acid and the like. Hydroxycarboxylic acids include hydroxyacetic acid, α-hydroxypropionic acid, β
-Hydroxypropionic acid, α-hydroxybutyric acid, β-
Hydroxyacetic acid, γ-hydroxybutyric acid, salicylic acid, 3
Amides such as -hydroxybenzoic acid and 4-hydroxybenzoic acid include formamide, N-methylformamide, acetamide, N-methylacetamide, phthalamide, isophthalamide, terephthalamide, benzamide, toluamide, 4-hydroxybenzamide, 3-hydroxybenzamide and the like can be mentioned. Examples of 1,3-diketones include acetylacetone, cyclohexane-1,3,5-trione and the like. Examples of 1,3-dicarboxylic acid and its esters include malonic acid, 2-methylmalonic acid and the like, and mono- and diesters thereof. Examples of 3-ketocarboxylic acid and its esters include acetoacetic acid and its esters. Further, alcohols, phenols, mercaptans, thiophenols, mercapto alcohols, carboxylic acids, and amides having an unsaturated group are specifically shown below. Examples of the alcohol having an unsaturated group include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
2-hydroxypropyl acrylate, 1,3-dimethacryloxy-2-propanol, 1,3-diacryloxy-2-propanol, 1-acryloxy-3-methacryloxy-2-propanol, pentaerythritol trimethacrylate, pentaerythritol triacrylate, bis ( Pentamethacrylate of 2,2,2-trimethylolethyl) ether, pentaacrylate of bis (2,2,2-trimethylolethyl) ether, trimethylolpropane dimethacrylate, trimethylolpropane diacrylate, allyl alcohol, crotyl alcohol , Methylvinylcarbinol, cinnamyl alcohol, 4-vinylbenzyl alcohol, 3-vinylbenzyl alcohol, 2- (4-vinylbenzylthio) ethanol, (3-vinylbenzylthio) ethanol, 1,3-bis (4-vinylbenzylthio) -2
-Propanol, 1,3-bis (3-vinylbenzylthio) -2-propanol, 2,3-bis (4-vinylbenzylthio) -1-propanol, 2,3-bis (3-
Vinylbenzylthio) -1-propanol, 3-phenoxy-2-hydroxypropyl acrylate, 2-hydroxyethyl isocyanurate bis (acrylate),
2-hydroxyethyl isocyanurate bis (methacrylate), 2-hydroxyethyl cyanurate bis (acrylate), 2-hydroxyethyl cyanurate bis (methacrylate), 3-methyl-1-butyn-3-ol, 3-methyl-1 Monohydroxy compounds such as pentyn-3ol and propargyl alcohol; pentaerythritol dimethacrylate, pentaerythritol diacrylate, pentaerythritol monomethacrylate, pentaerythritol monoacrylate, trimethylolpropane monomethacrylate, trimethylolpropane monoacrylate, 2-hydroxy Ethyl isocyanurate mono (acrylate), 2-hydroxyethyl isocyanurate mono (methacrylate), 2-hydroxyethyl cyanu Tomono (acrylate), 2
Polyhydroxy compounds such as hydroxyethyl cyanurate mono (methacrylate), and epoxy compounds described below such as 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane, and acrylic acid or methacrylic acid Unsaturated polyhydroxy compounds formed by an acid addition reaction can be exemplified. Examples of the phenol having an unsaturated group include 2-vinylphenol, 3-vinylphenol, and 4-vinylphenol. Examples of mercapto alcohols having an unsaturated group include 2- (4-vinylbenzylthio)
-2-mercaptoethanol, 2- (3-vinylbenzylthio) -2-mercaptoethanol, and the like. Examples of carboxylic acids having an unsaturated group include acrylic acid, methacrylic acid, crotonic acid, phthalic acid monohydroxyethyl acrylate, maleic acid, fumaric acid,
Monoallyl phthalate, cinnamic acid and the like can be mentioned. Examples of the amide having an unsaturated group include amides of α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and fumaric acid;
Vinyl formamide and the like can be mentioned. From the viewpoint of heat resistance, preferred compounds are mercapto alcohols,
Hydroxythiophenols and alcohols having an unsaturated group. These may be used alone or as a mixture of two or more kinds, and 0.001 to 40 parts by weight can be used with respect to 100 parts by weight of the composition of the present invention.

In the present invention, the method for producing an optical material to be dyed comprises a raw material compound having at least one structure represented by the formula (1) in one molecule, a catalyst and, if desired, the aforementioned antioxidant. Additives such as components, adhesion improvers, antioxidants other than the above-mentioned antioxidant components, and various performance improvers are added in an amount of 0.001% to 80%, preferably 0.01% to the total composition.
After mixing 50%, more preferably 0.01% to 30%,
It is polymerized and cured as described below to obtain an optical material such as a lens. That is, the raw materials after mixing are poured into a glass or metal mold, the polymerization and curing reaction is advanced by heating, and then the mold is removed from the mold.

Before casting a compound having one or more structures represented by the formula (1) in one molecule or a composition thereof, in the presence or absence of a catalyst, with or without stirring, before casting.
After preliminarily polymerizing at 100 to 160 ° C for 0.1 to 72 hours, it is also possible to prepare a composition and perform casting. The preliminary polymerization conditions are preferably between -10 and -1.
1 to 48 hours at 00 ° C, more preferably 1 to 48 hours at 0 to 60 ° C.
Performed in ~ 48 hours. The curing time is 0.1 to 100 hours, usually 1 to 48 hours, and the curing temperature is -10 to 16
0 ° C, usually -10 to 140 ° C. The polymerization can be carried out by holding at a predetermined polymerization temperature for a predetermined time, raising the temperature from 0.1 ° C to 100 ° C / h, lowering the temperature from 0.1 ° C to 100 ° C / h, or a combination thereof. After the curing is completed, annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing distortion of the optical material of the present invention. Further, if necessary, a surface treatment such as dyeing, hard coating, anti-reflection, and anti-fogging property can be performed.

The method for producing the cured resin optical material of the present invention comprises:
The details are as follows. As described above, after mixing the main raw material and the auxiliary raw material, the mixture is injected and cured into a mold, and is manufactured. A compound having one or more structures represented by the formula (1) in one molecule or a composition thereof and Compounds having two or more functional groups capable of reacting with the catalyst and optionally used epithio groups, or compounds having one or more of these functional groups and one or more other homopolymerizable functional groups, homopolymerizable Compounds having one or more functional groups, one functional group capable of reacting with an epithio group and capable of homopolymerization
Compounds having a plurality, further used as desired, an antioxidant component, a radical polymerization initiator, and further an adhesion improver, a stabilizer, etc. Raw materials may be added and mixed stepwise, or several components may be separately mixed and then remixed in the same container. The respective raw materials and the auxiliary raw materials may be mixed in any order. Upon mixing, the set temperature, the time required for the mixing, and the like may be basically set as long as the components are sufficiently mixed, but an excessive temperature and time may cause an undesired reaction between the raw materials and additives, Furthermore, it is not appropriate because the viscosity increases and the casting operation becomes difficult. The mixing temperature should be in the range of about -50 ° C to 100 ° C, the preferred temperature range is -30 ° C to 50 ° C, more preferably,
-5 ° C to 30 ° C. The mixing time is 1 minute to 5 hours, preferably 5 minutes to 2 hours, more preferably 5 minutes to 30 minutes, and most preferably about 5 minutes to 15 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.
Hg. Furthermore, filtering and purifying impurities or the like of these mixtures or the main and auxiliary raw materials before mixing with a filter having a pore size of about 0.1 to 3 micron is also necessary for further improving the quality of the optical material of the present invention. preferable.

In the present invention, the dyeing of the polymerized and cured optical material is usually carried out in a solution containing 0.01% or more of a polar inorganic and / or organic compound at a temperature of −50 ° C. to 200 ° C.
It is carried out after immersion treatment at a temperature of not more than ℃. This immersion treatment can also be said to be a pre-dyeing treatment step, and this liquid is a pre-dyeing treatment liquid. As a result, even a material that is difficult to be dyed even at a high temperature for a long time can be dyed well in a short time. The immersion treatment temperature is preferably from -20C to 200C, more preferably from 0C to 150C. If the immersion temperature is too low, the pretreatment effect becomes insufficient, and if it is too high, the material is undesirably deformed. The pre-dyeing solution is a solution containing 0.1% or more of a polar inorganic and / or organic compound, and is not particularly limited as long as the condition is satisfied. More specifically, the liquid is prepared by adding a polar inorganic and / or organic compound to water or an organic solvent or a mixture of both.
% Or more is a liquid prepared by dissolving or dispersing or a polar inorganic and / or organic compound itself. In the former case, the concentration of the polar inorganic and / or organic compound in the solution prepared by dissolution or dispersion is preferably 1% or more, more preferably 5% or more, further preferably 10% or more, and particularly preferably. It is at least 20%, most preferably at least 30%. Specific examples of the organic solvent used as necessary include methanol, ethanol, butanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, diethylene glycol,
Triethylene glycol, glycerin, xylylene diol, methyl cellosolve, ethyl cellosolve, acetic acid, ethyl acetate, butyl acetate, tetrahydrofuran, methyltetrahydrofuran, acetone, butanone, DMF, DM
SO, 2-hydroxyethylamine, 2,2′-iminodiethanol, mercaptoethanol and the like.

In the present invention, the inorganic and / or organic compounds having polarity used as a pre-dyeing solution are shown below. Examples of the inorganic compound having polarity include basic substances such as inorganic acids, salts of inorganic acids and ammonia, alkali metals or alkaline earth metals, hydroxides, sulfides and carbonates. Specific examples of inorganic acids include mineral acids exemplified as curing catalysts, nitric acid, hydrochloric acid, perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, boric acid, arsenic acid, arsenous acid,
Pyroarsenic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, nitric anhydride, sulfuric anhydride, boron oxide Arsenic pentoxide, phosphorus pentoxide, chromic anhydride, sulfuryl chloride, silica gel, silica alumina, silicic acids, boron tetrafluoride and the like. Specific examples of the salt of an inorganic acid and ammonia, an alkali metal or an alkaline earth metal include sodium nitrate, magnesium sulfate, and ammonium sulfate. Specific examples of the basic substance such as hydroxide, sulfide or carbonate include phosphorus sulfide, sodium hydroxide, calcium carbonate and the like. These compounds can be used alone or in combination.

The organic compounds having polarity include amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, Lewis acids exemplified as curing catalysts. , Silicic acids, boric acid tetrafluoride, and other acidic substances. Examples of this acidic substance include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, naphthenic acid, methyl mercaptonate, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, and cyclohexanecarboxylic acid. Acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid,
2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, benzylic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, thiodipropionic acid, dithiodipropionic acid Carboxylic acids such as peracetic acid, thioacetic acid, tartaric acid, salicylic acid, maleic anhydride, benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, mono, di and trimethyl phosphate, mono, di and triethyl phosphate , Phosphoric acids such as mono, di and triisobutyl phosphates, mono, di and tributyl phosphates, mono, di and trilauryl phosphates, and phosphites in which these phosphate moieties are phosphites, and dialkyls represented by dimethyldithiophosphoric acid Dithio Organic phosphorus compounds such as phosphoric acids,
Phenol, catechol, resorcin, hydroquinone, phloroglucin, pyrogallol, 2-cresol,
3-cresol, 4-cresol, 2-ethylphenol, 4-ethylphenol, 4-propylphenol,
4-butylphenol, 4- (1,1,3,3-tetramethylbutyl) phenol, 4-nonylphenol,
2,4-di-t-butylphenol, 2,6-di-t-
Butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-4,6-dimethylphenol,
2,6-di-t-butyl-4-methylphenol, 2,
6-di-t-butyl-4-ethylphenol, 4-methylcatechol, 4-ethylcatechol, 4-propylphenol, 4-t-butylcatechol, 4- (1,1,
3,3-tetramethylbutyl) catechol, methylhydroquinone, 2-t-butylhydroquinone, 2,5-
Di-t-butylhydroquinone, 2,6-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,5-di (1,1,3,3-tetramethylbutyl) hydroquinone, -Methoxyphenol, 4-methoxyphenol, 2,4-dimethoxyphenol,
2,6-dimethoxyphenol, 2,4,6-trimethoxyphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 3-
Methoxy catechol, 4-methoxy catechol, 3,5
-Dimethoxycatechol, 3,6-dimethoxycatechol, catechol-l-4-carboxylic acid, salicylic acid, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, dimethylsalicylic acid, di-t- Butylsalicylic acid, salicylosalicylic acid,
Salicylamide, sodium salicylate, 5-sulfosalicylic acid, 4-hydroxy-3-methylbenzenesulfonic acid, 4-hydroxybenzoic acid, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4 Phenyl-hydroxybenzoate, butyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
-Hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetic acid amide, methyl hydroxyphenylacetate, hydroxyphenethyl alcohol, hydroxyphenethylamine, acetaminophenone, aminophenol , Cyanophenol, nitrophenol, nitrosophenol, 2-mercaptophenol, 4-mercaptophenol, 2,4-dimercaptophenol, 2,6
-Dimercaptophenol, 2,4,6-trimercaptophenol, 2-fluorophenol, 4-fluorophenol, 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, , 4,6-trichlorophenol, 2-
Bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 2,
4,6-tribromophenol, 2-iodophenol, 4-iodophenol, hydroxyphenethylamine, hydroxybenzaldehyde, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 2,2′-biphenol, 4,4′-biphenol, bisphenol-A, bisphenol-F, bisphenol-S, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl -4-hydroxyphenyl) sulfide, 1-naphthol, 2-naphthol, dihydroxynaphthalenes, octadecyl-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6- t-butylphenol),
2,2′-methylenebis (2,6-di-t-butylphenol), 4,4′-butylidenebis (3-methyl-6
-T-butylphenol), 4,4'-thiobis (3-
Methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tbutyllphenyl) butane, 1,3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2-t-butyl-6- (3'-t-
Butyl-5'-methyl-2'-hydroxybenzyl)-
4-methylphenyl acrylate, 2,4-bis (n-
Octylthio) -6- (4-hydroxy-3,5-di-
phenols such as t-butylanilino) -1,3,5-triazine, methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p- -Toluene sulfonic acid, ethyl benzene sulfonic acid, butyl benzene sulfonic acid, dodecyl benzene sulfonic acid, p-phenol sulfonic acid, o-cresol sulfonic acid, methanilic acid, sulfanilic acid, 4B-acid, diaminostilbene sulfonic acid, biphenyl sulfonic acid,
Sulfonic acids such as α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peric acid, Laurent acid, and phenyl J acid, and mercaptans mentioned as compounds having one or more SH groups as antioxidant components. Further aromatic compounds not belonging to the above include benzene, biphenyl, naphthalene, anthracene, phenanthrene, alkylbenzenes, styrene, α-alkylnaphthalenes, β-alkylnaphthalenes, α-vinylnaphthalene, β-vinylnaphthalene, phenylethers Benzoic acid esters, salicylic acid esters, phthalic acid mono- and diesters, isophthalic acid mono- and diesters, terephthalic acid mono- and diesters, benzenesulfinic acid, toluenesulfinic acid, and the like. Is also possible. Among these, preferred are inorganic acids and organic acids, and particularly preferred are inorganic compounds having a sulfate group, organic compounds, carboxylic acids, and monovalent to divalent phenols. More preferred are organic compounds having a sulfone group, carboxylic acids, and monovalent to divalent phenols.

The pretreatment for dyeing is carried out by immersing a resin optical material such as a lens after curing polymerization in a pretreatment liquid, but the immersion time may be long or short as long as the effect is substantially obtained. The temperature of the immersion liquid is not particularly limited as long as a dyeing effect can be obtained.
C is preferred. Before and after the immersion, if necessary, the resin optical material is subjected to a treatment such as washing with water, an aqueous alkali solution, an aqueous acid solution, or an organic solvent. preferable.

The dyeing method may be any method as long as it is a usual resin dyeing method.
The method described in Japanese Patent Application Publication No. 0-095, for example, may be mentioned, but the method is not limited thereto, and is usually carried out in a dyeing bath at a temperature from about room temperature to about 200 ° C. Depending on the bath components, the desired temperature may not be obtained by ordinary overheating, but in this case, a component capable of increasing the boiling point is added under pressure or
A desired dyeing temperature is realized by a so-called boiling point raising method.
When the boiling point is increased by pressurization, the dyeing is usually carried out at 1.1 to 20 atm using a pressure cooker or an autoclave. As the boiling point increasing component, when water is used as the bath component, it is possible to add an inorganic salt and a water-soluble organic compound which usually exhibit a molar boiling point increasing effect. The use of the inorganic salt is not limited as long as it is a general water-soluble inorganic substance represented by calcium chloride, potassium iodide and the like. The use of the water-soluble organic compound is not limited as long as it is a general water-soluble organic substance represented by urea, sodium acetate and the like. The dyeing bath usually contains 0.01 g to 100 g of a dye in 1 liter of water and, if necessary, 0.00 g of a surfactant.
1 g to 50 g and 0.001 g of the carrier compound
Is heated from room temperature to 200 ° C., and the material is immersed therein. The amount of the dye used in the liquid composition is 0.001 g to 100 g per liter of water, preferably 0.05 g to 50 g,
More preferably, it is 0.1 g to 25 g. The dye is 0.
If the amount is less than 01 g, the dyeing time will be long and sufficient dyeability will not be obtained. If the amount is more than 100 g, the dye becomes lump or hard to disperse, and adversely affects the dyeability or generates uneven dyeing. Dyes, disperse dyes, reactive dyes conventionally used in the field,
Typical examples thereof include cationic dyes, acid dyes, sulfur dyes, and inglein dyes, but are not particularly limited as long as they exhibit the same effect. For example, under the trade name of Dystar Japan, Dianix-Yellow, Orange
e, Scarret, Red, Pink, Viole
t, Blue, Gray, Black and other disperse dyes;
emazol-Yellow, Red, Blue, Gr
ey, Black and other reactive dyes, Astrazon-Y
yellow, Red, Violet, Blue, Gre
and cationic dyes such as en, black and the like, and these may be mixed and used depending on the application. The carrier compound may not be necessary in some cases, but if necessary, the addition amount is usually 0.001 g to 50 g, preferably 0.005 g to 50 g, per liter of water. When the amount of the carrier compound is less than 0.001 g, the effect of the carrier cannot be sufficiently exhibited, and when the amount is more than 50 g, uniform dyeing becomes difficult. The carrier compound is
Although represented by an aromatic compound and an ester-based aromatic compound, the compound is not limited to these compounds as long as they exhibit the same effect. Examples of the above compounds include, for example, phenol, cresol, naphthol, resorcin, catechol, bisphenol A, pyrogallol, and the like as described on pages 205 and 286 of "Introduction to Dyeing and Processing Engineering" (published by Textile Research Institute). Aromatic compounds having a phenolic hydroxyl group such as phloroglucin; alcohols such as methanol, ethanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, glycerin and xylylene diol; Benzoic acid, salicylic acid,
Esters such as diphenylphenol, orthophenylphenol, paraphenylphenol, naphthalene, benzoate, salicylate, phthalate mono and diester, isophthalate mono and diester, terephthalate mono and diester, alkylbenzene, monochlorobenzene, dichlorobenzene, Examples thereof include trichlorobenzene, styrene, naphthalene, α-alkylnaphthalene, β-alkylnaphthalene, α-vinylnaphthalene, and β-vinylnaphthalene. These compounds may be appropriately mixed and used as needed.

[0031]

According to the dyeing method of the present invention, that is, a compound having at least one structure represented by the formula (1) in one molecule, which can hardly be dyed by the conventional dyeing technique by the dyeing pretreatment method, or a compound having the same It has become possible to dye a resin obtained by polymerizing and curing a composition containing the resin. As a result, an optical material having high dyed refractive index and Abbe number balance was realized for the first time.

[0032]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation of the obtained polymer, the staining method, and the chromosome evaluation were performed by the following methods. Dyeability: Dipped in a dye bath having the following composition at 90 ° C. for 30 minutes, and the following was defined as the dyeability. Dyeing property = 100-total light transmittance (%) Dye bath composition: Seiko Plux Diamond Coat Brown D 0.2% by weight Seiko Plux Dyeing aid 0.3% by weight Benzyl alcohol 2.0% by weight Refractive index (nD), Abbe number (νD): Measured at 25 ° C. using an Abbe refractometer. In Table 1, the concentrations of the compounds used for the pre-dyeing treatment are weight ratios, and the rest is water.

Example 1 0.5 parts by weight of 2-diethylaminoethanol as a catalyst was mixed with 100 parts by weight of bis (β-epithiopropyl) sulfide, and the mixture was stirred at room temperature to obtain a homogeneous liquid. This was then poured into a 2.5 mm thick flat lens mold and heated in an oven from 10 ° C. to 120 ° C. over 22 hours to polymerize and cure, producing a lens. The obtained lens showed good heat resistance and oxidation resistance, and not only had excellent optical and physical properties, but also had a good surface condition, and little striae and surface deformation were observed. .
As a pre-staining treatment, the obtained lens was immersed in concentrated sulfuric acid (98%) at 20 ° C. for 30 minutes, and then stained.
The stained lens had no staining unevenness, had a good surface condition, and did not undergo surface deformation. Table 1 shows the optical properties and staining properties of the obtained lens.

Examples 2-8 Instead of immersing in concentrated sulfuric acid at 20 ° C. for 30 minutes before dyeing,
The same operation as in Example 1 was repeated except that the pretreatment for staining was performed under the conditions shown in Table 1. The results are shown in Table 1.

Examples 9 to 14 Lenses were prepared from the compositions shown in Table 1 instead of 100 parts by weight of bis (β-epithiopropyl) sulfide.
The same operation as in Example 1 was repeated except that the pre-staining treatment was performed under the conditions shown in (1). The results are shown in Table 1.

Examples 15 to 23 Lenses were prepared from the compositions shown in Table 2 instead of 100 parts by weight of bis (β-epithiopropyl) sulfide.
The same operation as in Example 1 was repeated except that the pre-staining treatment was performed under the conditions shown in (1). The results are shown in Table 2.

Comparative Example 1 The same operation as in Example 1 was repeated except that the pretreatment for dyeing was not performed. The results are shown in Table 3.

Comparative Example 2 The same operation as in Example 9 was repeated, except that no pre-dyeing treatment was performed. The results are shown in Table 3.

Comparative Example 3 The same operation as in Example 18 was repeated except that the pretreatment for dyeing was not performed. The results are shown in Table 3.

Comparative Example 4 The same operation as in Example 1 was repeated, except that the pre-dyeing treatment was carried out by immersion in liquid paraffin at 120 ° C. for 60 minutes instead of immersion in concentrated sulfuric acid at 20 ° C. for 30 minutes before dyeing. Was.
The results are shown in Table 3.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02C 7/00 B41M 1/30 Z // B41M 1/30 C08J 7/00 Z C08J 7/00 7/14 CEZ 7/14 CEZ G02B 1/10 Z (72) Inventor Tokiki Niimi 6-1-1 Shinjuku, Katsushika-ku, Tokyo Inside Mitsubishi Research Institute Tokyo Research Laboratory (72) Inventor Hiroshi Horikoshi 6-1-1 Shinjuku, Katsushika-ku, Tokyo No. 1 Inside Tokyo Research Laboratory, Mitsubishi Gas Chemical Co., Ltd.

Claims (6)

[Claims] 1. A resin obtained by polymerizing and curing a compound having at least one structure represented by the following formula (1) in one molecule or a composition containing the compound is converted into a polar inorganic and / or polar resin. A dyeing method, comprising immersing in a liquid containing an organic compound and then dyeing. Embedded image (Wherein, R ¹ is a hydrocarbon having 1 to 10 carbon atoms, R ² ,
R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents S or O, and n is 0 or 1
Represents ) 2. A resin obtained by polymerizing and curing a compound having at least one structure represented by the following formula (2) in one molecule or a composition containing this compound, is converted into a polar inorganic and / or polar resin. A dyeing method, comprising immersing in a liquid containing an organic compound and then dyeing. Embedded image (Wherein, R ¹ is a hydrocarbon having 1 to 10 carbon atoms, R ² ,
R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents S or O. ) 3. A resin obtained by polymerizing and curing a compound having at least one structure represented by the following formula (3) in one molecule or a composition containing this compound is converted into a polar inorganic and / or polar resin. A dyeing method, comprising immersing in a liquid containing an organic compound and then dyeing. Embedded image (Wherein, R ¹ is a hydrocarbon having 1 to 10 carbon atoms, R ² ,
R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. ) 4. A resin obtained by polymerizing and curing a compound represented by the following formula (4) alone or a composition containing this compound is immersed in a liquid containing a polar inorganic and / or organic compound. Thereafter, dyeing is performed. Embedded image (Wherein, R ^{5 to} R ¹⁰ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. X represents S or O;
Is 50% or more on average with respect to the total of S and O constituting the three-membered ring. m shows 1-6 and n shows 0-4. ) 5. A dyeing method according to claim 1, wherein the composition contains a compound having at least one SH group. 6. A dyed optical material produced by the dyeing method according to claim 1.