JP2000345480A - Dyeing method for resin for optical materials - Google Patents

Abstract

(57) [Summary] (Modifications) [Problem] To uniformly and uniformly dye a resin for a hydrophobic optical material, which is difficult to dye due to its high hydrophobicity due to its sulfur-containing structural characteristics, at an appropriate dyeing speed. Provide a way. An optical material resin (for example, 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 used: After immersion in an inorganic acid and / or an organic acid, dyeing is performed. (Wherein, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents O, S, Se or Te. N = 0 to
5, m = 1 to 5, and p represents 0 or 1. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Plastic materials have been widely used in recent years for various optical materials, particularly for spectacle lenses, because they are lightweight, rich in toughness and easy to dye. The performance required for optical materials, particularly spectacle lenses, is a low refractive index, 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 thin, the high Abbe number reduces the chromatic aberration of the lens, and the high heat resistance and the high strength facilitate secondary processing and are important from the viewpoint of safety and the like. However,
Plastic materials have a lower refractive index than inorganic lenses,
In order to obtain optical properties equivalent to that of a glass lens, it is necessary to increase the edge thickness and the curvature of the lens, and it is inevitable that the lens becomes thick as a whole. For this reason, not only can the lightness characteristic of plastics not be utilized, but also the appearance becomes poor. Therefore, development of a resin for an optical material having a higher refractive index has been desired. In the prior art, a material having a high refractive index is a thermosetting optical material having a thiourethane structure obtained by reacting a polythiol compound and a polyisocyanate compound (Japanese Patent Publication No. 4-58489, Japanese Unexamined Patent Publication No.
148340), 1,4-dithiane-2,5-
Material using dimercaptomethyl (Japanese Patent Publication No. 6-5323)
No. 2) and other sulfur-containing resins. on the other hand,
Another important performance required for optical materials is that 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 found a novel sulfur-containing compound having an epithio structure that enables an optical material having a small thickness and low chromatic aberration to have an index of 1.70 or more and an Abbe number of 35 or more. Patent applications have already been filed (Japanese Patent Application Laid-Open Nos. 9-71580 and 9-11
0979, JP-A-9-255781). As described above, the introduction of sulfur into the resin for optical materials is indispensable with the increase in the refractive index, and the content thereof is increasing with the increase in the refractive index. Diethylene glycol bisallyl carbonate (hereinafter referred to as CR-39) known as a material having a refractive index of 1.50 does not contain a sulfur atom, but a material having a refractive index of 1.60 and an Abbe number of 40 or more has a sulfur content of 25 to 30. %. On the other hand, a refractive index of 1.70, at which a high refractive index and a high Abbe number were simultaneously realized by the present inventors.
More than 50% of the material having the Abbe number of 35 or more is sulfur. Such a high refractive index makes it possible to reduce the center thickness, edge thickness, and curvature of the lens as compared with CR-39, thereby making it thinner as a whole, making use of the lightness characteristic of plastic, and It became possible to improve the appearance. However, there is a problem that dyeing, which is another characteristic of plastics, becomes difficult. CR-39 can be dyed sufficiently by immersing it in an aqueous disperse dye solution. However, these high-refractive-index materials have a strong hydrophobic property (low water absorbency) due to the structural characteristics of sulfur-containing, and therefore, disperse dyes can be used. The conventional method of immersing in an aqueous solution for dyeing has a disadvantage that it is difficult to dye. In addition, improvements in conventional dyeing techniques, i.e., improvements in the addition of various carriers such as aromatic compounds, phenolic compounds, alcohols, carboxylic acids, and the same esters as well as various surfactants to the aqueous disperse dye solution, are sufficient. No improvement effect was obtained. As described above, it is difficult to dye the sulfur-containing resin, and this tendency becomes remarkable because the hydrophobicity becomes stronger as the sulfur content increases. For these reasons, development of a new technique for dyeing a resin for optical materials has been desired.

[0003]

An object to be solved by the present invention is to provide a resin for an optical material, particularly with the increase in refractive index.
It is an object of the present invention to develop a method for dyeing a sulfur-containing resin, which is difficult to dye, and to obtain a resin for optical materials having a high refractive index and excellent dyeing performance, which was impossible with conventional techniques.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve such problems, and as a result, have found that the following problems can be solved as will be described later, and have reached the present invention. .

That is, the gist of the present invention is to dye a resin for an optical material, particularly a sulfur-containing resin which is difficult to be dyed with a high refractive index, after immersing the resin in an inorganic acid and / or an organic acid. This is a characteristic staining method.

[0006] The resin for optical materials used in the present invention is not particularly limited, and may be (meth) acrylic resin, ester resin, carbonate resin, olefin resin, urethane resin, thiourethane resin, episulfide resin, epoxy resin, unsaturated polyester. Examples thereof include resins, polystyrene and copolymers thereof, polyvinyl chloride, polyethylene terephthalate, diethylene glycol bisallyl carbonate polymer, and copolymers of tetrabromobisphenol A dimethacrylate and styrene. Particularly effective are sulfur-containing resins such as thiourethane resin and episulfide resin, among which resins having high hydrophobicity and high sulfur content (here, the sulfur content is the ratio of the weight of sulfur to the total weight) That is). In particular, the effect of the present invention is remarkably exhibited in a resin having a sulfur content of 30% by weight or more.

[0007] Examples of the sulfur-containing resin include the following. 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.

[0008]

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 O, S, Se or Te.
n = 0 to 5, m = 1 to 5, and p represents 0 or 1. )

A composition containing a compound having at least one structure represented by the above formula (1) in one molecule is a compound containing one or more structures represented by the above formula (1) in one molecule. 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more.

In order to exhibit a high refractive index, a high Abbe number and a good balance of the resin for optical materials, R ¹ in the above formula (1) is preferably methylene or ethylene, and R ² , R ³ And R ⁴ are preferably hydrogen or a methyl group. More preferably, R ¹ is methylene and R ² , R ³ and R ⁴ are hydrogen. Y is O, S,
Indicating Se or Te, S, Se or Te is preferred when a higher refractive index is desired. Further, n is preferably 0 or 1, and m is preferably 1.

The episulfide compound having one or more structures represented by the formula (1) in one molecule of the present invention includes all the organic compounds satisfying this condition, and more preferably the episulfide compound represented by the formula (1) It is a compound having two or more structures represented. Specific examples of the compound having one or more structures represented by the formula (1) in one molecule are as follows. (A) Organic compound having epithio group (B) Organic compound having epithioalkyloxy group (C) Organic compound having epithioalkylthio group (D) Organic compound having epithioalkyl seleno group (E) Epithioalkyl Organic compound having telluro group The above organic compounds (A), (B), (C), (D) and (E) are chain compounds, branched compounds, aliphatic cyclic compounds, aromatic compounds, or nitrogen. , Oxygen, sulfur, selenium,
Having a heterocyclic compound containing a tellurium atom as a main skeleton and having an epithio group, an epithioalkyloxy group, an epithioalkylthio group, an epithioalkylseleno group, and an epithioalkyltelluro group simultaneously in one molecule. It doesn't matter. Further, these compounds may contain a bond such as sulfide, selenide, telluride, ether, sulfone, ketone, ester, amide, or urethane in the molecule.

A preferred specific example of (A) an organic compound having one or more epithio groups is a compound having one or more epoxy groups substituted by an epithio group in a compound having an epoxy group (not a glycidyl group). I can give it. Taking a more specific example method, the following can be given as typical examples. Organic compound having a chain 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, tetrakis (β-epithiopropyl)
Methane, 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 and the like. Compound having an aliphatic cyclic skeleton: 1, 3, or 1,
4-bis (epithioethyl) cyclohexane, 1,3 or 1,4-bis (β-epithiopropyl) cyclohexane, 2,5-bis (epithioethyl) -1,4-dithiane, 2,5-bis (β-epi Thiopropyl) -1,4
Compounds having one aliphatic cyclic structure, such as -dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 4-epoxy-1,2-cyclohexene sulfide, and 2,2-bis [4- (epithioethyl) cyclohexyl ] Propane, 2,2-bis [4- (β-epithiopropyl) cyclohexyl] propane, bis [4- (epithioethyl) cyclohexyl] methane, bis [4- (β
Compounds having two aliphatic cyclic structures, such as -epithiopropyl) cyclohexyl] methane, bis [4- (β-epithiopropyl) cyclohexyl] sulfide, bis [4- (epithioethyl) cyclohexyl] sulfide, and the like. Compound having an aromatic skeleton: 1,3 or 1,4-bis (epithioethyl) benzene, 1,3
Or a compound having one aromatic skeleton such as 1,4-bis (β-epithiopropyl) benzene or 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, 4,4'-bis (β-epithiopropyl)
Compounds having two aromatic skeletons such as biphenyl are exemplified. Further, compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also exemplified.

A preferred specific example of the organic compound (B) having one or more epithioalkyloxy groups is one of the glycidyl groups of an epoxy compound derived from epihalohydrin.
Compounds in which at least one is substituted with an epithioalkyloxy group (thioglycidyl group) can be mentioned as a typical example. Specific examples of the epoxy compound include those produced by condensing epihalohydrin with polyhydric phenol compounds such as hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, and novolak resin. Phenolic epoxy compounds; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Pentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythritol, 1,3- Is a polyhydric alcohol compound such as 1,4-cyclohexanediol, 1,3- or 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 4,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p-phenylenediamine,
2,4- or 2,6-tolylenediamine, m- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2
Primary diamines such as-(4,4'-diaminodiphenyl) propane, 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-
Amine-based epoxy compounds produced by condensation of a secondary diamine such as piperidyl) -butane and epihalohydrin,
Urethane-based epoxy compounds produced from the above-mentioned polyhydric alcohols, phenol compounds, diisocyanates, glycidol and the like can be mentioned. 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-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-β-epithiopropyloxyethyl) oxyethyl] oxy] ethane, tetrakis (β-epithiopropyloxymethyl) methane,
1,1,1-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, 1 , 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
-Trithiaundecane and the like. Compounds having an aliphatic cyclic skeleton: 1,3 or 1,4-bis (β-epithiopropyloxy) cyclohexane, 1,3 or 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-epithiopropyloxymethyl) -1,4-dithiane, 2,5 -Bis (β-epithiopropyloxyethyloxymethyl)
-1,4-dithiane and the like. Compounds having an aromatic skeleton: aromatics such as 1,3 or 1,4-bis (β-epithiopropyloxy) benzene, 1,3 or 1,4-bis (β-epithiopropyloxymethyl) benzene A compound having one skeleton, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4
-(Β-epithiopropylthio) phenyl] propane,
Aromas such as bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, and 4,4′-bis (β-epithiopropylthio) biphenyl Compounds having two group skeletons are exemplified. Further, 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 (C) having one or more epithioalkylthio groups include a compound having a mercapto group and an epoxyalkylthio group of an epoxy compound derived from epihalohydrin (specifically, β-
Compounds in which one or more of (epoxypropylthio groups) are substituted with epithioalkylthio groups can be mentioned as typical examples. If a more specific example method is used, the following can be given as typical examples. Organic compounds having a chain aliphatic skeleton: bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis (β-epithiopropylthio) Methane, bis (β-epithiopropyldithio) methane, bis (β-epithiopropyldithio) ethane, bis (β-epithiopropyldithioethyl) sulfide, bis (β-epithiopropyldithioethyl) disulfide, 1, 2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithio Propylthio) -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-epithiopropylthioethyl) thioethyl] thio] ethane tetrakis (β-epithiopropylthiomethyl) methane, tetrakis (β-epithiopropyldithiomethyl)
Methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,2,3-tris (β-epithiopropyldithio) propane, 1,5-bis (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1,6-bis (β-epithiopropyldithiomethyl) -2- (β-epithiopropyldithioethylthio) -4-thiahexane, 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, 1,8
-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 and the like can be mentioned. A chain compound having an ester group and an epithioalkylthio group: 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. Compound having an aliphatic cyclic skeleton:
1,3 or 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 or 1,4-bis (β-
Epithiopropylthiomethyl) cyclohexane 2,5-
Bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthio) Compounds having one aliphatic cyclic skeleton such as ethylthiomethyl) -1,4-dithiane, and bis [4-
(Β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio)
Cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,2-
Compounds having two aliphatic cyclic skeletons such as bis [4- (β-epithiopropylthio) cyclohexyl] propane and bis [4- (β-epithiopropylthio) cyclohexyl] sulfide are exemplified. Compound having an aromatic skeleton: 1,3 or 1,4-bis (β-epithiopropylthio) benzene, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) benzene, 1,3 or Compounds having one aromatic skeleton such as 1,4-bis (β-epithiopropyldithiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [ 4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4-
(Β-epithiopropylthio) phenyl] sulfone,
Compounds having two aromatic skeletons such as 4,4′-bis (β-epithiopropylthio) biphenyl are exemplified. Furthermore, compounds in which at least one hydrogen of the β-epithiopropyl group of these compounds is substituted with a methyl group are also specific examples.

(D) Preferred specific examples of the organic compound having an epithioalkylseleno group include selenium compounds such as metal selenium, alkali metal selenide, alkali metal selenol, alkyl (aryl) selenol, hydrogen selenide and epihalohydrin. A typical example is a compound in which one or more epoxyalkylseleno groups (specifically, β-epoxypropylseleno groups) of an epoxy compound are substituted with epithioalkylseleno groups.
If a more specific example method is used, the following can be mentioned as typical examples. Organic compounds having a linear aliphatic skeleton: bis (β-epithiopropyl) selenide,
Bis (β-epithiopropyl) diselenide, bis (β-
Epithiopropyl) triselenide, bis (β-epithiopropylseleno) methane, 1,2-bis (β-epithiopropylseleno) ethane, 1,3-bis (β-epithiopropylseleno) propane, 1,2 -Bis (β-epithiopropylseleno) propane, 1- (β-epithiopropylseleno) -2- (β-epithiopropylselenomethyl) propane, 1,4-bis (β-epithiopropylseleno) butane 1,3-bis (β-epithiopropylseleno) butane, 1- (β-epithiopropylseleno)-
3- (β-epithiopropylselenomethyl) butane,
1,5-bis (β-epithiopropylseleno) pentane, 1- (β-epithiopropylseleno) -4- (β-
Epithiopropylselenomethyl) pentane, 1,6-bis (β-epithiopropylseleno) hexane, 1- (β
-Epithiopropylseleno) -5-([beta] -epithiopropylselenomethyl) hexane, 1-([beta] -epithiopropylseleno) -2-[(2- [beta] -epithiopropylselenoethyl) thio] ethane, -(Β-epithiopropylseleno) -2-[[2- (2-β-epithiopropylselenoethyl) selenoethyl] thio] ethane, tetrakis (β-epithiopropylselenomethyl) methane, 1,
1,1-tris (β-epithiopropylselenomethyl)
Propane, 1,5-bis (β-epithiopropylseleno) -2- (β-epithiopropylselenomethyl) -3
-Thiapentane, 1,5-bis (β-epithiopropylseleno) -2,4-bis (β-epithiopropylselenomethyl) -3-thiapentane, 1- (β-epithiopropylseleno) -2,2 -Bis (β-epithiopropylselenomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylselenomethyl) -4- (β-epithiopropylselenomethyl) -3-thiahexane, 8-
Bis (β-epithiopropylseleno) -4- (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno)-
4,5 bis (β-epithiopropylselenomethyl)-
3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -4,4-bis (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-
Bis (β-epithiopropylseleno) -2,4,5-tris (β-epithiopropylselenomethyl) -3,6-
Dithiaoctane, 1,8-bis (β-epithiopropylseleno) -2,5-bis (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,9-bis (β
-Epithiopropylseleno) -5-([beta] -epithiopropylselenomethyl) -5-[(2- [beta] -epithiopropylselenoethyl) selenomethyl] -3,7-dithianonane, 1,10-bis ([beta]- Epithiopropyl seleno)-
5,6-bis [(2-β-epithiopropylselenoethyl) thio] -3,6,9-trithiadecane, 1,11-
Bis (β-epithiopropylseleno) -4,8-bis (β-epithiopropylselenomethyl) -3,6,9-
Trithiaundecane, 1,11-bis (β-epithiopropylseleno) -5,7-bis (β-epithiopropylselenomethyl) -3,6,9-trithiaundecane,
1,11-bis (β-epithiopropylseleno) -5
7-[(2-β-epithiopropylselenoethyl) selenomethyl] -3,6,9-trithiaundecane, 1,1
1-bis (β-epithiopropylseleno) -4,7-bis (β-epithiopropylselenomethyl) -3,6,9
-Trithiaundecane, tetra [2- (β-epithiopropylseleno) acetylmethyl] methane, 1,1,1-
Tri [2- (β-epithiopropylseleno) acetylmethyl] propane, tetra [2- (β-epithiopropylselenomethyl) acetylmethyl] methane, 1,1,1-
Tri [2- (β-epithiopropylselenomethyl) acetylmethyl] propane, bis (5,6-epithio-3-
Selenohexyl) selenide, 2,3-bis (6,7-thioepoxy-1-selena-4-selenoheptyl) -1-
(3,4-thioepoxy-1-selenobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-selenopentyl) -2-selenapropane, bis (4,5-thioepoxy-2) -Selenopentyl)-
3,6,9-triselenaundecane-1,11-bis (3,4-thioepoxy-1-selenobutyl), 1,4
-Bis (3,4-thioepoxy-1-selenobutyl)-
2,3-bis (6,7-thioepoxy-1-selena-4
-Selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-selena-6-thiaoctane-1,8-bis (3,4-thioepoxy-1-selenobutyl), bis (5,6 -Epithio-3-selenohexyl) telluride, 2,3-bis (6,7-thioepoxy-1-tellura-4-selenoheptyl) -1- (3,4
-Thioepoxy-1-selenobutyl) propane, 1,
1,3,3-tetrakis (4,5-thioepoxy-2
-Selenopentyl) -2-tellurapropane, bis (4
5-thioepoxy-2-selenopentyl) -3,6,9
-Tritereoundecan-1,1,1-bis (3,4-thioepoxy-1-selenobutyl), 1,4-bis (3,
4-thioepoxy-1-selenobutyl) -2,3-bis (6,7-thioepoxy-1-tellura-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-tellura- 6-thiaoctane-1,
8-bis (3,4-thioepoxy-1-selenobutyl)
And the like. Compound having an aliphatic cyclic skeleton:
(1,3 or 1,4) -bis (β-epithiopropylseleno) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropylselenomethyl) cyclohexane, bis [4- (β- Epithiopropylseleno) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylseleno) cyclohexyl] propane, bis [4- (β-epithiopropylseleno) cyclohexyl] sulfide, 2,5-bis (Β-epithiopropylselenomethyl) -1,4-dithiane, 2,5-bis (β
-Epithiopropylselenoethylthiomethyl) -1,4
-Dithiane, (2,3,2,5 or 2,6) -bis (3,4-epithio-1-selenobutyl) -1,4-diselenane, (2,3,2,5 or 2,6)- Bis (4,5-epithio-2-selenopentyl) -1,4-
Diselenane, (2,4,2,5 or 5,6) -bis (3,4-epithio-1-selenobutyl) -1,3-diselenane, (2,4,2,5 or 5,6) -bis (4,5-epithio-2-selenopentyl) -1,3-
Diselenane, (2,3,2,5,2,6 or 3,5)
-Bis (3,4-epithio-1-selenobutyl) -1-
Thia-4-selenane, (2,3,2,5,2,6 or 3,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-4-selenane, (2,4 Or 4,
5) -Bis (3,4-epithio-1-selenobutyl)-
1,3-diselenolan, (2,4 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1,3-
Diselenolan, (2,4,2,5 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-
3-selenolane, (2,4,2,5 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-3-selenolane, 2,6-bis (4,5- Epithio-2-selenopentyl-1,3,5-triselenane, bis (3,4-epithio-1-selenobutyl) tricycloselenaoctane, bis (3,4-epithio-1-selenobutyl) dicycloselennanan, 2,3,2,4,
2,5 or 3,4) -bis (3,4-epithio-1-
Selenobutyl) selenophane, (2,3,2,4,2,
5 or 3,4) -bis (4,5-epithio-2-selenopentyl) selenophane, 2- (4,5-thioepoxy-2-selenopentyl) -5- (3,4-thioepoxy-1-selenobutyl ) -1-Selenacyclohexane,
(2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (3,4-thioepoxy-1-selenobutyl) -1-selenacyclohexane, (2 , 3,
2,4,2,5,2,6,3,4,3,5 or 4,
5) -Bis (4,5-thioepoxy-2-selenopentyl) -1-selenacyclohexane, (2,3,2,5 or 2,6) -bis (3,4-epithio-1-selenobutyl) -1 , 4-Ditelluran, (2,3,2,5 or 2,6) -bis (4,5-epithio-2-selenopentyl) -1,4-ditelluran, (2,4,2,5 or 6) -Bis (3,4-epithio-1-selenobutyl) -1,3-ditellurane, (2,4,2,5 or 5,6) -bis (4,5-epithio-2-selenopentyl)- 1,3-ditellurane, (2,3,2,5,2,6
Or 3,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-4-telluran, (2,3,2,
5,2,6 or 3,5) -bis (4,5-epithio-
2-selenopentyl) -1-thia-4-telluran,
(2,4 or 4,5) -bis (3,4-epithio-1
-Selenobutyl) -1,3-ditellolane, (2,4 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1,3-ditellolane, (2,4,2,5 or 4 , 5) -Bis (3,4-epithio-1-selenobutyl) -1-thia-3-tellurolan, (2,4,2,5
Or 4,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-3-tellurolan, 2,6-bis (4,5-epithio-2-selenopentyl-1,3,5
-Tritellurane, bis (3,4-epithio-1-selenobutyl) tricyclotelluraoctane, bis (3,4-epithio-1-selenobutyl) dicyclotelluranonane,
(2,3,2,4,2,5 or 3,4) -bis (3,
4-epithio-1-selenobutyl) tellurophan,
(2,3,2,4,2,5 or 3,4) -bis (4
5-epithio-2-selenopentyl) tellurophane, 2
-(4,5-thioepoxy-2-selenopentyl) -5
-(3,4-thioepoxy-1-selenobutyl) -1-
Telluracyclohexane, (2,3,2,4,2,5,
2,6,3,4,3,5 or 4,5) -bis (3,4
-Thioepoxy-1-selenobutyl) -1-telluracyclohexane, (2,3,2,4,2,5,2,6,3
4,3,5 or 4,5) -bis (4,5-thioepoxy-2-selenopentyl) -1-telluracyclohexane and the like. Compound having aromatic skeleton: (1,3
Or 1,4) -bis (β-epithiopropylseleno)
Benzene, (1,3 or 1,4) -bis (β-epithiopropylselenomethyl) benzene, bis [4- (β-
Epithiopropylseleno) phenyl] methane, 2,2-
Bis [4- (β-epithiopropylseleno) phenyl]
Propane, bis [4- (β-epithiopropylseleno)
Phenyl] sulfide, bis [4- (β-epithiopropylseleno) phenyl] sulfone, 4,4′-bis (β-epithiopropylseleno) biphenyl and the like. Furthermore, compounds in which at least one hydrogen of the β-epithiopropyl group of these compounds is substituted with a methyl group are also specific examples.

Preferred examples of (E) an organic compound having an epithioalkyltelluro group are derived from a tellurium compound such as metal tellurium, alkali metal telluride, alkali metal tellurol, alkyl (aryl) tellurol, hydrogen telluride and epihalohydrin. A typical example is a compound in which one or more epoxyalkyltelluro groups (specifically, β-epoxypropyltelluro group) of an epoxy compound are substituted with epithioalkyltelluro groups.
If a more specific example method is used, the following can be mentioned as typical examples. Organic compound having a chain aliphatic skeleton: bis (β-epithiopropyl) telluride,
Bis (β-epithiopropyl) ditelluride, bis (β-
Epithiopropyl) tritelluride, bis (β-epithiopropyltelluro) methane, 1,2-bis (β-epithiopropyltelluro) ethane, 1,3-bis (β-epithiopropyltelluro) propane, 1,2 -Bis (β-epithiopropyltelluro) propane, 1- (β-epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) propane, 1,4-bis (β-epithiopropyltelluro) butane 1,3-bis (β-epithiopropyltelluro) butane, 1- (β-epithiopropyltelluro)-
3- (β-epithiopropyltelluromethyl) butane,
1,5-bis (β-epithiopropyltelluro) pentane, 1- (β-epithiopropyltelluro) -4- (β-
Epithiopropyltelluromethyl) pentane, 1,6-bis (β-epithiopropyltelluro) hexane, 1- (β
-Epithiopropyltelluro) -5- (β-epithiopropyltelluromethyl) hexane, 1- (β-epithiopropyltelluroethyl) -2-[(2-β-epithiopropyltelluroethyl) thio] ethane, 1 -(Β-epithiopropyltelluro) -2-[[2- (2-β-epithiopropyltelluroethyl) telluroethyl] thio] ethane, tetrakis (β-epithiopropyltelluromethyl) methane, 1,
1,1-tris (β-epithiopropyltelluromethyl)
Propane, 1,5-bis (β-epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) -3
-Thiapentane, 1,5-bis (β-epithiopropyltelluro) -2,4-bis (β-epithiopropyltelluromethyl) -3-thiapentane, 1- (β-epithiopropyltelluro) -2,2 -Bis (β-epithiopropyltelluromethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropyltelluromethyl) -4- (β-epithiopropyltelluromethyl) -3-thiahexane, 8-
Bis (β-epithiopropyltelluro) -4- (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro)-
4,5 bis (β-epithiopropyltelluromethyl)-
3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -4,4-bis (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-
Bis (β-epithiopropyltelluro) -2,4,5-tris (β-epithiopropyltelluromethyl) -3,6-
Dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -2,5-bis (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,9-bis (β
-Epithiopropyltelluro) -5-([beta] -epithiopropyltelluromethyl) -5-[(2- [beta] -epithiopropyltelluroethyl) selenomethyl] -3,7-dithianonane, 1,10-bis ([beta]- Epithiopropyltelluro)-
5,6-bis [(2-β-epithiopropyltelluroethyl) thio] -3,6,9-trithiadecane, 1,11-
Bis (β-epithiopropyltelluromethyl) -4,8-bis (β-epithiopropyltelluromethyl) -3,6,9-
Trithiaundecane, 1,11-bis (β-epithiopropyltelluro) -5,7-bis (β-epithiopropyltelluromethyl) -3,6,9-trithiaundecane,
1,11-bis (β-epithiopropyltelluro) -5
7-[(2-β-epithiopropyltelluroethyl) selenomethyl] -3,6,9-trithiaundecane, 1,1
1-bis (β-epithiopropyltelluro) -4,7-bis (β-epithiopropyltelluromethyl) -3,6,9
-Trithiaundecane, tetra [2- (β-epithiopropyltelluro) acetylmethyl] methane, 1,1,1-
Tri [2- (β-epithiopropyltelluromethyl) acetylmethyl] propane, tetra [2- (β-epithiopropyltelluromethyl) acetylmethyl] methane, 1,1,1-
Tri [2- (β-epithiopropyltelluromethyl) acetylmethyl] propane, bis (5,6-epithio-3-
Tellurohexyl) selenide, 2,3-bis (6,7-thioepoxy-1-selena-4-telluroheptyl) -1-
(3,4-thioepoxy-1-tellurobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-telluropentyl) -2-selenapropane, bis (4,5-thioepoxy-2- Telluropentyl)-
3,6,9-triselenaundecane-1,11-bis (3,4-thioepoxy-1-tellurobutyl), 1,4
-Bis (3,4-thioepoxy-1-tellurobutyl)-
2,3-bis (6,7-thioepoxy-1-selena-4
-Telluroheptyl) butane, tris (4,5-thioepoxy-2-tellulopentyl) -3-selena-6-thiaoctane-1,8-bis (3,4-thioepoxy-1-tellurobutyl), bis (5,6-epithio) -3-tellurohexyl) telluride, 2,3-bis (6,7-thioepoxy-1-tellura-4-telluroheptyl) -1- (3,4
-Thioepoxy-1-tellurobutyl) propane, 1,
1,3,3-tetrakis (4,5-thioepoxy-2
-Telluropentyl) -2-tellurapropane, bis (4,
5-thioepoxy-2-tellulopentyl) -3,6,9
-Tritereoundecan-1, 11-bis (3,4-thioepoxy-1-tellurobutyl), 1,4-bis (3
4-thioepoxy-1-tellurobutyl) -2,3-bis (6,7-thioepoxy-1-tellura-4-telluroheptyl) butane, tris (4,5-thioepoxy-2-tellulopentyl) -3-tellura-6 Thiaoctane-1,
8-bis (3,4-thioepoxy-1-tellurobutyl)
And the like. Compound having an aliphatic cyclic skeleton:
(1,3 or 1,4) -bis (β-epithiopropyltelluro) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropyltelluromethyl) cyclohexane, bis [4- (β- Epithiopropyltelluro) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyltelluro) cyclohexyl] propane, bis [4
-(Β-epithiopropyltelluro) cyclohexyl] sulfide, 2,5-bis (β-epithiopropyltelluromethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyltelluroethylthiomethyl) -1,4-dithiane, (2,3,2,5 or 2,6) -bis (3,4
-Epithio-1-tellurobutyl) -1,4-diselenane, (2,3,2,5 or 2,6) -bis (4,5-
Epithio-2-telluropentyl) -1,4-diselenane, (2,4,2,5 or 5,6) -bis (3,4-
Epithio-1-tellurobutyl) -1,3-diselenane,
(2,4,2,5 or 5,6) -bis (4,5-epithio-2-telluropentyl) -1,3-diselenane,
(2,3,2,5,2,6 or 3,5) -bis (3,
4-epithio-1-tellurobutyl) -1-thia-4-selenane, (2,3,2,5,2,6 or 3,5) -bis (4,5-epithio-2-telluropentyl) -1- Thia-4-selenane, (2,4 or 4,5) -bis (3,4-epithio-1-tellurobutyl) -1,3-diselenolane, (2,4 or 4,5) -bis (4,5 −
Epithio-2-telluropentyl) -1,3-diselenolane, (2,4,2,5 or 4,5) -bis (3,4-
Epithio-1-tellurobutyl) -1-thia-3-selenolan, (2,4,2,5 or 4,5) -bis (4,5
-Epithio-2-telluropentyl) -1-thia-3-selenolane, 2,6-bis (4,5-epithio-2-telluropentyl-1,3,5-triselenane, bis (3,4
-Epithio-1-tellurobutyl) tricycloselenaoctane, bis (3,4-epithio-1-tellurobutyl) dicycloselenanane, (2,3 or 2,4 or 2,
5 or 3,4) -bis (3,4-epithio-1-tellurobutyl) selenophane, (2,3,2,4,2,5 or 3,4) -bis (4,5-epithio-2- Telluropentyl) selenophane, 2- (4,5-thioepoxy-
2-telluropentyl) -5- (3,4-thioepoxy-
1-tellurobutyl) -1-selenacyclohexane,
(2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (3,4-thioepoxy-1-tellurobutyl) -1-selenacyclohexane, (2 , 3,
2,4,2,5,2,6,3,4,3,5 or 4,
5) -Bis (4,5-thioepoxy-2-tellulopentyl) -1-selenacyclohexane, (2,3,2,5 or 2,6) -bis (3,4-epithio-1-tellurobutyl) -1, 4-ditellurane, (2,3,2,5 or 2,6) -bis (4,5-epithio-2-telluropentyl) -1,4-ditellurane, (2,4,2,5 or 5,6) -Bis (3,4-epithio-1-tellurobutyl) -1,3-ditellurane, (2,4,2,5 or 5,6) -bis (4,5-epithio-2-telluropentyl) -1,3 -Ditellurane, (2,3,2,5,2,6
Or 3,5) -bis (3,4-epithio-1-tellurobutyl) -1-thia-4-telluran, (2,3,2,
5,2,6 or 3,5) -bis (4,5-epithio-
2-telluropentyl) -1-thia-4-telluran,
(2,4 or 4,5) -bis (3,4-epithio-1
-Tellurobutyl) -1,3-ditellolane, (2,4 or 4,5) -bis (4,5-epithio-2-tellulopentyl) -1,3-ditellolane, (2,4,2,5 or 4, 5) -Bis (3,4-epithio-1-tellurobutyl) -1-thia-3-tellurolan, (2,4,2,5
Or 4,5) -bis (4,5-epithio-2-tellulopentyl) -1-thia-3-tellurolan, 2,6-bis (4,5-epithio-2-tellulopentyl-1,3,5
-Tritellurane, bis (3,4-epithio-1-tellurobutyl) tricyclotelluraoctane, bis (3,4-epithio-1-tellurobutyl) dicyclotelluranonane,
(2,3,2,4,2,5 or 3,4) -bis (3,
4-epithio-1-tellurobutyl) tellurophan,
(2,3,2,4,2,5 or 3,4) -bis (4
5-epithio-2-telluropentyl) tellurophane, 2
-(4,5-thioepoxy-2-telluropentyl) -5
-(3,4-thioepoxy-1-tellurobutyl) -1-
Telluracyclohexane, (2,3,2,4,2,5,
2,6,3,4,3,5 or 4,5) -bis (3,4
-Thioepoxy-1-tellurobutyl) -1-telluracyclohexane, (2,3,2,4,2,5,2,6,3,
4,3,5 or 4,5) -bis (4,5-thioepoxy-2-telluropentyl) -1-telluracyclohexane and the like. Compound having aromatic skeleton: (1,3
Or 1,4) -bis (β-epithiopropyltelluro)
Benzene, (1,3 or 1,4) -bis (β-epithiopropyltelluromethyl) benzene, bis [4- (β-
Epithiopropyltelluro) phenyl] methane, 2,2-
Bis [4- (β-epithiopropyltelluro) phenyl]
Propane, bis [4- (β-epithiopropyltelluro)
Phenyl] sulfide, bis [4- (β-epithiopropyltelluro) phenyl] sulfone, 4,4′-bis (β-epithiopropyltelluro) biphenyl and the like. Furthermore, compounds in which at least one hydrogen of the β-epithiopropyl group of these compounds is substituted with a methyl group are also specific examples.

Further, organic compounds having an unsaturated group are also included in the above (A) to (E). Preferred specific examples of these include vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, and allylthioglycidyl ether.

Other specific examples of the compound having one or more epithio groups include ethylene sulfide,
Compounds such as propylene sulfide and thioglycidol; thioglycidyl esters of monocarboxylic acids such as acetic acid, propionic acid and benzoic acid; thioglycidyl such as methyl thioglycidyl ether, ethyl thioglycidyl ether, propyl thioglycidyl ether and butyl thioglycidyl ether Ethers can be mentioned.

Among these, (B) an organic compound having an epithioalkyloxy group, (C) an organic compound having an epithioalkylthio group, (D) an organic compound having an epithioalkylseleno group, (E) An organic compound having an epithioalkyltelluro group, particularly preferred are (C) an organic compound having an epithioalkylthio group, and (D) an organic compound having an epithioalkylseleno group. Specific examples of particularly preferable ones are the above-mentioned specific examples of the β-epithiopropylthio group, a chain compound having a β-epithiopropylseleno group, a branched compound, an aliphatic cyclic compound, an aromatic compound, and a heterocyclic ring. Compound.

According to the present invention, immersing the resin for optical material in a liquid comprising an inorganic acid and / or an organic acid means that the resin for optical material is immersed in an inorganic acid and / or an organic acid, or an inorganic acid and / or an organic acid. This is to be immersed in a solution containing 0.1% by weight or more of an acid. The content of the inorganic acid and / or the organic acid is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more,
It is particularly preferably at least 20% by weight, most preferably at least 30% by weight. This immersion treatment can be said to be a pre-dyeing treatment step, and this liquid is a pre-dyeing treatment liquid. Various dispersants, surfactants, antioxidants, stabilizers, and other additives can be added to the pretreatment solution as needed.

It is possible to use water and / or an organic solvent as a solvent for the pretreatment solution. The solvent used here is not limited as long as it dissolves these acids. Specific examples of the organic solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, benzyl alcohol, phenethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, xylylene diol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and ethyl acetate. , Butyl acetate, tetrahydrofuran, methyltetrahydrofuran, dioxane, diethyl ether,
1,2-dimethoxyethane, acetone, acetonitrile, butanone, benzene, toluene, xylene, naphthalene, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, N, N-dimethylformamide, dimethylsulfoxide, 2-hydroxyethylamine, 2,
2′-iminodiethanol, 2-mercaptoethanol and the like. These compounds can be used alone or in combination. Preferred among these are methanol, ethanol, benzyl alcohol, ethylene glycol, diethylene glycol, methyl cellosolve, ethyl cellosolve, toluene, xylene, naphthalene, N, N-dimethylformamide, and dimethylsulfoxide. However, when the acid contained in the pre-dyeing treatment liquid is only an organic acid, the effect of the pre-dyeing treatment may be reduced if water is contained. Therefore, when the acid contained in the pretreatment solution is only an organic acid, not mixing water is effective in enhancing the dyeing effect.

Specific examples of the inorganic acid used in the present invention include carbonic acid, nitric acid, hydrochloric acid, perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, pyrosulfuric acid, boric acid, and arsenic acid. Acid, arsenous acid, pyroarsenic acid, phosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid ,
Examples include nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, sulfuryl chloride, silica gel, silica alumina, silicic acids, and boron tetrafluoride. These compounds can be used alone or in combination. Preferred among these are hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.

The organic acid used in the present invention is an organic compound exhibiting acidity. Specific examples include compounds having a sulfone group, compounds having a carboxyl group, compounds having a phenolic hydroxyl group, compounds having a mercapto group,
Examples thereof include sulfinic acids, enol-type compounds, imides, oximes, aromatic sulfonamides, phosphoric esters, and phosphites. These compounds can be used alone or in combination. Preferred among the organic acids are compounds having at least one group selected from a sulfone group, a carboxyl group and a phenolic hydroxyl group.

Specific examples of the compound having a sulfone group of the present invention include methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid and p-toluenesulfonic acid. -Toluenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, o-phenolsulfonic acid, m-phenolsulfonic acid, p-phenolsulfonic acid, o-cresolsulfonic acid, m-cresolsulfonic acid, p -Cresolsulfonic acid, metanylic acid, sulfanilic acid, 4B-
Acid, diaminostilbene sulfonic acid, biphenyl sulfonic acid, α-naphthalene sulfonic acid, β-naphthalene sulfonic acid, peric acid, lauric acid, phenyl J acid, 4-hydroxy-3-methylbenzene sulfonic acid, α-naphthol sulfonic acid, Examples thereof include sulfonic acid compounds such as β-naphtholsulfonic acid, and sulfonated compounds of compounds having a phenolic hydroxyl group exemplified below. The above compounds can be used alone or in combination. Preferred among these are aromatic compounds. In general, the sulfonic acid compound often has water of crystallization, but those treated with heat, reduced pressure, etc. to remove water show particularly good pretreatment effects.

Specific examples of the compound having a carboxyl group of the present invention include formic acid, acetic acid, propionic acid, 2-ethylhexanoic acid, butyric acid, valeric acid, caproic acid, caprylic acid, naphthenic acid, oxalic acid, malonic acid, and succinic acid. Acid, glutaric acid, adipic acid, maleic acid, cyclohexanecarboxylic 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, acetic anhydride, peracetic acid, thioacetic acid, oxalic acid, tartaric acid , Salicylic acid, maleic anhydride, benzoic anhydride, phthalic anhydride, trimellitic anhydride, Lomellitic acid and the like. These compounds can be used alone or in combination. Of these, aromatic carboxylic acids and monovalent aliphatic carboxylic acids are preferred.

The compound having a phenolic hydroxyl group of the present invention does not have a sulfone group. Specifically, 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-butyl-phenol, 2,6-di-t-butyl-phenol, 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, 2-methoxyphenol, 4-methoxyphenol, 2, 4-dimethoxyphenol, 2,6-dimethoxyphenol, 2,4,6
-Trimethoxyphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 3-methoxycatechol, 4-methoxycatechol, 3,5-dimethoxycatechol, 3,6-dimethoxycatechol Catechol-4-carboxylic acid, salicylic acid, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, dimethyl salicylic acid, di-t-butyl salicylic acid, salicylosalicylic acid, salicylamide, sodium salicylate , 4-hydroxybenzoic acid, methyl 4-hydroxybenzoate, 4-
Ethyl hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 -Hydroxy-
4-ethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetic amide, methyl hydroxyphenylacetate, hydroxyphenethyl alcohol, hydroxyphenethylamine,
Acetaminophen, 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, 2,
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 ( 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′-
Methylene bis (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-t-butylphenyl) butane, 1,3,5-trimethyl-2 , 4,6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) ) -4-Methylphenyl acrylate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazine and the like. These compounds can be used alone or in combination. Of these, preferred are monovalent or divalent phenols, and more preferred are phenol, chlorophenol, phenylphenol, catechol, t-butylcatechol, hydroquinone, xylenol, and cresol.

In the present invention, a mixture of a compound having a sulfone group and a compound having a phenolic hydroxyl group as the organic acid is defined as a compound having at least one sulfone group as the organic acid and at least one phenol compound as the organic acid. That is, a mixture with a compound having a hydrophilic hydroxyl group is used. Preferred compounds having a sulfone group are aromatic compounds. The weight ratio [(I) / (II)] of the compound (I) having a sulfone group and the compound (II) having a phenolic hydroxyl group is not particularly limited, but the storage stability of the pretreatment solution and the pretreatment Considering the persistence of the effect, it is preferably 0.001 or more and 100 or less, more preferably 0.005 or more and 50 or less, still more preferably 0.005 or more and 10 or less, and most preferably 0.1 or more.
01 or more and 2.0 or less.

In the present invention, the dyeing of the resin for an optical material is performed by:
It is carried out after immersion treatment in a liquid containing an inorganic acid and / or an organic acid or an inorganic acid and / or an organic acid at a temperature of -50C to 200C. This immersion treatment can be said to be a pre-dyeing treatment step, and this liquid is a pre-dyeing treatment liquid. By the pre-dyeing pretreatment operation, materials that are difficult to be dyed can be dyed well. The temperature of the immersion liquid may be high or low as long as a dyeing effect can be obtained, but is preferably -20 ° C to 200 ° C, more preferably 0 ° C to 150 ° C. If the immersion temperature is too low, the effect of the pre-dyeing treatment becomes insufficient, and if it is too high, the material is deformed or the like, which is not preferable. The immersion time may be long or short as long as the effect is obtained, but is usually 1 second to 24 hours, preferably 10 seconds to 10 hours, more preferably 10 seconds to 5 hours. . If the immersion time is too short, the effect of the pretreatment for dyeing becomes insufficient and the dyeing is not sufficiently performed. In addition, in order to further reduce uneven dyeing, it is preferable to stir the pre-dyeing treatment liquid.

The pre-dyeing treatment is carried out by immersing the resin for optical material after curing and polymerization in a pre-dyeing treatment solution. It is preferable in terms of enhancing the pretreatment effect and also in obtaining good dyeing results without unevenness. In particular, when dyeing is performed while the pretreatment solution is attached, not only unevenness tends to occur, but also the staining solution is contaminated, so that a washing operation is required after immersion in the pretreatment solution. The washing solution is not particularly limited as long as it dissolves the components of the pretreatment solution, but usually, water, an aqueous alkali solution, an aqueous acid solution, an organic solvent, or the like is used. As a washing liquid, preferably, an aqueous solution of an alkali or alkaline earth metal hydroxide such as an aqueous solution of sodium hydroxide or potassium hydroxide, an alcohol such as isopropyl alcohol, ethylene glycol or diethylene glycol;
Ethers such as 1,4-dioxane; halogenated hydrocarbons such as dichloromethane; amines such as N, N-dimethylformamide, diethylethanolamine and methyldiethanolamine; and dimethyl sulfoxide. These may be used alone or in combination of some, but preferably, an organic solvent such as washing with an organic solvent and then washing with an aqueous solvent, or washing with an aqueous solvent and then washing with an organic solvent. And washing with a water solvent alternately. As a finish of the washing, it is preferable to wash with pure water. The temperature of the washing solution is preferably -20 ° C.
To 200 ° C, more preferably 0 ° C to 150 ° C. If the cleaning temperature is too low, the cleaning effect becomes insufficient, and if it is too high, deformation of the material or the like occurs, which is not preferable. The washing time may be long or short as long as the pretreatment solution can be removed, but it is usually 1 second to 24 hours, preferably 10 seconds to 10 hours, more preferably 10 seconds to 5 hours. Between. If the cleaning time is too short, the cleaning effect becomes insufficient, and if it is too long, the material is deformed or the surface is roughened. Further, in order to enhance the cleaning effect, it is preferable to add a surfactant to the cleaning liquid and perform cleaning using a stirring device or an ultrasonic cleaning device. Further, before and after immersing the resin for optical material in the pre-dyeing treatment liquid, it is preferable to apply a reduced pressure and / or a heat treatment as necessary, since a uniform and good dyeing effect can be exhibited.

Dyeing is usually carried out by heating a liquid composition containing a dye and, if necessary, a surfactant or a carrier compound to room temperature to 200 ° C., and immersing the material therein. The amount of the dye used in the liquid composition is 0.01 to 1 L of water.
g to 100 g, preferably 0.05 g to 50 g, more preferably 0.1 g to 25 g. When the amount of the dye is less than 0.01 g, the dyeing time is prolonged and sufficient dyeability cannot be obtained. If the amount is more than 100 g, the dye becomes hard to disperse due to lumps,
Conversely, it adversely affects the dyeability and causes uneven dyeing. Dyes are conventionally used disperse dyes in the art, reactive dyes, cationic dyes, acid dyes, sulfur dyes,
Ingredients and the like are not particularly limited as long as they exhibit the same effect. For example, with the product name of Dystar Japan Co., Ltd., Dianix-Yell
ow, Orange, Scarret, Red, Pin
k, Violet, Blue, Gray, Black and other disperse dyes, Remazol-Yellow, Red,
Reactive dyes such as Blue, Gray, Black, etc., Ast
razon-Yellow, Red, Violet, B
Examples include cationic dyes such as lue, green, and black, and these may be mixed and used depending on the application.

The surfactant may not be necessary in some cases, but if necessary, the amount of the surfactant is usually 0.001 g to 5 g per 1 L of water.
0 g, preferably 0.005 g to 50 g. When the amount of the surfactant is less than 0.001 g, the effect cannot be sufficiently exhibited, and when the amount is more than 50 g, uniform dyeing becomes difficult. Examples of surfactants include alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, aromatic sulfonic acid formalin condensate, anionic surfactant such as lauryl sulfate, polyoxyethyl alkyl ether, alkyl Examples include nonionic surfactants such as amine ethers and polyoxyethylene sorbitan fatty acid esters.

The carrier compound may not be necessary in some cases, but if necessary, the addition amount is usually 0.001 to 1 L of water.
g to 50 g, preferably 0.005 g to 50 g. 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 typified by an aromatic compound, but it is not necessary to limit the carrier compound as long as it exhibits the same effect. For example, aromatics having phenolic hydroxyl groups such as phenol, cresol, naphthol, resorcin, catechol, bisphenol A, pyrogallol, and phloroglucin, as described on pages 205 and 286 of “Introduction to Dyeing and Processing Technology” (Textile Research Institute). Group compounds, methanol, ethanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, glycerin, alcohols such as xylylene diol, benzoic acid esters,
Salicylic acid esters, phthalic acid mono- and diesters,
Esters such as isophthalic acid mono- and diesters, terephthalic acid mono- and diesters, alkylbenzene,
Examples thereof include aromatic compounds such as chlorobenzene, dichlorobenzene, styrene, naphthalene, α-alkylnaphthalene, β-alkylnaphthalene, α-vinylnaphthalene, and β-vinylnaphthalene. These compounds may be appropriately mixed and used as needed. The temperature of the dyeing solution may be high or low as long as a dyeing effect can be obtained, but is preferably 20 ° C to 200 ° C, more preferably 20 ° C to 150 ° C. If the temperature is too low, the dyeing becomes insufficient, and if the temperature is too high, deformation of the material or the like occurs, which is not preferable. Depending on the liquid components, the desired temperature may not be obtained by ordinary heating, but in this case, the desired dyeing temperature is realized under a pressure or by adding a component capable of increasing the boiling point, by a so-called boiling point increasing method. . When the boiling point is raised by pressurization, the dyeing is usually carried out at 1.1 to 20 atm using a pressure cooker or an autoclave. Examples of the components to be added by the boiling point raising method include inorganic salts and water-soluble organic compounds capable of realizing a molar boiling point raising effect when the bath component is water. As inorganic salts,
The use is not limited as long as it is a common 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 immersion time in the dyeing solution may be long or short as long as the dyeing effect can be obtained, but is usually 1 second to 10 hours, preferably 5 seconds to 5 hours. If the immersion time is too short, the dyeing becomes insufficient, and if the immersion time is too long, deformation or the like of the material occurs, which is not preferable. It is preferable to stir the dyeing solution in order to enhance the dyeing effect.

[0034]

According to the dyeing method of the present invention, that is, a resin for optical materials which cannot be dyed at a high concentration by the conventional dyeing technique by the dyeing pretreatment method, particularly a sulfur-containing resin which is difficult to dye,
Above all, it became possible to dye a resin having a high sulfur content at a high concentration. As a result, a resin for an optical material having a high refractive index dyed at a high concentration has been realized for the first time.

[0035]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. The staining was performed by the following method. Dyeing method: Dipped in a dyeing solution having the following composition at 90 ° C. for 5 minutes. Staining solution composition (solvent is water) Seiko Plux Diamond Coat Brown D 0.2% by weight Seiko Plux Dyeing aid 0.3% by weight Benzyl alcohol 2.0% by weight The degree of staining was determined by fitting. Staining degree = 100−total light transmittance (%) The composition ratios in Tables 1 and 2 are weight ratios.

Example 1 A lens made of a resin obtained by curing and polymerizing bis (β-epithiopropyl) sulfide (a flat plate having a thickness of 2.5 mm)
Was pre-stained, immersed in sulfuric acid at 30 ° 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 degree of staining of the obtained lens.

Example 2 Instead of immersing in sulfuric acid at 30 ° C. for 30 minutes before dyeing,
The same operation as in Example 1 was repeated except that the pre-staining treatment was performed under the conditions shown in Table 1. Table 1 shows the degree of staining of the lens (2.5 mm thick flat plate) made of the obtained resin.

Examples 3 to 77 The same procedures as in Example 1 were carried out except that a pre-staining treatment was carried out under the conditions shown in Table 1 using a lens made of the resin shown in Table 1 instead of bis (β-epithiopropyl) sulfide. Operation was repeated. Table 1 shows the degree of staining of the lens (2.5 mm thick flat plate) made of the obtained resin.

Comparative Examples 1 to 15 Using the lenses made of the resins shown in Table 2, dyeing was performed without pre-dyeing treatment. Table 2 shows the degree of staining of the obtained lens (2.5 mm thick flat plate).

Comparative Example 16 The same operation as in Example 1 was repeated, except that the pre-dyeing treatment was performed by immersing in liquid paraffin at 120 ° C. for 60 minutes instead of immersing in concentrated sulfuric acid at 20 ° C. for 30 minutes before dyeing. Was.
Table 2 shows the degree of staining of the obtained lens (2.5 mm thick flat plate).
It was shown to.

Examples 78 to 107 On the day when the pretreatment solution shown in Table 3 was prepared (day 0), 10 days after preparation, and 30 days after preparation, a lens (2.5 mm (Thick plate), pre-dyeing treatment was performed under the conditions shown in Table 1, and then dyed. The degree of staining is shown in Table 3.

The compositions of the resins A to W in Tables 1 to 3 are shown below. A: Heat (β-ethyl thiol) sulfite B: Heat (β-ethyl thiol) sulfite / n-butylthio glycolate = 9
5/5 C: Pease (β-Ethyl isopropyl) sulfite / 2-mercaptoethanol = 95/5 D: Pease (β-Ethyl isopropyl) sulfite / Pease (2-mercaptoethyl) sulfite = 95/5 E: Pease (β-Ethylfluoropropyl) sulfite / n-butylthioglycolate / 2-mercaptoethanol = 94.5 / 2.5 / 3 F: Hose (β-ethylthiopropyl) sulfite / n-butylthiochololate / 2-Hethyloxyethyl methacrylate = 93/6/1 G: Pease (β-Ethyl thiol) sulfite / Phase (2-mercaptoethyl) sulphite / 2-Human oxyethyl methacrylate = 90/5/5 H: Pease (β-Ethyl chlorophyll) Sulfite / Bis (2-mercaptoethyl) sulphite / 3-phenoxy-2-human peroxyfluoro acrylate = 90/5/5 I Heat (β-Efficient Hydro) Sulfite / Heat (2-mercaptoethyl) Sulfite / Crysitol = 92/5/3, J: Heath (β-Efficient Hydro) Sulfite K: Heath (β-Efficient) n-butylthioglycolate = 9
5/5 L: Pease (β-Ethyl thiol) sulfide / 2-mercaptoethanol = 95
/ 5 M: Pease (β-Echio-Profil) Sulfite / Pease (2-mercaptoethyl) Sulfite = 95/5 N: Peace (β-Echio-Profile) Sulfite O: Peace (β-Echio-Profile) Sulfite P: pulse (β-ethyl thiopropyl) trisulfite, Q: pulse (β-ethyl chloropropyl) ethyl ether R: 2,5-bis (mercaptomethyl) -1,4-ztian / pentaerythritol tetrakis mercaptofluorothionate / 1,3-bis (isocyanatomethyl) cyclohexane = 26/26/48 S: bis (mercaptoethyl) trithioglycerin / m-xylene diisocyanate = 48/5
2 T: bis (mercaptoethyl) trithioglycerin / cyclocyclohexylmethane-4,4'-diisocyanate = 40/60 U: pentaerythritol tetrakis-3-mercaptofluoropionate / m-xylene diisocyanate = 56/44 V: polyethylene glycol discharge Allyl carbonate W: Phase (β-ethyl thiol) selenite

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

The composition of the pretreatment solution shown in Table 3 is shown below. a: m-xylene sulfonic acid / 3,5-xylenol / naphthalene = 50/25/25 b: m-xylene sulfonic acid / 3,5-xylenol / naphthalene = 60/20/20 c: sulfuric acid / p-toluene sulfone Acid / catechol = 85/10/5 d: sulfuric acid / p-toluenesulfonic acid / catechol = 75/20/5 e: phenolsulfonic acid / catechol / o-phenylphenol = 5/10/85 f: phenolsulfonic acid / Catechol / o-phenylphenol = 80/10/10 g: benzenesulfonate / o-phenylphenol = 5/95 h: benzenesulfonate / o-phenylphenol = 90/10

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04 1/10 G02C 7/10 G02C 7/10 G02B 1/10 Z (72) Inventor Hiroshi Horikoshi 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory (72) Inventor Daiko Takasuga 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo In the laboratory

Claims (7)

[Claims] 1. A method for dyeing a resin for an optical material, comprising immersing the resin for an optical material in a liquid comprising an inorganic acid and / or an organic acid, and then dyeing the resin. 2. The dyeing method according to claim 1, wherein the resin for an optical material is a sulfur-containing resin. 3. The resin for an optical material is a resin obtained by polymerizing and curing a compound alone having at least one structure represented by the following formula (1) in one molecule or a composition containing the compound. Item 6. The dyeing method according to Item 1. 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 O, S, Se or Te.
n = 0 to 5, m = 1 to 5, and p represents 0 or 1. ) 4. The inorganic acid is at least one compound selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the organic acid is at least one compound selected from a sulfone group, a carboxyl group and a phenolic hydroxyl group. The dyeing method according to claim 1, which is a compound having the above group. 5. The method according to claim 1, wherein the organic acid is a mixture of a compound having a sulfone group and a compound having a phenolic hydroxyl group. 6. The weight ratio [(I) / (II)] of the compound (I) having a sulfone group to the compound (II) having a phenolic hydroxyl group is 0.01 to 2.0. Dyeing method. 7. A resin for optical materials dyed by the dyeing method according to claim 1. Description: