JP2003048883A - Method for producing episulfide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical material excellent in transparency, obtained by polymerizing and curing an episulfide compound. SOLUTION: This method for producing the episulfide compound comprises the following processes: (1) A first process of producing a halohydrin compound by reacting epihalohydrin having <=1,000 ppm residue after its evaporation with hydrogen sulfide or a mercapto compound in the presence of a catalyst. (2) A second process of producing an epoxy compound by performing a reaction of the halohydrin compound obtained in the first process with a basic compound. (3) A third process of producing the episulfide compound by reacting the epoxy compound obtained in the second process with an agent for forming a sulfide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a plastic lens,
The present invention relates to a method for producing an episulfide compound, which is a raw material for an optical material such as a prism, an optical fiber, an information recording substrate, and a filter, and a method for producing an optical material obtained from the episulfide compound.

[0002]

2. Description of the Related Art Plastic materials have been widely used in recent years for various optical materials, particularly spectacle lenses, because they are lightweight, rich in toughness, and easy to dye. Optical materials, especially
In addition to low specific gravity, the performances required for spectacle lenses are high refractive index and high Abbe number as optical performance, and high heat resistance and high strength as physical performances. A high refractive index enables thinning of the lens, a high Abbe number reduces chromatic aberration of the lens, and high heat resistance and high strength facilitate secondary processing and are important from the viewpoint of safety and the like. The present inventors have developed a sulfur-containing compound having an episulfide structure, which enables an optical material having a refractive index of 1.7 or more and an Abbe number of 35 or more, which has a thin thickness and low chromatic aberration, and has previously filed a patent application. (JP-A 09-71580, JP-A 09-
-110979). However, an optical material produced by polymerizing and curing a compound having an episulfide structure according to the present invention (hereinafter referred to as an episulfide compound) may have cloudiness or the like to reduce transparency, thereby obtaining stable physical properties. The development of the manufacturing method for it was desired.

[0003]

The problem to be solved by the present invention is to improve the drawbacks in producing an optical material by polymerizing and curing the above episulfide compound, and to provide an optical material having excellent transparency with uniform quality. To provide in.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, found that the above problems can be solved by the method described below, and arrived at the present invention. .

That is, the gist of the present invention is, firstly, a method for producing an episulfide compound, which comprises the following steps. (1) A first step of producing a halohydrin compound by reacting an epihalohydrin having an evaporation residue of 1000 ppm or less with hydrogen sulfide or a mercapto compound in the presence of a catalyst. (2) A second step of producing an epoxy compound by reacting the halohydrin compound obtained in the first step with a basic compound. (3) A third step of reacting the epoxy compound obtained in the second step with a thiating agent to produce an episulfide compound.

Secondly, there is provided a method for producing an optical material by polymerizing and curing the episulfide compound obtained in the first invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The episulfide compound of the present invention is a compound having one or more structures represented by the following formula (1) in one molecule.

[0008]

[Chemical 1] (In the formula, 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. X represents S or O, and the number of S is 3
It is 50% or more on the average with respect to the total of S and O constituting the member ring. )

First, the first step will be described. A mercapto compound represented by the following formula (2) or hydrogen sulfide (H ₂ S) is reacted with epihalohydrin in the presence or absence of a solvent, optionally in the presence of an acidic substance or a basic substance as a catalyst,

[0010]

Embedded image R- (SH) n (2) (In the above formula (2), n represents an integer of 1 or more.
R represents a hydrocarbon group having 1 to 20 carbon atoms, and these may contain a bond such as sulfide, ether, sulfone, ester, and ketone in the group. ) A halohydrin compound having one or more corresponding structures represented by the following formula (3) in one molecule is obtained.

[0011]

[Chemical 3] (In the above formula (3), R¹ Is carbonized with 1 to 10 carbon atoms
Hydrogen, R² , R³ And R ^Four Each has 1 to 10 carbon atoms
Indicates a hydrocarbon group or hydrogen. Y is fluorine, chlorine, bromine
Or indicate iodine. )

The epihalohydrin of the present invention includes epichlorohydrin, epibromohydrin, and at least one hydrogen of the epoxy group of these compounds has 1 carbon atom.
Compounds substituted with a hydrocarbon group such as an alkyl group, an aryl group, an allyl group, a vinyl group, an aralkyl group, etc. of 10 are mentioned. It is preferably epichlorohydrin.

Specific examples of the mercapto compound represented by the formula (2) of the present invention include mercaptans, thiophenols, mercapto alcohols and vinyl, aromatic vinyl, methacryl having one or more SH groups in the molecule. , Mercaptans having an unsaturated group such as acryl and allyl, thiophenols and mercapto alcohols. More specifically, the mercaptans include 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-mercaptopropionate), Ethyl (3-mercaptopropionate),
3-methoxybutyl (3-mercaptopropionate), n-butyl (3-mercaptopropionate),
2-ethylhexyl (3-ercaptopropionate), n-octyl (3-mercaptopropionate)
Monomercaptans such as; 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-mercapto Methyl-1,
3-dimercaptopropane, 2-mercaptomethyl-
1,4-dimercaptobutane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-
Bis (2-mercaptoethylthio) -3-mercaptopropane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3- Mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane Tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptocetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,4-dimercapto Cyclohexane, 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-Thian, 2,5-bis (2-mercaptoethyl)
-1-Thian, 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- (mercaptomethyl) phenyl] sulfide, bis [4- (mercaptomethyl) phenyl] ether, 2,2-bis [4-
Polymercaptans such as (mercaptomethyl) phenyl] propane, 2,5-dimercapto-1,3,4-thiadiazole, and 3,4-thiophedithiol. The thiophenols include thiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 4,
Examples thereof include thiophenols such as 4'-thiodi (mercaptobenzene). The mercapto alcohols include 2-mercaptoethanol and 3-mercapto-
1,2-propanediol, 2-mercapto-1,3-
Propanediol etc. can be mentioned. Further, mercaptans and thiophenols having an unsaturated group are specifically shown below. Examples of mercaptans having an unsaturated group include allyl mercaptan, 2-vinylbenzyl mercaptan, 3-vinylbenzyl mercaptan, 4-vinylbenzyl mercaptan, 3- (1,2-dimercaptoethyl) styrene, 4- (1,2) -Dimercaptyl) styrene and the like. Examples of the thiophenol having an unsaturated group include 2-vinylthiophenol, 3-vinylthiophenol, 4-vinylthiophenol, 2,3-dimercaptostyrene, 2,4-dimercaptostyrene,
Examples thereof include 3,4-dimercaptostyrene and 3,5-dimercaptostyrene. Particularly preferred compounds are mercaptans and thiophenols. These may be used alone or in combination of two or more.

To exemplify a compound having one or more structures represented by formula (3) in one molecule, specific examples of compounds having one structure represented by formula (3) in one molecule As, at least one hydrogen atom of the 2-chloro-1-hydroxyethyl group of bis (3-chloro-2-hydroxypropyl) sulfide and bis (3-chloro-2-hydroxypropyl) sulfide is an alkyl group such as a methyl group. And compounds substituted with an aryl group such as a phenyl group and an allyl group such as a 2-propenyl group.
The compound having two or more structures represented by the formula (3) in one molecule is (A) an organic compound having a chained aliphatic skeleton in which two or more structures represented by the formula (3) are bonded in one molecule. Organic compound having a cycloaliphatic skeleton in which two or more structures represented by formula (B) (3) are bonded in one molecule, and two or more structures represented by formula (C) (3) are bonded in one molecule. Compound having an aromatic skeleton, and at least one hydrogen atom of the 2-chloro-1-hydroxyethyl group of these compounds is an alkyl group such as a methyl group, an aryl group such as a phenyl group, an allyl group such as a 2-propenyl group. Examples thereof include compounds substituted with groups and the like.
The molecule may contain a bond such as sulfide, ether, sulfone, ketone and ester.

The organic compound having a chain aliphatic skeleton (A) is classified into a straight chain and a branched chain, and specific examples thereof are bis (3-chloro-2-hydroxypropylthio) methane. , 1,2-bis (3-chloro-2-
Hydroxypropylthio) ethane, 1,3-bis (3-
Chloro-2-hydroxypropylthio) propane, 1,
2-bis (3-chloro-2-hydroxypropylthio)
Propane, 1- (3-chloro-2-hydroxypropylthio) -2-[(3-chloro-2-hydroxypropylthio) methyl] propane, 1,4-bis (3-chloro-
2-hydroxypropylthio) butane, 1,3-bis (3-chloro-2-hydroxypropylthio) butane,
1- (3-chloro-2-hydroxypropylthio) -3
-[(3-chloro-2-hydroxypropylthio) methyl] butane, 1,5-bis (3-chloro-2-hydroxypropylthio) pentane, 1- (3-chloro-2-hydroxypropylthio) -4 -[(3-chloro-2-hydroxypropylthio) methyl] pentane, 1,6-bis (3-chloro-2-hydroxypropylthio) hexane, 1- (3-chloro-2-hydroxypropylthio)
-5-[(3-chloro-2-hydroxypropylthio)
Methyl] hexane, 1- (3-chloro-2-hydroxypropylthio) -2- [2- (3-chloro-2-hydroxypropylthio) ethylthio] ethane, 1- (3-chloro-2-hydroxypropylthio) ) -2- [2- [2
A chain 3-chloro-2-hydroxypropylthio compound such as-(3-chloro-2-hydroxypropylthio) ethylthio] ethylthio] ethane; tetrakis [(3-chloro-2-hydroxypropylthio) methyl] methane,
1,1,1-Tris [(3-chloro-2-hydroxypropylthio) methyl] propane, 1,5-bis (3-chloro-2-hydroxypropylthio) -2-[(3-chloro-2- Hydroxypropylthio) methyl] -3-thiapentane, 1,5-bis (3-chloro-2-hydroxypropylthio) -2,4-bis [(3-chloro-2-
Hydroxypropylthio) methyl] -3-thiapentane, 1- (3-chloro-2-hydroxypropylthio)
-2,2-bis [(3-chloro-2-hydroxypropylthio) methyl] -4-thiahexane, 1,5,6-tris (3-chloro-2-hydroxypropylthio) -4
-[(3-chloro-2-hydroxypropylthio) methyl] -3-thiahexane, 1,8-bis (3-chloro-
2-hydroxypropylthio) -4-[(3-chloro-
2-Hydroxypropylthio) methyl] -3,6-dithiaoctane, 1,8-bis (3-chloro-2-hydroxypropylthio) -4,5-bis [(3-chloro-2-
Hydroxypropylthio) methyl] -3,6-dithiaoctane, 1,8-bis (3-chloro-2-hydroxypropylthio) -4,4-bis [(3-chloro-2-hydroxypropylthio) methyl]- 3,6-Dithiaoctane, 1,8-bis (3-chloro-2-hydroxypropylthio) -2,4,5-tris [(3-chloro-2-hydroxypropylthio) methyl] -3,6-dithiaoctane , 1,8-bis (3-chloro-2-hydroxypropylthio) -2,5-bis [(3-chloro-2-hydroxypropylthio) methyl] -3,6-dithiaoctane, 1,9-bis ( 3-chloro-2-hydroxypropylthio) -5-[(3-chloro-2-hydroxypropylthio) methyl] -5-[[2- (3-chloro-2-hydroxypropylthio) ) Ethylthio] methyl] 3,7
-Dithianonane, 1,10-bis (3-chloro-2-hydroxypropylthio) -5,6-bis [2- (3-chloro-2-hydroxypropylthio) ethylthio]-
3,6,9-Trithiadecane, 1,11-bis (3-chloro-2-hydroxypropylthio) -4,8-bis [(3-chloro-2-hydroxypropylthio) methyl] -3,6,9 -Trithiaundecane, 1,11-bis (3-chloro-2-hydroxypropylthio) -5,
7-bis [(3-chloro-2-hydroxypropylthio) methyl] -3,6,9-trithiaundecane, 1,
11-bis (3-chloro-2-hydroxypropylthio) -5,7-[[2- (3-chloro-2-hydroxypropylthio) ethylthio] methyl] -3,6,9-trithiaundecane, 1 , 11-bis (3-chloro-2-
Hydroxypropylthio) -4,7-bis [(3-chloro-2-hydroxypropylthio) methyl] -3,6
Branched 3-chloro-2-, such as 9-trithiaundecane
Hydroxypropylthio compounds; and at least one hydrogen atom of the 2-chloro-1-hydroxyethyl group of these compounds is an alkyl group such as a methyl group, an aryl group such as a phenyl group, an allyl group such as a 2-propenyl group, and the like. And the like.

Specific examples of the organic compound having a cycloaliphatic skeleton (B) include 1,3 and 1,4-bis (3-chloro-2-hydroxypropylthio) cyclohexane, 1,3 and 1, 4-bis [(3-chloro-2
-Hydroxypropylthio) methyl] cyclohexane,
Bis [4- (3-chloro-2-hydroxypropylthio) cyclohexyl] methane, 2,2-bis [4- (3
-Chloro-2-hydroxypropylthio) cyclohexyl] propane, bis [4- (3-chloro-2-hydroxypropylthio) cyclohexyl] sulfide, 2,5
-Bis [(3-chloro-2-hydroxypropylthio)
Methyl] -1,4-dithiane, 2,5-bis [[2-
Cycloaliphatic 3-chloro-2-hydroxypropylthio compounds such as (3-chloro-2-hydroxypropylthio) ethylthio] methyl] -1,4-dithiane and 2-chloro-1-hydroxyethyl groups of these compounds Examples thereof include compounds in which at least one of the hydrogen is substituted with an alkyl group such as a methyl group, an aryl group such as a phenyl group, an allyl group such as a 2-propenyl group, and the like.

Specific examples of the organic compound having an aromatic-aliphatic skeleton (C) include 1,3 and 1,4-bis (3
-Chloro-2-hydroxypropylthio) benzene,
1,3 and 1,4-bis [(3-chloro-2-hydroxypropylthio) methyl] benzene, bis [4- (3
-Chloro-2-hydroxypropylthio) phenyl] methane, 2,2-bis [4- (3-chloro-2-hydroxypropylthio) phenyl] propane, bis [4- (3
-Chloro-2-hydroxypropylthio) phenyl] sulfide, bis [4- (3-chloro-2-hydroxypropylthio) phenyl] sulfone, 4,4'-bis (3-chloro-2-hydroxypropylthio) biphenyl At least one hydrogen of the aromatic 3-chloro-2-hydroxypropylthio compound and the 2-chloro-1-hydroxyethyl group of these compounds is an alkyl group such as a methyl group, an aryl group such as a phenyl group, 2 -Examples include compounds substituted with an allyl group such as a propenyl group and the like.

The molar ratio of the epoxy group in the epihalohydrin to the SH group of the mercapto compound or the H of hydrogen sulfide is usually 0.3 to 4, preferably 0.4 to 3, and more preferably 0.5 to 2.

As the catalyst of the first step, known basic substances and acidic substances can be mentioned, but acidic substances are preferable, and by-products are suppressed and a high-purity halohydrin compound is obtained as compared with the case of using an alkaline substance. Obtainable. As the acidic substance in the present invention, inorganic acids, organic acids, Lewis acids, silicic acids, boric acids, quaternary ammonium salts, salts formed from amine compounds and acids, and the like are used. Specific examples include hydrochloric acid, hydrobromic acid,
Inorganic acids such as hydroiodic acid, sulfuric acid, fuming sulfuric acid, boric acid, nitric acid, phosphoric acid, carbonic acid and hydrocyanic acid and their half-esters; formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, Hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylbutanoic acid, 3-ethylbutanoic acid, heptanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexane Acid, 5-methylhexanoic acid, 2-ethylpentanoic acid,
3-ethylpentanoic acid, 4-ethylpentanoic acid, octanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid,
4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 4-ethylhexanoic acid, 5-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid , Dodecanoic acid,
Tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid,
Isocrotonic acid, oleic acid, elaidic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, o-toluic acid, m-toluic acid, p -Organic acids such as toluic acid, hydroatropic acid, atropic acid, cinnamic acid, trimellitic acid, pyromellitic acid, fulic acid, tenic acid, nicotinic acid, isonicotinic acid, and their half-esters; tetramethylammonium chloride , Tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide,
Tetraethylammonium acetate, tetra-n-butylammonium fluoride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, tetra-n- Butyl ammonium borohydride, tetra-n-butyl ammonium hexafluorophosphite, tetra-n-butyl ammonium hydrogen sulfite, tetra-n-butyl ammonium tetrafluoroborate, tetra-n-butyl ammonium tetraphenyl borate, tetra-n- Butyl ammonium paratoluene sulfonate, tetra-n-hexyl ammonium chloride, tetra-n-hexyl ammonium iodide, te La-n-hexyl ammonium acetate, tetra-n-octyl ammonium chloride, tetra-n-octyl ammonium iodide, tetra-n-octyl ammonium acetate, trimethyl-n-octyl ammonium chloride, trimethylbenzyl ammonium chloride, trimethylbenzyl ammonium bromide , Triethyl-n-octylammonium chloride, triethylbenzylammonium chloride, triethylbenzylammonium bromide, tri-n-butyl-n-octylammonium chloride, tri-n-butylbenzylammonium fluoride, tri-n-butylbenzylammonium chloride, Tri-n-butylbenzylammonium bromide, tri-n-butylbenzylan Niodide, methyltriphenylammonium chloride, methyltriphenylammonium bromide, ethyltriphenylammonium chloride, ethyltriphenylammonium bromide, n-butyltriphenylammonium chloride, n-butyltriphenylammonium bromide, N-methylpyridinium bromide, N
-Ethylpyridinium bromide, N-n-butylpyridinium bromide, Nn-hexylpyridinium bromide, N-n-octylpyridinium bromide,
N-n-dodecylpyridinium bromide, N-phenylpyridinium bromide, N-methyl-2-picolinium bromide, N-methyl-3-picolinium bromide, N-methyl-4-picolinium bromide, N-
Ethyl-2-picolinium bromide, N-ethyl-3
-Picolinium bromide, N-ethyl-4-picolinium bromide, Nn-butyl-2-picolinium bromide, Nn-butyl-3-picolinium bromide, N-n-butyl-4-picolinium bromide , N
-N-hexyl-2-picolinium bromide, Nn
-Hexyl-3-picolinium bromide, Nn-hexyl-4-picolinium bromide, Nn-octyl-2-picolinium bromide, Nn-octyl-
3-picolinium bromide, Nn-octyl-4-
Picolinium bromide, Nn-dodecyl-2-picolinium bromide, Nn-dodecyl-3-picolinium bromide, Nn-dodecyl-4-picolinium bromide, N-phenyl-2-picolinium bromide, N-phenyl-3-picolinium bromide, N-
The following (4) such as phenyl-4-picolinium bromide
A quaternary ammonium salt represented by the formula:

[0020]

[Chemical 4] (Here, R ⁵ , R ⁶ , R ⁷ , and R ⁸ represent a hydrocarbon group. At least two of these and N to which they are bonded may form a ring structure. , O,
Heteroatoms such as S and N may be contained. X represents halogen. ) Salts formed from amine compounds and mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acids, etc .; 3
Lewis acids such as boron fluoride and boron trifluoride etherate; complexes of amine compounds with borane or boron trifluoride; silicic acid and half-esters of silicic acid;
Boric acid and boric acid half-esters; and the like. You may use these individually or in mixture of 2 or more types. Among these, preferred are organic acids, quaternary ammonium salts and amine compounds and mineral acids, Lewis acids, organic acids,
It is a salt formed from silicic acid, tetrafluoroboric acid, etc. More preferred are salts formed from quaternary ammonium salts and amine compounds and mineral acids, Lewis acids, organic acids, silicic acid, tetrafluoroboric acid and the like, and most preferred are quaternary ammonium salts. More specifically, among quaternary ammonium salts, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide,
Tetraethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, tetra-n-butylammonium fluoride, tetra-n-
Butyl ammonium chloride, tetra-n-butyl ammonium iodide, tetra-n-butyl ammonium acetate, tetra-n-butyl ammonium borohydride, tetra-n-butyl ammonium hexafluorophosphite, tetra-n-butyl ammonium hydrogen sulfite , Tetra-n-butylammonium tetrafluoroborate, tetra-n-butylammonium tetraphenylborate, tetra-n-butylammonium paratoluene sulfonate, tetra-
n-hexyl ammonium chloride, tetra-n-hexyl ammonium iodide, tetra-n-hexyl ammonium acetate, tetra-n-octyl ammonium chloride, tetra-n-octyl ammonium iodide, tetra-n-octyl ammonium acetate, trimethyl- n-octyl ammonium chloride, trimethylbenzyl ammonium chloride, trimethylbenzyl ammonium bromide, triethyl-
n-octyl ammonium chloride, triethylbenzyl ammonium chloride, triethyl benzyl ammonium bromide, tri-n-butyl-n-octyl ammonium chloride, tri-n-butyl benzyl ammonium fluoride, tri-n-butyl benzyl ammonium chloride, tri-n -Butylbenzylammonium bromide, tri-n-butylbenzylammonium iodide, methyltriphenylammonium chloride, methyltriphenylammonium bromide, ethyltriphenylammonium chloride, ethyltriphenylammonium bromide, n-butyltriphenylammonium chloride, n- Butyltriphenylammonium bromide and the like are preferable. The amine compounds referred to in the present invention include ethylamine, n-propylamine, sec-propylamine, n-butylamine,
sec-butylamine, i-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, mistyrylamine, 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,
Primary amines such as aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine and furfurylamine; ethylenediamine, 1,2-diaminopropane,
1,3-diaminopropane, 1,2-diaminobutane,
1,3-diaminobutane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-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- Alternatively, 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethyl Piperidine, 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'-diaminodiphenyl sulfone, 4,4'-diaminoditolyl sulfone, methylenebis (o-chloroaniline), 3,9
-Bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine,
Triethylenetetramine, tetraethylenepentamine,
Pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4 Primary amines such as -diaminophenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octyl Amine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-
Picoline, 2,4-, 2,6-, 3,5-lupetidine,
Diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole,
Secondary amines such as 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,
Secondary polyamines such as 4-di- (4-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-s
ec-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-diethylethanolamine, N, N-dimethylethanolamine, N-ethyldiethanolamine, triethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethyl Benzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N −
Tertiary amines such as diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1,3,2-dioxabornane; tetramethylethylenediamine, pyrazine, N, N'-dimethylpiperazine, N,
N'-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ', N'-
Tetramethyl-1,3-butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N- Tertiary polyamines such as dimethylaminomethyl) phenol and heptamethylisobiguanide; imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N -Butylimidazole, 2-butylimidazole, N-undecylimidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-methylimidazole Sol, N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis -(2-ethyl-4-methylimidazolyl) methane,
Various imidazoles such as adduct of alkylimidazole and isocyanuric acid, condensate of alkylimidazole and formaldehyde; 1,8-diazabicyclo (5,4,4)
0) undecene-7,1,5-diazabicyclo (4,
3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7 and other amidines; Moreover, the amount of the acidic catalyst is usually 1 × 10 ^{−5 to} 5 with respect to 1 mol of the epoxy group of epihalohydrin.
Use ^{x10 -2} mol.

The basic substance referred to in the present invention includes inorganic bases and organic bases. Specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide,
Inorganic bases such as sodium hydrosulfide, sodium sulfide, and ammonia; methylamine, ethylamine, n-propylamine, sec-propylamine, n-butylamine,
sec-butylamine, i-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, mistyrylamine, 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,
Primary amines such as aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine and furfurylamine; ethylenediamine, 1,2-diaminopropane,
1,3-diaminopropane, 1,2-diaminobutane,
1,3-diaminobutane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-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- Alternatively, 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethyl Piperidine, 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'-diaminodiphenyl sulfone, 4,4'-diaminoditolyl sulfone, methylenebis (o-chloroaniline), 3,9
-Bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine,
Triethylenetetramine, tetraethylenepentamine,
Pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4 Primary amines such as -diaminophenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octyl Amine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-
Picoline, 2,4-, 2,6-, 3,5-lupetidine,
Diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole,
Secondary amines such as 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,
Secondary polyamines such as 4-di- (4-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-s
ec-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-diethylethanolamine, N, N-dimethylethanolamine, N-ethyldiethanolamine, triethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethyl Benzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N −
Tertiary amines such as diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1,3,2-dioxabornane; tetramethylethylenediamine, pyrazine, N, N'-dimethylpiperazine, N,
N'-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ', N'-
Tetramethyl-1,3-butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N- Tertiary polyamines such as dimethylaminomethyl) phenol and heptamethylisobiguanide; imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N -Butylimidazole, 2-butylimidazole, N-undecylimidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-methylimidazole Sol, N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis -(2-ethyl-4-methylimidazolyl) methane,
Various imidazoles such as adduct of alkylimidazole and isocyanuric acid, condensate of alkylimidazole and formaldehyde; 1,8-diazabicyclo (5,4,4)
0) undecene-7,1,5-diazabicyclo (4,
3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7 and other amidines; and other organic amines. These may be used alone or in combination of two or more. The amount of the basic catalyst is usually 1 × 10 ^{−3 to} 5 × 10 ³ relative to 1 mol of the epoxy group of epihalohydrin.
^{-Use 1} mol.

Next, the second step will be described. The halohydrin compound obtained in the first step is reacted with a basic substance to obtain an epoxy compound having one or more corresponding structures represented by the following formula (5) in one molecule.

[0023]

[Chemical 5] (In the above formula (5), R¹ Is carbonized with 1 to 10 carbon atoms
Hydrogen, R² , R³And R ^Four Each has 1 to 10 carbon atoms
Indicates a hydrocarbon group or hydrogen. ) The above reaction is a halohydride
0.5 to 10 mol of basic substance for 1 mol of phosphorus structure
use. The basic substance here means inorganic bases and
And organic bases. To give an example of a basic substance,
Lithium hydroxide, sodium hydroxide, potassium hydroxide
Etc., rubidium hydroxide, beryllium hydroxide, hydroxide
Magnesium, calcium hydroxide, strontium hydroxide
Aluminum, ferrous hydroxide, ferric hydroxide, aluminum hydroxide
Metal hydroxides such as; lithium carbonate, sodium carbonate, charcoal
Potassium acid, rubidium carbonate, beryllium carbonate, carbonic acid
Magnesium, calcium carbonate, strontium carbonate, etc.
Inorganic basic substances such as metal carbonates;
Examples include organic bases such as amine compounds exemplified in the description.
Be done. These can be used alone or as a mixture of two or more.
It doesn't matter.

To exemplify the compound having one or more structures represented by formula (5) in one molecule, specific examples of the compounds having one structure represented by formula (5) in one molecule Examples of the glycidyl sulfide and a compound in which at least one hydrogen of the epoxy group of glycidyl sulfide is substituted with an alkyl group such as a methyl group, an aryl group such as a phenyl group, an allyl group such as a 2-propenyl group, and the like, As the compound having two or more structures represented by the formula (5) in one molecule, (D) glycidyl disulfide, at least one hydrogen of the epoxy group of glycidyl disulfide is an alkyl group such as a methyl group, a phenyl group or the like. Compounds substituted with an aryl group, an allyl group such as a 2-propenyl group, etc., and a chain fat in which two or more structures represented by the formula (5) are bonded in one molecule Organic compound having a group skeleton (E) Organic compound having a structure represented by formula (5) (2) or more bonded in one molecule (F) (5) Structure represented by formula is in one molecule Organic compounds having two or more aromatic skeletons bonded to each other, at least one hydrogen of the epoxy groups of these compounds is an alkyl group such as a methyl group, an aryl group such as a phenyl group, an allyl group such as a 2-propenyl group, etc. And compounds substituted with a compound such as sulfide,
It may contain a bond such as an ether, a sulfone, a ketone or an ester.

The organic compound having a chain-like aliphatic skeleton (D) is classified into a straight chain and a branched chain, and specific examples thereof are bis (β-epoxypropylthio) methane, 1,2. -Bis (β-epoxypropylthio) ethane, 1,3-bis (β-epoxypropylthio) propane, 1,2-bis (β-epoxypropylthio) propane, 1- (β-epoxypropylthio) -2 -[(Β-
Epoxypropylthio) methyl] propane, 1,4-bis (β-epoxypropylthio) butane, 1,3-bis (β-epoxypropylthio) butane, 1- (β-epoxypropylthio) -3-[( β-epoxypropylthio) methyl] butane, 1,5-bis (β-epoxypropylthio) pentane, 1- (β-epoxypropylthio) -4-[(β-epoxypropylthio) methyl] pentane, 1, 6-bis (β-epoxypropylthio) hexane, 1- (β-epoxypropylthio) -5-
[(Β-epoxypropylthio) methyl] hexane, 1
-(Β-epoxypropylthio) -2- (2-β-epoxypropylthioethylthio) ethane, 1- (β-epoxypropylthio) -2- [2- (2-β-epoxypropylthioethylthio) Chain β such as ethylthio] ethane
-Epoxypropylthio compound; tetrakis [(β-epoxypropylthio) methyl] methane, 1,1,1-tris [(β-epoxypropylthio) methyl] propane, 1,5-bis (β-epoxypropylthio) -2-
[(Β-Epoxypropylthio) methyl] -3-thiapentane, 1,5-bis (β-epoxypropylthio)-
2,4-bis [(β-epoxypropylthio) methyl]
-3-Thiapentane, 1- (β-epoxypropylthio) -2,2-bis [(β-epoxypropylthio) methyl] -4-thiahexane, 1,5,6-tris (β-
Epoxypropylthio) -4-[(β-epoxypropylthio) methyl] -3-thiahexane, 1,8-bis (β-epoxypropylthio) -4-[(β-epoxypropylthio) methyl] -3, 6-dithiaoctane,
1,8-bis (β-epoxypropylthio) -4,5-
Bis [(β-epoxypropylthio) methyl] -3,6
-Dithiaoctane, 1,8-bis (β-epoxypropylthio) -4,4-bis [(β-epoxypropylthio) methyl] -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -2,4,5-Tris [(β-epoxypropylthio) methyl] -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -2,5-bis [(β-epoxypropylthio) ) Methyl] -3,6-dithiaoctane, 1,9-bis (β-
Epoxypropylthio) -5-[(β-epoxypropylthio) methyl] -5-[[2- (β-epoxypropylthio) ethylthio] methyl] -3,7-dithianonane, 1,10-bis (β- Epoxypropylthio)-
5,6-bis [2- (β-epoxypropylthio) ethylthio] -3,6,9-trithiadecane, 1,11-bis (β-epoxypropylthio) -4,8-bis [(β
-Epoxypropylthio) methyl] -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropylthio) -5,7-bis [(β-epoxypropylthio) methyl] -3,6 , 9-Trithia undecane, 1,
11-bis (β-epoxypropylthio) -5,7-
[[2- (β-Epoxypropylthio) ethylthio] methyl] -3,6,9-trithiaundecane, 1,11-
Bis (β-epoxypropylthio) -4,7-bis [(β-epoxypropylthio) methyl] -3,6,9
A branched β-epoxypropylthio compound such as trithiaundecane; and at least one hydrogen of the epoxy group of these compounds is an alkyl group such as a methyl group, an aryl group such as a phenyl group, a 2-propenyl group or the like. Examples thereof include compounds substituted with an allyl group and the like.

Specific examples of the organic compound having a cyclic aliphatic skeleton (E) include 1,3 and 1,4-bis (β-epoxypropylthio) cyclohexane, 1,3
And 1,4-bis [(β-epoxypropylthio) methyl] cyclohexane, bis [4- (β-epoxypropylthio) cyclohexyl] methane, 2,2-bis [4
-(Β-epoxypropylthio) cyclohexyl] propane, bis [4- (β-epoxypropylthio) cyclohexyl] sulfide, 2,5-bis [(β-epoxypropylthio) methyl] -1,4-dithiane, 2 , 5-
Cyclic aliphatic β-epoxypropylthio compounds such as bis [[(β-epoxypropylthio) ethylthio] methyl] -1,4-dithiane and at least one hydrogen of the epoxy group of these compounds is an alkyl such as methyl group. And compounds substituted with an aryl group such as a phenyl group and an allyl group such as a 2-propenyl group.

Specific examples of the organic compound having an aromatic-aliphatic skeleton (F) include 1,3 and 1,4-bis (β
-Epoxypropylthio) benzene, 1,3 and 1,
4-bis [(β-epoxypropylthio) methyl] benzene, bis [4- (β-epoxypropylthio) phenyl] methane, 2,2-bis [4- (β-epoxypropylthio) phenyl] propane, bis [4- (β-epoxypropylthio) phenyl] sulfide, bis [4-
(Β-epoxypropylthio) phenyl] sulfone,
Aromatic β-epoxypropylthio compounds such as 4,4′-bis (β-epoxypropylthio) biphenyl, and at least one hydrogen of the epoxy group of these compounds is an alkyl group such as a methyl group or an aryl such as a phenyl group. Base, 2
Examples include compounds substituted with an allyl group such as a propenyl group.

Next, the third step will be described. The epoxy compound obtained in the second step is reacted with a thiating agent such as thiocyanate, thiourea, triphenylphosphine sulfide or 3-methylbenzothiazole-2-thione, preferably with thiocyanate or thiourea. Thus, an episulfide compound having one or more corresponding structures represented by the formula (1) in one molecule is obtained.

To exemplify a compound having one or more structures represented by formula (1) in one molecule, specific examples of compounds having one structure represented by formula (1) in one molecule Is at least one hydrogen atom of the epithio group of bis (β-epithiopropyl) sulfide and bis (β-epithiopropyl) sulfide is an alkyl group such as a methyl group, an aryl group such as a phenyl group, or a 2-propenyl group. Examples of compounds having two or more structures represented by the formula (1) in one molecule include (G) bis (β-epithiopropyl) disulfide, bis ( At least one hydrogen atom in the epithio group of β-epithiopropyl) disulfide is substituted with an alkyl group such as a methyl group, an aryl group such as a phenyl group, an allyl group such as a 2-propenyl group, or the like. Compound and an organic compound having a chained aliphatic skeleton in which two or more structures represented by formula (1) are bonded in one molecule (H) Two or more structures represented by formula (1) are bonded in one molecule Organic compounds having cyclic aliphatic skeleton (I) Organic compounds having an aromatic skeleton in which two or more structures represented by the formula (1) are bonded in one molecule, and at least one hydrogen atom of the epithio group of these compounds Are compounds substituted with an alkyl group such as a methyl group, an aryl group such as a phenyl group, an allyl group such as a 2-propenyl group, and the like. Further, these compounds include sulfide,
It may contain a bond such as an ether, a sulfone, a ketone or an ester.

The organic compound having a chain aliphatic skeleton (G) is classified into a straight chain and a branched chain, and specific examples of these are bis (β-epithiopropylthio) methane, 1, 2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithio Propylthio) -2-[(β-
Epithiopropylthio) methyl] propane, 1,4-bis (β-epithiopropylthio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio)- 3-[(β-epithiopropylthio) methyl] butane, 1,5-bis (β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4-[(β-epithiopropyl Thio) methyl] pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β-epithiopropylthio) -5-
[(Β-Epithiopropylthio) methyl] hexane, 1
-(Β-Epithiopropylthio) -2- (2-β-epithiopropylthioethylthio) ethane, 1- (β-epithiopropylthio) -2- [2- (2-β-epithiopropyl Chain β such as thioethylthio) ethylthio] ethane
-Epithiopropylthio compound; tetrakis [(β-epithiopropylthio) methyl] methane, 1,1,1-tris [(β-epithiopropylthio) methyl] propane, 1,5-bis (β-epi Thiopropylthio) -2-
[(Β-Epithiopropylthio) methyl] -3-thiapentane, 1,5-bis (β-epithiopropylthio)-
2,4-bis [(β-epithiopropylthio) methyl]
-3-Thiapentane, 1- (β-epithiopropylthio) -2,2-bis [(β-epithiopropylthio) methyl] -4-thiahexane, 1,5,6-tris (β-
Epithiopropylthio) -4-[(β-epithiopropylthio) methyl] -3-thiahexane, 1,8-bis (β-epithiopropylthio) -4-[(β-epithiopropylthio) methyl ] -3,6-dithiaoctane,
1,8-bis (β-epithiopropylthio) -4,5-
Bis [(β-epithiopropylthio) methyl] -3,6
-Dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis [(β-epithiopropylthio) methyl] -3,6-dithiaoctane, 1,8-bis (β-epithio) Propylthio) -2,4,5-tris [(β-epithiopropylthio) methyl] -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5-bis [( β-Epithiopropylthio) methyl] -3,6-dithiaoctane, 1,9-bis (β-
Epithiopropylthio) -5-[(β-epithiopropylthio) methyl] -5-[[2- (β-epithiopropylthio) ethylthio] methyl] -3,7-dithianonane, 1,10-bis (Β-epithiopropylthio)-
5,6-bis [2- (β-epithiopropylthio) ethylthio] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis [(β
-Epithiopropylthio) methyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-bis [(β-epithiopropylthio) methyl]- 3,6,9-Trithiaundecane, 1,
11-bis (β-epithiopropylthio) -5,7-
[[2- (β-Epithiopropylthio) ethylthio] methyl] -3,6,9-trithiaundecane, 1,11-
Bis (β-epithiopropylthio) -4,7-bis [(β-epithiopropylthio) methyl] -3,6,9
-Branched β-epithiopropylthio compounds such as trithiaundecane; and at least one hydrogen of the epoxy group of these compounds is an alkyl group such as a methyl group, an aryl group such as a phenyl group, a 2-propenyl group, etc. And compounds substituted with an allyl group and the like.

Specific examples of the organic compound having a cyclic aliphatic skeleton (H) include 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3
And 1,4-bis [(β-epithiopropylthio) methyl] cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4
-(Β-Epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis [(β-epithiopropylthio) methyl] -1,4- Dithian, 2,5-
Cycloaliphatic β-epithiopropylthio compounds such as bis [[(β-epithiopropylthio) ethylthio] methyl] -1,4-dithiane and at least one hydrogen of the epoxy group of these compounds is a methyl group or the like. And compounds substituted with an aryl group such as a phenyl group and an allyl group such as a 2-propenyl group.

Specific examples of the organic compound having an aromatic-aliphatic skeleton (I) include 1,3 and 1,4-bis (β
-Epithiopropylthio) benzene, 1,3 and 1,
4-bis [(β-epithiopropylthio) methyl] 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,
Aromatic β-epithiopropylthio compounds such as 4,4′-bis (β-epithiopropylthio) biphenyl and at least one hydrogen atom of the epoxy group of these compounds is an alkyl group such as a methyl group, a phenyl group, etc. Aryl groups of 2
Examples include compounds substituted with an allyl group such as a propenyl group.

When thiocyanate is used as the thiating agent, preferred thiocyanates are alkali or alkaline earth metal salts, and more preferred are potassium thiocyanate and sodium thiocyanate. In addition, thiocyanates and thioureas that are thiating agents are
Although the number of moles corresponding to the number of epoxy groups of the epoxy compound is used stoichiometrically, if importance is attached to the purity of the product, reaction rate, economic efficiency, etc., it may be used below or above this amount. I don't care. Preferably, the reaction is carried out using a stoichiometric amount to 10 times the stoichiometric amount. More preferably, the reaction is carried out using a stoichiometric amount to 5 times the stoichiometric amount. The reaction may be carried out without solvent or in a solvent, but when a solvent is used, it is desirable to use one in which any of thiocyanate, thiourea and epoxy compound is soluble. Specific examples include water, alcohols such as methanol and ethanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; hydroxy ethers such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; benzene, toluene, xylene and the like. Aromatic hydrocarbons; halogenated hydrocarbons such as dichloroethane, chloroform, chlorobenzene, and the like, and the combined use of these, for example, a combination of alcohols and water, ethers, hydroxy ethers, halogenated hydrocarbons, A combination of aromatic hydrocarbons and alcohols may be effective. Also, adding an acid, an acid anhydride or the like as a polymerization inhibitor to the reaction solution is an effective means from the viewpoint of improving the reaction results. Specific examples of acids and acid anhydrides include:
Nitric acid, hydrochloric acid, sulfuric acid, fuming sulfuric acid, boric acid, arsenic acid, phosphoric acid, prussic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, maleic acid, benzoic acid, anhydrous nitric acid, anhydrous sulfuric acid , Boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride,
Examples thereof include succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, silica gel, silica-alumina, aluminum chloride and the like, and it is possible to use some of them in combination. The amount added is usually 0.00 based on the total amount of the reaction solution.
It is used in the range of 1 to 10 wt%, but preferably 0.
It is 01 to 1 wt%. The reaction temperature is usually 0 to 100 ° C, preferably 20 to 70 ° C. The reaction time may be any time as long as the reaction is completed under the above-mentioned various conditions, but usually 20 hours or less is suitable. The stability can be improved by washing the reaction product with an acidic aqueous solution. Specific examples of the acid used in the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid,
Phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid,
Examples include succinic acid and maleic acid. These may be used alone or in combination of two or more. Aqueous solutions of these acids usually exhibit effects at pH 6 or lower, but a more effective range is pH 3 or lower.

The first, second and third steps of the present invention may or may not be distilled at the end of each step if possible.

In the method for producing an episulfide compound of the present invention, the evaporation residue in epihalohydrin is 1000 ppm.
The following are preferred. When the evaporation residue exceeds 1000 ppm, the transparency of the optical material obtained by polymerizing and curing the episulfide compound decreases. Furthermore, the evaporation residue is 500p
It is preferably pm or less, and most preferably 200 ppm or less.

The evaporation residue as referred to in the present invention is the amount of the non-evaporated part when the epihalohydrin is evaporated to dryness, and can be determined as follows. That is, the evaporation residue can be measured according to the method described in JISK0067. To give a concrete example, the sample is placed in a constant-volume evaporation dish, precisely weighed, and heated in an electric furnace while flowing a water bath, an oil bath or an inert gas to evaporate to dryness. After being dried and solidified, the evaporation dish is put in a drier and dried by heating for 2 hours, and left to cool in a desiccator and weighed precisely. Drying to precise weighing is repeated until the evaporation dish has a constant weight. The evaporation residue is calculated by the following formula. Evaporation residue (%) = (B−A) / sample weight × 100 A: evaporation pan weight B: (residual + evaporation pan) weight

There is a correlation between the evaporation residue of epihalohydrin and the turbidity when epihalohydrin is mixed with a suitable solvent, and it is possible to estimate the evaporation residue by measuring the turbidity. is there.

Hereinafter, epichlorohydrin will be described in more detail as an example of epihalohydrin. In general, commercially available epichlorohydrin has an evaporation residue of about 3 to 7 ppm, and the amount of evaporation residue increases remarkably during storage until it is used for producing an episulfide compound.

According to the present invention, the number of storage days, the storage temperature, and the material of the storage container are appropriately adjusted to suppress the increase of the evaporation residue to 1000 ppm or less.

The number of storage days is preferably 200 days or less, more preferably 100 days or less. Storage temperature is 50 ℃
The following is preferable, it is preferably 40 ° C. or lower, and particularly preferably 30 ° C. or lower. The storage container may be one that is not corroded by epichlorohydrin, and is preferably a glass or stainless steel container. In the case of a stainless steel container, it is also preferable to subject the storage container to a surface treatment such as buffing or electrolytic polishing.

Further, the contents of impurities such as allyl alcohol, chloroallyl alcohol, and epichlorohydrin dimer in epichlorohydrin are each 1%.
It is preferably not more than ppm, more preferably 0.1.
It is 1 ppm or less.

By heat-polymerizing the episulfide compound of the present invention in the presence or absence of a curing catalyst, a cured resin advantageous for optical materials and the like can be produced. A preferable method for producing a cured resin is to use a curing catalyst, and examples of the curing catalyst include amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, and secondary iodonium salts. , Mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acids and the like.

As a specific example, (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-
Primary amines such as phenylethylamine, naphthylamine and furfurylamine; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-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-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-
Aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, menthanediamine,
1,4-bisaminopropylpiperazine, o-, m-,
Alternatively, 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-
Alternatively, 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'-diaminodiphenyl sulfone, 4,4'-diaminoditolyl sulfone, methylenebis (o-chloroaniline), 3,9-bis (3-aminopropyl) 2,
4,8,10-Tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N −
Aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4
-Primary polyamines such as bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diaminophenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutyl. Amine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine,
2-, 3-, 4-picoline, 2,4-, 2,6-, 3,
Secondary amines such as 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)
Secondary polyamines such as propane, 1,4-di- (4-piperidyl) butane, tetramethylguanidine; trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropyl Amine, 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-diethylethanolamine, 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-methylpiperidine, 2-
(2-dimethylaminoethoxy) -4-methyl-1,
Tertiary amines such as 3,2-dioxabornane; tetramethylethylenediamine, pyrazine, N, N'-dimethylpiperazine, N, N'-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N,
N ', N'-tetramethyl-1,3-butanamine, 2
-Dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N)
-Dimethylaminomethyl) phenol, tertiary polyamines such as heptamethylisobiguanide; imidazole, N-
Methyl imidazole, 2-methyl imidazole, 4-methyl imidazole, N-ethyl imidazole, 2-ethyl imidazole, 4-ethyl imidazole, N-butyl imidazole, 2-butyl imidazole, N-undecyl imidazole, 2-undecyl imidazole, N-phenylimidazole, 2-phenylimidazole, N-
Benzylimidazole, 2-benzylimidazole, 1
-Benzyl-2-methylimidazole, N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-
Cyanoethyl) -2-undecylimidazole, N-
(2'-cyanoethyl) -2-phenylimidazole,
Various imidazoles such as 3,3-bis- (2-ethyl-4-methylimidazolyl) methane, adduct of alkylimidazole and isocyanuric acid, condensate of alkylimidazole and formaldehyde; 1,8-diazabicyclo (5,4 , 0) Undecene-7,1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-
1,8-diazabicyclo (5,4,0) undecene-7
Amidines such as; amine compounds represented by the above. (2) A complex of the amine 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
-Butyl ammonium hydrogen sulfite, tetra-n-butyl ammonium tetrafluoroborate, tetra-n-butyl ammonium tetraphenyl borate, tetra-n-butyl ammonium paratoluene sulfonate, tetra-n-hexyl ammonium chloride, tetra-n -Hexyl ammonium bromide, tetra-n-hexyl ammonium acetate,
Tetra-n-octyl ammonium chloride, tetra-n-octyl ammonium 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 , Tetrakis hydroxymethylphosphonium bromide, tetraki 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) Hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid and other mineral acids and their half-esters. (9) Lewis acids represented by boron trifluoride, boron trifluoride etherate, and the like. (10) Organic acids and their half-esters. (11) Silicic acid, tetrafluoroboric acid. Etc. Among these, amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, and secondary iodonium salts are preferable because of less coloring of the cured product. These may be used alone or in combination of two or more.

The above-mentioned curing catalyst is usually used in an amount of 0.0001 to 1.0 mol, preferably 0.0001 to 0.5 mol, and more preferably 0.0001 to 0. 1 mol, most preferably 0.
0001 to 0.05 mol is used. The amount of curing catalyst is
If it is more than 1.0 mol, the refractive index and heat resistance of the cured product will be lowered, and coloring will occur. Further, if it is less than 0.0001 mol, it is not sufficiently cured and the heat resistance becomes insufficient.

The episulfide compound of the present invention is a compound having two or more functional groups capable of reacting with an episulfide group, or a compound having one or more of these functional groups and one or more of another homopolymerizable functional group. Can also be polymerized and cured with a compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization to produce an optical material. Examples of compounds having two or more functional groups capable of reacting with these episulfide groups include epoxy compounds, known episulfide compounds, polycarboxylic acids, polycarboxylic anhydrides, mercaptocarboxylic acids, polymercaptans, mercaptoalcohols and mercaptos. Examples thereof include phenol, polyphenol, amines and amides. On the other hand, as a compound having at least one functional group capable of reacting with an episulfide group and at least one other homopolymerizable functional group, an epoxy having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl, allyl, etc. Compounds, episulfide compounds, carboxylic acids, carboxylic anhydrides, mercaptocarboxylic acids, mercaptans, phenols,
Examples include amines and amides.

Specific examples of compounds having two or more functional groups capable of reacting with an episulfide group are shown below.

Specific examples of the epoxy compound include hydroquinone, catechol, resorcin, bisphenol A,
Phenolic epoxy compounds produced by condensation of polyhalogenated phenol compounds such as bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, novolac resin and epihalohydrin; ethylene glycol, diethylene glycol, triethylene glycol, Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-
Butanediol, 1,6-hexanediol, neopentyl glycol, 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. Alcohol-based epoxy compound produced by condensation; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid,
Phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid,
Glycidyl ester-based epoxy compounds produced by condensation of epihalohydrin with polyvalent carboxylic acid compounds such as benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid and diphenyl dicarboxylic acid; 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, m-, or p-xylylenediamine, 1,5-, or
Primary diamines such as 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and 2,2-bis (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)
An amine epoxy compound produced by condensation of a secondary diamine such as ethane, 1,3-di- (4-piperidyl) -propane, 1,4-di- (4-piperidyl) -butane and epihalohydrin; 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclihexanedioxide, 2-
Aliphatic epoxy compounds such as (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) adipate; cyclopentadiene epoxide, epoxidation Epoxy compounds produced by epoxidation of unsaturated compounds such as soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide; urethane type epoxy compounds produced from the above-mentioned polyhydric alcohols, phenol compounds and diisocyanates, glycidol, etc. You can

Specific examples of known episulfide compounds include episulfide compounds obtained by episulfide-forming part or all of the epoxy groups of the above epoxy compounds.

Polycarboxylic acid, polycarboxylic anhydride,
Specific examples of polyphenols, amines, and the like include the above-mentioned materials as a raw material of a partner to be reacted with the epihalohydrin described in the above-mentioned epoxy compound.

Specific examples of polymercaptans include:
The polymer captans shown in the above description of the first step can be mentioned. Specific examples of mercapto alcohol include 2-mercaptoethanol and 3-mercapto-1.
-Propanol, 1-mercapto-2-propanol,
4-mercapto-1-butanol, 3-mercapto-2
-Butanol, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol,
1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1-mercaptomethyl-1,1-dimethylolpropane, 1,1-bis (mercaptomethyl) -1-methylolpropane, mercaptomethyl Tris (hydroxymethyl) methane, bis (mercaptomethyl) bis (hydroxymethyl) methane, tris (mercaptomethyl) hydroxymethylmethane, 2-
(2-mercaptoethylthio) ethanol and the like can be mentioned. Specific examples of mercaptophenol include:
4-mercaptophenol, 2-mercaptohydroquinone, 4-hydroxy-4, -mercaptobiphenyl and the like can be mentioned. Specific examples of mercaptocarboxylic acid include thioglycolic acid, 2-thiopropionic acid,
Examples include 3-thiopropionic acid, thiolactic acid, mercaptosuccinic acid, thiomalic acid, N- (2-mercaptopropionyl) glycine, 2-mercaptobenzoic acid, 2-mercaptonicotinic acid, and 3,3-dithioisolethric acid. it can.

Representative specific examples of compounds having one or more functional groups capable of reacting with an episulfide group and one or more other homopolymerizable functional groups are shown below. Examples of the epoxy compound having an unsaturated group include vinylphenyl glycidyl ether, vinylbenzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether. The episulfide compound having an unsaturated group is a compound obtained by episulfide-forming an epoxy group of the above-mentioned epoxy compound having an unsaturated group, for example, vinylphenyl thioglycidyl ether, vinylbenzyl thioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, ari. Examples thereof include ruthioglycidyl ether.

Examples of the carboxylic acid compound having an unsaturated group include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and fumaric acid. Examples of the amides having an unsaturated group include the amides of the above α, β-unsaturated carboxylic acids.

A preferred specific example of the compound having one functional group capable of reacting with the episulfide group and capable of homopolymerization is a compound having one epoxy group or episulfide group. More specifically, ethylene oxide, monoepoxy compounds such as propyroxide, acetic acid, propionic acid, glycidyl esters of monocarboxylic acids such as benzoic acid, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl. Glycidyl ethers such as ethers, monoepisulfide compounds such as ethylene sulfide and propylene sulfide, and thioglycidyl esters having a structure derived from the above monocarboxylic acid and thioglycidol (1,2-epithio-3-hydroxypropane) , Methylthioglycidyl ether (1,2-epithiopropyloxymethane),
Examples thereof include thioglycidyl ethers such as ethyl thioglycidyl ether, propyl thioglycidyl ether and butyl thioglycidyl ether. Of these, more preferred are compounds having one episulfide group.

A compound having two or more functional groups capable of reacting with the episulfide group of the episulfide compound, or
A compound having one or more of these functional groups and one or more other homopolymerizable functional groups, and further, a compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization is a polymerization curing catalyst. Can be polymerized and cured to produce a cured resin. The curing catalyst is the above-mentioned amines,
Phosphines, acids, etc. are used. As a specific example,
The above is also used here.

Further, when a compound having an unsaturated group is used, it is a preferable method to use a radical polymerization initiator as a polymerization accelerator. The radical polymerization initiator may be any one that generates a radical by heating or ultraviolet rays or electron beams, and examples thereof include cumyl peroxy neodecanoate, diisopropyl peroxy dicarbonate, diallyl peroxy dicarbonate and di-n-. Propyl peroxydicarbonate, dimyristyl peroxydicarbonate, cumyl peroxy neohexanoate, ter-hexyl peroxy neodecanoate,
ter-butyl peroxy neodecanoate, ter-
Hexyl peroxy neohexanoate, ter-butyl peroxy neohexanoate, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide,
Peroxides such as dicumyl peroxide and di-ter-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-toxy-2,4-dimethyl-valeronitrile 2,2'-azobis (2-methylpropane), 2,2'-azobis Examples thereof include known thermal polymerization catalysts such as azo compounds such as (2,4,4-trimethylpentane) and known photopolymerization catalysts such as benzophenone and benzoin benzoin methyl ether. Among 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 other azo compounds. Moreover, all of these can be mixed and used. The amount of the radical polymerization initiator compounded varies depending on the components of the composition and the curing method, and therefore cannot be determined in a lump.
% -5.0 wt%, preferably 0.1 wt% -2.0 w
It is in the range of t%.

In addition, when a cured resin is produced by polymerizing and curing an episulfide compound, it is of course possible to add known additives such as an antioxidant and an ultraviolet absorber to further improve the practicality. Also known external and / or
Alternatively, an internal release agent may be used or added to improve the releasability of the resulting cured material from the mold. The internal release agent referred to here is a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl fourth
Grade ammonium salt, phosphoric acid ester, acidic phosphoric acid ester,
Oxyalkylene-type acidic phosphoric acid ester, alkali metal salt of acidic phosphoric acid ester, alkali metal salt of oxyalkylene-type acidic phosphoric acid ester, metal salt of higher fatty acid, higher fatty acid ester, triglycerides, phthalic acid esters, paraffin, wax, higher fat Examples thereof include group amides, higher aliphatic alcohols, polysiloxanes, and aliphatic amine ethylene oxide adducts.

When the cured resin is obtained by polymerizing and curing the episulfide compound, the raw material is the episulfide compound, and further, the above-mentioned curing catalyst and, if desired, an episulfide group having an unsaturated group, which can react with, for example, glycidyl methacrylate, thioglycidyl. When used together with methacrylate (epoxy sulfide of glycidyl methacrylate), radical polymerization initiator, radically polymerizable monomer, mold release agent, antioxidant, polymerization regulator, UV absorber, etc. After mixing the additives described above, they are polymerized and cured to obtain an optical material such as a lens.

Examples of the antioxidant include phenol-based, phosphite-based, thioether-based phosphite-based antioxidants, catechol and the like. Examples of the ultraviolet absorber include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate ultraviolet absorbers.

Further, a method of polymerizing and curing the episulfide compound to produce an optical material will be described in detail below. A raw material prepared by mixing a desired additive with an episulfide compound is poured into a mold made of glass or metal, and a polymerization and curing reaction is allowed to proceed by heating, and then the mold is removed from the mold to manufacture. The curing time is 0.1 to 100 hours, usually 1 to 48 hours, and the curing temperature is -10 to 160 ° C, usually -10 to 140 ° C.
Also, after the curing is completed, the material is heated to a temperature of 50 to 150 ° C. for 1
The annealing treatment for about 0 minutes to 5 hours is a preferable treatment for removing the strain of the optical material of the present invention. Further, surface treatment such as hard coating, antireflection and antifogging property can be carried out if necessary. The method for producing the cured resin optical material of the present invention will be described below in more detail. As described above, it is produced by mixing the main raw material and additives and then injecting and curing it into a mold. It has two or more functional groups capable of reacting with a main raw material, a diepisulfide compound, and optionally an episulfide group. Or a compound having one or more of these functional groups and another homopolymerizable functional group
A compound having one or more compounds, a compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization, and further used as desired, a curing catalyst, a radical polymerization initiator, further a releasing agent, a stabilizer Etc., all may be mixed in the same container at the same time under stirring, each raw material may be added stepwise and mixed, or several components may be mixed separately and then remixed in the same container. Upon mixing, the set temperature, the time required for this, etc. may basically be the conditions under which the respective components are sufficiently mixed, but the excessive temperature and time are not preferable reactions between the respective raw materials and additives, Furthermore, it is not suitable because the viscosity increases and the casting operation becomes difficult. Mixing temperature is -10
It should be carried out in the range of about 100 ° C to 100 ° C, preferably -10 ° C to 50 ° C, and more preferably -5 ° C to 30 ° C. Mixing time is from 1 minute to 5
Time, preferably 5 minutes to 2 hours, more preferably 5
Minutes to 30 minutes, most preferably 5 minutes to 15 minutes. Degassing operation under reduced pressure before, during, or after mixing of the respective raw materials and additives is a preferable method from the viewpoint of preventing bubbles from being generated during the subsequent casting polymerization and curing.
The degree of decompression at this time is about 0.1 mmHg to 700 mmHg, preferably 10 mmHg to 300 mm.
Hg. Further, it is preferable to remove impurities and the like by filtering with a microfilter or the like at the time of injecting into the mold from the viewpoint of further improving the quality of the optical material of the present invention.

[0060]

EFFECT OF THE INVENTION By producing an optical material by polymerizing and curing an episulfide compound produced by using an epihalohydrin having an evaporation residue of 1000 ppm or less, an optical material having excellent transparency can be provided with uniform quality. It became so.

[0061]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. The performance of the obtained polymer was measured by the following measuring method. The evaporation residue of epihalohydrin was measured gravimetrically. The details of the measuring method are as follows. The evaporation residue of epihalohydrin was measured by the gravimetric method according to the method described in JISK0067. The details of the measuring method are as follows. A 100 ml platinum evaporating dish was weighed (A
After g), about 100 g of the sample was placed in a platinum pan and precisely weighed (sample weight), heated in a water bath and evaporated to dryness. Next, 11
After drying for 2 hours in a constant temperature dryer adjusted to 0 ° C., it was left to cool in a desiccator and weighed precisely. Drying in a constant temperature dryer to cooling in a desiccator was repeated until the evaporation dish had a constant weight (Bg). The evaporation residue is calculated using the weight obtained above.
It was calculated by the following formula. Evaporation residue (ppm) = (B−A) / sample weight × 10 ⁶ The transparency of the episulfide compound molded body was visually observed, and the one with good cloudiness and no transparency was Δ, and the one with good transparency. Was marked with ◯, and particularly excellent transparency was marked with ⊚. Further, x was cloudy and poor in transparency, and x was particularly bad in transparency.

Example 1 (First step) 185 g of epichlorohydrin having an evaporation residue of 860 ppm, 50 ml of toluene and 0.43 g of 2-ethylhexanoic acid were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a dropping funnel, and nitrogen was added. Bis (2-mercaptoethyl) sulfide 154 with stirring under an atmosphere
g was added dropwise while maintaining the liquid temperature at 21 to 25 ° C, and 1- (3
-Chloro-2-hydroxypropylthio) -2- [2-
(3-Chloro-2-hydroxypropylthio) ethylthio] ethane was synthesized. (Second step) After the completion of the first step, 20% saline solution 7 was added to the reaction solution.
00 ml was added, and a 40% aqueous sodium hydroxide solution 19
8 g was added dropwise while maintaining the reaction liquid temperature at 0 to 10 ° C.
After completion of dropping, the mixture was further stirred at 0 to 10 ° C for 1 hour.
After completion of stirring, 400 ml of toluene was added to extract the reaction product, and this toluene solution was washed with 150 ml of water three times. After washing, remove toluene under reduced pressure to
241 g of (β-epoxypropylthio) -2- [2- (β-epoxypropylthio) ethylthio] ethane was obtained. (Third step) 1- (β-obtained in the second step was placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel.
Epoxypropylthio) -2- [2- (β-epoxypropylthio) ethylthio] ethane 200 g and thiourea 2
28.5 g, 12 g of acetic anhydride, 1000 ml of toluene and 100 ml of methanol as solvents were charged, and the mixture was reacted at 30 ° C. for 10 hours. Toluene 200 after reaction
0 ml was added, the mixture was washed with 220 ml of 10% sulfuric acid, and subsequently washed with 150 ml of water four times. Evaporate the solvent,
1- (β-epithiopropylthio) -2- [2- (β-
205 g of epithiopropylthio) ethylthio] ethane were obtained. (Polymerization and curing) 100 parts by weight of 1- (β-epithiopropylthio) -2- [2- (β-epithiopropylthio) ethylthio] ethane synthesized in the third step was mixed with N, N-diethylethanolamine. 0.5 part by weight was compounded and poured into a mold composed of two glass plates adjusted to have a thickness of 10 mm, and the temperature was raised from 20 ° C. to 110 ° C. over 24 hours to polymerize and cure to obtain an optical material. Obtained. The obtained material was colorless and transparent, and was good without clouding. The results are shown in Table 1.

Examples 2 and 3 The same operation as in Example 1 was performed using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 1.

Example 4 (First Step) A flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel was charged with 185 g of epichlorohydrin having an evaporation residue of 31 ppm, 30 ml of toluene, and 0.1 ml of acetic acid.
8 g was put, 94 g of 1,2-ethanedithiol was added dropwise while stirring under a nitrogen atmosphere while maintaining the liquid temperature at 21 to 25 ° C., and 1,2-bis (3-chloro-2-hydroxypropylthio) ethane was added. Synthesized. (Second step) After the completion of the first step, the reaction solution was mixed with 20% saline solution 6
40 ml was added, and 40% aqueous sodium hydroxide solution 19
8 g was added dropwise while maintaining the reaction liquid temperature at 0 to 10 ° C.
After completion of dropping, the mixture was further stirred at 0 to 10 ° C for 1 hour.
After completion of stirring, 300 ml of toluene was added to extract the reaction product, and the toluene solution was washed with 100 ml of water three times. After washing, remove toluene under reduced pressure to remove 1,2
188 g of -bis (β-epoxypropylthio) ethane were obtained. (Third step) 120 g of 1,2-bis (β-epoxypropylthio) ethane obtained in the second step and 177 g of thiourea were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel. Then, 12 g of acetic anhydride, 600 ml of toluene and 600 ml of methanol as a solvent were charged, and the mixture was reacted at 30 ° C. for 10 hours. Toluene 120 after reaction
0 ml was added, and the mixture was washed with 240 ml of 10% sulfuric acid, and subsequently washed with 180 ml of water four times. Evaporate the solvent,
1,2-bis (β-epithiopropylthio) ethane 12
6 g was obtained. (Polymerization and curing) 100 parts by weight of 1,2-bis (β-epithiopropylthio) ethane synthesized in the third step was mixed with N, N-
0.5 parts by weight of diethylethanolamine was mixed and poured into a mold composed of two glass plates adjusted to have a thickness of 10 mm, and the temperature was raised from 20 ° C to 110 ° C over 24 hours to polymerize and cure. , An optical material was obtained. The obtained material was colorless and transparent, and was good without clouding. The results are shown in Table 1.

Example 5 (First Step) 185 g of epichlorohydrin having an evaporation residue of 16 ppm, 10 ml of toluene and 0.97 g of tetra-n-butylammonium bromide were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a gas blowing tube. 34 g of hydrogen sulfide was blown into the flask under a nitrogen atmosphere while stirring while maintaining the liquid temperature at 21 to 25 ° C. to synthesize bis (3-chloro-2-hydroxypropyl) sulfide. (Second step) After the completion of the first step, the reaction solution was mixed with 20% saline solution 6
40 ml was added, and 40% aqueous sodium hydroxide solution 19
7 g was added dropwise while maintaining the reaction liquid temperature at 0 to 10 ° C.
After completion of dropping, the mixture was further stirred at 0 to 10 ° C for 1 hour.
After completion of stirring, 300 ml of toluene was added to extract the reaction product, and the toluene solution was washed with 100 ml of water three times. After washing, toluene was removed under reduced pressure to obtain 135 g of bis (β-epoxypropyl) sulfide. (Third step) The bis (β-obtained in the second step was placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel.
Epoxypropyl) sulfide 120g and thiourea 25
0 g and acetic anhydride 10 g, and toluene 5 as a solvent
Charge 00 ml and methanol 700 ml, 30 ℃
And reacted for 10 hours. After the reaction, 1200 ml of toluene was added, washed with 240 ml of 10% sulfuric acid, and then 150 m
It was washed 4 times with 1 l of water. The solvent was distilled off, and bis (β-
134 g of epithiopropyl) sulfide were obtained. (Polymerization and curing) 0.5 parts by weight of N, N-diethylethanolamine was added to 100 parts by weight of bis (β-epithiopropyl) sulfide synthesized in the third step, and the mixture was made to a thickness of 1
The mixture was poured into a mold composed of two glass plates adjusted to 0 mm, heated from 20 ° C. to 110 ° C. over 24 hours, and polymerized and cured to obtain an optical material. The obtained material was colorless and transparent, and was good without clouding. The results are shown in Table 1.

Example 6 (First Step) 185 g of epichlorohydrin having an evaporation residue of 33 ppm, 70 ml of toluene and 0.5 g of triethylammonium chloride were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a dropping funnel, and the mixture was placed under a nitrogen atmosphere. , 5-bis (mercaptomethyl) -with stirring
212 g of 1,4-dithiane was added dropwise while maintaining the liquid temperature at 21 to 25 ° C. to synthesize 2,5-bis [(3-chloro-2-hydroxypropylthio) methyl] -1,4-dithiane. (Second step) After the completion of the first step, 20% saline solution 7 was added to the reaction solution.
00 ml was added, and a 40% aqueous sodium hydroxide solution 19
6 g was added dropwise while maintaining the reaction solution temperature at 0 to 10 ° C.
After completion of dropping, the mixture was further stirred at 0 to 10 ° C for 1 hour.
After completion of stirring, 400 ml of toluene was added to extract the reaction product, and this toluene solution was washed with 150 ml of water three times. After washing, remove toluene under reduced pressure for 2,5
-Bis [(β-epoxypropylthio) methyl] -1,
293 g of 4-dithiane was obtained. (Third step) 2,5-bis [(β-epoxypropylthio) methyl] -1, obtained in the second step was placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel. 4-
Dithian 200 g, thiourea 188 g, acetic anhydride 12
g, 1000 ml of toluene and 1000 ml of methanol as a solvent were charged, and the reaction was carried out at 30 ° C. for 10 hours. After the reaction, 2000 ml of toluene was added, the mixture was washed with 220 ml of 10% sulfuric acid, and subsequently washed with 150 ml of water four times. The solvent was distilled off, and 200 g of 2,5-bis [(β-epithiopropylthio) methyl] -1,4-dithiane
Got (Polymerization and curing) 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane 100 synthesized in the third step
0.5 parts by weight of N, N-diethylethanolamine is added to parts by weight.
Part by weight is mixed and poured into a mold composed of two glass plates adjusted to have a thickness of 10 mm, and the mixture is heated at 20 to 110 ° C.
The temperature was increased to 24 ° C. over 24 hours to polymerize and cure to obtain an optical material. The obtained material was colorless and transparent, and was good without clouding. The results are shown in Table 1.

Example 7 (First Step) A flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a dropping funnel was charged with 185 g of epichlorohydrin having an evaporation residue of 27 ppm, 40 ml of toluene and 0.1 ml of acetic acid.
8 g was added, and 134 g of 2- (2-mercaptoethylthio) -1,3-dimercaptopropane was added dropwise while stirring under a nitrogen atmosphere while maintaining the liquid temperature at 21 to 25 ° C.
1,5-bis (3-chloro-2-hydroxypropylthio) -2-[(3-chloro-2-hydroxypropylthio) methyl] -3-thiapentane was synthesized. (Second step) After the completion of the first step, the reaction solution was mixed with 20% saline solution 6
40 ml was added, and 40% aqueous sodium hydroxide solution 19
9 g was added dropwise while maintaining the reaction solution temperature at 0 to 10 ° C.
After completion of dropping, the mixture was further stirred at 0 to 10 ° C for 1 hour.
After completion of stirring, 300 ml of toluene was added to extract the reaction product, and the toluene solution was washed with 100 ml of water three times. After washing, remove toluene under reduced pressure to remove 1,5
-Bis (β-epoxypropylthio) -2-[(β-epoxypropylthio) methyl] -3-thiapentane 19
1 g was obtained. (Third step) The 1,5-bis (β-epoxypropylthio) -2-[(β was obtained in the second step in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel. -Epoxypropylthio) methyl] -3-thiapentane 120
g, 175 g of thiourea, 6 g of acetic anhydride, 1000 ml of toluene and 1000 ml of methanol as solvents.
Was charged and reacted at 30 ° C. for 10 hours. After the reaction, 2000 ml of toluene was added, the mixture was washed with 220 ml of 10% sulfuric acid, and subsequently washed with 150 ml of water four times. The solvent was distilled off and 1,5-bis (β-epithiopropylthio)-
121 g of 2-[(β-epithiopropylthio) methyl] -3-thiapentane was obtained. (Polymerization and curing) 100 parts by weight of 1,5-bis (β-epithiopropylthio) -2-[(β-epithiopropylthio) methyl] -3-thiapentane synthesized in the third step,
0.5 parts by weight of N, N-diethylethanolamine was mixed and poured into a mold composed of two glass plates adjusted to a thickness of 10 mm, and the temperature was raised from 20 ° C to 110 ° C to 24 ° C.
The temperature was elevated over time to polymerize and cure to obtain an optical material. The obtained material was colorless and transparent, and was good without clouding. The results are shown in Table 1.

Example 8 (First Step) 185 g of epichlorohydrin having an evaporation residue of 46 ppm, 60 ml of toluene and 0.5 g of triethylammonium chloride were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a dropping funnel, and the mixture was placed under a nitrogen atmosphere. While stirring, 164 g of 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane was adjusted to a liquid temperature of 2
While maintaining the temperature at 1 to 25 ° C., 1,8-bis (3-chloro-2-hydroxypropylthio) -4-[(3-chloro-2-hydroxypropylthio) methyl] -3,6-
Dithiaoctane was synthesized. (Second step) After the completion of the first step, the reaction solution was mixed with 20% saline solution 6
40 ml was added, and a 40% aqueous sodium hydroxide solution 18 was added.
7 g was added dropwise while maintaining the reaction liquid temperature at 0 to 10 ° C.
After completion of dropping, the mixture was further stirred at 0 to 10 ° C for 1 hour.
After completion of stirring, 300 ml of toluene was added to extract the reaction product, and the toluene solution was washed with 100 ml of water three times. After washing, remove toluene under reduced pressure for 1,8
217 g of -bis (β-epoxypropylthio) -4-[(β-epoxypropylthio) methyl] -3,6-dithiaoctane were obtained. (Third step) In a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel, 1,8-bis (β-epoxypropylthio) -4-[(β -Epoxypropylthio) methyl] -3,6-dithiaoctane 1
20 g, 147 g of thiourea, 6 g of acetic anhydride, 1000 ml of toluene and 1000 of methanol as solvents.
ml was charged and reacted at 30 ° C. for 10 hours. After the reaction, 2000 ml of toluene was added, the mixture was washed with 220 ml of 10% sulfuric acid, and subsequently washed with 150 ml of water four times. The solvent was distilled off, and 1,8-bis (β-epithiopropylthio)
-4-[(β-epithiopropylthio) methyl] -3,
119 g of 6-dithiaoctane was obtained. (Polymerization and curing) 1,8-bis (β-epithiopropylthio) -4-[(β-epithiopropylthio) methyl] -3,6-dithiaoctane synthesized in the third step was mixed with 100 parts by weight of N, 0.5 parts by weight of N-diethylethanolamine was blended, poured into a mold composed of two glass plates adjusted to a thickness of 10 mm, and heated from 20 ° C. to 110 ° C. over 24 hours for polymerization. After curing, an optical material was obtained.
The obtained material was colorless and transparent, and was good without clouding.
The results are shown in Table 1.

Example 9 (first step) Evaporation residue 16 ppm
Of Example 5 using the epichlorohydrin of (first step)
The same operation was performed to synthesize bis (3-chloro-2-hydroxypropyl) sulfide. (Second step) After completion of the first step, (second step) of the fifth embodiment
After performing the same operation as above, vacuum distillation (60 to 65
C., 30 Pa) 101 g of bis (β-epoxypropyl) sulfide was obtained. (Third step) The bis (β-obtained in the second step was placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel.
Epoxypropyl) sulfide 100g and thiourea 21
0 g and acetic anhydride 8 g, and toluene as solvent 50
0 ml and 700 ml of methanol were charged and reacted at 20 ° C. for 10 hours. After the reaction, 1000 ml of toluene was added and washed with 220 ml of 10% sulfuric acid, then 150 ml.
It was washed with water 4 times. The solvent was distilled off to obtain 91 g of bis (β-epithiopropyl) sulfide. (Polymerization and curing) 90 parts by weight of bis (β-epithiopropyl) sulfide synthesized in the third step was mixed with 0.5 part by weight of N, N-diethylethanolamine to give a thickness of 10
The mixture was poured into a mold composed of two glass plates adjusted to mm, heated from 20 ° C. to 110 ° C. over 24 hours, and polymerized and cured to obtain an optical material. The obtained material was colorless and transparent, and was good without clouding. The results are shown in Table 1.

Example 10 (First step) 200 g of epichlorohydrin having an evaporation residue of 16 ppm, 20 ml of toluene and 4 ml of toluene were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a gas blowing tube.
Add 1.00 g of 0% sodium hydroxide, and under stirring in a nitrogen atmosphere, add 80 g of hydrogen sulfide to a liquid temperature of 21 to 25.
Blow while keeping at ℃. After the completion of blowing, the solution was stirred for 1 hour while maintaining the liquid temperature at 20 to 25 ° C.
1, 181 g of sodium hydrogen carbonate was added, and iodine 274 was added.
g was added over 1 hour while maintaining the reaction temperature at 10 to 20 ° C. After adding iodine, aging was carried out for 3 hours while maintaining the liquid temperature at 10 to 20 ° C. to synthesize bis (3-chloro-2-hydroxypropyl) disulfide. (Second step) After the first step, 200 g of salt is added to the reaction solution,
Toluene (500 ml) was added, and 40% aqueous sodium hydroxide solution (230 g) was added dropwise while maintaining the reaction liquid temperature at 0 to 10 ° C. After completion of dropping, the mixture was further stirred at 0 to 10 ° C for 1 hour. After completion of stirring, 500 ml of toluene was added, and the toluene layer was separated by liquid separation. This toluene solution was washed 3 times with 100 ml of water. After washing, toluene was removed under reduced pressure and further distilled to obtain 116 g of bis (β-epoxypropyl) disulfide. (Third step) The bis (β-obtained in the second step was placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel.
Epoxypropyl) disulfide 100 g and thiourea 2
Charge 00 g and acetic anhydride 10 g, and further add 500 ml of toluene and 700 ml of methanol as solvents,
The reaction was carried out at 0 ° C for 10 hours. After the reaction, 1200 ml of toluene was added, washed with 240 ml of 10% sulfuric acid, and then washed with 150 ml.
It was washed 4 times with ml of water. The solvent was distilled off under reduced pressure to obtain 86 g of bis (β-epithiopropyl) disulfide. (Polymerization and curing) 0.4 parts by weight of N, N-diethylethanolamine was mixed with 80 parts by weight of bis (β-epithiopropyl) disulfide synthesized in the third step, and the mixture was mixed to give a thickness of 1
The mixture was poured into a mold composed of two glass plates adjusted to 0 mm, heated from 20 ° C. to 110 ° C. over 24 hours, and polymerized and cured to obtain an optical material. The obtained material was colorless and transparent, and was good without clouding. The results are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was carried out using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

Comparative Example 2 The same operation as in Example 4 was carried out using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

Comparative Example 3 The same operation as in Example 5 was carried out using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

Comparative Example 4 The same operation as in Example 6 was carried out using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

Comparative Example 5 The same operation as in Example 7 was carried out using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

Comparative Example 6 The same operation as in Example 8 was carried out using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

Comparative Example 7 The same operation as in Example 9 was performed using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

Comparative Example 8 The same operation as in Example 10 was performed using epichlorohydrin containing the evaporation residue shown in Table 1. The results are shown in Table 2.

[0079]

[Table 1]

[0080]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/04 G02B 1/04 (72) Inventor Masaki Tamura 1-3-2, Funamachi, Taisho-ku, Osaka-shi, Osaka No. Mitsubishi Gas Chemical Co., Ltd. Naniwa Factory F-term (reference) 4C048 AA01 BB01 BC17 CC01 CC02 UU03 XX02 4J030 BA04 BA32 BB02 BB13 BC21 BF07 BG25

Claims (3)

[Claims] 1. A method for producing an episulfide compound, which comprises the following steps. (1) A first step of producing a halohydrin compound by reacting an epihalohydrin having an evaporation residue of 1000 ppm or less with hydrogen sulfide or a mercapto compound in the presence of a catalyst. (2) A second step of producing an epoxy compound by reacting the halohydrin compound obtained in the first step with a basic compound. (3) A third step of reacting the epoxy compound obtained in the second step with a thiating agent to produce an episulfide compound. 2. The method for producing an episulfide compound according to claim 1, wherein the epihalohydrin is epichlorohydrin. 3. A method for producing an optical material, which comprises polymerizing and curing the episulfide compound obtained by the method according to claim 1.