JP3491660B2 - Novel linear alkyl sulfide type episulfide compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The linear alkyl sulfide type episulfide compound of the present invention is a plastic lens,
It is suitably used as a raw material for optical materials such as prisms, optical fibers, information recording substrates, and filters, and in particular, plastic lenses for spectacles.

[0002]

2. Description of the Related Art Plastic materials have been widely used in recent years in various optical materials, especially spectacle lenses, because they are lightweight, rich in toughness, and easy to dye. Optical materials, especially
In addition to a low specific gravity, the performances required for a spectacle lens are a high refractive index and a high Abbe number as optical performance, and physical performances are high heat resistance and high strength. 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 typical early plastic materials in the prior art are those obtained by polymerizing diethylene glycol bisallyl carbonate, the bisallyl carbonate and diallyl phthalate, and various methacrylic acid compounds. It was These have a refractive index of about 1.5 to 1.55, which increases the thickness of the lens, resulting in loss of lightness. Therefore, a material having a high refractive index is desired, and a refractive index of 1.
Various efforts have been made up to 6 or more. A thermosetting optical material having a urethane structure obtained by the reaction of a methacrylic acid compound containing chloro or bromine atoms, or a hydroxy compound containing bromine atoms with an isocyanate compound (JP-A-58-164).
No. 615, etc.) has been proposed. However, when a compound containing a chlorine atom or a bromine atom is used, the specific gravity becomes large, and in this case also the result is that the lightness is impaired.
Therefore, a thermosetting optical material having a thiourethane structure obtained by the reaction of a polythiol compound and a polyisocyanate compound is disclosed in Japanese Examined Patent Publication No. 4-58489.
-148340. In addition, various novel polythiol compounds as raw materials for these thiourethanes have been proposed. That is, JP-A-5-148340 discloses a branched polythiol compound having four sulfur atoms in one molecule, and JP-A-2-270859 discloses a branched polythiol compound having five sulfur atoms in one molecule. JP-A-6-192250 proposes a polythiol compound having a dithian ring structure in the molecule.
Although the optical materials having these thiourethane structures have improved the refractive index Abbe number to some extent, they have been insufficient. Furthermore, the technology of obtaining a lens by polymerizing an epoxy resin or an episulfide resin with a bifunctional or higher functional compound,
It is proposed in JP-A-1-98615, JP-A-3-81320, and International Publication WO 89/10575. The refractive index of the optical material obtained by curing and polymerizing the epoxy and episulfide compounds of these conventional techniques is not sufficient, the Abbe number is low, and the balance between the refractive index and the Abbe number is unsatisfactory. In any case, these conventional sulfur-containing compounds and the like have solved the problems of thinner wall thickness and lighter weight to some extent, but it goes without saying that a higher refractive index is desirable. On the other hand, another important performance required for optical materials is that chromatic aberration is small. The higher the Abbe number, the better the chromatic aberration. Therefore, a material with a high Abbe number is desired. That is, simultaneous realization of a high refractive index and a high Abbe number is also desired. However, in general,
The Abbe number tends to decrease with an increase in the refractive index, and is a plastic material made of diethylene glycol bisallyl carbonate and conventional compounds represented by polythiol compounds and polyisocyanate compounds, epoxies, episulfide compounds, etc. Then, the refractive index is 1.5
In the case of 1 to 1.55, the Abbe number is about 50 to 55, in the case of the refractive index of 1.60 the limit is 40, and in the case of 1.66 the refractive index is about 30. In this case, the Abbe number was about 30 or less, which was not practical. Furthermore, in the case of conventional techniques, especially thiourethane materials, etc., the molecular weight of the raw material sulfur compound becomes large in order to realize a high refractive index, which lowers the crosslink density, and the alkyl group content in order to express a high Abbe number. Therefore, the rigidity of the molecules constituting the raw material compound is lowered, and as a result, heat resistance is lowered.

[0003]

The problem to be solved by the present invention is to find a novel sulfur-containing compound which enables an optical material having a thin wall thickness and low chromatic aberration. There is a limit to increasing the refractive index of optical materials using episulfide compounds, polythiol compounds, and isocyanate compounds obtained by conventional techniques.Furthermore, increasing the refractive index causes a decrease in the Abbe number. There were two points that I could not get the balance of numbers.

[0004]

The problems of the present invention are (1)
It has been solved by a novel linear alkyl sulfide type episulfide compound represented by the formula.

[Chemical 3] (Here, m represents an integer of 1 to 6, n represents an integer of 0 to 4. X represents S or O, and the number of S is the sum of S and O constituting the three-membered ring. The average is 50% or more.) In the formula (1), n represents an integer of 0 to 4, preferably 0 to 3, and more preferably 0 to 2. m represents an integer of 1 to 6, preferably 2 to 4, more preferably 2 to 3, and most preferably 2. X represents S or O, and the number of S is 50% or more on average with respect to the total of S and O constituting the three-membered ring, preferably 80 to 100%, more preferably 90 to
100%, particularly preferably 95-100%. Most preferably, it is 100%. This is because when n exceeds 4, the heat resistance of the optical material obtained by polymerization and curing decreases, and it cannot be used as an optical material. Further, even when n is 4 or less, it is advantageous that the heat resistance is small, and when it is too small, the flexibility of the material is impaired and the material becomes brittle. When m is from 4 to 6, the sulfur content is lowered, the high refractive index is not achieved, and the heat resistance of the material is lowered. When m is 1, the compound becomes somewhat thermally unstable and requires careful attention such as setting conditions in the production of this compound. When the number of S in X is 80% or less on the average with respect to the sum of S and O constituting the three-membered ring, particularly less than 50%, the sulfur content is lowered and the high refractive index is not achieved, and the compound As the reactivity decreases, polymerization under high temperature conditions is required, so that the material is colored. As described above, the performances of the compound of the present invention and the optical material obtained by polymerizing and curing the compound are integers n and m.
And the proportion of S in X, however, the preferred embodiments, etc. are not determined by fitting the integers n and m independently within the above range. As a preferable example, n =
Compounds in which 0 and n = 1 to 4 and m = 1 to 4 are included. Among these, more preferable examples include compounds in the range of n = 0 and n = 1 to 4, and in the range of m = 2 to 4. Among these, more preferable examples are n = 0 and n = 1 to 3
And a compound in the range of m = 2-4. Among these, particularly preferable examples (n = 0, n = 1 and m = 2 to 4 and n = 2 and m = 2) are actually shown below.

[Chemical 4] The most preferable of these are the following specific examples.

[Chemical 5]

Novel linear alkyl sulfide of the present invention
The type episulfide compound is represented by the formula (3).
A dimercapto compound having a rutile sulfide structure, HS [(CH₂) MS] nH (3) (Where m is an integer of 1 to 6 and n is 1 to 4
Represents an integer. ) Hydrogen sulfide (H₂S) Furthermore, hydrosulfide
(NaSH) or soda sulfide (Na ₂S) and epic
Alkaline epihalohydrin typified by lorohydrin
Linear alkyl represented by the formula (4) by reacting in the presence of
Obtain sulfide type epoxy compound

[Chemical 6] Then, the epoxy compound is produced by reacting with a thiocyanate, thiourea, triphenylphosphine sulfide, a thiating agent such as 3-methylbenzothiazol-2-thione, and preferably with a thiocyanate or thiourea. .
In the method for producing the epoxy compound represented by the formula (4), epichlorohydrin is preferable as the epihalohydrin compound. The epihalohydrin compound is used stoichiometrically in an amount of twice the molar amount of the dimercapto compound of formula (3), hydrogen sulfide, sodium hydrosulfide or sodium sulfide.
If the purity of the product, the reaction rate, the economical efficiency and the like are emphasized, the amount may be less than or more than this. It is preferable to use 2 to 30 times mol for the reaction. The reaction may be carried out without solvent or in a solvent,
When a solvent is used, it is desirable to use one in which one of epihalohydrin, dimercapto compound of formula (3), metal salt of dimercapto compound, hydrogen sulfide, sodium hydrosulfide or sodium sulfide is soluble. . Specific examples include water, alcohols, ethers, aromatic hydrocarbons, halogenated hydrocarbons and the like. The reaction easily proceeds in the presence of a stoichiometric amount of base or more. That is, when the dimercapto compound of the formula (3) and hydrogen sulfide are used, it can proceed in the presence of a double molar amount of these compounds, and in the case of soda hydrosulfide, it can proceed in the presence of an equimolar amount of the base. In the case of soda sulfide, it proceeds even in the absence. Examples of the base include tertiary amines such as pyridine, triethylamine and diazabicycloundecene, and hydroxides of alkali or alkaline earth metals. Preferred are hydroxides of alkali or alkaline earth metals. There are more preferable ones, such as sodium hydroxide and potassium hydroxide. The reaction temperature is usually -10 to 100 ° C.
However, it is preferably -10 to 60 ° C. The reaction time may be any time as long as the reaction is completed under the various conditions described above, but usually 10 hours or less is suitable. In the method for producing an episulfide compound of formula (1) from an epoxy compound represented by formula (4), when thiocyanate is used as a thiating agent, preferable thiocyanate is amine, alkali or alkaline earth metal. And more preferably potassium thiocyanate,
It is sodium thiocyanate. Although thiocyanate is used in a stoichiometric amount, it is twice the molar amount of the epoxy compound represented by the formula (4). May be used in any amount. Preferably, the reaction is carried out using a 2 to 10-fold molar amount. More preferably, the reaction is carried out using 2 to 5 times the molar amount. The reaction may be carried out without solvent or in a solvent,
When a solvent is used, it is desirable to use one in which any of thiocyanate or thiourea and the epoxy compound of the formula (4) is soluble. As a specific example, water,
Alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; hydroxy ethers such as methyl cellosolve, ethyl cellosolve and butyl cellosolve;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Examples include halogenated hydrocarbons such as dichloroethane, chloroform, chlorobenzene, etc.
For example, ethers, hydroxy ethers, halogenated hydrocarbons, and combinations of aromatic hydrocarbons and alcohols are 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 the acid and acid anhydride include nitric acid, hydrochloric acid, sulfuric acid, fuming sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid,
Tartaric acid, propionic acid, butyric acid, succinic acid, maleic acid,
Benzoic acid, nitric acid anhydride, sulfuric acid anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, Examples thereof include silica gel, silica alumina, aluminum chloride and the like, and it is possible to use some of them in combination. The addition amount is usually 0.001 to 10 wt% with respect to the total amount of the reaction solution. 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 reaction product can be washed with an acidic aqueous solution to improve the stability of the resulting compound. 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, 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 more effectively at pH 3 or lower.

As another method other than the above, the epoxy compound of formula (4) is prepared by oxidizing the corresponding unsaturated compound of formula (5) with an organic peracid, alkylhydroperoxide, hydrogen peroxide, etc. By the above method
The method of using the episulfide compound of CH ₂ = CHCH ₂ S [(CH ₂₎ mS] _{nCH 2 CH = CH 2 (5} ) ( where, m is an integer from 1 to 6, n is an integer of 0 to 4.) Equation (5 The unsaturated compound (1) is produced by, for example, condensing a dimercapto compound of the formula (3) with hydrogen sulfide, sodium hydrosulfide or sodium sulfide chloride, or an allyl halide compound such as allyl bromide in the presence of a base. It is possible. Further, as another method, from the dihalodimercapto compound represented by the formula (6),
Production by dehydrohalogenation reaction is also a powerful method. XCH ₂ CHSHCH ₂ S [(CH ₂ ) mS] nCH ₂ CHSHCH ₂ X (6) (where m is an integer of 1 to 6, n is an integer of 0 to 4,
X represents a chlorine or bromine atom. It is known that the dihalodimercapto compound of the formula (6) can be easily synthesized from the unsaturated compound of the formula (5) and sulfur chlorides (for example, F. Lautenschla).
erger et al. Org. Chem. , 34 , 396
(1969)).

The novel linear alkyl sulfide type episulfide compound of the present invention can be heat-polymerized in the presence or absence of a curing catalyst to produce a resin. A preferred method is to use a curing catalyst, and as the curing catalyst, amines, phosphines, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid, etc. are used. Specific examples include (1) 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, aminomethylcyclohexane , Primary amines such as 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, diethyl Aminopropyl amine, bis -
(3-aminopropyl) ether, 1,2-bis- (3
-Aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2'-dimethylpropane, aminoethylethanolamine, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3-
Or 1,4-bisaminoethylcyclohexane,
1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2
-Or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylmorpholine, N
-Aminopropylmorpholine, isophoronediamine, menthanediamine, 1,4-bisaminopropylpiperazine, o-, m-, or p-phenylenediamine,
2,4- or 2,6-tolylenediamine, 2,4-
Toluenediamine, m-aminobenzylamine, 4-chloro-o-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 -Diaminophenyl) sulfone, etc. Liamine; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n
-Pentylamine, di-3-pentylamine, dihexylamine, octylamine, di (2-ethylhexyl)
Amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2,
Secondary amines such as 4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole and morpholine; N, N'-dimethylethylenediamine,
N, N'-dimethyl-1,2-diaminopropane, N,
N'-dimethyl-1,3-diaminopropane, N, N '
-Dimethyl-1,2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane, N, N'-dimethyl-
1,4-diaminobutane, N, N′-dimethyl-1,5
-Diaminopentane, N, N'-dimethyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine,
N, N'-diethyl-1,2-diaminopropane, N,
N'-diethyl-1,3-diaminopropane, N, N '
-Diethyl-1,2-diaminobutane, N, N'-diethyl-1,3-diaminobutane, N, N'-diethyl-
1,4-diaminobutane, N, N′-diethyl-1,6
-Diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) Ethane, 1,3-
Di- (4-piperidyl) propane, 1,4-di- (4-
Secondary polyamines such as piperidyl) butane and tetramethylguanidine; trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3
-Methoxypropylamine, tri-n-butylamine,
Tri-iso-butylamine, tri-sec-butylamine, tri-pentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine, tri-dodecylamine, Tri-laurylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, triethanolamine, tribenzylamine, N, N- Dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol,
N, N-dimethylaminomethylphenol, 2- (N,
N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine,
Tertiary amines such as 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-
Tertiary polyamines such as dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, 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, N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2-undecylimidazole, N- ( 2'-shear Various imidazoles such as ethyl) -2-phenylimidazole, 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)
Amidines such as undecene-7; amine compounds represented by the above. (2) Amines and halogens of (1), mineral acids, Lewis acids,
Quaternary ammonium salts with organic acids, silicic acid, tetrafluoroboric acid, etc. (3) A complex of the amine of (1) with borane and boron trifluoride. (4) trimethylphosphine, triethylphosphine,
Tri-iso-propylphosphine, tri-n-butylphosphine, tri-n-cyclohexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (diethylamino)
Phosphines such as phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, and chlorodiphenylphosphine. (5) Hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid and other mineral acids and their half-esters. (6) Boron trifluoride, Lewis acids represented by etherate of boron trifluoride and the like. (7) Organic acids represented by carboxylic acids and their half-esters. (8) Silicic acid, tetrafluoroboric acid and the like. Among these, preferred are those having less coloration of the cured product, and primary monoamines, secondary monoamines, tertiary monoamines, tertiary polyamines, imidazoles, amidines,
These are quaternary ammonium salts and phosphines. More preferred are secondary monoamines, tertiary monoamines, tertiary polyamines, imidazoles, amidines, quaternary ammonium salts, and phosphines, which have at most one group capable of reacting with an episulfide group. These may be used alone or in combination of two or more. The above curing catalyst is usually 0.0001 with respect to 1 mol of the diepisulfide compound.
The amount used is 1.0 to 1.0 mol, preferably 0.00
01 mol to 0.5 mol, more preferably 0.000
1 mol to less than 0.1 mol, most preferably 0.00
Use from 01 to 0.05 mol. If the amount of the curing catalyst is larger than this, the refractive index and heat resistance of the cured product will decrease, and coloring will occur. If it is less than this range, it is not sufficiently cured and heat resistance becomes insufficient.

The novel linear alkyl sulfide type episulfide compound of the present invention is a compound having two or more functional groups capable of reacting with an episulfide group, or one or more of these functional groups and another homopolymerizable functional group. It is also possible to produce an optical material by curing and polymerizing with a compound having one or more of the above, and further with a compound having one functional group capable of reacting with the episulfide group and capable of homopolymerization. Examples of compounds having two or more functional groups capable of reacting with these episulfide groups include epoxy compounds, known episulfide compounds, polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, mercaptocarboxylic acids, polymercaptans, mercapto alcohols, and mercaptos. Examples thereof include phenol, polyphenol, amines and amides. On the other hand, the compound having at least one functional group capable of reacting with an episulfide group and at least one other homopolymerizable functional group is an epoxy having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl, and allyl. Examples thereof include compounds, episulfide compounds, carboxylic acids, carboxylic acid anhydrides, mercaptocarboxylic acids, mercaptans, phenols, 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 compounds 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, benzophenonetetracarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and other polyvalent carboxylic acid compounds and glycidyl ester epoxy compounds produced by condensation of epihalohydrin; ethylenediamine, 1,2
-Diaminopropane, 1,3-diaminopropane, 1,
2-diaminobutane, 1,3-diaminobutane, 1,4
-Diaminobutane, 1,5-diaminopentane, 1,6
-Diaminohexane, 1,7-diaminoheptane, 1,
8-diaminooctane, bis- (3-aminopropyl)
Ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,
2'-Dimethylpropane, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethyl Cyclohexane, 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 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-
Primary diamines such as (4,4′-diaminodiphenyl) propane, N, N′-dimethylethylenediamine, N,
N'-dimethyl-1,2-diaminopropane, N, N '
-Dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane, N, N'-dimethyl-1,
4-diaminobutane, N, N'-dimethyl-1,5-diaminopentane, N, N'-dimethyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N '-Diethylethylenediamine, N,
N'-diethyl-1,2-diaminopropane, N, N '
-Diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane, N, N'-diethyl-1,3-diaminobutane, N, N'-diethyl-1,
4-diaminobutane, N, N'-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine,
2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) -methane,
1,2-di- (4-piperidyl) -ethane, 1,3-di- (4-piperidyl) -propane, 1,4-di- (4-
An amine-based epoxy compound produced by condensation of a secondary diamine such as piperidyl) -butane and epihalohydrin;
3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclihexanedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, Alicyclic epoxy compounds such as bis (3,4-epoxycyclohexyl) adipate; epoxy compounds produced by epoxidation of unsaturated compounds such as cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide; The urethane-based epoxy compounds produced from the polyhydric alcohols, phenol compounds, diisocyanates, glycidol and the like can be mentioned.

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

Polyvalent carboxylic acid, polyvalent carboxylic acid anhydride,
Specific examples of polyphenols, amines and the like include those mentioned above as a raw material of a partner to be reacted with the epihalohydrin explained in the above-mentioned epoxy compound.

Specific examples of polymercaptans include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane and di (2-mercaptoethyl). ) Linear mercaptan compounds such as sulfide and 1,2- [bis (2-mercaptoethylthio)] ethane; 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-di Mercaptobutane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis [(2-mercaptoethylthio)]-
Branched aliphatic polymercaptan compounds such as 3-mercaptopropane, 1,1,1-tris (mercaptomethyl) propane and tetrakismercaptomethylmethane; ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, 1,4-butane Diol dithioglycolate, 1,4-butanediol dithiopropionate, trimethylolpropane tris (β-thioglycolate), trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (β-thioglycolate) ), Pentaerythritol tetrakis, (β-thiopropionate) and other ester-containing aliphatic polymercaptan compounds; 1,4-dimercaptocyclohexane, 1,3-dimercaptocyclohexane,
1,4-dimercaptomethylcyclohexane, 1,3-
Dimercaptomethylcyclohexane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptoethyl-1,4-dithiane, 2,5-dimercaptomethyl-1-thiane, 2,5-di Examples thereof include aliphatic cyclic dimercaptan compounds such as mercaptoethyl-1-thian.

Representative 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 one episulfide group. More specifically, monoepoxy compounds such as ethylene oxide and propylene oxide, glycidyl esters of monocarboxylic acids such as acetic acid, propionic acid, and benzoic acid, methylglycidyl ether, ethylglycidyl ether, and propylglycidyl ether. -Derived from glycidyl ethers such as ter and butyl glycidyl ethers or monoepisulfide compounds such as ethylene sulfide and propylene sulfide, and the above monocarboxylic acids and thioglycidyl (1,2-epithio-3-hydroxypropane) Having a structure of thioglycidyl ester, methylthioglycidyl ether (1,2-epithiopropyloxymethane),
Examples thereof include thioglycidyl ethers such as ethyl thioglycidyl ether, propyl thioglycidyl ether, and butyl thioglycidyl ether. Among these, more preferred are compounds having one episulfide group.

The compound having two or more functional groups capable of reacting with the episulfide group of the diepisulfide compound of the present invention, or the compound having one or more functional groups and one or more other homopolymerizable functional group and episulfide The compound having one functional group capable of reacting with a group and capable of homopolymerization can be produced by curing polymerization in the presence of a curing polymerization catalyst. As the curing catalyst, the above-mentioned amines, phosphines, acids and the like are used. As specific examples, those mentioned above are 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-methoxy-2,4-dimethyl-valeronitrile 2,2'-azobis (2-methylpropane), 2,2'-azobis Known thermal polymerization catalysts such as azo compounds such as (2,4,4-trimethylpentane),
Known photopolymerization catalysts such as benzophenone and benzoin benzoin methyl ether may be mentioned. 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%.

When the novel linear alkyl sulfide type episulfide compound of the present invention is polymerized and cured to obtain an optical material, known additives such as an antioxidant and an ultraviolet absorber are added to the obtained material for practical use. Of course, it is possible to improve the sex. 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,
Examples thereof include alkali metal salts of acidic phosphoric acid esters, metal salts of higher fatty acids, higher fatty acid esters, paraffins, waxes, higher aliphatic amides, higher aliphatic alcohols, polysiloxanes, and aliphatic amine ethylene oxide adducts.

When the novel linear alkyl sulfide type episulfide compound of the present invention is polymerized and hardened to obtain an optical material, the raw material is an episulfide compound, and further, if desired, the aforementioned curing catalyst and an episulfide having an unsaturated group. When a group capable of reacting with a group such as glycidyl methacrylate or thioglycidyl methacrylate (epoxy group of glycidyl methacrylate is episulfided) is used in combination, a radical polymerization initiator, a radically polymerizable monomer, and Is mixed with additives such as a release agent, an antioxidant and an ultraviolet absorber, and then polymerized and cured as described below to obtain an optical material such as a lens. That is, the mixed raw materials are poured into a mold made of glass or metal, the polymerization and curing reaction is advanced by heating, and then the mold is removed from the mold for production. Curing time is 0.1-10
0 hours, usually 1 to 48 hours, the curing temperature is -10 to
It is 160 ° C, usually -10 to 140 ° C. After the completion of curing, annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the 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, the main raw material and the auxiliary raw material are mixed, and then the mixture is injected and cured into a mold. The main raw material is a diepisulfide compound, and optionally two or more functional groups capable of reacting with the episulfide group. Or a compound having at least one of these functional groups and at least one other homopolymerizable functional group and a compound having at least one homopolymerizable functional group capable of reacting with an episulfide group, and further, if desired. The curing catalyst, the radical polymerization initiator, the mold release agent, the stabilizer, etc., used as all are mixed together under stirring in the same container at the same time, or each raw material is added stepwise and mixed, It is possible to mix several components separately and then remix them 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 the respective raw materials and an unfavorable reaction between the additives occurs, Furthermore, it is not suitable because the viscosity increases and the casting operation becomes difficult. The mixing temperature should be in the range of -10 ° C to 100 ° C, and the preferable temperature range is -10 ° C to 50 ° C, and more preferably,
The temperature is from -5 ° C to 30 ° C. The mixing time is 1 minute to 5 hours, preferably 5 minutes to 2 hours, more preferably 5 minutes to 30 minutes, and most preferably about 5 minutes to 15 minutes. 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.

[0020]

The cured resin optical material obtained by polymerizing and curing the diepirfide compound of the present invention has a sufficiently high refractive index, which is difficult as long as the compound of the prior art is used as a raw material,
A resin optical material having a good balance of refractive index and Abbe number has become possible. That is, the novel compound of the present invention has made remarkable progress in reducing the weight and thickness of resin optical materials and reducing chromatic aberration. This makes it possible to manufacture a material preferable for use in lenses such as eyeglasses. Further, the novel resin-cured material of the present invention has excellent heat resistance and strength and can be used in various applications.

[0021]

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. Refractive index, Abbe number: Measured at 25 ° C using an Abbe refractometer. Specific gravity: Measured at 25 ° C. using an electronic hydrometer and corrected by a conventional method. Heat resistance: ○ 1 with a Vicat softening point of 120 ° C or higher
Those having a temperature of less than 20 ° C and 80 ° C or more were evaluated as Δ, and those having a temperature of less than 80 ° C were evaluated as x. Strength: In a three-point bending test measurement using an autograph, a strain with a strain of 0.1 or more is ◯, and a strain less than 0.1 is 0.05.
The above items were evaluated as Δ, and those less than 0.05 were evaluated as x.

Example 1 (n = 1, m = 2) 1.0 mol of 1,2-dimercaptoethane (94.2)
g) and epichlorohydrin 2.0 mol (185.0
g) is cooled to a liquid temperature of 10 ° C., and sodium hydroxide 10
An aqueous solution obtained by dissolving mmol (0.4 g) in 4 ml of water was added, and the mixture was stirred at this temperature for 1 hour. After that, increase the liquid temperature to 40-
The mixture was stirred for 2 hours while maintaining the temperature around 45 ° C. Return to room temperature,
80 ml of water containing 2 mol (80.0 g) of sodium hydroxide
The aqueous solution dissolved in was added dropwise while maintaining the liquid temperature around 40-45 ° C, and then stirred for 3 hours while maintaining the liquid temperature around 40-45 ° C. 200 ml of water was added to the reaction mixture,
It is extracted with 300 ml of toluene, and the toluene layer is 200 m in water.
Wash 3 times with 1. The toluene layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 202.0 g (theoretical amount of 9-theoretical amount) of 1,2-bis (glycidylthio) ethane was obtained as a colorless transparent liquid.
9%). Then, 0.3 mol (79.9 g) of 1,2-bis (glycidylthio) ethane obtained here
40 ml of ethanol and potassium thiocyanate 87.5
g (0.9 mol) was added to an aqueous solution prepared by dissolving 60 ml of water, the liquid temperature was raised to 45 ° C. over 1 hour, and the reaction was carried out at this temperature for 5 hours. To the reaction mixture was added water (500 ml) and extracted with toluene (500 ml).
Wash 3 times with 0 ml. The toluene layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and white solid 1,2-bis (β-epithiopropylthio) ethane (m of the formula (1) =
2, n = 1) was obtained (78.1 g, 88% of theory). Elemental analysis value: (Analysis value) (Calculation value) C 40.19% 40.30% H 6.05% 5.95% S 53.79% 53.64% Mass spectrum (EI): M ^{+ ·} 238 ( Theoretical molecular weight 238) Infrared absorption spectrum: 620 cm ^-1 (stretching vibration of episulfide ring) ¹ H-NMR: 2.2 ppm (hydrogen attached to carbon at 1,10 position) 2.6 ppm (at carbon at 1,10 position) Attached hydrogen) 2.7ppm (hydrogen attached to carbons at the 2,9th position) 2.9ppm (hydrogen attached to carbons at the 5th and 6th positions) 3.0ppm (hydrogen attached to carbons at the 3rd and 8th positions) 3 .1 ppm (hydrogen attached to carbon at 3,8 position) ¹³ C-NMR: 25.7 ppm (carbon at 1,10 position) 32.5 ppm (carbon at 2,9 position) 34.0 ppm (for 5,6 position) Carbon) 38.4 ppm (carbon at the 1st and 10th positions) Tributylamine to compound 100 parts by weight of 1
Part by weight was mixed and poured into a mold consisting of two glass plates adjusted to a thickness of 2 mm and polymerized and cured at 80 ° C. for 5 hours to obtain an optical material. The refractive index, Abbe number and The specific gravity was measured and the results are shown in Table 1.

Example 2 (n = 1, m = 2) 1.0 mol of 1,2-dimercaptoethane was placed in a flask equipped with a stirrer, a dropping funnel, a thermometer and a nitrogen introducing tube.
(94.2 g), sodium hydroxide 10 mmol (0.
4 g) in 4 ml of water, methanol 100
ml, and epichlorohydrin 2.0 ml
(185.0 g) was added dropwise over 1 hour. The reaction temperature was kept at 0 to 10 ° C during the dropping. After the dropping was completed, the reaction was continued for another hour. Then, 6.0 ml (240 g) of caseiso-da dissolved in 360 ml of water was added dropwise over 1 hour. The reaction temperature was kept at 0 to 10 ° C during the dropping. After the dropping was completed, the reaction was continued for another 3 hours. After that, toluene extraction,
After washing with water, the solvent was distilled off, and 202.2 g (theoretical amount of 9-theoretical amount) of 1,2-bis (glycidylthio) ethane was obtained as a colorless transparent liquid.
9%) was obtained. Next, 0.3 mol (79.9 g) of 1,2-bis (glycidylthio) ethane and thiourea 1. were added to a flask equipped with a stirrer, a thermometer, and a nitrogen introducing tube.
25 mol (95.3 g) and acetic anhydride 0.03 mol
(2.96 g) Further, 250 ml of toluene and 250 ml of methanol were charged as a solvent, and the mixture was reacted at 30 ° C. for 9 hours. After the reaction, the mixture was extracted with toluene, washed with a 1% aqueous sulfuric acid solution, washed with water, and then the excess solvent was distilled off. As a result, white solid 1,2-bis (β-epithiopropylthio) ethane (m of the formula (1) = 2, n = 1) 82.0 g (theoretical amount of 93
%)Obtained. Elemental analysis value: (Analysis value) (Calculation value) C 40.19% 40.30% H 6.05% 5.95% S 53.79% 53.64% Mass spectrum (EI): M ^{+ ·} 238 ( Theoretical molecular weight 238) Infrared absorption spectrum: 620 cm ^-1 (stretching vibration of episulfide ring) ¹ H-NMR: 2.2 ppm (hydrogen attached to carbon at 1,10 position) 2.6 ppm (at carbon at 1,10 position) Attached hydrogen) 2.7ppm (hydrogen attached to carbons at the 2,9th position) 2.9ppm (hydrogen attached to carbons at the 5th and 6th positions) 3.0ppm (hydrogen attached to carbons at the 3rd and 8th positions) 3 .1 ppm (hydrogen attached to carbon at 3,8 position) ¹³ C-NMR: 25.7 ppm (carbon at 1,10 position) 32.5 ppm (carbon at 2,9 position) 34.0 ppm (for 5,6 position) Carbon) 38.4 ppm (carbon at the 1st and 10th positions) Tributylamine to compound 100 parts by weight of 1
Parts by weight were mixed and poured into a mold composed of two glass plates adjusted to have a thickness of 2 mm, and polymerized and cured at 80 ° C. for 5 hours to obtain an optical material. The refractive index, Abbe number and specific gravity of the obtained material were measured and the results are shown in Table 1.

Example 3 (n = 1, m = 4) Example 1 was repeated except that 1,4-dimercaptobutane was used in place of 1,2-dimercaptoethane in Example 1, 1,4 -Bis (β-epithiopropylthio) butane (m = 4, n = 1 in the formula (1)) in a total yield of 85
Earned in%. Elemental analysis value: (Analysis value) (Calculation value) C 44.89% 45.07% H 6.99% 6.81% S 48.00% 48.13% Mass spectrum (EI): M ^{+ ·} 266 ( Theoretical molecular weight 266) Infrared absorption spectrum: 620 cm ^-1 (stretching vibration of episulfide ring) ¹ H-NMR: 1.9 ppm (hydrogen on carbons at 6 and 7 positions) 2.2 ppm (at carbons at 1 and 12 positions) Attached hydrogen) 2.6 ppm (hydrogen attached to carbons at 1 and 12 positions) 2.7 ppm (hydrogen attached to carbons at 2 and 11 positions) 2.8 ppm (hydrogen attached to carbons at 5 and 8 positions) 3 0.0 ppm (hydrogen attached to carbons at the 3 and 10 positions) 3.1 ppm (hydrogen attached to carbons at the 3 and 10 positions) ¹³ C-NMR: 25.7 ppm (carbon at 1 and 12 position) 30.5 ppm (6 7th carbon) 31.3ppm (5th and 8th carbon) 32.5 ppm (2, 11 position carbon) 39.1ppm (3,10-position carbon) after polymerization curing, the refractive index of the resulting material, the results were measured Abbe number and specific gravity are shown in Table 1.

Example 4 (n = 2, m = 2) Example 1 was repeated except that dimercaptodiethyl sulfide was used in place of 1,2-dimercaptoethane in Example 1, and bis (β-epithio was used. Propylthioethyl) sulfide (m = 2, n = 2 of formula (1)) was obtained with a total yield of 88%. Elemental analysis value: (Analysis value) (Calculation value) C 40.08% 40.23% H 6.22% 6.08% S 53.55% 53.70% Mass spectrum (EI): M ⁺ 298 ( Theoretical molecular weight 298) Infrared absorption spectrum: 620 cm ^-1 (stretching vibration of episulfide ring) ¹ H-NMR: 2.2 ppm (hydrogen attached to carbon at 1,13 position) 2.6 ppm (at carbon at 1,13 position) Attached hydrogen) 2.7 ppm (hydrogen attached to carbons at the 2,12th position) 2.8-2.9ppm (hydrogen attached to carbons at the 5,6,8,9 position) 3.0ppm (3,11th place) Hydrogen on carbon of 3.1) 3.1 ppm (hydrogen on carbon of 3,11) ¹³ C-NMR: 25.7 ppm (carbon at 1,13 position) 32.4 ppm (carbon at 2,12 position) 32. 5ppm (6th and 8th place carbon) 34.0ppm (5th and 9th place) Of carbon) 38.4 ppm (carbons at the 3,11th position) After polymerization and curing, the refractive index, Abbe number and specific gravity of the obtained material were measured and the results are shown in Table 1.

Example 5 (n = 0) 1.0 mol of hydrogen sulfide in a completely sealed reactor.
(34.1 g) and epichlorohydrin 1.0 mol (9
2.5 g) was added, the liquid temperature was cooled to 10 ° C., an aqueous solution of 5 mmol (0.2 g) of an aqueous sodium hydroxide solution in 4 ml of water was added, and the mixture was stirred at this temperature for 1 hour. Then, the mixture was stirred for 2 hours while maintaining the liquid temperature at around 40-45 ° C. The liquid temperature was cooled again to 10 ° C., and epichlorohydrin 1.0 mol (92.5 g) and sodium hydroxide 5 m
An aqueous solution in which mol (0.2 g) was dissolved in 4 ml of water was added, and the mixture was stirred at 10 ° C for 1 hour and at 40-45 ° C for 2 hours.
After returning to room temperature, sodium hydroxide 80.0 g (2 mol)
Solution of water in 80 ml of water at 40-45 ° C
The solution was added dropwise while maintaining the temperature around it, and then stirred for 3 hours while maintaining the liquid temperature at around 40-45 ° C. After the completion of the reaction, the same treatment as in Example 1 was carried out to obtain 92.2 g (theoretical amount: 63%). Then, this was also reacted with potassium thiocyanate in the same manner as in Example 1 to obtain bis (β-epithiopropyl) sulfide (n = 0 in the formula (1)) in a yield of 80%. Elemental analysis value: (Analysis value) (Calculation value) C 40.25% 40.41% H 5.81% 5.65% S 53.77% 53.94% Mass spectrum (EI): M ⁺ 178 ( Theoretical molecular weight 178) Infrared absorption spectrum: 620 cm ^-1 (stretching vibration of episulfide ring) ¹ H-NMR: 2.3 ppm (hydrogen attached to carbon at 1,7 position) 2.6 ppm (at carbon at 1,7 position) Attached hydrogen) 2.7 ppm (hydrogen attached to carbon at 2,6 position) 3.0-3.1 ppm (hydrogen attached to carbon at 3,5 position) ¹³ C-NMR: 25.6 ppm (1,7 Position carbon) 33.8 ppm (2,6 position carbon) 38.6 ppm (3,5 position carbon) After polymerization and curing, the refractive index, Abbe number and specific gravity of the obtained material were measured and the results are shown in Table 1. It was shown to.

Example 6 Example 1 was repeated except that 1,6-dimercaptohexane was used in place of 1,2-dimercaptoethane in Example 1 to repeat 1,6-bis (β-epithiopropylthio). ) Hexane was obtained with a total yield of 72%. Elemental analysis value: (Analysis value) (Calculation value) C 48.72% 48.93% H 7.77% 7.53% S 43.30% 43.54% Mass spectrum (EI): M ^{+ ·} 294 ( Theoretical molecular weight 294) Infrared absorption spectrum: 620 cm ^-1 (stretching vibration of episulfide ring) ¹ H-NMR: 1.6 ppm (hydrogen attached to carbon at 7 and 8 positions) 1.8 ppm (to carbon at 6 and 9 positions) Attached hydrogen) 2.2 ppm (hydrogen attached to carbons at 1,14th position) 2.6 ppm (hydrogen attached to carbons at 1,14th place) 2.7 ppm (hydrogen attached to carbons at 2,13th place) 2 .8 ppm (hydrogen on 5,10 carbons) 3.0 ppm (hydrogen on 3,12 carbons) 3.1 ppm (hydrogen on 3,12 carbons) ¹³ C-NMR: 25.7 ppm ( Carbon at 1,14th position) 27.8ppm (7th, 8th position) 31.6 ppm (carbons at the 6th and 9th positions) 32.0ppm (carbons at the 5th and 10th positions) 32.4ppm (carbons at the 2nd and 13th positions) 39.0ppm (carbons at the 3rd and 12th positions) After polymerization and curing The refractive index, Abbe number and specific gravity of the obtained material were measured and the results are shown in Table 1.

Comparative Example 1 1,2-Dihydroxyethane (ethylene glycol) was used in place of 1,2-dimercaptoethane in Example 1.
Example 1 is repeated except that is used to give 1,2-bis (β-epithiopropyloxy) ethane in a total yield of 58%.
Got with. After polymerization and curing, the refractive index, Abbe number and specific gravity of the obtained material were measured and the results are shown in Table 1.

Comparative Example 2 Example 2 was repeated except that 1,4-dihydroxybutane (1,4-butanediol) was used in place of 1,4-dimercaptobutane in Example 2, to give 1,4-bis. The total yield of (β-epithiopropyloxy) butane was 66.
Earned in%. After polymerization and curing, the refractive index, Abbe number and specific gravity of the obtained material were measured and the results are shown in Table 1.

Comparative Example 3 Example 3 was repeated except that dihydroxydiethyl ether (diethylene glycol) was used in place of dimercaptodiethyl sulfide in Example 3, and the total yield of bis (β-epithiopropyloxyethyl) ether was 68. Earned in%. After polymerization and curing, the refractive index of the obtained material,
The Abbe number and the specific gravity were measured and the results are shown in Table 1.

Comparative Example 4 Example 1 was repeated except that 0.8 mol of potassium thiocyanate was used per 1 mol of 1,2-bis (glycidylthio) ethane. The obtained product has n = 1 and m = 2 of the formula (1) according to the NMR spectrum, and the number of S in X is 30% on average with respect to the total of S and O constituting the three-membered ring. Met. After polymerization and curing, the refractive index, Abbe number and specific gravity of the obtained material were measured and the results are shown in Table 1.

[0032]

[Table 1]

Further, the present invention will be specifically described below with reference to examples. The physical properties of the obtained polymer were measured by the following measuring methods. Refractive index (nd), Abbe number (νD): An Abbe refractometer was used at 25 ° C. Specific gravity: Measured at 25 ° C. using an electronic hydrometer and corrected by a conventional method. Color tone: b value was measured by a spectrocolorimeter. Heat resistance: The temperature at which the needle penetrated 0.1 mm as measured by the Vicat softening point was defined as the softening point. Bending strength: Three-point bending test measurement using an autograph was performed.

Example 8 2 kg (11.6 mol) of epichlorohydrin was placed in a flask equipped with a stirrer, a dropping funnel, a thermometer and a nitrogen introducing tube.
Then, 390 g (2.5 mol) of 70% sodium hydrosulfide dissolved in 1 L of methanol was added dropwise thereto over 1 hour. During the dropping, the reaction temperature was kept at 10 to 15 ° C. After the dropping was completed, the reaction was continued for another hour. After this, 400 g (10.0 mol) of caustic soda dissolved in 1 liter of water
Was added dropwise over 1 hour. During the dropping, the reaction temperature is 10 to 1
It was kept at 5 ° C. After completion of the dropping, the mixture was extracted with dichloromethane, washed with water, the solvent and excess epichlorohydrin were distilled off, and further distilled under reduced pressure to obtain 521 g of glycidyl sulfide (yield 73%) at a fraction of 62 to 64 ° C./0.25 mmHg. Then, in a flask equipped with a stirrer, a thermometer, and a nitrogen introducing tube, 365.5 g (2.5 mol) of the above distillate, 952.6 g (12.5 mol) of thiourea and 29.6 g of acetic anhydride were placed.
(0.3 mol), and 2.5 L of toluene as a solvent
Then, 2.5 L of methanol was charged and reacted at 30 ° C. for 9 hours. After the reaction, the reaction mixture was extracted with toluene, washed with a 1% sulfuric acid aqueous solution, washed with water, and then the excess solvent was distilled off to obtain 401.1 g (yield 90%) of colorless and transparent bis (β-epithiopropyl) sulfide. 100 parts by weight of the present compound is 10 mmH
It was thoroughly degassed under reduced pressure of g. Further, 1 part by weight of piperidine was added as a catalyst to prepare a uniform solution. Then, the mixture was poured into a mold and then polymerized and cured in an oven at 80 ° C. for 20 hours to produce a flat plate-shaped test piece. The physical properties of the obtained test piece are shown in Table-
Shown in 2. Both the refractive index and the Abbe number showed high values that were not achieved by the prior art, and further, the heat resistance and the strength were sufficiently excellent, and the b value was low and the yellowness was low.

Example 9 100 parts by weight of bis (β-epithiopropyl) sulfide was sufficiently degassed under a reduced pressure of 10 mmHg. Further, 0.2 parts by weight of triethylamine was blended as a catalyst to prepare a uniform solution. Then, after pouring into the mold, 40 ° C in the oven.
To 100 ° C. over 10 hours to polymerize and cure.
The physical properties of the obtained flat plate test piece are shown in Table 2.

Example 10 100 parts by weight of bis (β-epithiopropyl) sulfide was used as a catalyst and 0.5 of N, N-diethylethanolamine was used as a catalyst.
After mixing 8 parts by weight, a uniform solution was prepared. Further, deaeration was performed under a reduced pressure of 10 mmHg. Then, after pouring into the mold, the temperature was raised from 40 ° C. to 80 ° C. in an oven over 10 hours to polymerize and cure. The physical properties of the obtained test piece are shown in Table 2.

Example 11 100 parts by weight of bis (β-epithiopropyl) sulfide was mixed with 0.1 part by weight of triphenylphosphine as a catalyst to prepare a uniform solution. Further, deaeration was performed under a reduced pressure of 10 mmHg. Then, the mixture was poured into a mold and then polymerized and cured in an oven at 80 ° C. for 15 hours to produce a flat plate-shaped test piece.
Table 2 shows the physical properties of the obtained test pieces.

Example 12 Example 11 was repeated except that it was polymerized and cured in an oven at 80 ° C. for 10 hours. Table 2 shows the physical properties of the obtained test pieces.

Example 13 Example 11 was repeated except that the polymerization and curing were carried out in an oven at 80 ° C. for 5 hours. Table 2 shows the physical properties of the obtained test pieces.

Example 14 Example 11 was repeated except that it was polymerized and cured in an oven at 80 ° C. for 2 hours. Table 2 shows the physical properties of the obtained test pieces.

Example 15 100 parts by weight of bis (β-epithiopropyl) sulfide was mixed with 5 parts by weight of hydrogenated 4,4 ^, -diaminodiphenylmethane as a catalyst to prepare ^a uniform solution. Further, deaeration was sufficiently performed under a reduced pressure of 10 mmHg. Then, after injecting into the mold,
A flat plate-shaped test piece was produced by polymerizing and curing in an oven at 80 ° C. for 15 hours. The physical properties of the obtained test piece are shown in Table 2.

Example 16 Example 15 was repeated except that 10 parts by weight of hydrogenated 4,4 ^, -diaminodiphenylmethane was added as a catalyst. The physical properties of the obtained test piece are shown in Table 2.

Example 17 Example 15 was repeated except that 15 parts by weight of hydrogenated 4,4 ^, -diaminodiphenylmethane was added as a catalyst. The physical properties of the obtained test piece are shown in Table 2.

Example 18 100 parts by weight of bis (β-epithiopropyl) sulfide, 0.1 part by weight of triphenylphosphine as a catalyst, and 2,6-di-ter-butyl-4- as an antioxidant.
0.2 parts by weight of methylphenol, 2 as UV absorber
-(2-hydroxy-5-ter-octylphenyl)
After blending 0.1 part by weight of benzotriazole, the mixture was stirred at room temperature to obtain a uniform liquid. Further, deaeration was sufficiently performed under a reduced pressure of 10 mmHg. Then, it was poured into a lens mold and polymerized and cured in an oven at 80 ° C. for 15 hours to produce a lens.
The polymer was easily released from the mold and was not peeled off during the polymerization, and a lens could be obtained. The obtained lens not only has unprecedented excellent optical and physical properties, but also has a colorless color tone (b value = 0.65), has a good surface condition, and has almost no striae and surface deformation. I was not able to admit. It was judged that it can be sufficiently used as a new lens material. In addition, Table 2 shows the physical properties of the obtained lens.

Comparative Example 5 Example 8 was repeated using bis (β-epoxypropyl) ether, but the polymerization curing was insufficient and a test piece could not be obtained.

Comparative Example 6 Although Example 8 was repeated using bis (β-epoxypropyl) sulfide, a test piece was obtained, but the heat resistance was a yellow soft material at about room temperature. The refractive index and Abbe number are shown in Table 2.

Comparative Example 7 Example 8 was repeated using 1,2-bis (β-epithiopropyloxy) ethane. The physical properties of the obtained test piece are shown in Table 1.

Comparative Example 8 2,2-bis {4- (β-epithiopropyloxy)}
Example 8 was repeated using phenylpropane. Table 2 shows the physical properties of the obtained test pieces.

Comparative Example 9 2,2-bis {4- (β-epithiopropyloxy)}
Example 8 was repeated using 75 parts by weight of phenylpropane and 25 parts by weight of 1-mercapto-4-hydroxybenzene. Table 2 shows the physical properties of the obtained test pieces.

Comparative Example 10 1,8-Dimercapto-4-mercaptomethyl-3,6
Mixing 48 parts by weight of dithiaoctane and 52 parts by weight of metaxylylene diisocyanate with 0.1 part by weight of dibutyltin chloride as a curing catalyst based on 100 parts by weight of the mixture to form a uniform liquid, and further degassing it under a reduced pressure of 10 mmHg. went. Then, the mixture was poured into a mold and then polymerized and cured in an oven at 80 ° C. for 20 hours to produce a flat plate-shaped test piece. Table 2 shows the physical properties of the obtained test pieces.

[0051]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G02C 7/02 G02C 7/02 (72) Inventor Yutaka Horikoshi 6-1-1 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Company, Inc. Tokyo Inside the laboratory (72) Kenichi Takahashi 6-1-1, Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Inside the Tokyo laboratory (56) Reference JP-A-3-81320 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 75/08 C08G 65/04 C07D 303/34 C07D 331/02

Claims (7)

(57) [Claims] 1. A linear alkyl sulfide type episulfide compound represented by the formula (1). [Chemical 1] (Here, m represents an integer of 1 to 6, n represents an integer of 0 to 4. X represents S or O, and the number of S is the sum of S and O constituting the three-membered ring. The average is 50% or more.) 2. A bis (epithiopropyl) sulfide compound represented by the formula (2): (Here, m represents an integer of 1 to 6, and n represents an integer of 0 to 4.) 3. A resin obtained by polymerizing and curing the linear alkyl sulfide type episulfide compound according to claim 1. 4. An optical material obtained by polymerizing and curing the linear alkyl sulfide type episulfide compound according to claim 1. 5. A method for obtaining a resin optical material by polymerizing and curing the linear alkyl sulfide type episulfide compound according to claim 1. 6. A method for obtaining a resin optical material by polymerizing and curing the linear alkyl sulfide type episulfide compound according to claim 1 in the presence of a curing catalyst. 7. An optical material obtained by polymerizing and curing the bis (epithiopropyl) sulfide compound according to claim 2.