JP2004307868A - New episulfide compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new episulfide compound and an optical material having a high refractive index and a high Abbe number obtained by curing and polymerizing it. <P>SOLUTION: This compound has two or more units of the structure shown in formula (1). The optical material is obtained by polymerizing it. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The episulfide compound of the present invention is suitably used as a raw material for plastic lenses, prisms, optical fibers, information recording substrates, filters, and other optical materials, particularly, plastic lenses for eyeglasses.

BACKGROUND ART Plastic materials are lightweight and rich in toughness, and are easily used for dyeing. Therefore, plastic materials are widely used in recent years for various optical materials, particularly for spectacle lenses. An early representative plastic material in the prior art was obtained by polymerizing compounds such as diethylene glycol bisallyl carbonate, the bisallyl carbonate, diallyl phthalate, and various methacrylates. These have a refractive index of about 1.5 to 1.55, so that the thickness of the lens is increased, and as a result, lightness is lost. Therefore, a material having a high refractive index is desired, and various efforts have been made to increase the refractive index to 1.6 or more. A polymer of a methacrylate compound containing a chloro or bromine atom and a thermosetting optical material having a urethane structure obtained by reacting a hydroxy compound containing a bromine atom with an isocyanate compound (JP-A-58-164615, etc.) have been proposed. Have been. However, when a compound containing a chloro or bromine atom is used, the specific gravity becomes large, and in this case also, the lightness is impaired. For this reason, thermosetting optical materials having a thiourethane structure obtained by reacting a polythiol compound with a polyisocyanate compound have been proposed in Japanese Patent Publication No. 4-58489 and Japanese Patent Application Laid-Open No. 5-148340.

Also, various novel polythiol compounds serving 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-2-27059 discloses a branched polythiol compound having five sulfur atoms in one molecule. However, JP-A-6-192250 proposes a polythiol compound having a dithiane ring structure in the molecule. Further, the epoxy groups of known epoxy compounds such as amine-based epoxy resins, phenol-based epoxy resins, alcohol-based epoxy resins, unsaturated compound-based epoxy resins, glycidyl ester-based epoxy resins, urethane-based epoxy resins, and alicyclic epoxy resins. JP-A-3-83320 proposes a method for producing a lens material using a compound in which a part or all of the compound is converted to an episulfide group. The thiourethane resin lens obtained from the polythiol compound and the polyisocyanate compound has a maximum refractive index of about 1.66. However, an episulfide resin lens obtained from an episulfide compound derived from a known epoxy resin has a limit of a refractive index of about 1.6. In any case, the problems of thinner thickness and lighter weight have been solved to some extent by these conventional sulfur-containing compounds, but it goes without saying that a higher refractive index is desirable. On the other hand, another important performance required for the optical material is that the chromatic aberration is small. Since the chromatic aberration becomes better as the Abbe number becomes higher, a material having a higher 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 shows a tendency to decrease with an increase in the refractive index, and the conventional diethylene glycol bisallyl carbonate and a known episulfide compound, and furthermore, a plastic using a conventional compound such as a polythiol compound and a polyisocyanate compound as a raw material. For materials, the Abbe number is about 50 to 55 when the refractive index is 1.5 to 1.55, and is about 40 when the refractive index is 1.60 and about 32 when the refractive index is 1.66. On the other hand, various attempts have been made to improve the heat resistance by using a polyfunctional compound and a crosslinking agent. However, in general, in order to achieve a high refractive index, the molecular weight of the raw material sulfur compound becomes large, so that the crosslink density decreases. Further, in order to achieve a higher Abbe number, the alkyl group content increases, and thus the rigidity of the molecules constituting the raw material compound decreases. As a result, sufficient improvement in heat resistance has not been obtained. It is the current situation.

The problem to be solved by the present invention is to find an optical material which has a small thickness, low chromatic aberration and high heat resistance at the same time. In optical materials typified by a cured resin obtained by a polythiol compound and an isocyanate compound obtained by a conventional technique, there is a limit to a high refractive index, and further, a high refractive index leads to a decrease in Abbe number, and The improvement in the characteristics has led to a decrease in heat resistance, and as a result, there have been three points that a sufficiently high refractive index and Abbe number cannot be balanced.

The object of the present invention has been solved by an episulfide compound having at least two structures represented by the formula (1) and having a cyclic skeleton and a branched alkylsulfide-type episulfide compound.

（１）式で表される構造を２個以上有すると共に、環状骨格を有するエピスルフィド化合物は、具体的には、（ａ）環状骨格が、脂環族骨格であるエピスルフィド化合物。（ｂ）環状骨格が、芳香族骨格であるエピスルフィド化合物。（ｃ）環状骨格が、硫黄原子を異種原子とする複素環骨格であるエピスルフィド化合物。であり、さらにこれらの化合物は、分子内に、スルフィド、エーテル、スルフィン、ケトン、エステル等の結合を含んでも良い。

(1) An episulfide compound having two or more structures represented by the formula and having a cyclic skeleton is specifically (a) an episulfide compound in which the cyclic skeleton is an alicyclic skeleton. (B) An episulfide compound in which the cyclic skeleton is an aromatic skeleton. (C) An episulfide compound in which the cyclic skeleton is a heterocyclic skeleton having a sulfur atom as a different atom. Further, these compounds may contain a bond such as sulfide, ether, sulfine, ketone, ester or the like in the molecule.

Further, the branched alkyl sulfide-type episulfide compound is specifically a compound represented by the formula (2).

Preferred specific examples of the episulfide compound having an alicyclic skeleton of (a) include 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 and 1,4-bis (β -Epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- ( β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β-epithiopropylthio) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1, 4-dithiane and the like can be mentioned.

Preferred specific examples of the episulfide compound having an aromatic skeleton (b) include 1,3 and 1,4-bis (β-epithiopropylthio) benzene 1,3 and 1,4-bis (β-epithio). Propylthiomethyl) benzenebis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithio) Propylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfine, 4,4-bis (β-epithiopropylthio) biphenyl and the like.

As the episulfide compound having a heterocyclic skeleton having a sulfur atom as a different atom in (c), an episulfide compound having a structure represented by the formula (3) can be given.

（ここで、Ｅｐｓは（４）式で表されるエピチオプロピル基を表し、Ｙは−（ＣＨ２ＣＨ２Ｓ）−を表し、Ｚは水素原子、炭素数１から５のアルキル基あるいは、−（ＣＨ２）ｍＳＹｎＥｐｓを表し、Ｕは水素原子、炭素数１から５のアルキル基を表す。ｍは１から５の整数を表し、ｎは０から４の整数を表す）

(Here, Eps represents an epithiopropyl group represented by the formula (4), Y represents-(CH2CH2S)-, Z represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or-(CH2) represents mSYnEps, U represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 to 5, and n represents an integer of 0 to 4)

（ここに、ＸはＳまたはＯを表し、このＳの個数は三員環を構成するＳとＯの合計に対して平均で５０％以上である。）（３）式において、ｎは０から４の整数を表すが、好ましくは、０から３であり、より好ましくは、０から２であり、最も好ましくは０である。ｍは１から５の整数を表すが、好ましくは１から４、より好ましくは１から３、最も好ましくは１である。（４）式において、ＸはＳまたはＯを表すが、このＳの個数は三員環を構成するＳとＯの合計に対して平均でが５０％以上であり、好ましくは８０〜１００％、より好ましくは９０〜１００％、、特に好ましくは９５〜１００％である。最も好ましくは１００％である。ｎが４より大きい場合重合硬化して得られる光学材料の耐熱性が低下し光学材料として使用に耐えなくなる。また、ｎが４以下の場合であっても耐熱性的には小さいほうが有利であり、材料の柔軟性からは大きい方が有利となる。ｍは４および５の場合、硫黄含有量が低下し高屈折率が達成されず、さらに材料の耐熱性が低下する。ｍが１の場合、屈折率、耐熱性的には最も有利となる。（４）式において、Ｘ中のＳの個数は三員環を構成するＳとＯの合計に対して平均で８０％以下、特に５０％以下の場合、硫黄含有量が低下し高屈折率が達成されず、化合物の反応性低下に伴い高温条件下での重合が必要となるため、材料に着色が生じる。本発明の化合物およびこれを重合硬化して得られる光学材料の性能は以上のように整数ｎとｍおよびＸ中のＳの割合により決定される、しかしながら、好ましい具体例等は、整数ｎとｍを独立に上述の範囲にあてはめ決定されない。好ましい例としては、ｎ＝０〜３の範囲でかつｍ＝１〜４の範囲である化合物が挙げられる。これらのなかでより好ましい例としては、ｎ＝０〜２の範囲で、かつｍ＝１〜３の範囲の化合物が挙げられる。これらのなかで最も好ましい例としては、ｎ＝０で、かつｍ＝１の化合物が挙げられる。また、ＵはＵは水素原子、炭素数１から５のアルキル基のいずれでもかまわないが、屈折率を高く保つためには水素原子が好ましい、Ｚもは水素原子、炭素数１から５のアルキル基あるいは、−（ＣＨ２）ｍＳＹｎＥｐｓのいずれでもかまわないが、高耐熱性の観点からは架橋密度の高くなる−（ＣＨ２）ｍＳＹｎＥｐｓが望ましいが、材料の柔軟性とのバランスを考慮した場合水素原子が最も好ましい。

(Here, X represents S or O, and the number of S is 50% or more on average with respect to the sum of S and O constituting the three-membered ring.) In the formula (3), n is from 0 to Represents an integer of 4, preferably 0 to 3, more preferably 0 to 2, and most preferably 0. m represents an integer of 1 to 5, preferably 1 to 4, more preferably 1 to 3, and most preferably 1. In the formula (4), 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%. It is more preferably 90 to 100%, particularly preferably 95 to 100%. Most preferably, it is 100%. When n is greater than 4, the heat resistance of the optical material obtained by polymerization and curing is reduced, and the optical material cannot be used as an optical material. Further, even when n is 4 or less, a smaller heat resistance is advantageous, and a larger flexibility is advantageous from the viewpoint of material flexibility. When m is 4 or 5, the sulfur content decreases, a high refractive index is not achieved, and the heat resistance of the material further decreases. When m is 1, it is most advantageous in terms of refractive index and heat resistance. In the formula (4), when the number of S in X is 80% or less on average with respect to the sum of S and O constituting the three-membered ring, particularly when the number is 50% or less, the sulfur content decreases and the high refractive index decreases. This is not achieved, and the material needs to be polymerized under high temperature conditions as the reactivity of the compound decreases, so that the material is colored. The performance of the compound of the present invention and the optical material obtained by polymerizing and curing the compound are determined by the integers n and m and the ratio of S in X as described above. However, preferred specific examples are the integers n and m Are not independently determined in the above-mentioned range. Preferred examples include compounds in which n = 0-3 and m = 1-4. Of these, more preferred examples include compounds in the range of n = 0 to 2 and m = 1 to 3. The most preferable example among these is a compound in which n = 0 and m = 1. U may be any one of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, but is preferably a hydrogen atom in order to keep the refractive index high. Z is also a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. Any of a group or-(CH2) mSYnEps may be used, but from the viewpoint of high heat resistance,-(CH2) mSYnEps, which has a high crosslinking density, is desirable. Most preferred.

Among these, some of the specific examples are actually shown below by way of example. That is, the following 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2,5 -Bis (β-epithiopropylthioethyl) -1,4-dithiane; 2,3,5-tri (β-epithiopropylthioethyl) -1,4-dithiane;

Preferred specific examples of the branched alkyl sulfide type episulfide compound include 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) propane and 1,2-bis [( 2-β-epithiopropylthioethyl) thio] -3- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropyl) Thiomethyl) propane and the like.

The cured resin optical material of the present invention may be any one of (a), (b) and (c), a branched alkyl sulfide-type episulfide compound, or a mixture of these, and the mixture may be cured if the object of the present invention is achieved. It may be something you did.

The episulfide compound having two or more structures represented by the formula (1) and having a cyclic skeleton and the branched alkylsulfide-type episulfide compound used in the present invention include (a), (b), (c), A compound of the formula (5) having two or more mercapto groups corresponding to a branched alkyl sulfide type episulfide compound is reacted with epihalohydrin represented by epichlorohydrin in the presence of an alkali, and represented by the formula (6) A compound having an epoxy group is obtained, and then the epoxy compound is treated with a thiocyanate such as thiocyanate, thiourea, triphenylphosphine sulfide, or 3-methylbenzothiazole-2-thione, and preferably with thiocyanate or thiocyanate. It is produced by reacting with urea.

〔（５）、（６）式においては、ｎは２以上の整数を表す。Ｒは炭素数１から２０の環状構造を有する化合物、分岐状のアルキル基を表し、これらは、スルフィド、エーテル、スルフォン、エステル、ケトン等の結合を基内に含んでも良い。〕

[In the formulas (5) and (6), n represents an integer of 2 or more. R represents a compound having a cyclic structure having 1 to 20 carbon atoms or a branched alkyl group, and these may include a bond such as sulfide, ether, sulfone, ester, or ketone in the group. ]

(6) In the method for producing the epoxy compound represented by the formula, the preferred epihalohydrin compound is epichlorohydrin. The epihalohydrin compound is stoichiometrically used in the number of moles corresponding to the number of mercapto groups in the mercaptan compound of the formula (5). However, if importance is attached to the purity of the product, the reaction rate, economic efficiency, etc. However, larger amounts can be used. Preferably, the reaction is carried out using stoichiometric to 5 times the stoichiometric mole. More preferably, the reaction is carried out using stoichiometric to 2.5 times the stoichiometric mole. The reaction may be carried out without a solvent or in a solvent. When a solvent is used, epihalohydrin or a mercaptan compound of the formula (5) or a metal salt of a mercaptan compound which is soluble in the solvent may be used. desirable. Specific examples include water, alcohols, ethers, aromatic hydrocarbons, halogenated hydrocarbons, and the like. The reaction proceeds easily in the presence of a stoichiometric or more base. Examples of the base include tertiary amines such as pyridine, triethylamine and diazabicycloundecene, and hydroxides of alkali or alkaline earth metals, and preferred are hydroxides of alkali or alkaline earth metals. Yes, more preferred are sodium hydroxide, potassium hydroxide and the like. The reaction is usually carried out at a temperature of 0 to 100 ° C, preferably 0 to 60 ° C. The reaction time may be any time as long as the reaction is completed under the above-mentioned various conditions, but is usually preferably 10 hours or less.

(6) In the method for producing a novel episulfide compound of the present invention from the epoxy compound represented by the formula, when a thiocyanate is used as a thiocyanating agent, a preferable thiocyanate is a salt of an alkali or alkaline earth metal. And more preferred are potassium thiocyanate and sodium thiocyanate. Also, thiocyanates and thioureas, which are thiocyanating agents, stoichiometrically use the number of moles corresponding to the number of epoxy groups in the epoxy compound, but it is important to focus on the purity of the product, the reaction rate, economy, etc. However, less or more may be used. Preferably, the reaction is carried out using stoichiometric to 5 times the stoichiometric mole. More preferably, the reaction is carried out using a stoichiometric amount to 2.5 times the stoichiometric amount. The reaction may be carried out without a solvent or in a solvent. When a solvent is used, it is preferable to use one in which a thiocyanate or a thiourea or an epoxy compound of the formula (6) is soluble. . Specific examples include alcohols such as water, 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, and chlorobenzene; and the like, and their combined use, for example, combinations of alcohols and water, ethers, hydroxyethers, halogenated hydrocarbons, Combinations of aromatic hydrocarbons and alcohols may be effective. Addition of 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, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid , Maleic acid, benzoic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride , Phthalic anhydride, silica gel, silica alumina, aluminum chloride, etc., and some of them can be used in combination. The addition amount is usually used in the range of 0.001 to 10% by weight based on the total amount of the reaction solution, but is preferably 0.01 to 1% by weight. The reaction is usually carried out at a temperature of 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 is suitably 20 hours or less. The stability of the obtained compound 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, succinic acid, and maleic acid. These may be used alone or in combination of two or more. Aqueous solutions of these acids usually work below pH 6, but a more effective range is between pH 3 and 0.

As another production method, an unsaturated compound of the formula (7) corresponding to the epoxy compound of the formula (6) is produced by oxidation with an organic peracid, alkyl hydroperoxide, hydrogen peroxide or the like. There is also a method for producing an episulfide compound having two or more structures represented by the formula (1) by the method. R (-SCH2CH = CH2) n (7) [In the formula (7), X represents a chlorine or bromine atom, and R and n have the same meaning as in the formula (5)]

Further, as another method, production from a halomercaptan compound represented by the formula (8) by a dehydrohalogenation reaction is also an effective method. It is known that halomercaptans can be easily synthesized from the above-mentioned unsaturated compounds and sulfur chlorides (for example, F. Lautenschlagerger et al., J. Org. Chem., 34 , 396 (1969)). R (-SCH2CHSHCH2X) n (8) [In the formula (8), X represents a chlorine or bromine atom, and R and n have the same meaning as in the formula (5)]

The novel episulfide compound of the present invention can be heated and polymerized in the presence or absence of a curing catalyst to produce a cured resin advantageous for optical materials and the like. A preferred method for producing a cured resin is a method using a curing catalyst. As the curing catalyst, amines, phosphines, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid and the like are used. Specific examples include (1) ethylamine, n-propylthioamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, and 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) ) Primary monoamines such as propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine and furfurylamine; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-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- or p-phenyl Diamine, 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'-diaminodiphenylether, 4,4'-thiodianiline, 4,4'-diaminodiphenylsulfone, 4,4'- Diaminoditolyl sulfone, methylenebis (o-chloroaniline), 3,9-bis (3-aminoprop ) 2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylene Hexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diamino Primary polyamines such as phenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octylamine, Di (2 -Ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2,4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N- Secondary monoamines such as 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- Secondary polyamines such as (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- (4-piperidyl) butane, tetramethylguanidine; Tylamine, 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, tridodecylamine, trilaurylamine, tricyclohexylamine, dicyclohexyl Ethylamine, monocyclohexyldiethylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, triethanolamine, N, N-di Tylethanolamine, N-ethyldiethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, -(N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy)- Tertiary monoamines such as 4-methyl-1,3,2-dioxabornane; tetramethylethylenediamine, pyrazine, N, N′-dimethylpiperazine, N, N′-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine , N, N, N ', N'-tetra Methyl-1,3-butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethyl Tertiary polyamines such as aminomethyl) 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 N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis- Various imidazoles such as (2-ethyl-4-methylimidazolyl) methane, adducts of alkylimidazole and isocyanuric acid, and condensates of alkylimidazole and formaldehyde; 1,8-diazabicyclo (5,4,0) undecene-7 Amidines such as 1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; amine compounds represented by the above . (2) Quaternary ammonium salts of the amines of (1) with halogens, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid and the like. (3) A complex of the amines of (1) with borane and boron trifluoride. (4) trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine Fin, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, tris (4-methylphenyl) phosphine, dimethylphenyl Phosphins such as phosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, and chlorodiphenylphosphine . (5) Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid and half esters thereof. (6) Lewis acids represented by boron trifluoride etherate of boron trifluoride. (7) Organic acids represented by carboxylic acids and their half esters. And so on. Among these, preferred are those with less coloring of the cured product, such as primary monoamines, secondary monoamines, tertiary monoamines, tertiary polyamines, imidazoles, amidines, quaternary ammonium salts, and phosphines. , Tertiary monoamines, tertiary polyamines, imidazoles, amidines, quaternary ammonium salts, and phosphines having at most one group that can react with an episulfide group. These may be used alone or in combination of two or more. The above curing catalyst is usually used in an amount of 0.0001 mol to 1.0 mol per 1 mol of the diepisulfide compound.

In addition, the novel 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 other homopolymerizable functional groups. An optical material can also be produced by curing and polymerizing with a compound having one functional group capable of reacting with an episulfide group and capable of being homopolymerized. 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, mercapto alcohols, mercapto alcohols Phenol, polyphenol, amines, amides and the like can be mentioned. On the other hand, compounds having at least one functional group capable of reacting with an episulfide group and at least one other functional group capable of being homopolymerized include epoxy having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl, and allyl. Examples include compounds, episulfide compounds, carboxylic acids, carboxylic anhydrides, mercaptocarboxylic acids, mercaptans, phenols, amines, amides and the like.

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

Specific examples of epoxy compounds include hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, and condensation of epihalohydrin with a polyhydric phenol compound such as a novolak resin. Phenolic epoxy compounds produced; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol , Neopentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythri Litol, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, etc. Alcohol-based epoxy compounds produced by condensation of a polyhydric alcohol compound and epihalohydrin; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid Polyvalent carboxylic acid compounds such as, hetonic acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalenedicarboxylic acid, and diphenyldicarboxylic acid Glycidyl ester-based epoxy compound produced by the condensation of ethylene and epihalohydrin; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane , 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy ) Ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4 -Bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1, 4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine , M- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2-bis (4,4 ' Primary diamines such as -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-methyl Piperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) -methane, 1,2-di- (4-piperidyl) -ethane, 1,3-di Amine-based epoxy compounds produced by condensation of a secondary diamine such as (4-piperidyl) -propane, 1,4-di- (4-piperidyl) -butane and epihalohydrin; 3,4-epoxycyclohexylmethyl-3,4 -Epoxycyclohexanecarboxylate, vinylcyclohexanedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) adipate Epoxy compounds produced by epoxidation of unsaturated compounds such as cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, and vinylcyclohexene epoxide; the above-mentioned polyhydric alcohols, phenol compounds and diisocyanate Urethane-based epoxy compounds produced from bets and glycidol and the like.

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

Specific examples of polycarboxylic acids, polycarboxylic anhydrides, polyphenols, amines, and the like include those mentioned above as the raw materials to be reacted with epihalohydrin described in the above epoxy compound.

Specific examples of the polymercaptan include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, and bis (2-mercaptoethyl) sulfide Linear dimercaptan compounds such as 1,1,2- [bis (2-mercaptoethylthio)] ethane; 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane , 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis [(2-mercaptoethylthio)]-3-mercaptopropane, 1,1,1-tris (mercaptomethyl) Branched aliphatic polymercaptan compounds such as propane and tetrakismercaptomethylmethane; ethylene glycol dithioglycolate , Ethylene glycol dithiopropionate, 1,4-butanediol dithioglycolate, 1,4-butanediol dithiopropionate, trimethylolpropane tris (β-thioglycolate), trimethylolpropane tris (β-thiopro Ester-containing aliphatic polymercaptan compounds such as pionate), pentaerythritol tetrakis (β-thioglycolate), pentaerythritol tetrakis, (β-thiopropionate); 1,4-dimercaptocyclohexane, 1,3-di Mercaptocyclohexane, 1,4-dimercaptomethylcyclohexane, 1,3-dimercaptomethylcyclohexane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptoethyl-1,4-dithiane, , 5-dimercaptomethy And aliphatic cyclic dimercaptan compounds such as ru-1-thiane and 2,5-dimercaptoethyl-1-thiane. Specific examples of mercapto alcohol include 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-propanol, 4-mercapto-1-butanol, 3-mercapto-2-butanol, and 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, mercaptomethyltris (hydroxymethyl) methane, bis (mercaptomethyl) bis (hydroxymethyl) methane, tris (mercaptomethyl) hydroxymethylmethane, 2- (2- Mercaptoethylthio) ethanol And the like can be given. Specific examples of mercaptophenol include 4-mercaptophenol, 2-mercaptohydroquinone, 4-hydroxy-4, -mercaptobiphenyl and the like. Specific examples of mercaptocarboxylic acid include thioglycolic acid, 2-thiopropionic acid, 3-thiopropionic acid, thiolactic acid, mercaptosuccinic acid, thiomalic acid, N- (2-mercaptopropionyl) glycine, 2-mercaptobenzoic acid , 2-mercaptonicotinic acid, 3,3-dithioisomeric acid and the like.

In addition, representative specific examples of compounds having at least one functional group capable of reacting with an episulfide group and at least one other functional group capable of being homopolymerized 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. As the episulfide compound having an unsaturated group, a compound obtained by episulfide-forming an epoxy group of the epoxy compound having an unsaturated group described above, for example, vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, Ali And luthioglycidyl 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 amide having an unsaturated group include amides of the above α, β-unsaturated carboxylic acids.

Preferred specific examples of the compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization include 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, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether and 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-mentioned monocarboxylic acid and thioglycidol (1,2-epithio-3-hydroxypropane) Thioglycidyl ethers (1,2-epithiopropyloxymethane), ethylthioglycidyl ether, propylthioglycidyl ether, butylthioglycidyl ether, etc. It is possible to increase the ethers. Among these, a compound having one episulfide group is more preferable.

A compound having two or more functional groups capable of reacting with an episulfide group of the novel aliphatic cyclic episulfide compound of the present invention, or a compound having one or more of these functional groups and one or more other homopolymerizable functional groups, Is a compound having one functional group capable of reacting with an episulfide group and capable of being homopolymerized, and can be cured and polymerized in the presence of a curing polymerization catalyst to produce a cured resin. As the curing catalyst, the above-mentioned amines, phosphines, acids and the like are used. As specific examples, those described above are also used here.

Further, when a compound having an unsaturated group is used, it is preferable to use a radical polymerization initiator as a polymerization accelerator. The radical polymerization initiator is not particularly limited as long as it generates a radical by heating or ultraviolet light or an electron beam. For example, cumyl peroxy neodecanoate, diisopropyl peroxy dicarbonate, diallyl peroxy dicarbonate, di-n- Propyl peroxy dicarbonate, dimyristyl peroxy dicarbonate, cumyl peroxy neohexanoate, ter-hexyl peroxy neodecanoate, ter-butyl peroxy neodecanoate, ter-hexyl peroxy neodecanoate Peroxides such as tert-butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide; cumene hydroperoxide Hydroperoxides such as side and tert-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-tox-2,4-dimethyl-valeronitrile 2,2′-azobis (2 -Methylpropane), a known thermal polymerization catalyst such as an azo compound such as 2,2′-azobis (2,4,4-trimethylpentane), benzophenone, Known photopolymerization catalysts such zone in benzoin methyl ether. Of these, preferred are peroxides, hydroperoxides and azo compounds, more preferred are peroxides and azo compounds, and most preferred are 2,2′-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) Azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2'-azobis (2-methylpropane) 2,2 ' Azobis, azo compounds such as (2,4,4-trimethylpentane). These can all be mixed and used. Although the amount of the radical polymerization initiator varies depending on the components of the composition and the curing method, it cannot be generally determined, but is usually 0.01 wt% to 5.0 wt%, preferably 0 wt%, relative to the total amount of the composition. 0.1 wt% to 2.0 wt%.

In addition, when the novel aliphatic cyclic episulfide compound of the present invention is polymerized and cured to obtain a cured resin, known additives such as an antioxidant and an ultraviolet absorber are added to further improve the practicality of the obtained material. Is of course possible. It is also possible to use or add known external and / or internal release agents to improve the releasability of the resulting cured material from the mold. The term "internal release agent" as used herein means a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, a phosphoric ester, an acidic phosphate, an oxyalkylene-type acidic phosphate, or an alkali of an acidic phosphate. Metal salts, alkali metal salts of oxyalkylene type acidic phosphates, metal salts of higher fatty acids, higher fatty acid esters, paraffins, waxes, higher fatty amides, higher fatty alcohols, polysiloxanes, aliphatic amine ethylene oxide adducts, etc. Is raised.

When polymerizing and curing the novel aliphatic cyclic episulfide compound of the present invention to obtain a cured resin, the raw material, the episulfide compound and, if desired, the above-mentioned curing catalyst, capable of reacting with an episulfide group having an unsaturated group, for example, When using glycidyl methacrylate, thioglycidyl methacrylate (episulfide of glycidyl methacrylate), a radical polymerization initiator, a radically polymerizable monomer, a mold release agent, an antioxidant, an ultraviolet absorber After the addition of the additives, the composition is polymerized and cured in the following manner to obtain an optical material such as a lens. That is, the raw material after mixing is poured into a glass or metal mold, the polymerization and curing reaction is advanced by heating, and then the mold is removed from the mold. The curing time is from 0.1 to 100 hours, usually from 1 to 48 hours, and the curing temperature is from -10 to 160C, usually from -10 to 140C. After the curing is completed, annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the distortion of the optical material of the present invention. Further, if necessary, a surface treatment such as hard coating, antireflection, imparting anti-fogging property can be performed. 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 injection-hardened into a mold. The die raw material is a main raw material and two or more functional groups capable of reacting with an episulfide group used as desired. Or a compound having at least one of these functional groups and at least one other functional group capable of homopolymerization, a compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization, and further desirably. Depending on the curing catalyst, radical polymerization initiator, further mold release agent, stabilizer, etc., all may be mixed under stirring simultaneously in the same container, or each material may be added and mixed stepwise. After several components are separately mixed, they may be mixed again in the same container. Upon mixing, the set temperature, the time required for the mixing, etc. may be basically any conditions under which each component is sufficiently mixed, but an excessive temperature and time may cause an undesired reaction between each raw material and additive, Further, it is not appropriate because the viscosity increases and the casting operation becomes difficult. The mixing temperature should be in the range of about -10 ° C to 100 ° C, the preferred temperature range is -10 ° C to 50 ° C, more preferably -5 ° C to 30 ° C. The mixing time is 1 minute to 5 hours, preferably 5 minutes to 2 hours, more preferably 5 minutes to 30 minutes, and most preferably about 5 minutes to 15 minutes. Performing a degassing operation under reduced pressure before, during or after mixing of the raw materials and additives is a preferable method from the viewpoint of preventing the formation of bubbles during the subsequent casting and curing. At this time, the degree of pressure reduction is from about 0.1 mmHg to 700 mmHg, preferably from 10 mmHg to 300 mmHg. Further, it is preferable to remove impurities and the like by filtering them with a micro filter or the like at the time of injection into the mold from the viewpoint of further improving the quality of the optical material of the present invention.

The novel episulfide compound of the present invention has made it possible to obtain a resin optical material having a sufficiently high refractive index and a good balance between the refractive index and the Abbe number, which were difficult as long as the compound of the prior art was used as a raw material. That is, the novel compound of the present invention has made remarkable progress in reducing the weight, thickness, and reducing chromatic aberration of the resin optical material. Further, the novel cured resin material of the present invention has excellent heat resistance and strength and can be used for various applications.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In addition, the performance of the obtained polymer was measured by the following measurement 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: A sample having a Vicat softening point of 120 ° C. or higher was rated as ○, a sample having a Vicat softening point of less than 120 ° C. and 80 ° C. or higher was rated △, and a sample having a Vicat softening point lower than 80 ° C. was rated X. Strength: In a three-point bending test measurement using an autograph, those with a strain of 0.1 or more were rated as ○, those with less than 0.1 and 0.05 or more as Δ, and those with less than 0.05 as x.

Example 1
170.3 g of 1,4-bis (mercaptomethyl) benzene and 185.1 g of epichlorohydrin were cooled to 10 ° C., and an aqueous solution obtained by dissolving 0.4 g of an aqueous sodium hydroxide solution in 4 ml of water and 40 ml of methanol were added. For 1 hour. Thereafter, an aqueous solution in which 80.0 g of sodium hydroxide was dissolved in 80 ml of water was added dropwise while maintaining the liquid temperature at about 0 to 10 ° C, and the mixture was stirred at this temperature for 3 hours. 200 ml of water was added to the reaction mixture, extracted with 300 ml of toluene, the toluene layer was dried over sodium sulfate, the solvent was distilled off, and 275.8 g of 1,4-bis (glycidylthiomethyl) benzene as a colorless and transparent liquid (theoretical). 97% of the amount). Next, 142.2 g of 1,4-bis (glycidylthiomethyl) benzene, 304.2 g of thiourea, 11.3 g of acetic anhydride, and 1 L of toluene as a solvent were placed in a flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube. 1 L of methanol was charged and 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 the excess solvent was distilled off to obtain 141.5 g of a product. The product was found to be 1,4-bis (β-epithiopropylthiomethyl) benzene from elemental analysis, mass analysis, NMR analysis and IR analysis (yield 90%).
Elemental analysis value : (Analysis value) (Calculated value)
C 53.30% 53.46%
H 5.91% 5.77%
S 40.50% 40.78%
Mass spectrum (EI): M @ + 314 (theoretical molecular weight: 314)
Infrared absorption spectrum : 620 cm -1 (stretching vibration of episulfide ring)
1 H-NMR : 7.2 ppm (t, 1H) 7.0 ppm (m, 3H) 3.6 ppm (m, 2H) 3.1 ppm (m, 2H) 3.0 ppm (m, 2H) 2.7 ppm (m , 2H) 2.6 ppm (m, 2H) 2.2 ppm (m, 2H) Further, 100 parts by weight of the present compound was mixed with 0.5 part by weight of N, N-diethylethanolamine, and this was added to a thickness of 2 mm. The mixture was poured into a mold composed of two adjusted glass plates 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 2
Example 1 was repeated, except that 1,4-bis (mercaptomethyl) cyclohexane was used instead of 1,4-bis (mercaptomethyl) benzene. Thiopropylthiomethyl) cyclohexane was obtained in a total yield of 80%.
Elemental analysis value : (Analysis value) (Calculated value)
C 52.34% 52.45%
H 7.66% 7.55%
S 39.90% 40.01%
Mass spectrum (EI): M + · 320 (theoretical molecular weight: 320)
Infrared absorption spectrum : 620 cm -1 (stretching vibration of episulfide ring)
1 H-NMR : 3.2-2.9 ppm (m, 10H) 2.7 ppm (m, 2H) 2.6 ppm (m, 2H) 2.2 ppm (m, 2H) 3.0 ppm (m, 2H) 1 0.9 to 0.9 ppm (m, 8H) 2.6 ppm (m, 2H) 2.2 ppm (m, 2H)

Example 3 (Z = H, U = H, m = 1, n = 0 in the formula (2)) In Example 1, instead of 1,4-bis (mercaptomethyl) benzene, 2,5-bis ( Example 1 was repeated except that mercaptomethyl) -1,4-dithiane was used to obtain 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane in a total yield of 82%. .
Elemental analysis value : (Analysis value) (Calculated value)
C 40.33% 40.41%
H 5.77% 5.65%
S 53.79% 53.94%
Mass spectrum (EI): M + · 356 (theoretical molecular weight: 356)
Infrared absorption spectrum : 620 cm -1 (stretching vibration of episulfide ring)
1 H-NMR : 3.2-2.9 ppm (m, 14H) 2.7 ppm (m, 2H) 2.6 ppm (m, 2H) 2.2 ppm (m, 2H) The refractive index, Abbe number and specific gravity were measured, and the results are shown in Table 1.

Example 4 (Z = H, U = H, m = 2, n = 0 in the formula (2)) In Example 1, 2,5-bis (mercaptoethyl) was used instead of 1,4-bis (mercaptomethyl) benzene. ) Example 1 was repeated except that -1,4-dithiane was used, and 2,5-bis (β-epithiopropylthioethyl) -1,4-dithiane was obtained in a total yield of 85%.
Elemental analysis value : (Analysis value) (Calculated value)
C 43.55% 43.71%
H 6.39% 6.29%
S 49.81% 50.01%
Mass spectrum (EI): M @ + .384 (theoretical molecular weight: 384)
Infrared absorption spectrum : 620 cm-1 (stretching vibration of episulfide ring)
1 H-NMR : 3.2-2.9 ppm (m, 14H) 2.7 ppm (m, 2H) 2.6 ppm (m, 2H) 2.2 ppm (m, 2H) 2.0 ppm (m, 4H) After 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 (Z = H, U = H, m = 1, n = 1 in the formula (2)) In Example 1, 2,5-bis (mercaptoethyl) was used instead of 1,4-bis (mercaptomethyl) benzene. Example 1 was repeated except that thiomethyl) -1,4-dithiane was used to obtain 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane in a total yield of 87%. Was.
Elemental analysis value : (Analysis value) (Calculated value)
C 40.19% 40.29%
H 6.05% 5.92%
S 43.70% 53.79%
Mass spectrum (EI): M@+.476 (theoretical molecular weight: 476)
Infrared absorption spectrum : 620 cm -1 (stretching vibration of episulfide ring)
1 H-NMR : 3.2-2.8 ppm (m, 22H) 2.7 ppm (m, 2H) 2.6 ppm (m, 2H) 2.2 ppm (m, 2H) The refractive index, Abbe number and specific gravity were measured, and the results are shown in Table 1.

Example 6 (in the formula (2), Z = CH2SEps, U = H, m = 1, n = 0) In Example 1, instead of 1,4-bis (mercaptomethyl) benzene, 2,3,5,6- Example 1 was repeated except that tetrakis (mercaptomethyl) -1,4-dithiane was used to obtain 2,3,5,6-tetrakis (β-epithiopropylthiomethyl) -1,4-dithiane in total yield. Obtained at 82%.
Elemental analysis value : (Analysis value) (Calculated value)
C 40.39% 40.50%
H 5.55% 5.44%
S 53.99% 54.06%
Mass spectrum (EI): M + .592 (theoretical molecular weight 592)
Infrared absorption spectrum : 620 cm -1 (stretching vibration of episulfide ring)
1 H-NMR : 3.3-2.9 ppm (m, 20H) 2.7 ppm (m, 4H) 2.6 ppm (m, 4H) 2.2 ppm (m, 4H) The refractive index, Abbe number and specific gravity were measured, and the results are shown in Table 1.

Example 7 Example 1 was repeated except that 2- (2-mercaptoethylthio) -1,3-dimercaptopropane was used in place of 1,4-bis (mercaptomethyl) benzene. (2-β-epithiopropylthio) propane was obtained in a total yield of 85%. Elemental analysis value : (Analysis value) (Calculated value)
C 45.15% 40.34%
H 5.99% 5.80%
S 53.69% 53.85%
Mass spectrum (EI): M + · 416 (theoretical molecular weight: 416)
Infrared absorption spectrum : 620 cm -1 (stretching vibration of episulfide ring) 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 Example 1 was repeated except that 2,5-bis (hydroxymethyl) -1,4-dioxane was used instead of 1,4-bis (mercaptomethyl) benzene. -Bis (β-epithiopropyloxymethyl) -1,4-dioxane was obtained in a total yield of 52%. After the 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 1 was repeated except that 2,5-bis (hydroxyethyloxymethyl) -1,4-dioxane was used in place of 1,4-bis (mercaptomethyl) benzene. , 5-Bis (β-epithiopropyloxyethyloxymethyl) -1,4-dioxane was obtained in a total yield of 55%. After the 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 1 was repeated, except that 50 g of thiourea was used for 162.3 g of 1,4-bis (glycidylthiomethyl) benzene. From the NMR spectrum, the obtained product has Z = H, U = H, m = 1, and n = 0 in the formula (1), and the number of S in X in the formula (2) forms a three-membered ring. The average was 30% of the total of S and O. After the 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 4 Dibutyltin chloride was used as a curing catalyst in a mixture of 48 parts by weight of 1,8-dimercapto-4-mercaptomethyl-3,6-dithiaoctane and 52 parts by weight of metaxylylene diisocyanate in an amount of 0.1 part by weight based on 100 parts by weight of the mixture. After blending, the mixture was made a homogeneous liquid, and further degassed sufficiently under a reduced pressure of 10 mmHg. Then, after pouring into the mold, polymerization curing was performed at 80 ° C. for 20 hours in an oven. The refractive index, Abbe number and specific gravity of the obtained material were measured, and the results are shown in Table 1.

Claims (7)

(1) A composition having two or more structures represented by the formula and containing at least one or more episulfide compounds having a cyclic skeleton (excluding the compound represented by the following formula (γ)).

(In the formula, 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.)

The composition according to claim 1, wherein the cyclic skeleton is an alicyclic skeleton. The composition according to claim 1, wherein the cyclic skeleton is an aromatic skeleton. The composition according to claim 1, wherein the cyclic skeleton is a heterocyclic skeleton having a sulfur atom as a different atom. A cured resin obtained by polymerizing and curing the composition according to claim 1. An optical material obtained by polymerizing and curing the composition according to claim 1. A method for producing an optical material by polymerizing and curing the composition according to claim 1.