JP2006257421A - 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 polymerizing it into a hardend article. <P>SOLUTION: The compound has two or more units of the structure represented by formula (1) and the optical material is obtained by polymerizing the compound, wherein X is S or O, and the number of S is of 50% or more, on the average, relative to the total number of S and O constituting three-membered rings. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

In recent years, plastic materials have been widely used in various optical materials, particularly spectacle lenses, because they are lightweight, tough and easy to dye. Early typical plastic materials in the prior art were obtained by polymerizing compounds such as diethylene glycol bisallyl carbonate, the bisallyl carbonate and diallyl phthalate, and various methacrylates. These have a refractive index of about 1.5 to 1.55, and thus the thickness of the lens is increased, resulting in a loss of lightness. For this reason, a material having a high refractive index is desired, and various efforts have been made so far to increase the refractive index to 1.6 or more. A polymer of a methacrylate compound containing chloro and bromo atoms, and a thermosetting optical material having a urethane structure obtained by the reaction of a hydroxy compound containing bromo atoms and an isocyanate compound (Japanese Patent Laid-Open No. 58-164615, etc.) have been proposed. Has been. However, when a compound containing chloro and bromo atoms is used, the specific gravity increases, and in this case as well, the lightness is impaired. For this reason, thermosetting optical materials having a thiourethane structure obtained by a reaction between a polythiol compound and a polyisocyanate compound have been proposed in Japanese Patent Publication Nos. 4-58489 and 5-148340.

Various novel polythiol compounds that serve as raw materials for these thiourethanes have also been proposed. That is, JP-A-5-148340 discloses a branched polythiol compound having 4 sulfur atoms in one molecule, and JP-A-2-270859 discloses a branched polythiol compound having 5 sulfur atoms in one molecule. However, JP-A-6-192250 proposes a polythiol compound having a dithiane ring structure in the molecule. Furthermore, the epoxy group of epoxy compounds such as known amine epoxy resins, phenolic epoxy resins, alcoholic epoxy resins, unsaturated compound epoxy resins, glycidyl ester epoxy resins, urethane epoxy resins, alicyclic epoxy resins, etc. JP-A-3-81320 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. A thiourethane resin lens obtained from a polythiol compound and a polyisocyanate compound has a refractive index of about 1.66 at the maximum. However, an episulfide resin lens obtained from an episulfide compound derived from a known epoxy resin has a refractive index of about 1.6. In any case, these conventional sulfur-containing compounds have solved the problem of thinner wall thickness and weight reduction to some extent, but it goes without saying that a higher refractive index is desirable. On the other hand, there is little chromatic aberration as another important performance required for optical materials. Since the chromatic aberration becomes better as the Abbe number becomes higher, a high Abbe number material 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 as the refractive index increases, and conventional diethylene glycol bisallyl carbonate and known episulfide compounds, as well as plastics made from known compounds such as polythiol compounds and polyisocyanate compounds as raw materials In the case of materials, the Abbe number was about 50 to 55 when the refractive index was 1.5 to 1.55, the limit was about 40 when the refractive index was 1.60, and about 32 when the refractive index was 1.66. On the other hand, various attempts have been made to improve heat resistance by using polyfunctional compounds and crosslinking agents. However, in general, in order to develop a high refractive index, the molecular weight of the raw material sulfur compound becomes large, and thus the crosslinking density decreases. In addition, in order to further increase the Abbe number, the alkyl group content is increased, and therefore the rigidity of the molecules constituting the raw material compound is lowered, and as a result, sufficient heat resistance improvement is not obtained. Currently.

The problem to be solved by the present invention is to find an optical material having a thin wall thickness, low chromatic aberration and high heat resistance at the same time. In optical materials typified by polythiol compounds obtained by conventional techniques and cured resins obtained by isocyanate compounds, there is a limit to increasing the refractive index. Furthermore, increasing the refractive index reduces the Abbe's number. The improvement in characteristics caused a decrease in heat resistance, and for this reason, there were three points that a sufficiently high balance between refractive index and Abbe number could not be obtained.

The object of the present invention has been solved by an episulfide compound and a branched alkyl sulfide type episulfide compound having two or more structures represented by the formula (1) and having a cyclic skeleton.

The novel episulfide compound of the present invention enables a resin optical material having a sufficiently high refractive index, which is difficult as long as a conventional compound is used as a raw material, and a good balance between the refractive index and the Abbe number. That is, the novel compound of the present invention has made significant progress in reducing the weight and thickness of resin optical materials and reducing chromatic aberration. Moreover, the novel cured resin material of the present invention is excellent in heat resistance and strength and can be used for various applications.

(1) The 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 heteroatom. Furthermore, these compounds may contain bonds such as sulfide, ether, sulfine, ketone, ester and the like in the molecule.

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

Preferable 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 etc. can be mentioned.

Preferable specific examples of the episulfide compound having an aromatic skeleton of (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.

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

(Where Eps represents an epithiopropyl group represented by formula (4), Y represents — (CH 2 CH 2 S) —, Z represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH 2) 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 total of S and O constituting the three-membered ring.) In the formula (3), n is from 0 It 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%, More preferably, it is 90 to 100%, and particularly preferably 95 to 100%. Most preferably, it is 100%. When n is larger than 4, the heat resistance of the optical material obtained by polymerization and curing is lowered and the optical material cannot be used. Further, even when n is 4 or less, it is advantageous that the heat resistance is small, and the larger is advantageous from the viewpoint of the flexibility of the material. When m is 4 or 5, the sulfur content is lowered, a high refractive index is not achieved, and the heat resistance of the material is further lowered. 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 total of S and O constituting the three-membered ring, especially 50% or less, the sulfur content decreases and the high refractive index is high. This is not achieved, and since the polymerization under high temperature conditions is required as the reactivity of the compound decreases, the material is colored. The performance of the compound of the present invention and the optical material obtained by polymerizing and curing the compound is determined by the integers n and m and the ratio of S in X as described above. However, preferred specific examples include the integers n and m. Is not independently determined within the above range. Preferable examples include compounds where n = 0 to 3 and m = 1 to 4. Among these, more preferred examples include compounds in the range of n = 0-2 and m = 1-3. Among these, the most preferred examples include compounds where n = 0 and m = 1. U may be either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, but in order to keep the refractive index high, Z is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. -(CH2) mSYnEps may be used, but from the viewpoint of high heat resistance,-(CH2) mSYnEps is preferable because the crosslink density is high. Most preferred.

Among these, some specific examples are actually shown below as examples. 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 and the like can be mentioned.

Preferable specific examples of the branched alkyl sulfide type episulfide compound include 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) propane, 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.

If the object of the present invention is met, the cured resin optical material of the present invention can be any one of (a), (b), (c), a branched alkyl sulfide type episulfide compound, or a mixture copolymerized and cured thereof. It does not matter if it is

〔（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。〕 The episulfide compound and branched alkyl sulfide type episulfide compound having two or more structures represented by the formula (1) and having a cyclic skeleton used in the present invention are (a), (b), (c), The compound of the formula (5) having two or more mercapto groups corresponding to the branched alkyl sulfide type episulfide compound is reacted with an epihalohydrin typified by epichlorohydrin in the presence of an alkali, and is represented by the formula (6) A compound having an epoxy group is obtained, and then the epoxy compound is mixed with a thiocyanating agent such as thiocyanate, thiourea, triphenylphosphine sulfide, 3-methylbenzothiazol-2-thione, preferably thiocyanate, thio Produced by reaction with urea.

[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 and a branched alkyl group, and these may contain a bond such as sulfide, ether, sulfone, ester, ketone and the like. ]

In the process for producing an epoxy compound represented by the formula (6), a preferable epihalohydrin compound is epichlorohydrin. In addition, the epihalohydrin compound stoichiometrically uses the number of moles corresponding to the number of mercapto groups in the mercaptan compound of formula (5), but if the importance of product purity, reaction rate, economy, etc. is emphasized, it is less than this. But you can use more than this. Preferably, the reaction is carried out using 5 times mole of stoichiometric to stoichiometric. More preferably, the reaction is carried out using a molar amount of 2.5 times the molar amount. The reaction may be either without solvent or in a solvent, but when a solvent is used, an epihalohydrin, a mercaptan compound of formula (5), or a metal salt of a mercaptan compound 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 more than stoichiometric base. Examples of the base include tertiary amines such as pyridine, triethylamine, and diazabicycloundecene, and alkali or alkaline earth metal hydroxides. Preferred are alkali or alkaline earth metal hydroxides. More preferred are sodium hydroxide, potassium hydroxide and the like. Although reaction temperature is normally implemented at 0-100 degreeC, Preferably it is 0-60 degreeC. 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 appropriate.

(6) In the method for producing the novel episulfide compound of the present invention from the epoxy compound represented by the formula, when thiocyanate is used as the thiating agent, preferred thiocyanate is an alkali or alkaline earth metal salt. More preferred are potassium thiocyanate and sodium thiocyanate. In addition, thiocyanate and thiourea, which are thiocyanating agents, use the number of moles corresponding to the number of epoxy groups of the epoxy compound in terms of quantity, but may place importance on the purity, reaction rate, economy, etc. of the product. For example, a smaller amount or a larger amount may be used. Preferably, the reaction is carried out using 5 times mole of stoichiometric to stoichiometric. More preferably, the reaction is carried out using a molar amount of 2.5 times the molar amount. The reaction may be in the absence of a solvent or in a solvent. However, when a solvent is used, it is desirable to use a thiocyanate or thiourea, or a compound in which either of the epoxy compounds of 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, chlorobenzene, etc., and combinations thereof, such as combinations of alcohols and water, ethers, hydroxy ethers, halogenated hydrocarbons, Combinations of aromatic hydrocarbons and alcohols may be effective. Moreover, adding an acid, an acid anhydride, or the like as a polymerization inhibitor to the reaction solution is an effective means for 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, succinic acid, tartaric acid, propionic acid, butyric acid, succinic acid , Maleic acid, benzoic acid, anhydrous nitric acid, 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 and the like, and some of them can be used in combination. The amount added is usually in the range of 0.001 to 10 wt% with respect to the total amount of the reaction solution, but preferably 0.01 to 1 wt%. The reaction temperature is usually 0-100 ° C., preferably 20-70 ° C. The reaction time may be a time for completing the reaction under the various conditions described above, but usually 20 hours or less is appropriate. The reaction product can improve the stability of the resulting compound by washing with an acidic aqueous solution. Specific examples of the acid used for 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, succinic acid, tartaric acid, succinic acid, maleic acid and the like. These may be used alone or in combination of two or more. These acid aqueous solutions are usually effective at a pH of 6 or less, but a more effective range is a pH of 3 to 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, an alkyl hydroperoxide, hydrogen peroxide, etc. The method of manufacturing the episulfide compound which has 2 or more of structures represented by Formula (1) by a method is also mentioned. 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, it is also effective to produce the halomercaptan compound represented by the formula (8) by dehydrohalogenation reaction. It is known that halomercaptan can be easily synthesized from the above-mentioned unsaturated compounds and sulfur chlorides (for example, F. Lautenschlager 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 polymerized by heating in the presence or absence of a curing catalyst to produce a cured resin that is advantageous for optical materials and the like. A preferable method for producing the cured resin is a method using a curing catalyst, and amines, phosphine, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid and the like are used as the curing catalyst. Specific examples include (1) ethylamine, n-propylthioamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine. , Laurylamine, mystyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) ) Primary monoamines such as propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine, 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-feni 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'-diaminodiphenyl ether, 4,4'-thiodianiline, 4,4'-diaminodiphenyl sulfone, 4,4'- Diaminoditolyl sulfone, methylene bis (o-chloroaniline), 3,9-bis (3-aminopropy ) 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, 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 Tilethanolamine, N-ethyldiethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2 -(N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy)- 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-butaneamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethyl) (Aminomethyl) tertiary polyamines such as 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 alkyl imidazole and isocyanuric acid, condensates of alkyl imidazole 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 above . (2) A quaternary ammonium salt of the amine of (1) and a halogen, mineral acid, Lewis acid, organic acid, silicic acid, tetrafluoroboric acid or the like. (3) A complex of the amine of (1) with borane and boron trifluoride. (4) Trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine Fins, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, tris (4-methylphenyl) phosphine, dimethylphenyl Phosphine such as phosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, chlorodiphenylphosphine . (5) Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, and half esters thereof. (6) Lewis acids typified by boron trifluoride and boron trifluoride etherate. (7) Organic acids represented by carboxylic acid and half-esters thereof. Etc. Among these, preferred are those with little coloration of the cured product, such as primary monoamine, secondary monoamine, tertiary monoamine, tertiary polyamine, imidazoles, amidines, quaternary ammonium salts, and phosphine, and more preferable ones. And secondary monoamines, tertiary monoamines, tertiary polyamines, imidazoles, amidines, quaternary ammonium salts and phosphine having 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 used in an amount of 0.0001 mol to 1.0 mol with respect to 1 mol of the diepisulfide compound.

Further, 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 functional groups capable of homopolymerization. An optical material can also be produced by curing polymerization with a compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization. The 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, mercaptoalcohols, mercaptos. Examples thereof include phenol, polyphenol, amines, amides and the like. On the other hand, as a compound having one or more functional groups capable of reacting with an episulfide group and one or more other functional groups capable of homopolymerization, an epoxy having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl or allyl. Examples thereof include compounds, episulfide compounds, carboxylic acids, carboxylic anhydrides, mercaptocarboxylic acids, mercaptans, phenols, amines, amides and the like.

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

Specific examples of epoxy compounds include condensation of polyhalogen compounds such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, novolac resin and epihalohydrin. Phenol-based epoxy compound produced; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol , Neopentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythritol Lititol, 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 monohydric alcohol compounds and epihalohydrins; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid , Polycarboxylic acid compounds such as heptic acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid Glycidyl ester epoxy compound produced by condensation of phenoxy 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'-diaminodiphenyl ether, 2,2-bis (4,4 ' -Primary diamine 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 secondary diamines such as (4-piperidyl) -propane, 1,4-di- (4-piperidyl) -butane and epihalohydrins; 3,4-epoxycyclohexylmethyl-3,4 -Epoxycyclohexanecarboxylate, vinylcyclohexanedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) adipate Cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, epoxy compound produced by epoxidation of unsaturated compound such as vinylcyclohexene epoxide; polyhydric alcohol, phenol compound and diisocyanate described above Urethane-based epoxy compounds produced from bets and glycidol and the like.

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

Specific examples of the polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyphenol, amines, and the like can include those described above as the starting materials for the reaction with the epihalohydrin described in the above-mentioned 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 1,2- [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) Pionate), ester-containing aliphatic polymercaptan compounds such as 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, 2 , 5-Dimercaptomethi And aliphatic cyclic dimercaptan compounds such as ru-1-thian and 2,5-dimercaptoethyl-1-thian. 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-dithioisobutyric acid and the like.

The following are typical examples of compounds having one or more functional groups capable of reacting with episulfide groups and one or more other functional groups capable of homopolymerization. Examples of the epoxy compound having an unsaturated group include vinyl phenyl glycidyl ether, vinyl benzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether. As the episulfide compound having an unsaturated group, a compound obtained by episulfiding an epoxy group of the epoxy compound having the above unsaturated group, for example, vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, 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 amides having an unsaturated group include amides of the above α, β-unsaturated carboxylic acids.

A preferred example of a compound having one functional group capable of reacting with an 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, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl Glycidyl ethers such as ethers, monoepisulfide compounds such as ethylene sulfide and propylene sulfide, and thioglycidyl esters having a structure derived from the above monocarboxylic acid and thioglycidol (1,2-epithio-3-hydroxypropane) Thioglycidyl such as methylthioglycidyl ether (1,2-epithiopropyloxymethane), ethylthioglycidyl ether, propylthioglycidyl ether, butylthioglycidyl ether 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 the 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, The compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization can be cured and polymerized in the presence of a curing polymerization catalyst to produce a cured resin. As the curing catalyst, the aforementioned amines, phosphines, acids and the like are used. As a specific example, the above-mentioned ones are also used here.

Furthermore, when using a compound having an unsaturated group, it is a preferable method to use a radical polymerization initiator as a polymerization accelerator. The radical polymerization initiator is not particularly limited as long as it generates radicals by heating or ultraviolet rays or electron beams. For example, cumyl peroxyneodecanoate, diisopropyl peroxydicarbonate, diallyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, dimyristyl peroxydicarbonate, cumyl peroxyneohexanoate, ter-hexylperoxyneodecanoate, ter-butylperoxyneodecanoate, ter-hexylperoxyneohexanoate , Ter-butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, dicumyl peroxide, di-ter-butyl peroxide, and the like; cumene hydropero Hydroperoxides such as side 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-toxi-2,4-dimethyl-valeronitrile 2, 2′-azobis (2 -Methylpropane), 2,2′-azobis (2,4,4-trimethylpentane) and other known thermal polymerization catalysts such as azo compounds, benzophenone, Known photopolymerization catalysts such zone in benzoin methyl ether. Among these, peroxides, hydroperoxides, and azo compounds are preferable, peroxides and azo compounds are more preferable, and 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 used in combination. The blending amount of the radical polymerization initiator varies depending on the components of the composition and the curing method, and thus cannot be determined at a glance, but is usually 0.01 wt% to 5.0 wt%, preferably 0 with respect to the total amount of the composition. The range is from 1 wt% to 2.0 wt%.

In addition, when a novel aliphatic cyclic episulfide compound of the present invention is polymerized and cured to obtain a cured resin, additives such as known antioxidants and ultraviolet absorbers are added to further improve the practicality of the resulting material. Of course it is possible. It is also possible to use or add a known external and / or internal mold release agent to improve the mold release properties of the resulting cured material from the mold. The internal mold release agent mentioned here is a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, a phosphate ester, an acidic phosphate ester, an oxyalkylene-type acidic phosphate ester, an alkali of an acidic phosphate ester. Metal salts, alkali metal salts of oxyalkylene acid phosphates, higher fatty acid metal salts, higher fatty acid esters, paraffins, waxes, higher aliphatic amides, higher aliphatic alcohols, polysiloxanes, aliphatic amine ethylene oxide adducts, etc. Can be given.

When the novel aliphatic cyclic episulfide compound of the present invention is polymerized and cured to obtain a cured resin, it is possible to react with the episulfide compound as a raw material, and further with the above-described curing catalyst and episulfide group having an unsaturated group, if desired. When used in combination with glycidyl methacrylate, thioglycidyl methacrylate (an episulfide-modified glycidyl methacrylate epoxy group), radical polymerization initiator, radical polymerizable monomer, mold release agent, antioxidant, UV absorber After mixing additives such as the above, it is polymerized and cured as follows to obtain an optical material such as a lens. That is, the mixed raw material is poured into a glass or metal mold, the polymerization curing reaction is advanced by heating, and then the mold is removed from the mold. The curing time is 0.1 to 100 hours, usually 1 to 48 hours, and the curing temperature is −10 to 160 ° C., usually −10 to 140 ° C. In addition, 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. Furthermore, surface treatments such as hard coating, antireflection and imparting antifogging properties can be performed as necessary. The manufacturing method of the cured resin optical material of the present invention is as follows in more detail. As described above, the main raw material and auxiliary raw material are mixed and then injected and cured into a mold. The main raw material is a diepisulfide compound and two or more functional groups capable of reacting with an episulfide group used as desired. A compound having one or more of these functional groups and one or more other homopolymerizable functional groups, a compound having one functional group capable of reacting with an episulfide group and capable of homopolymerization, and further as desired. Depending on the curing catalyst, radical polymerization initiator, mold release agent, stabilizer, etc. used depending on the situation, they may be mixed in the same container at the same time under stirring, or each raw material may be added and mixed in stages. Alternatively, several components may be mixed separately and then remixed in the same container. In mixing, the set temperature, the time required for this, etc., basically need only be the conditions that each component is sufficiently mixed, but the excessive temperature, time is an undesirable reaction between each raw material and additive, Furthermore, the viscosity is increased, making the casting operation 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, and 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 the degassing operation under reduced pressure before, during or after mixing the raw materials and additives is a preferable method from the viewpoint of preventing the generation of bubbles during the subsequent cast polymerization curing. The degree of decompression at this time is about 0.1 mmHg to 700 mmHg, and preferably 10 mmHg to 300 mmHg. Furthermore, it is preferable to remove impurities and the like by filtering with a microfilter or the like when injecting 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 enables a resin optical material having a sufficiently high refractive index, which is difficult as long as a conventional compound is used as a raw material, and a good balance between the refractive index and the Abbe number. That is, the novel compound of the present invention has made significant progress in reducing the weight and thickness of resin optical materials and reducing chromatic aberration. Moreover, the novel cured resin material of the present invention is excellent in heat resistance and strength and can be used for various applications.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the performance measurement of the obtained polymer was performed 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: ◯ when the Vicat softening point is 120 ° C. or higher, Δ when less than 120 ° C. and 80 ° C. or more, and × when less than 80 ° C. Strength: In a three-point bending test measurement using an autograph, a strain of 0.1 or more was evaluated as ◯, a strain of less than 0.1 and 0.05 or more was evaluated as Δ, and a strain of less than 0.05 was evaluated as ×.

Example 1
A solution temperature of 170.3 g of 1,4-bis (mercaptomethyl) benzene and 185.1 g of epichlorohydrin was cooled to 10 ° C., and an aqueous solution of 0.4 g of aqueous sodium hydroxide dissolved in 4 ml of water and 40 ml of methanol were added. For 1 hour. Thereafter, an aqueous solution obtained by dissolving 80.0 g of sodium hydroxide in 80 ml of water was dropped while keeping the liquid temperature around 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 (theoretical) of 1,4-bis (glycidylthiomethyl) benzene as a colorless transparent liquid. 97% of the amount) obtained. Next, a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 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. 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 1% aqueous sulfuric acid solution, washed with water, and then the excess solvent was distilled off to obtain 141.5 g of a product. Elemental analysis, mass spectrometry, NMR analysis, and IR analysis revealed that the product was 1,4-bis (β-epithiopropylthiomethyl) benzene (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, 0.5 parts by weight of N, N-diethylethanolamine is added to 100 parts by weight of the present compound, and this is 2 mm thick. It 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)
In Example 1, Example 1 was repeated except that 1,4-bis (mercaptomethyl) cyclohexane was used instead of 1,4-bis (mercaptomethyl) benzene, and 2,5-bis (β-epi Thiopropylthiomethyl) cyclohexane was obtained with 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 .9 to 0.9 ppm (m, 8H) 2.6 ppm (m, 2H) 2.2 ppm (m, 2H)

(Example 3)
(In formula (2), Z = H, U = H, m = 1, n = 0) In Example 1, instead of 1,4-bis (mercaptomethyl) benzene, 2,5-bis (mercaptomethyl) Example 1 was repeated except that -1,4-dithiane was used, and 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane was obtained 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
(In formula (2), Z = H, U = H, m = 2, n = 0) In Example 1, 2,5-bis (mercaptoethyl) -1 instead of 1,4-bis (mercaptomethyl) benzene Example 1 was repeated except that 2,4-dithiane was used to obtain 2,5-bis (β-epithiopropylthioethyl) -1,4-dithiane 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) polymerization 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)
(In formula (2), Z = H, U = H, m = 1, n = 1) In Example 1, 2,5-bis (mercaptoethylthiomethyl) instead of 1,4-bis (mercaptomethyl) benzene Example 1 was repeated except that -1,4-dithiane was used, and 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane was obtained in a total yield of 87%.
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 formula (2), Z = CH2SEps, U = H, m = 1, n = 0) In Example 1, 2,3,5,6-tetrakis (mercapto) instead of 1,4-bis (mercaptomethyl) benzene Example 1 was repeated except that methyl) -1,4-dithiane was used, and 2,3,5,6-tetrakis (β-epithiopropylthiomethyl) -1,4-dithiane was obtained in a total yield of 82%. Obtained.
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 instead of 1,4-bis (mercaptomethyl) benzene in Example 1, and 2- (2- β-epithiopropylthio) propane was obtained with 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)
In Example 1, Example 1 was repeated except that 2,5-bis (hydroxymethyl) -1,4-dioxane was used instead of 1,4-bis (mercaptomethyl) benzene, and 2,5-bis ( β-epithiopropyloxymethyl) -1,4-dioxane was obtained with a total yield of 52%. 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)
In Example 1, Example 1 was repeated except that 2,5-bis (hydroxyethyloxymethyl) -1,4-dioxane was used in place of 1,4-bis (mercaptomethyl) benzene. Bis (β-epithiopropyloxyethyloxymethyl) -1,4-dioxane was obtained in a total yield of 55%. 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)
In Example 1, Example 1 was repeated except that 50 grams of thiourea was used per 162.3 grams of 1,4-bis (glycidylthiomethyl) benzene. The obtained product is Z = H, U = H, m = 1, n = 0 in the formula (1) from the NMR spectrum, and the number of S in X in the formula (2) constitutes a three-membered ring. It was 30% on the average with respect to the sum of S and O. 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 4)
After blending 0.1 part by weight of dibutyltin chloride as a curing catalyst with a mixture of 48 parts by weight of 1,8-dimercapto-4-mercaptomethyl-3,6-dithiaoctane and 52 parts by weight of metaxylylene diisocyanate Then, the mixture was uniformly degassed under a reduced pressure of 10 mmHg. Then, after pouring into the mold, it was cured by polymerization in an oven at 80 ° C. for 20 hours. 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 at least one episulfide compound (excluding a compound represented by the following formula (α)) having at least two structures represented by the formula and having a cyclic skeleton.

(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 heteroatom. 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.