KR20150014418A - Preparation method of polythiol compounds by ring open and the polythiol compounds, and the resin composition for optical material using it - Google Patents

Abstract

The present invention relates to a polythiol compound, a method for preparing the polythiol compound, and a resin composition for a urethane-based optical material using the polythiol compound and, in particular, to a polythiol compound in which a chain is extended through ring-opening by adding a compound having terminal thiol group to a cyclic episulfide or thietane compound, a method for preparing the same, and a resin composition for an optical material using the polythiol compound. The optical material obtained using the polythiol compound (chemical formula 1) developed in the present invention enhances refractive index, has excellent heat resistance and reactivity, and can thus be used for optics related products including lens such as glasses lens and camera lens, prism, an optical pipe, an optical disk, a magnetic disk, a recording medium system, a colored filter, an infrared absorber filter, and other plastic processed products.

Description

Chain extended polythiol compound by ring opening, a process for producing the same, and a resin composition for a urethane-based optical material using the same, and a resin composition for a urethane-

TECHNICAL FIELD The present invention relates to a polythiol compound, a method for producing the same, and a resin composition for a urethane-based optical material using the same. More particularly, the present invention relates to a polythiol compound having a chain extending through a ring opening by adding a compound having a terminal thiol group to a cyclic episulfide or thianthene compound. Thiol compound, a process for producing the same, and a resin composition for an optical material using the same.

The plastic optical resin is lighter and easier to break than an optical material made of an inorganic material, and can be dyed. In recent years, various optical resin plastic materials have been applied to optical materials, and their required physical properties are increasing day by day. Specifically, properties such as high refractive index, high impact and high tensile strength have been required. In accordance with such a demand, various kinds of resins for optical materials have been developed and used so far.

Among them, the polyurethane-based resin is particularly strong against impacts, and has excellent extreme workability, and has recently been in the limelight, and proposals have been made actively. In Korean Patent Laid-Open Publication No. 10-1990-0009576, epichlorohydrin is reacted with 2-mercaptoethanol while cooling, thiourea and inorganic acid are added thereto, reacted under refluxing conditions, and then hydrolyzed with a base to obtain a mercapto compound (Thiol compound) is obtained. The thiol provided in most of the thiourethane-based optical materials does not propose a specific method of extending the chain or increasing the viscosity, and the optical lens is manufactured with a resin composition for an optical material obtained by mixing a commonly used aliphatic isocyanate compound and a thiol compound , The reaction rate is slow, which causes the adhesive on the back side of the tape to elute and cause whitening. Also, Korean Patent Laid-Open Publication No. 10-1996-0041233 discloses that a polythiol compound having four or more functional groups is mixed with an unsaturated or epoxy group or an isocyanate group to be used in an optical material. However, unsaturated compounds meet with a radical catalyst, There is a problem that does not happen. Korean Patent Publication No. 10-0241989 proposes a method in which a polyisocyanate compound is reacted with a polyisocyanate compound so that the -SH / -NCO molar ratio is in the range of 3 to 7 beforehand, but in this case, The reaction has been caused to cause polymerization imbalance due to the difference in reactivity of the mixtures.

The present inventors have also attempted to solve this problem in Korean Patent Application No. 10-2010-0038562 by preparing a polymerizable composition by increasing the -SH / -NCO molar ratio by 7 or more, but it has not been able to completely solve the polymerization imbalance in optical lens production. That is, it has been attempted to solve the problem of tape whitening, which is a problem of the prior art, by partially pre-polymerizing isocyanate to the polythiol compound to increase the viscosity. However, the prepolymer that has been polymerized in advance has not helped to improve the refractive index, and polymerization imbalance or dye imbalance .

Accordingly, the present invention provides a novel polythiol compound chain extended by ring opening and a method for producing the same by developing a chain extending method of a polythiol compound capable of controlling refractive index, heat resistance, impact resistance, Abbe number or viscosity, do. In the present invention, it is also possible to use the polythiol compound thus obtained to improve the viscosity of the resin composition for an optical material without deteriorating the compatibility with isocyanate, thereby reducing the solubility of the resin composition for optical materials, To provide a resin composition.

A resin composition for an optical material using an aliphatic isocyanate and a low molecular weight (molecular weight: 300 or less) thiol compound as it is as a resin composition for a thiourethane-based optical material conventionally has good solubility and low viscosity and reactivity, There has been a problem of bleaching phenomenon and bubble generation. In the present invention, a novel polythiol compound chain-extended by ring-opening is prepared, and resin compositions for optical materials obtained by using the polythiol compounds are successfully used to solve problems of whitening or bubble generation in optical lens production. In addition, a novel polythiol compound capable of controlling refractive index, heat resistance, impact resistance, Abbe number, viscosity, and the like has been developed and applied to a resin composition for optical materials to obtain an improved optical lens resin.

In the present invention,

There is provided a process for producing a polythiol compound represented by the following Reaction Scheme 1, characterized by reacting a cyclic episulfide or a thiotanic compound with a compound having a terminal thiol group in the presence of a catalyst or a catalyst, / RTI >

[Reaction Scheme 1]

Wherein X and Y are an episulfide group or a thieno group which is at least one or more,

R and Z each independently represents a linear or branched alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, an alkylaryl group; Or an alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, or an alkylaryl group, which contains at least one oxygen atom or sulfur atom,

p is an integer of 0 to 4 and q is an integer of 1 to 4, and when p is 1, it is sulfide or disulfide,

n is an integer from 2 to 20;

Further, in the present invention, there is provided a chain extended polythiol compound represented by the following general formula (1), obtained by the above production method.

Wherein Z represents an independent linear or branched alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, an alkylaryl group; Or an alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, or an alkylaryl group, which contains at least one oxygen atom or sulfur atom,

q is an integer from 1 to 4,

n is an integer from 2 to 20;

Further, in the present invention, a resin composition for an optical material comprising the polythiol compound of the formula (1) is provided. The resin composition for an optical material of the present invention may further comprise an isocyanate compound or a thioisocyanate compound.

Further, in the present invention, there is provided an optical product comprising a resin for an optical material obtained by curing the resin composition for an optical material and a resin for the optical material. The optical product includes a spectacle lens, a 3D polarizing lens, a polarizing lens, a prism film, an optical fiber, an optical disk, a magnetic disk, a recording medium substrate, a coloring filter, and an ultraviolet absorbing filter.

In the resin composition for optical materials using the novel polythiol compound (I) extended by chain opening by the ring-opening of the present invention, the whitening phenomenon did not appear at the edge of the lens due to the dissolution of the pressure- In addition, since the viscosity is maintained, the problem of the air bubble at the edge of the lens due to the leakage does not appear. The optical material obtained by using the polythiol compound (formula (1)) developed by the present invention can increase the refractive index, is excellent in heat resistance and reactivity, and can be used as a lens such as a spectacle lens or a camera lens, a prism, a light pipe, , A recording medium engine, a color filter, an infrared absorption filter, and other plastic processed products.

The present inventors have found that, in order to apply a conventional technique and to produce a resin composition for optical materials of superior quality, the inventors of the present invention have found that by ring-opening a cyclic episulfide or thiotane compound with a compound having a terminal thiol group, By controlling the molecular weight and adjusting the viscosity, we tried to solve the problem of whitening, bubble problem and polymerization imbalance, which are frequently occurred in optical lens manufacturing while minimizing the whitening phenomenon. The polythiol compound is fairly stable at room temperature, but the episulfide compound or the thiazane compound is self-cured by heat, and when kept at a low temperature (below 10 ° C) for a long period of time, self-curing occurs and polymerized. Such a solution was able to produce a polythiol compound whose molecular weight and viscosity could be controlled while the substance was stable, by producing a polythiol compound by chain extension by ring opening of an episulfide compound or a thiazane compound. In addition, the molecular weight can be controlled by adjusting the ratio of cyclic episulfide, thietane compound and thiol group (SH), and chain extension through ring opening can be controlled by temperature. The polythiol compound thus prepared can be mixed with an aliphatic isocyanate compound and can be applied to a resin composition for an optical material, and polymerization imbalance does not occur during production of an optical lens, and heat resistance and whitening can be controlled.

The present invention relates to a process for producing a polythiol compound by chain extension by ring-opening reaction with a compound having a terminal thiol group (including hydrogen sulfide) to a cyclic episulfide or thiazane compound (component I) .

[Reaction Scheme 1]

Wherein X and Y are an episulfide group or a thieno group which is at least one or more,

R and Z each independently represents a linear or branched alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, an alkylaryl group; Or an alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, or an alkylaryl group, which contains at least one oxygen atom or sulfur atom,

p is an integer of 0 to 4 and q is an integer of 1 to 4, and when p is 1, it is sulfide or disulfide,

n is an integer from 2 to 20;

Preferably, the compound having a terminal thiol group (including hydrogen sulfide) and the cyclic episulfide compound are reacted at a molar ratio ((-SH) / (episulfide group, or thienane group)) at a ratio of 0.5 to 20 to extend the chain. When the molar ratio of thiol ((-SH) / (episulfide group or thienane group)) is 0.5 or less, the self-reaction of the episulfide or thiazane compound increases to increase the molecular weight and increase the viscosity of the resin composition for optical material Making manufacture difficult. Further, when the molar ratio ((-SH) / (episulfide group, or thienane group)) is 20 or more, the starting material of the thiol compound remains large and the effect of extending the chain is reduced. The preferred molar ratio ((-SH) / (episulfide group, or thietane group)) is 1.0-10.

In the production of the polythiol compound (formula (1)) in which hydrogen sulfide is added and the episulfide compound is extended by ring-opening, the reaction temperature should be 10 ° C or lower to cause the cyclic ring to be gradually extended, The molar ratio of the sulfide groups is not critical. However, in this reaction, when the temperature is 30 ° C or higher, the episulfide itself reacts to form an oligomer thiol compound or a polymer.

Further, in the production of the polythiol compound (formula (1)), the reaction temperature and the role of the catalyst are important when the chain is extended by ring-opening. The reaction is accelerated at a temperature of 30 ° C or higher, so that episulfide or thiotane itself becomes highly polymerized, and the same problem may occur even when the amount of catalyst used is large. The temperature required for the reaction is suitably 30 ° C or lower, and after at least 90% conversion, the reaction is completed by aging at 60 ° C for 2 hours.

Also, the catalyst used in the production of the polythiol compound (Formula 1) is advantageous in that it is a basic catalyst, and is useful as an alkali (alkali hydroxide or alkaline earth metal), an amine (including amines having a heterocyclic ring), an organic acid and its salt, But the present invention is not limited thereto, and examples thereof include, but are not limited to, a mineral acid, a Lewis acid, a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt, a phosphine, The amount of the catalyst to be used is preferably 0.0001 to 10%, more preferably 0.01 to 5%, and even more preferably 0.1 to 3% based on the amount of thiol used.

The compound having a terminal thiol group may be hydrogen sulfide, methanedithiol, ethanedithiol, 1,2-ethanedithiol; 1,1-propanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 2,2-propanedithiol; 2,5-hexanedithiol; 1,6-hexanedithiol; 2,9-decanedithiol; 1,4-bis (1-mercaptoethyl) benzene; Cyclohexanedithiol; 1,2,3-propanetriethiol; 1,1-bis (mercaptomethylcyclohexane); 1,2-dimercapto propyl methyl ether; 2,3-dimercapto propyl methyl ether; 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Bis (2-mercaptoethyl) ether; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; Bis (2,3-dimercaptopropanel) sulfide; Bis (2,3-dimercaptopropanel) disulfide; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 1,2-bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) ethane; Bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide; 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio-propane-1-thiol; 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester; Ethylthio) propane-1-thiol (2-mercaptoethylthio) -3- (2- (2- [ ; Trimethylolpropane tris (mercaptopropionate); Trimethylolethane tris (mercaptopropionate); Glycerol tris (mercaptopropionate); Trimethylolchlorotris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate); Trimethylol ethane tris (mercaptoacetate); Pentaerythritol tetrakis (mercaptopropionate) (PETMP); Pentaerythritol tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether-hexakis (mercaptopropionate) (BPEHMP); Bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA); Bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); Bistrimethylolpropane tetrakis (3-mercaptopropionate) (BTMPMP); Bistrimethylolpropane tetrakis (2-mercaptoacetate) (BTMPMA) and the like may be used alone or in combination. These thiol compounds can also be added to the polythiol compound (formula (1)) to be included in the resin composition for an optical material of the present invention.

The episulfide compound used as a chain extender may be at least one selected from the group consisting of bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis ) Methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,4- (3-epithiopropylthioethyl) sulfide, 2,5-bis (? -epithiopropylthiomethyl) -1,4- -Bis [(2-β-epithiopropylthioethyl) thio] 3- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthio) Propyl thiomethyl) methane, 1,1,1-tris (beta -epithiopropylthiomethyl) propane, 1,1,1-tris (b-epithiopropyloxymethyl) Propyloxymethyl) methane, 1,1,1- Bis (β-epithiopropyloxymethyl) propane, 1,5-bis) β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) -3-thiapentane, -Epithiopropyloxy) -2,2-bis (? - epithiopropyloxy) -2,4-bis (? - epithiopropyloxymethyl) Methyl) -4-thiohexane, 1,5,6-tris (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl-thiohexane, 1,8- Oxy) -4 - (? - epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (? - epithiopropyloxy) -4,5-bis (? - epithiopropyloxymethyl ) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,4-bis (β-epithiopropyloxymethyl) Bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) 2,5-bis (? - epithiopropyltri Oxymethyl) -3,6-dithiaoctane, 1,9-bis ((β-epithiopropyloxy) -5- (b-epithiopropyloxymethyl) -5 - [(2- 1,3- and 1,4-bis (? - epithiopropyloxy) cyclohexane, 1,3- and 1,4-bis (? - epithiopropyloxy Methyl) cyclohexane, bis [(4- (beta -epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (beta -epithiopropyloxy) cyclohexyl] propane, bis [4- (Epithiopropyloxycyclohexyl) sulfide, 2,5-bis (? -Epithiopropyloxymethyl) -1,4-dithiane, 1,3- and 1,4- Oxy) benzene, and 1,4- (beta -epithiopropyloxymethyl) benzene may be used singly or in combination of two or more.

The thianthene compound used as the chain extender may be at least one selected from the group consisting of 3- (mercaptomethylthio) thietane, 3- (1-mercaptopropyl-3-thio) thietane, 3- 3- (mercaptoethylthioethylthio) thietane, 3- (mercaptoethylthioethylthio) thiotane, 3- (mercaptoethylthioethylthio) (3-mercapto-2-hydroxypropyl-1-thio) thietane, 3- (2-mercaptomethylthiourethane, (2-mercaptomethyl-1,4-diethan-5-methylthio) thietane, 3- (1-mercaptocyclohexan-2-thio) thiotane , 3- (1-mercaptocyclohexane-2-thio) thiotane, 3- (1-mercaptocyclohexane- , 3- (1-mercaptobenzene-2-methylthio) thiotane, 3- (1-mercaptobenzene- , 3- (1-mercaptomethylbenzene-3-methylthio) thiotane, 3- (2,3-epoxypropylthio) thiotane, 3- (2,3-epoxypropylthio) thiotane, 3- (2-ethylhexylthio) 3- (2,3-epoxypropylthioethylthio) thiotane, 3- (2,3-epoxypropylthioethylthio) thiotane, 3- 3- (2,3-epithiopropylthio) thiotane, 3- (2,3-epithiopropylthio) thietane, 3- (2,3-epithiopropylthio) 3- (2,3-epithiopropylthioethylthio) thietane, 3- (2,3-epithiopropylthiopropylthio) thietane, 3- (2,3-epithiopropylthioethylthio) 3- (2,3-epithiopropylthiomethylthiomethylthio) thietane, 3- (2,3-epithiopropylthioethylthioethylthio) thietane, 3- (2,3- 3-epithiopropylthiohydroxypropylthio) thietane, 3- [2- (2,3-epithiopropylthio) methylthiophene-5-methylthio] thietane, 3- off 3- (1- (2, 3-epithiopropylthio) methyl-1,4-dithiane-5-methylthio] thiotane, 3- [ (2,3-epithiopropylthio) cyclohexane-2-thio] thiotane, 3- [1- (2,3- (2,3-epithiopropylthio) benzene-2-thia] thiotane, 3- [1- (2,3- 3- (1- (2,3-epithiopropylthio) methylbenzene-2-methylthio] thiotane, 3- [ Methylthio] thiotane, 3- [1- (2,30 epithiopropylthio) methylbenzene-4-methylthio] thiotane, etc., May be used.

The chain extended polythiol compound of the present invention obtained by the above-mentioned method can be represented by the above formula (1). The chain extended polythiol compound of the present invention can be produced, for example, by reacting 1- (2-mercaptoethylthio) -3- [2-mercapto-3- (2- Propanol-2-thiol, 2- [2- (2-mercaptoethylthio) propane- (2-mercapto-3- [2- (2-mercapto-1-mercaptomethylethylthio) ethylthio] propylthio} propylthio) ethylthio] -Dithiol, 2- [2- (2-mercapto-3- {2-mercapto-3- [2- (2-mercapto- 1- mercaptomethylethylthio) ethylthio] propyldithio} propyl 3- [3- (3- {3- [3- (2,3-dimercaptopropylthio) -2-mercaptopropylthio] -2- Mercaptopropylthio} -2-mercaptopropylthio] propane-1,2-dithiol, 3- [3- (3- {3- [3- Mercaptopropylthio) -2-mercaptopropylthio] -2-mercaptopropyldithio} -2-mercap Propylthio] propane-1,2-dithiol, 3- [3- (3- {3- [3- (2,3- dimercaptopropylthio) -2-mercapto Propylthio] -2-mercaptopropylthio} -2-mercaptopropylthio) -2-mercaptopropylthio] propane-1,2-dithiol, 3- [3- (3- {3- [ - (2,3-dimercaptopropyldithio) -2-mercaptopropylthio] -2-mercaptopropyldithio} -2-mercaptopropylthio) -2-mercaptopropyldithio] , 2-dithiol, 3- [3- (3- {3- [3- (2,3-dimercaptopropyldithio) -2-mercaptopropylthio] -2-mercaptopropyldithio} 2- (2-mercaptopropylthio) -2-mercaptopropyldithio] propane-1,2-dithiol, 2- Ethylthio} propylthio} ethylthio} propane-1-thiol, 2- (2-mercaptoethylthio) propylthio] Mercaptoethylthio) -3- {2- [2-mercapto-3- (2-mercapto-3- {2- [3-mercapto- (4S, 8R, 24S, 28S) -4,8,24,28-tetrakis (2-mercaptoethylthio) propylthio] ethylthio} (Mercaptomethyl) -3,6,9,12,16,20,23,26,29-nona-aihectriene triacontan-1,14,18,31 -titratiol, (4S, 11R, 27S, 34S) -4,11,27,34-tetrakis (mercaptomethyl) -3,6,9,12,15,19,23,26,29,32,35-undecatrihectatauracontan-1, (4S, 8R, 20R, 24S) -8,20-bis ((2-mercaptoethyl) thio) -4,24- bis (mercaptomethyl) (4S, 8R, 21R, 25) -8,21-bis ((2-mercaptoethyl) -1,2,3,4-tetrahydronaphthalene- Thio) -4,25-bis (mercaptomethyl) -3,6,10,14,15,19,23,26-octadioxoic acid-1,12,17,28-tetrathiol Lt; / RTI >

The present invention provides a resin for an optical material comprising a chain extended polythiol compound of the present invention. The resin for the optical material may further comprise an isocyanate compound or an isothiocyanate compound. Examples of the isocyanate compound or isothiocyanate compound include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene- Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-iso Aliphatic polyisocyanate compounds such as cyanate methyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanate methyl ester and lysine triisocyanate; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylenediisocyanate, isopropylphenylenediisocyanate , Xylylene diisocyanate, tolylene-2,4-diisocyanate, diethylphenylenediisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, Diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatoethyl) -bis (isocyanatoethyl) isocyanurate, Benzene, bis (isocyanatopropyl) benzene,?,? ',?' - tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) Phthalic, bis (isocyanatomethyl phenyl) ether, bis (isocyanato ethyl) phthalate, 2,6-polyisocyanate compounds having an aromatic ring compound such as (isocyanatomethyl) furan; (Isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1 , 2,2,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,9-bis (isocyanatomethyl) tricyclo [ , 1,2,2,6] decane, 2,5 - bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) bicyclo [ ] Heptane, (Isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, Bis (4-isocyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3- isocyanatopropyl) Isocyanatomethylbicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [ , Isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl- - (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2- isocyanatomethyl-3- -6- (2-iso (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3- isocyanatopropyl) -6- Cyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) 1] -heptane, 2-isocyanatomethyl-2- (3- isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] , Polyisocyanate compounds having an alicyclic compound such as 3,5-tris (isocyanatomethyl) -cyclohexane, dicyclohexylmethane-4,4-diisocyanate (H ₁₂ MDI); Thiophene-2,5-diisocyanate, methylthiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, methyl 1,4- Diisocyanate, methyl 1,3-dithiolane-4,5-diisocyanate, methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate, ethyl 1 , 3-dithiolane-2,2-diisocyanate, tetrahydrothiophene-2,5-diisocyanate, methyltetrahydrothiophene-2,5-diisocyanate, ethyltetrahydrothiophene-2,5-diisocyanate , Methyltetrahydrothiophene-3,4-diisocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, Heterocyclic diisocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenedisothiocyanate, and cyclohexane diisothiocyanate; Bis (isocyanatoethyl) sulfide, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) Bis (isocyanatomethyl) disulfide, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) Methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl- Tris (isocyanatomethylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptane tetraisocyanate, 2 , 6-diisocyanatomethyl-3,5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanatomethylthiophene, 4-iso Sulfur-containing aliphatic polyisocyanate compounds such as isocyanato ethyl thio-2,6-thiazole-1,8-octane diisocyanate; Aromatic sulfide-based polyesters such as 2-isocyanatophenyl-4-isocyanatophenylsulfide, bis (4-isocyanatophenyl) sulfide and bis (4-isocyanatomethylphenyl) Isocyanate compounds; Bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis Bis (4-methoxy-3-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide and bis Isocyanate compounds; 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato- Dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanato Methyl) 1,3-dithiolane, 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane, and other sulfur-containing alicyclic polyisocyanate compounds; Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane and 1,6-diisothiocyanatohexane; Alicyclic polyisothiocyanate compounds such as cyclohexane diisothiocyanate; 1,2-diisothiocyanato benzene, 1,3-diisothiocyanato benzene, 1,4-diisothiocyanato benzene, 2,4-diisothiocyanato toluene, 2, 4-methylenebis (phenylisothiocyanate), 4,4-methylenebis (2-methylphenylisothiocyanate), 4,4-methylenebis 3-methylphenyl isothiocyanate), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyanato-3,3-dimethylbenzophenone, bis (4-isothiocyanato Phenyl) ether; aromatic polyisothiocyanate compounds such as benzoic acid; Carbonyl polyesters such as 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate and (2,2-pyridine) -4,4-dicarbonyldiisothiocyanate; Isothiocyanate compounds; Sulfur-containing aliphatic polyisothiocyanate compounds such as thiobis (3-isothiocyanato propane), thiobis (2-isothiocyanatoethane), and dithiobis (2-isothiocyanatoethane); 4-isothiocyanato-4 - [(2-isothiocyanato) thio] benzene, thiobis (4-isothiocyanatobenzene), sulphonyl (4-isothiocyanatobenzene) Sulfur-containing aromatic polyisothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene); Sulfur-containing alicyclic polyisothiocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-diisothiocyanato-1,4-dithiane; Isothiocyanatohexane, 1-isocyanato-4-isothiocyanatohexane, 4-isocyanato-4-isothiocyanatohexane, -Isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-iso A compound having an isothiocyanato group such as an isothiocyanato group, an isothiocyanato group, an isothiocyanato group, an isothiocyanato group, an isothiocyanato group, an isothiocyanato group, an isothiocyanato group, Can be used alone or in combination of two or more.

 The resin composition for an optical material of the present invention may contain an epoxy compound, a thioepoxy compound, a thiotane compound, an iso (thio) cyanate compound, a compound having a vinyl group or an unsaturated group (including an acrylic or an aryl group) . ≪ / RTI >

In order to improve the optical properties of the resin composition for an optical material of the present invention, it is also possible to use a thiol compound having a mercapto group (-SH) which can be used in combination with a polythiol compound (formula (I)), a thiol compound having an isocyanate compound or isothiocyanate An additive which can be used in combination with a nitrate compound can be included. The additives include in particular ultraviolet absorbers, stabilizers (heat stabilizers, light stabilizers), internal mold release agents, color correctors, polymerization initiators, antioxidants and the like. Specifically, examples of the ultraviolet absorber include benzophenone, benzotriazole, salicylate, cyanoacrylate, oxanilide and the like; The stabilizer (heat stabilizer) includes a metal fatty acid salt, phosphorus, lead, and organic solvent; The internal blowing agents include fluorine-based nonionic surfactants, silicone-based nonionic surfactants, alkyl quaternary ammonium salts, acidic phosphate esters, and the like; The polymerization initiator may be an amine type, an organosilicate type, or the like; Examples of the color correcting agent include pigments and dyes, pigments include organic pigments and inorganic pigments, and dyes include anthraquinone-based disperse dyes; Antioxidants include phenolic, amine, phosphorous, thioester, and the like. Among them, in order to improve the characteristics of the optical lens, one kind or a mixture of two or more kinds can be used.

 In the present invention, an optical material comprising a polyurethane resin is produced by casting polymerization. Specifically, various additives and a catalyst are dissolved in an isocyanate compound, and then a polythiol compound (Formula 1) or a thiol compound capable of being mixed therewith is added, followed by vacuum defoaming while cooling. After a suitable period of time, it is poured into a glass mold molded with a tape, and cured by gradually heating at a low temperature and a high temperature for about 24 to 48 hours.

Further, in the present invention, the optical material obtained by using the polythiol compound (formula (1)) can be improved in antireflection, hardness, abrasion resistance, chemical resistance, Physical and chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, nonreflective coat treatment, dyeing treatment and dimming treatment can be performed for the purpose.

[Example]

Hereinafter, the present invention will be described in detail with reference to specific examples. However, these embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these embodiments.

[ Synthesis Example 1 ]

BESGST Manufacturing

A thermometer and a condenser were attached to a 2 L four-necked flask, and 2 mol (521.06 g) of GST (2,3-bis (2-mercaptoethylthio) propane-1-thiol) 1 mole (178.34 g) of triphenylphosphine was added, and 6 g of triphenylphosphine was added thereto as a catalyst. The mixture was kept at 20 캜 for 8 hours while preventing the exothermic reaction. After raising the refractive index to 1.65, the temperature was raised to 60 DEG C and aged for 2 hours. The yield was quantitative and a colorless transparent liquid with a final refractive index of 1.654 (nD, 20 ° C) was obtained.

[ Synthesis Example 2 ]

BESTES Manufacturing

A thermometer and a condenser were placed in a 2 L four-necked flask and 1 mol (178.34 g) of bis (β-epithiopropyl) sulfide was added to 2 mol (308.64 g) of bis (2- mercaptoethyl) sulfide under nitrogen flow. 6 g of phenylphosphine was added and the mixture was kept at 20 캜 for 8 hours while preventing the exothermic reaction. The refractive index increased to 1.635 and the temperature was raised to 60 占 폚 and aged for 2 hours. The yield was quantitative, and a colorless transparent liquid with a final refractive index of 1.635 (nD, 20 ° C) was obtained.

[ Synthesis Example 3 ]

BESSTES Manufacturing

A thermometer and a condenser were attached to a 2 L four-necked flask, and 1 mol (210.41 g) of bis (β-epithiopropyl) disulfide was added to 2 mol (308.64 g) of bis (2- mercaptoethyl) sulfide in a nitrogen stream, 6 g of phenylphosphine was added and the mixture was kept at 20 캜 for 8 hours while preventing the exothermic reaction. The refractive index increased to 1.643 and the temperature was raised to 60 占 폚 and aged for 2 hours. The yield was quantitative and a colorless transparent liquid with a final refractive index of 1.643 (nD, 20 ° C) was obtained.

[ Synthesis Example 4 ]

BDPMS Manufacturing

A thermometer and a condenser are attached to a 1L reactor with a temperature controllable dive, and 1 mol (178.34 g) of bis (β-epithiopropyl) sulfide is added to the flask, and 100 g of toluene and 100 g of methanol are added. The reaction temperature was lowered to 5 to 10 DEG C, 2 mL of a 1 molar NaOH (aq) solution was added, and 2.2 mol of hydrogen sulfide obtained by the reaction of NaSH.xH ₂ O and HCl was reacted for 20 hours When the reaction was completed, the reaction temperature was raised to 60 DEG C and aged for 2 hours, and excess hydrogen sulfide was removed by passing through nitrogen gas. Removal of the solvent under reduced pressure gave a clear colored liquid with a yield of 1.6472 (nD, 20 占 폚), which was quantitative and had a final refractive index of 1.6472 (nD, 20 占 폚).

[ Synthesis Example 5 ]

BDPDS Manufacturing

A thermometer and a condenser are attached to a 1L reactor equipped with a temperature controllable dive, and 1 mol (210.41 g) of bis (β-epithiopropyl) disulfide is placed in a flask, and 100 g of toluene and 100 g of methanol are added. Lowering the reaction temperature to 10 ℃, 1 mol of NaOH (aq) solution was added to 2mL, then by the amount of the hydrogen sulfide obtained by the reaction of 2.2 mole NaSH.xH ₂ O and HCl while maintaining the supply 8 ℃ and reacted for 20 hours When the reaction was completed, the reaction temperature was raised to 60 DEG C and aged for 2 hours, and excess hydrogen sulfide was removed by passing through nitrogen gas. Removal of the solvent under reduced pressure yielded a clear colored liquid with a yield of quantitative and a final refractive index of 1.6722 (nD, 20 DEG C).

[ Example 1 ]

Optical lens manufacturing

(1) 41.85 g of BESGST and 11.16 g of BESGST were added to 42.94 g of isophorone diisocyanate and 4.04 g of xylylenediisocyanate, and while maintaining the temperature at 15 ° C, 0.1 g of Zelec UN, 1.5 g of HOPBT , HTAQ 20 ppm, PRD 10 ppm and BTC 0.1 g were added and stirred for 20 minutes in a nitrogen stream to obtain a resin composition for spectacle lenses. The mixture was degassed under a pressure of 0.1 torr for 1 hour 30 minutes and filled with nitrogen. And injected into a glass mold calibrated with a polyester adhesive tape (Diopta -5.00).

(2) The glass mold into which the resin composition for a spectacle lens was injected was maintained in a forced circulation oven at 35 DEG C, heated at 40 DEG C for 3 hours, heated at 120 DEG C for 12 hours, held at 120 DEG C for 2 hours, , And the mold was released from the solid material to obtain an optical lens having a center thickness of 1.2 mm.

(3) The optical lens obtained in (2) was processed to a diameter of 72 mm, ultrasonically washed in an alkaline aqueous washing solution, and annealed at 120 ° C for 2 hours.

(4) The lens obtained in (3) was surface-etched in a 5% KOH solution, then impregnated with a hard coating solution of Fine Coat Co., Ltd., and thermally cured. Then, silicon oxide, zirconium oxide, silicon oxide, ITO, , Silicon oxide, zirconium oxide, and water film (fluororesin) were vapor-deposited to obtain hard coated and multi coated spectacle lenses.

Physical properties test method

The material analysis and characteristics were measured according to the following methods, and the results are shown in Table 1. [

1) Refractive index: Measured using an Abbe refractometer modeled by Atago Co., 1T and DR-M4.

2) The glass transition temperature (Tg) was measured by TMA Q400 (TA Instruments, USA) at a heating temperature of 10 ° C / min under a high purity nitrogen stream.

3) Whitening phenomenon: After polymerizing the optical lens resin, 100 lenses with no surface treatment were irradiated at a luminance of 1800 LUX or more, and cloudy appearance was observed with the naked eye to calculate percentages.

4) Edge Bubbles: After polymerizing the optical lens resin, 100 lenses with no surface treatment are visually observed, and when the bubbles due to leakage appear at the edges of three or more lenses, 'X' is displayed. Respectively.

[ Example 2 ~ 6]

In the same manner as in Example 1, the respective compositions and lenses were prepared according to the compositions shown in Table 1, and their properties were tested. The results are shown in Table 1.

[ Comparative Example 1 ]

Except that 43.80 g of GST (2,3-bis (2-mercaptoethylthio) propane-1-thiol) and 56.20 g of isophorone diisocyanate were mixed to prepare a resin composition for an optical material The properties are shown in Table 1.

Example Comparative Example One 2 3 4 5 6 One


Monomer composition
(g) BESGST 41.85 40.55 40.24 BESTES 41.65 BESSTES 46.74 50.86 BDPMS 5.96 BDPDS 6.88 GST 11.16 12.75 8.41 8.34 43.8 IPDI 42.94 41.68 41.21 53.26 40.89 56.2 XDI 4.04 3.92 3.88 49.16 3.85 Release agent (g) Zelec UN 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ultraviolet absorber
(g) HOPBT 1.5 1.5 1.5 1.5 1.5 The polymerization initiator (g) BTC 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Organic dye (ppm)
HTAQ 20 20 20 20 20 20 20 PRD 10 10 10 10 10 10 10
Lens properties Refractive index (nE, 20 캜) 1.6295 1.6307 1.6327 1.5985 1.6695 1.6331 1.5989 Abe number 37 36 36 38 31 36 38 Whitening (%) 2 3 4 2 One 5 90 Edge bubble O O O O O O X

In the results of the properties of the lenses shown in Table 1, whitening phenomenon and edge bubble formation were not observed in the examples obtained by using the polythiol compound of the present invention, but whitening phenomenon and edge bubble formation were remarkably observed in Comparative Examples. This shows that the novel polythiol compound obtained in the present invention does not inhibit the miscibility with isocyanate and increases the viscosity and lowers the solubility of the resin composition for optical material, thereby reducing the occurrence of tape whitening and the generation of edge bubbles.

[Abbreviation]

Monomer

IPDI: Isophorone diisocyanate

XDI: Xylylene diisocyanate < RTI ID = 0.0 >

GST: 2,3-bis (2-mercaptoethylthio) propane-1-thiol (2,3-

BESGST: Synthesis of 1- [2,3-bis- (2-mercaptoethylthio) propylthio] -3- {3- [2,3-bis (2-mercaptoethylthio) propylthio] -2-mercapto Propylthio] -3- {3- [2,3-bis- (2-mercapto-ethylthio) -propylthio] propy

lthio] -2-mercapto-propylthio} -propane-2-thiol)

BESTES: 1- [2- (2-mercaptoethylthio) ethylthio] -3- {2-mercapto-3- [2- (2-mercaptoethylthio) ethylthio] propylthio} 2- (2-mercaptoethylthio) ethylthio] propylthio} -propane-2-thiol} -3-

BESSTES: 1- [2- (2-mercaptoethylthio) ethylthio] -3- {2-mercapto-3- [2- (2-mercaptoethylthio) ethylthio] 2- (2-Mercaptoethylthio) ethylthio] propyldithio} -propane-2-thiol)

BDPMS: bis (2,3-dimercapto-propanyl) sulphide {Bis (2,3-dimercapto-propanyl) sulfide}

BDPSDS: Bis (2,3-dimercapto-propanyl) disulfide}

Episulfide functional group:

Thiethane functional group:

Release agent

ZELEC UN: Acid phosphate ester manufactured by Stepan Co., Ltd. ZELEC UN ^TM

Ultraviolet absorber

HOPBT: 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole

(2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole)

Organic dye

HTAQ: 1-hydroxy-4- (p-toluidine) endoquinone

[1-hydroxy-4- (p-toluidine) anthraquinone]

PRD: Perinone dye

Polymerization initiator

BTC: dibutyl tin dichloride

Claims (15)

A process for producing a polythiol compound represented by the following reaction formula (1), characterized by reacting a cyclic episulfide or a thiotane compound with a compound having a terminal thiol group in the presence of a catalyst or a catalyst, thereby extending the chain through ring opening.
[Reaction Scheme 1]

Wherein X and Y are an episulfide group or a thieno group which is at least one or more,
R and Z each independently represents a linear or branched alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, an alkylaryl group; Or an alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, or an alkylaryl group, which contains at least one oxygen atom or sulfur atom,
p is an integer of 0 to 4 and q is an integer of 1 to 4, and when p is 1, it is sulfide or disulfide,
n is an integer from 2 to 20; The process according to claim 1, wherein the compound having a terminal thiol group (including hydrogen sulfide) and the cyclic episulfide compound are reacted at a molar ratio ((-SH) / (episulfide group or thienane group) To obtain a polythiol compound. The compound according to claim 1, wherein the terminal thiol group-containing compound is selected from the group consisting of hydrogen sulfide; Methanedithiol; Ethanedithiol; 1,2-ethanedithiol; 1,1-propanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 2,2-propanedithiol; 2,5-hexanedithiol; 1,6-hexanedithiol; 2,9-decanedithiol; 1,4-bis (1-mercaptoethyl) benzene; Cyclohexanedithiol; 1,2,3-propanetriethiol; 1,1-bis (mercaptomethylcyclohexane); 1,2-dimercapto propyl methyl ether; 2,3-dimercapto propyl methyl ether; 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Bis (2-mercaptoethyl) ether; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; Bis (2,3-dimercaptopropanel) sulfide; Bis (2,3-dimercaptopropanel) disulfide; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 1,2-bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) ethane; Bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide; 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio-propane-1-thiol; 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester; Ethylthio) propane-1-thiol (2-mercaptoethylthio) -3- (2- (2- [ ; Trimethylolpropane tris (mercaptopropionate); Trimethylolethane tris (mercaptopropionate); Glycerol tris (mercaptopropionate); Trimethylolchlorotris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate); Trimethylol ethane tris (mercaptoacetate); Pentaerythritol tetrakis (mercaptopropionate) (PETMP); Pentaerythritol tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether-hexakis (mercaptopropionate) (BPEHMP); Bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA); Bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); Bistrimethylolpropane tetrakis (3-mercaptopropionate) (BTMPMP); And bistrimethylol propane tetrakis (2-mercaptoacetate) (BTMPMA). 2. The process for producing a polythiol compound according to claim 1, The method of claim 1, wherein the cyclic episulfide compound is selected from the group consisting of bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis Bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3- , Bis (? - epithiopropylthioethyl) sulfide, 2,5-bis (? -Epithiopropylthiomethyl) -1,4-dithiane, 2- Bis ([beta] -epithiopropylthio) propane, 1,2-bis [(2-beta -epithiopropylthioethyl) thio] 3- (beta -epithiopropylthio) propane, tetrakis -Epithiopropylthiomethyl) methane, 1,1,1-tris (beta -epithiopropylthiomethyl) propane, 1,1,1-tris (b- epithiopropyloxymethyl) -propane, tetrakis - epithiopropyloxymethyl) methane, 1,1,1- Bis (β-epithiopropyloxymethyl) propane, 1,5-bis) β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) -3-thiapentane, -Epithiopropyloxy) -2,2-bis (? - epithiopropyloxy) -2,4-bis (? - epithiopropyloxymethyl) Methyl) -4-thiohexane, 1,5,6-tris (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl-thiohexane, 1,8- Oxy) -4 - (? - epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (? - epithiopropyloxy) -4,5-bis (? - epithiopropyloxymethyl ) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,4-bis (β-epithiopropyloxymethyl) Bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) 2,5-bis (? - epithiopropyltri Oxymethyl) -3,6-dithiaoctane, 1,9-bis ((β-epithiopropyloxy) -5- (b-epithiopropyloxymethyl) -5 - [(2- 1,3- and 1,4-bis (? - epithiopropyloxy) cyclohexane, 1,3- and 1,4-bis (? - epithiopropyloxy Methyl) cyclohexane, bis [(4- (beta -epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (beta -epithiopropyloxy) cyclohexyl] propane, bis [4- (Epithiopropyloxycyclohexyl) sulfide, 2,5-bis (? -Epithiopropyloxymethyl) -1,4-dithiane, 1,3- and 1,4- Oxy) benzene, and 1,4- (beta -epithiopropyloxymethyl) benzene. The polythiol compound according to claim 1, The composition of claim 1, wherein the thianthene compound is selected from the group consisting of 3- (mercaptomethylthio) thietane, 3- (1-mercaptopropyl-3-thio) thietane, 3- 3- (mercaptoethylthioethylthio) thietane, 3- (mercaptoethylthioethylthio) thiotane, 3- (mercaptoethylthioethylthio) (3-mercapto-2-hydroxypropyl-1-thio) thietane, 3- (2-mercaptoethylthiophene- (2-mercaptomethyl-1,4-diethan-5-methylthio) thietane, 3- (1-mercaptocyclohexan-2-thio) thiotane, 3- (1-mercaptocyclohexane-2-thio) thiotane, 3- (1-mercaptocyclohexane- 3- (1-mercaptobenzene-2-methylthio) thiotane, 3- (1-mercaptobenzene- 3- (1-mercaptomethylbenzene-3-methylthio) thiotane, 3- (1-mercapto 3- (2,3-epoxypropylthio) thietane, 3- (2,3-epoxypropylthio) thietane, 3- (2,3-epoxypropylthio) (2,3-epoxypropylthioethylthio) thiadiene, 3- (2,3-epoxypropylthioethylthio) thiazole, 3- (2,3-epithiopropylthio) thiotane, 3 (2,3-epithiopropylthio) thiotane, 3- - (2,3-epithiopropylthioethylthio) thietane, 3- (2,3-epithiopropylthiopropylthio) thietane, 3- (2,3-epithiopropylthiobutylthio) 3- (2,3-epithiopropylthiomethylthiomethylthio) thietane, 3- (2,3-epithiopropylthioethylthioethylthio) thietane, 3- (2,3-epithiopropylthio) 3- (2,3-epithiopropylthio) methylthiophene-5-methylthio] thietane, 3- (2,3-epithiopropylthio) 3- [1- (2,3-epiopropylthio) methyl-1,4-dithiane-5-methylthio] thiotane, 3- [ (2,3-epiopropylthio) cyclohexane-2-thio] thiotane, 3- [1- (2,3-epi-propylthio) benzene-2-thia] thiotane, 3- [1- 3- (1- (2,3-epithiopropylthio) methylbenzene-2-methylthio] thiotane, 3- [1- Thiopropylthio) methylbenzene-3-methylthio] thiotane, and 3- [1- (2,30 epithiopropylthio) methylbenzene-4-methylthio] thiotane. ≪ / RTI > 6. The method for producing a polythiol compound according to any one of claims 1 to 5, wherein the reaction is carried out at 30 DEG C or less. 6. The process according to any one of claims 1 to 5, wherein the reaction is carried out in the presence of an alkali (alkali metal hydroxide or alkaline earth metal hydroxide), an amine (including amines having a heterocyclic ring), an organic acid and its salt, , At least one catalyst selected from the group consisting of Lewis acids, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, phosphines, and amine salts. Gt; A chain-extended polythiol compound obtained by the production method of claim 1 and represented by the following formula (1).
[Formula 1]

Wherein Z represents an independent linear or branched alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, an alkylaryl group; Or an alkyl group, an alicyclic group, an allyl group, a heterocyclic group, an allylalkyl group, or an alkylaryl group, which contains at least one oxygen atom or sulfur atom,
q is an integer from 1 to 4,
n is an integer from 2 to 20; The method of claim 8, wherein the polythiol compound is at least one selected from the group consisting of 1- (2-mercaptoethylthio) -3- [2-mercapto-3- (2-mercaptoethylthio) propylthio] Propanol-2-thiol, 2- [2- (2-mercaptoethylthio) -3- [2-mercapto- Ethylthio] propylthio} propylthio) ethylthio] propane-1,3-dithiol, 2- (2-mercapto-3- Ethylthio] propyldithio} propylthio) ethylthio] propane (2-mercapto-3- {2-mercapto-3- [2- (2-mercapto-1-mercaptomethylethylthio) -1,3-dithiol, 3- [3- (3- {3- [3- (2,3-dimercaptopropylthio) -2-mercaptopropylthio] -2-mercaptopropylthio} 2-mercaptopropylthio) -2-mercaptopropylthio] propane-1,2-dithiol, 3- [3- (3- {3- [3- (2,3-dimercaptopropylthio) 2-mercaptopropylthio] -2-mercaptopropyldithio} -2-mercaptopropylthio) -2-mercap Propyl-1, 2-dithiol, 3- [3- (3- {3- [3- (2,3- dimercaptopropylthio) -2-mercaptopropyl] 3- [3- (3- {3- [3- (2,3-di (methoxytripropylthio) -2-mercaptopropylthio] -2-mercaptopropylthio] propane- Mercaptopropylthio] -2-mercaptopropylthio] -2-mercaptopropyldithio} -2-mercaptopropylthio) -2-mercaptopropyldithio] propane-1,2-dithiol, 3 - [3- (3- {3- [3- (2,3-dimercaptopropyldithio) -2-mercaptopropylthio] -2-mercaptopropyldithio} -2-mercaptopropylthio) 2- (2-mercaptoethylthio) propane-1,2-dithiol, 2- (2-mercaptoethylthio) -3- {2- [ Ethylthio} propylthio} propylthio} propane-1-thiol, 2- (2-mercaptoethylthio) propylthio] 3- {2- [2-mercapto-3- (2-mercapto-3- {2- [3-mercapto-2- (2- (4S, 8R, 24S, 28S) -4,8,24,28-tetrakis (mercaptomethyl) -3-ethylthio} propyldithio) propylthio] ethylthio} propane- (4S, 11R, 27S, 34S) -4,11,27-nonatriacenetriacontane-1,14,18,31-thiatrathiol, 6,9,12,16,20,23,26,29- , 34-tetrakis (mercaptomethyl) -3,6,9,12,15,19,23,26,29,32,35-undeca-hectathiolacontane-1,17,21,37-tetrathiol Bis ((2-mercaptoethyl) thio) -4,24-bis (mercaptomethyl) -3,6,10,14,18,22, (4S, 8R, 21R, 25) -8,21-bis ((2-mercaptoethyl) thio) -4,25-bis (Mercaptomethyl) -3,6,10,14,15,19,23,26-octa-dioxoic acid-1,12,17,28-tetrathiol. Chain extended polythiol compound. A resin composition for an optical material comprising the chain-extended polythiol compound of claim 9. The resin composition for an optical material according to claim 10, further comprising an isocyanate compound or a thioisocyanate compound. The resin composition for an optical material according to claim 11, further comprising at least one additive selected from a releasing agent, a stabilizer (heat stabilizer), an antioxidant, a catalyst, an ultraviolet absorber, and a color correcting agent (pigment, dye). A resin for an optical material obtained by curing the resin composition for an optical material according to any one of claims 10 to 12. An optical product comprising the resin for optical material according to claim 13. The optical product according to claim 14, wherein the optical product is any one of a spectacle lens, a 3D polarized lens, a polarizing lens, a prism film, an optical fiber, an optical disk, a magnetic disk, a recording medium substrate, a coloring filter, .