KR20120095328A - New polythiol compounds and the method of preparing it, and the composition for optical material using it - Google Patents

Abstract

PURPOSE: A polythiol compound is provided to obtain relatively high refractivity, and to prevent efflorescence phenomenon of tape by reducing solubility of a resin composition for optical material. CONSTITUTION: A polythiol compound is in chemical formula 1: (HS)x-R1-(SS)n-R2-(SH)y. In chemical formula 1, R1 and R2 is respectively aromatic organic moiety, cycloaliphatic organic moiety, aliphatic organic moiety, heterocyclic organic moiety, aromatic organic moiety comprising one or more sulfur atom, aliphatic organic moiety comprising one or more sulfur atom, or heterocyclic organic moiety comprising one or more sulfur atom, x+y is an integer form 3-10, n is an integer form 1-5, and a manufacturing method of the polythiol compound comprises a step of reacting a thiol compound and an oxidizer.

Description

New polythiol compounds and its preparation method and resin composition for urethane optical materials using the same {New polythiol compounds and the method of preparing it, and the composition for optical material using it}

The present invention relates to a novel polythiol compound having usefulness for optical lens materials, a method for producing the same, and a resin composition for an optical material using the same, and particularly to a resin composition for a polythiourethane-based optical material having high refractive index and excellent heat resistance and reactivity. It is about.

Urethane-based plastic optical lenses manufactured using mercapto compounds and isocyanates have been widely used as optical lens materials because of excellent optical properties, ie, transparency, Abbe number, and tensile strength. However, urethane-based plastic optical lenses have a low heat distortion temperature, which causes problems when the lens is hard and multi-coated (anti-reflective coating) on the surface of the lens after casting, causing deformation of the center of the lens. When exposed to heat, the thermal deformation of the lens is severe, causing a problem of severe cracking of the multi-film. This creates a cloudy film on the surface of the lens, which sharply degrades the transparency of the lens.

In Korean Patent Publication No. 1987-0008928, a urethane-based high refractive plastic optical lens having excellent transparency, Abbe number, and tensile strength was prepared by thermally curing 0.05 moles of xylylene diisocyanate and 0.025 moles of pentaerythritol tetrakis (mercaptopropionate). have. However, the urethane-based high refractive plastic optical lens manufactured as described above has a problem in that thermal deformation is severe when exposed to high temperature, so that the multi-film is easily cracked, and the lens center portion is deformed during hard and multi-coating on the lens surface. Also in Korean Patent Publication No. 1992-0005708, urethane-based ultrahigh refractive plastic optical lenses are manufactured by thermosetting xylylene diisocyanate and 2,3-bis (2-mercaptoethylthio) -propane-1-thiol. This lens has a high refractive index of 1.655, There is a problem in that the lens center portion is deformed during hard and multi-coating on the lens surface, and there is a problem in that the multi-film easily breaks due to severe thermal deformation when exposed to high temperature.

In order to solve this problem, Korean Patent Publication No. 1993-0006918 describes bis (isocyanatomethyl) triscyclo [5,2,1,02,6] decane and bis (isocyanato) in the production of urethane optical lenses. Thermosetting methyl) bicyclo [2,2,2] heptane compound and PETMP (pentaerythritol tetrakismercaptopropionate) or 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane To produce a urethane plastic optical lens. The urethane-based plastic optical lens thus prepared has a bis (isocyanatomethyl) triscyclo [5,2,1,02,6] decane, bis (isocyanatomethyl) bicyclo [2, 2,2] has a problem that is expensive to prepare heptane.

In addition, a method of prepolymerizing a mercapto compound and an isocyanate compound to produce a resin composition for an optical material is disclosed in Korean Patent No. 10-0472837. In order to increase the impact resistance of the lens, the optical lens is manufactured by curing a compound having a dihydric alcohol added to a polyisocyanate and a polythiol compound, but the resin composition and optical lens for optical materials having a high Abbe number and high impact resistance It could not be manufactured. In addition, the resin for the optical material resin optical material introduced in this patent is difficult to inject, there is a problem that a large amount of polymerization failure occurs during curing of the resin composition. In addition, the manufactured lens has a refractive index of 1.545 to 1.556, which has a problem that the edge of the lens becomes thick due to its low refractive index.

In addition, Korean Patent Registration Nos. 10-0237664 and 10-0241989 disclose that a component obtained by prepolymerizing a polythiol compound having a specific structure with a polyisocyanate compound comprises a component consisting of a (meth) acrylate compound and a compound copolymerizable with them. Polymerization curing with the composition provided an optical lens resin and an optical lens excellent in both physical properties and productivity of the lens. However, the prepolymer obtained by reacting the -SH / -NCO molar ratio of the resin composition for optical materials in the range of 3.0 to 7.0 can be blended with acrylic, but the viscosity is so high that it is directly blended with polyisocyanate, a urethane curing agent, and injected into the mold. Injecting is difficult, and there is a problem that a lot of polymerization failure occurs. In addition, the prepolymer having a -SH / -NCO molar ratio of 0.5 to 2.0 as disclosed in Japanese Patent Laid-Open No. 5-25240 has a higher viscosity and thus has the above problems in manufacturing a urethane-based optical lens.

A combination of 2,3-bis (2-mercaptoethylthio) propane-1-thiol (hereinafter referred to as "GST") and XDI (xylylene diisocyanate) is commercially available. GST has a high sulfur content but a low equivalent weight. It is relatively difficult to improve the refractive index because it is relatively less than the isocyanate, there is a problem that the heat resistance is poor because the crosslinking density is not high. In addition, GST has a low viscosity when working with other isocyanates, causing dissolution of the adhesive on the back of the tape, causing whitening.

The present inventors have developed a method of mixing isophorone diisocyanate or dicyclohexyl methane diisocyanate with 1,6-hexamethylene diisocyanate as a method of increasing the heat resistance of a lens while using a general-purpose isocyanate compound which is inexpensive. Has been elected. However, this method can achieve good heat resistance when the content of isophorone diisocyanate or dicyclohexyl methane diisocyanate in the isocyanate content is 40% by weight or more, in which case the reactivity with the mercapto compound decreases, resulting in high temperature. In the reaction proceeds, such a high reaction temperature is a problem that causes the whitening of the lens by eluting the adhesive of the adhesive tape fixing the mold to the edge of the lens. In addition, due to the expansion of the liquid composition in accordance with the increase in the temperature of the liquid leakage caused by the bubble is generated at the edge of the lens there is also a problem that a defect occurs. Therefore, the method of mixing 40% or more of isophorone diisocyanate or dicyclohexyl methane diisocyanate in isocyanate is the best method for improving the heat resistance of the lens, but there is a problem in using commercially available adhesive tapes.

In addition, in Korean Patent Application No. 10-2010-0038562, a solution of tape whitening was solved by prepolymerizing some isocyanate to polythiol compound to increase the viscosity, but in this case, the prepolymerized prepolymer did not help to improve the refractive index. Some imbalance and staining imbalance were caused.

In the present invention, in order to solve the above problems, obtain a higher refractive index and increase the heat resistance, it is to provide a novel polythiol compound disulfide without using a thiol compound as it is. When the new disulfide polythiol compound of the present invention is used, a higher refractive index can be obtained, and the heat resistance is increased to increase the viscosity, thereby reducing the solubility of the resin composition for optical materials, thereby solving the problem of tape whitening.

In the present invention,

Provided is a polythiol compound for an optical material represented by Formula 1 below.

Wherein R ₁ and R ₂ are aromatic organic residue, alicyclic organic residue, aliphatic organic residue, heterocyclic organic residue, aromatic organic residue containing one or more sulfur atoms, aliphatic organic residue containing one or more sulfur atoms, one It is any one of the heterocyclic organic residue containing the above sulfur atom,

x + y is an integer from 3 to 10,

n is an integer from 1 to 5.

In the present invention,

Provided is a method for preparing a polythiol compound represented by Chemical Formula 1, including reacting a thiol compound with an oxidizing agent.

Moreover, in this invention, the resin composition for optical materials containing the polythiol compound of said Formula 1 is provided. The resin composition for an optical material of the present invention may further include an isocyanate compound or a thioisocyanate compound. In addition, the resin composition for an optical material of the present invention may further include other thiol compounds in addition to the polythiol compound of Formula 1. The resin composition for an optical material comprising a disulfide-containing polythiol compound of the present invention had no problem of whitening or bubble formation during lens production.

Moreover, in this invention, the optical material resin obtained by hardening the said resin composition for optical materials, and the optical product which consists of this optical material resin are provided. Optical products include spectacle lenses, 3D polarized lenses, polarized lenses, prismatic films, optical fibers, optical disks, magnetic disks, recording medium substrates, color filters, ultraviolet absorbing filters.

In the resin composition for an optical material using the polythiol compound having the disulfide of the present invention (Formula 1), the whitening phenomenon did not appear at the edges of the lens due to the adhesive elution of the adhesive tape by lowering the solubility and maintaining an appropriate viscosity. No bubble problems at the edges of the lens due to leakage. The polythiol compound having disulfide is used as a raw material for optical materials, and the optical material obtained by using the same can increase the refractive index, and has excellent heat resistance and reactivity, such as lenses of glasses, camera lenses, prisms, optical pipes, optical disks, It can be usefully used for optical products such as recording medium engines such as magnetic disks, colored filters, and infrared absorption filters.

The novel polythiol compound provided by this invention has at least 1 or more disulfide, and is represented by following formula (1).

[Formula 1]

Wherein R ₁ and R ₂ are aromatic organic residue, alicyclic organic residue, aliphatic organic residue, heterocyclic organic residue, aromatic organic residue containing one or more sulfur atoms, aliphatic organic residue containing one or more sulfur atoms, one It is any one of the heterocyclic organic residue containing the above sulfur atom,

x + y is an integer from 3 to 10,

n is an integer from 1 to 5.

The polythiol compound of the present invention has at least one or more disulfide bonds formed in the reaction of the thiol compound and the oxidant, and is prepared by reacting the thiol compound and the oxidant. As an oxidizing agent for connecting the terminal thiol group of the thiol compound with disulfide, a halogen group compound, a radical catalyst, a peroxide such as sodium chlorite, etc. may be used, but is not limited thereto. More specific examples of the oxidizing agent may include oxygen, hydrogen peroxide, sodium hypochlorite, iodine, sulfyl chloride, iron (III) chloride, nitrogen oxide, and the like, but are not limited thereto. The amount of the chain extender to be used is preferably 0.05 to 1.5 moles with respect to the -SH molar ratio of the thiol compound, and preferably about 0.1 to 0.8 molar ratio. The use of less than 0.05 molar ratio did not help the problem of viscosity and tape whitening due to the small increase in viscosity and the equivalent, and the use of more than 1.5 molar ratio is too suitable for the resin composition for optical materials because the viscosity is too high to increase the molecular weight. Did not do it.

As a thiol compound which may be used to prepare the polythiol compound of Chemical Formula 1, 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; Bis (2,3-dimercaptopropanyl) sulfide; Bis (2,3-dimercaptopropanyl) disulfide; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,1,3,3-tetrakis (mercaptomethylthio) propane; 1,1,2,2-tetrakis (mercaptomethylthio) ethane; 4,6-bis (mercaptomethylthio) -1,3-dithiane; 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diene; Tris (mercaptomethylthio) methane; 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane; Bis (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl; 1,2,3-trimercaptobenzene; 1,3,5-tris (mercaptomethyl) benzene; 1,2 , 3-tris (mercaptomercaptoethyl) benzene; 1,3,5-tris (mercaptoethyl) benzene; 1,2,3-tris (mercaptomethylthio) benzene; 1,2,4-tris ( Mercaptomethylthio) benzene; 1,3,5-tris (mercaptomethylthio) benzene; 1,2,3-tris (mercaptoethylthio) benzene; 1,2,4-tris (mercaptoethylthio) Benzene; 1,3,5-tris (mercaptoethylthio) benzene; 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; 2- (2-mercaptoethylthio) -3- (2 -(2- [3-mercapto-2- (2-mercaptoethylthio) -prop Lofilo] ethylthio) ethylthio) propane-1-thiol; trimethylolpropane tris (mercaptopropionate); trimethylolethane tris (mercaptopropionate); glycerol tris (mercaptopropionate); trimethyl Allchloro tris (mercaptopropionate); trimethylolpropane tris (mercaptoacetate); trimethylolethane 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); bistrimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); bistrimethylolpropanetet Kiss may be used. (2-mercaptoacetate) (BTMPMA), but is not limited to the examples above.

In the preparation of Chemical Formula 1, thiol compounds that can be used include a thiol compound having an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, and a heterocyclic organic residue, including a halogen group and / or a hydroxy group or episulfide and thiethane. It may include. For example, mercaptomethanol; 2-mercaptoethanol; 1-chloro-3-mercapto-propan-2-ol; Thiethane-3-thiol; Oxylenyl methane thiol; Thylenyl methane thiol; 2-mercaptopropionic acid; 3-mercaptobutyric acid; 2-mercaptoisobutyric acid; 3-mercaptoisobutyric acid; Methanedithiol; 1,2-ethanedithiol; 1,1-propanedithiol, etc. can be used 1 or more types. However, it is not limited thereto.

In the present invention, a resin composition for an optical material including the polythiol compound of Formula 1 is provided, and the resin composition for the optical material may further include an isocyanate compound or a thioisocyanate compound. In addition, the resin composition for an optical material of the present invention may further include other thiol compounds in addition to the polythiol compound of Formula 1.

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-1,4 -Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-iso Aliphatic polyisocyanate compounds such as cyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, and lysine triisocyanate; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate , Xylylene diisocyanate, tolylene-2,4-diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4 '-Methylenebis (phenylisocyanate), 4,4-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatoethyl) Benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethyl xylylenediisocyanate, 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; Isophorone diisocyanate, 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1 , 02,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,9-bis (isocyanatomethyl) tricyclo [5,2 , 1,02,6] decane, 2,5 - bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) bicyclo [2,2,1 ] Heptane, Bis (isocyanatomethyl) cyclohexane, dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane diisocyanate, 2,2'-dimethyldicyclohexyl methane diisocyanate, Bis (4-isocyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2,2,1] -heptane , 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2 -(3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-iso Anatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -ratio Cyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 1 Polyisocyanate compounds having an alicyclic compound such as, 3,5-tris (isocyanatomethyl) -cyclohexane and dicyclohexylmethane-4,4-diisocyanate (H ₁₂ MDI); Thiophene-2,5-diisocyanate, methyl thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, methyl 1,4-dithiane-2,5-diisocyanate, 1,3-dithiolane-4,5-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, ethyl tetrahydrothiophene-2,5-diisocyanate , Methyl tetrahydrothiophene-3,4-diisocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, Heterocyclic diisocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenediisothiocyanate and cyclohexanediisothiocyanate; Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfide, Bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) Methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2, 3-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 polys such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, and bis (4-isocyanatomethylphenyl) sulfide Isocyanate compounds; Bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl Aromatic disulfide-based polys such as -6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, and bis (4-methoxy-3-isocyanatophenyl) disulfide Isocyanate compounds; 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato- 1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiorane, 4,5-bis (isocyanato Sulfur-containing alicyclic polyisocyanate compounds such as methyl) 1,3-dithiolane and 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane; Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane and 1,6-diisothiocyanatohexane; Alicyclic polyisothiocyanate compounds such as cyclohexanediisothiocyanate; 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2, 5-diisothiocyanato-m-xylene, 4,4-methylenebis (phenylisothiocyanate), 4,4-methylenebis (2-methylphenylisothiocyanate), 4,4-methylenebis ( 3-methylphenylisothiocyanate), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyanato-3,3-dimethylbenzophenone, bis (4-isothiocyanato Aromatic polyisothiocyanate compounds such as phenyl) ether; Carbonyl poly, such as 1, 3- benzenedicarbonyl diisothiocyanate, 1, 4- benzenedicarbonyl diisothiocyanate, (2, 2- pyridine) -4, 4- dicarbonyl diisothiocyanate Isothiocyanate compounds; Sulfur-containing aliphatic polyisothiocyanate compounds such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane) and dithiobis (2-isothiocyanatoethane); 1-isothiocyanato-4-[(2-isothiocyanato) thio] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (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; 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4 -Methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocy Compounds having isocyanato groups and isothiocyanato groups such as anatotophenyl-4-isothiocyanatophenyl sulfide and 2-isocyanato-ethyl-2-isothiocyanatoethyl disulfide It can be used 1 type or in mixture of 2 or more types.

As another thiol compound which can be used in addition to the polythiol compound of Formula 1, 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; Cyclohexanediol; 1,2,3-propanethiol; 1,1-bis (mercaptomethylcyclohexane); 1,2-dimercaptopropylmethyl ether; 2,3-dimercaptopropylmethyl 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-dimercaptopropanyl) 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; 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol ; Trimethylolpropane tris (mercaptopropionate); Trimethylolethane tris (mercaptopropionate); Glycerol tris (mercaptopropionate); Trimethylolchloro tris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate); Trimethylolethane 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); Bistrimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); Bistrimethylol propane tetrakis (2-mercapto acetate) (BTMPMA) etc. can be used 1 type (s) or 2 or more types.

All the chemicals (raw materials) used in the preparation of the polythiol compound (Formula 1) and the resin composition for an optical material of the present invention and the compound obtained by synthesizing the compound were used without purification or purification. Preferably, the resultant is purified using a purification method such as distillation under reduced pressure, washing, filtration, or the like, and more preferably, purified using high purity.

In the composition of the present invention, a compound for controlling other reactions may be added, and as the compound to be added for this purpose, a compound such as a vinyl group, a compound having a thioepoxy group, an epoxy compound, thiethane, or the like may be used alone or in combination. Can be.

In addition, the resin composition for optical materials of this invention may contain the additive for improving optical characteristics. Additives include in particular ultraviolet absorbers, stabilizers, internal mold release agents, color correctors (pigments, dyes), antioxidants, mold release agents and the like.

As the ultraviolet absorbent, any known ultraviolet absorbent surface usable for the optical lens can be used. For example, ethyl-2-cyano-3,3-diphenyl acrylate; 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzoxoxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,2'- dihydroxy-4,4'- dimethoxy benzophenone etc. can be used individually or in mixture of 2 or more types. Preferably, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, 2-hydroxy having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention. -4-methoxybenzophenone; Ethyl-2-cyano-3,3-diphenylacrylate; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3,5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole and 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like These may be used alone or in combination of two or more.

It is preferable to add the stabilizer for improving the optical characteristic of the resin composition for optical materials in 0.01 to 5.00 weight% of all the compositions. When the stabilizer is used at 0.01% by weight or less, the stability effect is weak, and when using at least 10.00% by weight, there is a problem in that the polymerization failure rate during curing is high and the stability of the cured product is lowered. For example, calcium stearate which is a metal fatty acid salt type; Barium stearate; Zinc stearate; Cadmium stearate; Lead stearate; Magnesium stearate; Aluminum stearate; Potassium stearate; One or two or more of compounds such as zinc octoate can be used, and phosphorus-based triphenyl phosphite; Diphenyldecylphosphite; Phenyl didecyl phosphite; Diphenyldodecyl phosphite; Trinolylphenyl phosphite; Diphenylisooctylphosphite; Tributyl phosphite; Tripropyl phosphite; Triethyl phosphite; Trimethyl phosphite; Tris (monodecyl phosphite); One kind or two or more kinds of compounds such as tris (monophenyl) phosphite can be used, and lead-based 3PbO.PbSO4.4H ₂ O; 2PbO.Pb (C ₈ H ₄ O ₄ ); _{3PbO.Ph (C 4 H 2 O 4} ) .H be one species or two or more kinds of the compounds, such as O ₂ is used, and sealed organotin dibutyltin diahwoo rate; Dibutyl tin maleate; Dibutyltin bis (isooctyl maleate); Dioctyl maleate; Dibutyltin bis (monomethylmaleate); Dibutyltin bis (lauryl mercaptide); Dibutyl bis (isooxylmercaptoacetate); Monobutyl tin tris (isooctyl mercaptoacetate); Dimethyl tin bis (isooctyl mercaptoacetate); Tris (isooctyl mercaptoacetate); Bioctyl tin bis (isooctyl mercaptoacetate); Dibutyltin bis (2-mercaptoethylorate); Monobutyl tin tris (2-mercaptoethyrate); Dimethyltin bis (2-mercaptoethylate); One kind or two or more kinds of compounds such as monomethyl tin tris (2-mercaptoethyl laurate) can be used. Moreover, you may mix and use 2 or more types of stabilizers mentioned above. More preferably, a phosphorus stabilizer is used. When the phosphorus stabilizer was used, the molded lens was able to greatly improve the stability of the optical lens without deteriorating the optical characteristics such as transparency, impact strength, heat resistance and polymerization yield as well as the initial color.

As an internal mold release agent used for this invention, Fluorine-type nonionic surfactant which has a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; Silicone nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; The component selected from the acidic phosphate ester can be used individually or in combination of 2 or more types. Preferably, acidic phosphate ester is used, and as acidic phosphate ester, isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof. In the embodiment of the present invention, ZELEC UN ™ (Stepan), which is an acidic phosphate ester, was found to exhibit the best demolding when demolding the mold from the lens after curing. The internal mold release agent may be used in an amount of 0.0001 to 10% by weight based on the total weight of the reaction mixture. Preferably, 0.005 to 2% by weight of the mold release agent in the lens has a high polymerization yield. If the amount of the release agent is less than 0.005%, a phenomenon may occur in which the lens adheres to the surface of the glass mold when the molded optical lens is separated from the glass mold, and if more than 2% by weight, the lens is separated from the glass mold during the polymerization of the mold. There is a problem that may cause stains on the surface.

Furthermore, a hard coat coating may be provided on the outer surface of the cast resin to increase the wear resistance of the surface. Further, by inserting a primer layer between the surface of the resin and the hard coat film, the adhesion of the resin to the hard coat film can be improved. In order to apply the hard coat agent on the outer surface of the resin for installing the hard coat film on the surface, a completely cured and annealed resin is first coated with a primer solution, and then a conventional known method such as immersion method or spin-film method. And a hard coat agent according to the flow-coating method, the spraying method and other methods. In addition, an anti-reflection film can be installed on the surface of the cast resin to prevent surface reflection on the surface of the optical element, thereby increasing the transmittance of visible light.

It was confirmed that the resin composition for an optical material including the polythiol compound of the present invention having disulfide had no problem of whitening or bubble generation during lens manufacture.

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. Optical products include spectacle lenses, 3D polarized lenses, polarized lenses, prismatic films, optical fibers, optical disks, magnetic disks, recording medium substrates, colored filters, ultraviolet absorbing filters and the like.

[ Example ]

Hereinafter, the present invention will be described in more 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.

Synthetic example  One

GSTDS Manufacturing

1 mole of GST (2,3-bis (2-mercaptoethylthio) propane-1-thiol) was added to a 4-necked 1 L flask, and diluted with 200 g of acetone. do. The temperature of the exotherm is maintained at 30 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 60 ° C. for 2 hours, and the solvent is removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.655 (nD, 20 ° C).

Synthetic example  2

GMTDS Manufacturing

1 mole of GMT (2- (2-mercaptoethylthio) propane-1,3-dithiol) was added to a 4-necked 1 L flask, and diluted with 200 g of acetone. . The temperature of the exotherm is maintained at 30 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 60 ° C. for 2 hours, and the solvent is removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.648 (nD, 20 degreeC).

Synthetic example  3

BDPSS Manufacturing

One mole of BDPS (bis (2,3-dimercaptopropanyl) sulfide) is added to a four-necked 1 L flask, and diluted with 200 g of acetone, and then slowly added while keeping 0.5 mole of hydrogen peroxide at 10 ° C or lower. The temperature of the exotherm is maintained at 15 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 60 ° C. for 2 hours, and the solvent is removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.662 (nD, 20 degreeC).

Synthetic example  4

BDPSDS Manufacturing

One mole of BDPSS (bis (2,3-dimercaptopropanyl) disulfide) is added to a four-necked 1-L flask, and diluted with 200 g of acetone, and then hydrogen peroxide is slowly added while maintaining 10 ° C or less. The temperature of exotherm was kept at 15 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 50 ° C. for 2 hours, and the solvent was removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.695 (nD, 20 degreeC).

Example  One

Optical lens manufacturers

(1) 2070 g of xylylene diisocyanate, 1656 g of isophorone diisocyanate, and 370 g of 1,6-hexamethylene diisocyanate are placed in a mixing vessel capable of vacuum defoaming stirring and kept at 15 ° C. while maintaining 15 ° C., Zelec UN 10 g, HOPBT 150 g 20 ppm of HTAQ, 10 ppm of PRD and 10 g of BTC were stirred for 20 minutes under a nitrogen stream to obtain a resin composition for the spectacle lens, and then degassed under 0.1 torr for 1 hour and 30 minutes, filled with nitrogen, and then charged with nitrogen. The glass mold was calibrated with polyester adhesive tape (Diopta -5.00).

(2) The glass mold in which the resin composition for the spectacle lens was injected was kept at 35 ° C. in a forced circulation oven, heated at 40 ° C. for 3 hours, heated at 120 ° C. for 12 hours, held at 120 ° C. for 2 hours, and at 70 ° C. for 2 hours. After cooling and heat curing, the mold was released from the solid 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 with an alkaline aqueous washing solution, and then annealed at 120 ° C. for 2 hours.

(4) The surface of the lens obtained in (3) was etched in KOH 5% solution, impregnated in fine coating hard solution, and then thermally cured, and silicon oxide, zirconium oxide, silicon oxide, ITO, and zirconium oxide on both surfaces. , Silicon oxide, zirconium oxide, water film (resin fluoride) was vacuum deposited to obtain a hard-coated and multi-coated spectacle lens.

Property test method

Material analysis and properties were measured in the following manner and shown in the examples.

1) Refractive index: It was measured using an Abbe refractometer of Atago Co., 1T and DR-M4 models.

2) Whitening phenomenon: 100 lenses obtained in step (2) were visually observed and marked with 'X' if whitening phenomenon appeared at the edges of three or more lenses.

3) Edge bubble: 100 lenses obtained in the process (2) were visually observed, and if bubbles due to leakage appeared on the edges of three or more lenses, they were marked as 'X'.

Experimental Example  2 ~ 3

Each composition and lens were prepared according to the composition described in Table 1 and the physical properties were tested in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1

2617 g of xylylene diisocyanate, 2094 g of isophorone diisocyanate, and 467 g of 1,6-hexyl methylene diisocyanate were mixed with 2,3-bis (2-mercaptoethylthio) propane-1-thiol 4823 g to prepare a resin composition for an optical material. Except for the preparation, it was carried out in the same manner as in Example 1 and its properties are shown in Table 1.

Example Comparative example One 2 3 4 One

Resin composition (g) for optical material
GSTDS 5702 GMTDS 5428 BDPSS 5143 BDPSDS 5700 XDI 2070 2277 2459 2173 2617 IPDI 1656 1844 1668 1739 2094 HDI 370 217 217 388 467 GST 4823 PETMP 203 234 Release agent (g) Zelec UN 10 10 10 10 10 UV absorbers
(g) HOPBT 150 150 150 150 150 Polymerization initiator (g) BTC 10 10 10 10 10 Organic dyes (ppm)
HTAQ 20 20 20 20 20 PRD 10 10 10 10 10
Lens property Refractive index (nD) 1.651 1.658 1.655 1.662 1.635 Whitening phenomenon O O O O X Bubble phenomenon O O O O X

[Abbreviation]

Monomer

IPDI: isophorone diisocyanate

HDI: 1,6-hexamethylene diisocyanate

XDI: xylylene diisocyanate

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

PETMP: pentaerythritol tetrakis (3-mercaptopropionate) (pentaerythritol-tetrakis (3-mercaptopropionate))

GSTDS: 2- (2-mercaptoethylthio) -3- (2- {2- [2-mercapto-1- (2-mercaptoethylthiomethyl) ethylthio] ethyltidithio} ethylthio)- Oligomer of propane-1-thiol (2- (2-Mercaptoethylthio) -3- (2- {2- [2-mercapto-1- (2-mercaptoethylthiomethyl) -ethylthio] -ethyldithio} ethylthio) propane-1-thiol) Disulfide Polythiol Compounds

GMTDS: 2- (2-mercaptoethylthio-3- [3-mercapto-2- (2-mercaptoethylthio) -propyldithio) -propane-1-thiol (2- (2-mercaptoethylthio-3 Oligomeric Disulfide Polythiol Compounds of-[3-mercapto-2- (2-mercapto ethylthio) -propyldithio] propane-1-thiol)

BDPSS: 3- {3- [3- (2,3-Dimercaptopropylthio) -2-mercaptopropylthio] -2-mercaptopropylthio} -propane-1,2-dithiol (3- { Oligomeric Disulfide Polythiol Compounds of 3- [3- (2,3-dimercaptopropylthio) -2-mercaptopropyldithio] -2-mercapto-propylthio} propane-1,2-dithiol)

BDPSDS: 3- {2- [3- (2,3-dimercaptopropylthio) -2-mercaptopropyldithio] -3-mercaptopropyldithio} -propane-1,2-dithiol (3 Oligomeric Disulfide Polythiol Compounds of-(2- [3- (2,3-dimercaptopropyldithio) -2-mercaptopropyldithio] -3-mercapto-propyldithio} propane-1,2-dithiol)

Release agent

ZELEC UN: An acidic phosphate ester compound manufactured by Stepan, trade name ZELEC UN ^TM

Ultraviolet absorber

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

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

Organic dyes

HTAQ: 1-hydroxy-4- (p-toludine) entroquinone

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

PRD: perinone dye

Polymerization initiator

BTC: dibutyl tin dichloride

According to the present invention, the novel polythiol compound is used as a raw material of the optical material and the optical material obtained by using the same can increase the refractive index, and excellent in heat resistance and reactivity.

The optical lens according to the present invention, in particular, can be applied to the spectacle lens, and used in 3D polarized lenses equipped with a polarizing film on the spectacle lens, recording medium substrate, coloring used in prism, optical fiber, optical disk, magnetic disk, etc. in addition to the spectacle lens It can be usefully used as various optical products, such as a filter and an ultraviolet absorption filter.

Claims (13)

Polythiol compound for optical materials represented by the following formula 1.
[Formula 1]

Wherein R ₁ and R ₂ are aromatic organic residue, alicyclic organic residue, aliphatic organic residue, heterocyclic organic residue, aromatic organic residue containing one or more sulfur atoms, aliphatic organic residue containing one or more sulfur atoms, one It is any one of the heterocyclic organic residue containing the above sulfur atom,
x + y is an integer from 3 to 10,
n is an integer from 1 to 5. A method for producing a polythiol compound according to claim 1, comprising reacting a thiol compound with an oxidizing agent. The method of claim 2, wherein the thiol compound is 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; Bis (2,3-dimercaptopropanyl) sulfide; Bis (2,3-dimercaptopropanyl) disulfide; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,1,3,3-tetrakis (mercaptomethylthio) propane; 1,1,2,2-tetrakis (mercaptomethylthio) ethane; 4,6-bis (mercaptomethylthio) -1,3-dithiane; 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diene; Tris (mercaptomethylthio) methane; 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane; Bis (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl; 1,2,3-trimercaptobenzene; 1,3,5-tris (mercaptomethyl) benzene; 1,2 , 3-tris (mercaptomercaptoethyl) benzene; 1,3,5-tris (mercaptoethyl) benzene; 1,2,3-tris (mercaptomethylthio) benzene; 1,2,4-tris ( Mercaptomethylthio) benzene; 1,3,5-tris (mercaptomethylthio) benzene; 1,2,3-tris (mercaptoethylthio) benzene; 1,2,4-tris (mercaptoethylthio) Benzene; 1,3,5-tris (mercaptoethylthio) benzene; 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; 2- (2-mercaptoethylthio) -3- (2 -(2- [3-mercapto-2- (2-mercaptoethylthio) -prop Lofilthio] ethylthio) ethylthio) propane-1-thiol; mercaptomethanol; 2-mercaptoethanol; 1-chloro-3-mercapto-propan-2-ol; thiethane-3-thiol; oxenylmethane Thiols; tyrenylmethanethiol; 2-mercaptopropionic acid; 3-mercaptobutyric acid; 2-mercaptoisobutyric acid; 3-mercaptoisobutyric acid; methanedithiol; 1,2-ethanedithiol; 1,1 Propanedithioltrimethylolpropane tris (mercaptopropionate), trimethylolethane tris (mercaptopropionate), glycerol tris (mercaptopropionate), trimethylolchloro tris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptopropionate) (PETMP); pentaerythritol tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether- Sakis (mercaptopropionate) (BPEHMP); bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA); bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); bis Trimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); And bistrimethylolpropanetetrakis (2-mercaptoacetate) (BTMPMA). 1. The method for producing a polythiol compound according to claim 2 or 3, wherein the oxidizing agent is any one of a halogen group compound, a radical catalyst, and a peroxide. The method for producing a polythiol compound according to claim 2 or 3, wherein the oxidizing agent is any one of oxygen, hydrogen peroxide, sodium hypochlorite, iodine, sulfuryl chloride, iron (III) chloride and nitrogen oxide. Resin composition for an optical material comprising the polythiol compound of claim 1. The resin composition for an optical material according to claim 6, further comprising an isocyanate compound or a thioisocyanate compound. The said isocyanate compound or the isothiocyanate compound is a hexamethylene diisocyanate, 2, 2- dimethylpentane diisocyanate, 2, 2, 4- trimethyl hexane diisocyanate, butene diisocyanate, 1, 3- Butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate Aliphatic polyisocyanate compounds such as iso-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester and lysine triisocyanate; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate , Xylylene diisocyanate, tolylene-2,4-diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4 '-Methylenebis (phenylisocyanate), 4,4-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatoethyl) Benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethyl xylylenediisocyanate, 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; Isophorone diisocyanate, 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1 , 02,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,9-bis (isocyanatomethyl) tricyclo [5,2 , 1,02,6] decane, 2,5 - bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) bicyclo [2,2,1 ] Heptane, Bis (isocyanatomethyl) cyclohexane, dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane diisocyanate, 2,2'-dimethyldicyclohexyl methane diisocyanate, Bis (4-isocyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2,2,1] -heptane , 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2 -(3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-iso Anatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -ratio Cyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 1 Polyisocyanate compounds having an alicyclic compound such as, 3,5-tris (isocyanatomethyl) -cyclohexane and dicyclohexylmethane-4,4-diisocyanate (H ₁₂ MDI); Thiophene-2,5-diisocyanate, methyl thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, methyl 1,4-dithiane-2,5-diisocyanate, 1,3-dithiolane-4,5-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, ethyl tetrahydrothiophene-2,5-diisocyanate , Methyl tetrahydrothiophene-3,4-diisocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, Heterocyclic diisocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenediisothiocyanate and cyclohexanediisothiocyanate; Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfide, Bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) Methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2, 3-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 polys such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, and bis (4-isocyanatomethylphenyl) sulfide Isocyanate compounds; Bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl Aromatic disulfide-based polys such as -6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, and bis (4-methoxy-3-isocyanatophenyl) disulfide Isocyanate compounds; 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato- 1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiorane, 4,5-bis (isocyanato Sulfur-containing alicyclic polyisocyanate compounds such as methyl) 1,3-dithiolane and 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane; Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane and 1,6-diisothiocyanatohexane; Alicyclic polyisothiocyanate compounds such as cyclohexanediisothiocyanate; 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2, 5-diisothiocyanato-m-xylene, 4,4-methylenebis (phenylisothiocyanate), 4,4-methylenebis (2-methylphenylisothiocyanate), 4,4-methylenebis ( 3-methylphenylisothiocyanate), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyanato-3,3-dimethylbenzophenone, bis (4-isothiocyanato Aromatic polyisothiocyanate compounds such as phenyl) ether; Carbonyl poly, such as 1, 3- benzenedicarbonyl diisothiocyanate, 1, 4- benzenedicarbonyl diisothiocyanate, (2, 2- pyridine) -4, 4- dicarbonyl diisothiocyanate Isothiocyanate compounds; Sulfur-containing aliphatic polyisothiocyanate compounds such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane) and dithiobis (2-isothiocyanatoethane); 1-isothiocyanato-4-[(2-isothiocyanato) thio] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), Sulfur-containing aromatic polyisothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene); Sulfur-containing alicyclic polyiso thiocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-diisothiocyanato-1,4-dithiane; 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4 -Methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocy One or two or more selected from the group consisting of anatotophenyl-4-isothiocyanatophenylsulfide and 2-isocyanato-ethyl-2-isothiocyanatoethyldisulfide Resin composition for materials. The method according to claim 7, further comprising a thiol compound other than the polythiol compound of Formula 1, wherein the other thiol compound is 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; Cyclohexanediol; 1,2,3-propanethiol; 1,1-bis (mercaptomethylcyclohexane); 1,2-dimercaptopropylmethyl ether; 2,3-dimercaptopropylmethyl 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-dimercaptopropanyl) 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; 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol ; Trimethylolpropane tris (mercaptopropionate); Trimethylolethane tris (mercaptopropionate); Glycerol tris (mercaptopropionate); Trimethylolchloro tris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate); Trimethylolethane 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); Bistrimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); And bistrimethylolpropane tetrakis (2-mercaptoacetate) (BTMPMA). The resin composition for an optical material, characterized in that one or more selected from the group consisting of. 8. The resin composition for an optical material according to claim 7, wherein one or two or more release agents, stabilizers (heat stabilizers), antioxidants, catalysts, ultraviolet absorbers, color correctors (pigments, dyes) are used. Resin for optical materials obtained by hardening | curing the resin composition for optical materials of Claim 7. An optical product comprising the resin for optical materials according to claim 11. The optical product according to claim 12, wherein the optical product is any one of an eyeglass 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 absorption filter. .