KR20210105219A - Methods for Manufacturing Episulfide Compounds for Optical Materials, Compositions for Optical Materials Containing the Same, and High Refractive Optical Materials - Google Patents

Abstract

The present invention relates to a composition for an optical material in which a rapid curing phenomenon occurring in the polymerization of an episulfide-based highly refractive optical material is suppressed, and a method for preparing an optical material using the same. The present invention provides a composition for an episulfide-based highly refractive optical material, including an episulfide compound represented by chemical formula 1, a 2,3-epoxypropyl(2,3-epithiopropyl)sulfide compound, a catechol compound, and a quaternary phosphonium salt as a polymerization catalyst. The composition according to the present invention prevents a rapid increase in viscosity occurring upon the polymerization of an episulfide-based highly refractive optical material, and maintains the curing rate constantly, and thus can be used as a high-quality lens material free from the problem of polymerization imbalance.

Description

Episulfide compound for optical material, composition for high refractive optical material containing same, and method for manufacturing optical material

The present invention relates to a method for producing an episulfide compound for an optical material, a composition for a high refractive optical material using the same, and a method for producing an optical material. It relates to a method for efficiently producing an episulfide compound for an optical material having good color and transparency by controlling the amount of hydrin added.

Plastic lenses are light, have good impact resistance, and are easy to color, so plastic lenses are used in most spectacle lenses in recent years. Plastic spectacle lenses have been developed in the direction of increasing lightness, high transparency, low yellowness, heat resistance, light resistance, and strength.

Korean Patent No. 10-0681218 proposes an episulfide-based plastic lens. Episulfide-based lenses have a high refractive index and high Abbe's number, but have many problems in terms of tensile strength, compressive strength, colorability, hard adhesion, productivity, and the like. In order to solve this problem, a method of copolymerizing two types of resins having different properties, that is, a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound therewith, is disclosed in Korean Patent No. 10-0417985, Japanese Patent Laid-Open Patent Publication No. It was proposed in Hei 11-352302, etc.

In recent years, in order to further increase the refractive index in an episulfide-based lens containing an episulfide compound to achieve an ultra-high refractive index of 1.71 or more and a high Abbe's number, a composition for an optical material containing an inorganic compound such as a sulfur atom or a selenium atom in the episulfide compound has been proposed (Japanese Patent Application Laid-Open No. 2001-2783).

However, hydrogen sulfide gas, which is used as a starting material for episulfide compounds, is difficult to transport and handle as a toxic substance. is difficult In addition, when an episulfide compound obtained by using a compound obtained without precisely controlling the reaction rate as a starting material is used as a monomer, the manufactured optical lens is cloudy and has poor transparency, so there is a problem that cannot be used commercially.

In addition, if the reaction rate is not precisely controlled when reacting the toxic hydrogen sulfide gas, there is a problem in that the process costs a lot and may lead to a serious accident. Due to these problems, the episulfide compound has been difficult to mass-produce.

Republic of Korea Patent Publication No. 10-0417985 Japanese Unexamined Patent Publication (Kokai) Hei 11-352302 Japanese Patent Laid-Open No. 2001-2783 Republic of Korea Patent Publication No. 10-2014-0122721

In the present invention, a method of producing an episulfide compound for an optical material that can precisely control the reaction rate by directly generating hydrogen sulfide gas and injecting it into the process and controlling the addition amount of hydrochloric acid and epichlorohydrin at a constant temperature and pressure. intended to provide

In the present invention, by preparing a compound with high purity and uniformity in the process of reacting hydrogen sulfide gas in this way, and using this to prepare an episulfide compound to be used as a monomer, finally providing an optical material with no haze and high transparency The purpose.

Another object of the present invention is to provide an economical and mass-produced episulfide compound, a composition for a high refractive optical material using the same, and a method for manufacturing the optical material.

In order to achieve the above object, in the present invention,

(a) into a sulphide to the reactor (A) was added sikidoe an acid reaction, while maintaining the reactor (A) to a temperature 1 ℃ ~ 50 ℃, pressure ^{0.001kgf / cm 2 ~ 10kgf / cm} 2 range generation of hydrogen sulfide gas, All of the generated hydrogen sulfide gas is generated in the reactor (B) of the following step of generating hydrogen sulfide gas;

(b) epichlorohydrin deurinreul into a reactor (B) while maintaining the reactor (B) to a temperature 1 ℃ ~ 30 ℃, pressure ^{0.002kgf / cm 2 ~ 10kgf / cm} 2 In the range of the hydrogen sulfide gas generated in the step to prepare bis((3-chloro-2-hydroxypropyl)sulfide by the reaction shown in Scheme 2 below; and

(c) reacting the prepared bis((3-chloro-2-hydroxypropyl)sulfide with thiourea to prepare an episulfide compound represented by Formula 1 below,

It provides a method for producing an episulfide compound for an optical material, characterized in that the reaction progress is controlled by adjusting the input amount of the acid and the epichlorohydrin.

[Scheme 2]

[Formula 1]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.)

In the manufacturing method, the reactor (A) maintains the reactor (A) at a temperature of 5 ℃ ~ 30 ℃, a pressure of 0.02kgf / cm ² ~ 5kgf / cm ² , the reactor (B) is a pressure of 0.02kgf / cm ² It is more preferable to maintain at ~5 kgf/cm ^{2 .}

In the reaction control step, in a preferred embodiment, when epichlorohydrin is detected by GC analysis of the reaction product of step (c), an acid is additionally added to the reactor (A), and 3-chloro-2-hydrogen When hydroxy-propane-1-thiol is detected, the progress of the reaction can be controlled by additionally adding epichlorohydrin to the reactor (B).

In addition, in the present invention,

preparing an episulfide compound for an optical material represented by Formula 1 by the above method;

It provides a method for preparing a composition for an episulfide-based high refractive optical material, comprising the step of preparing a composition comprising the episulfide compound and a polymerization catalyst.

Preparing the composition may further include any one or more of sulfur, a polythiol compound, and a polyisocyanate compound in the composition.

In addition, in the present invention,

preparing an episulfide compound for an optical material represented by Formula 1 by the above method;

preparing a composition for an optical material comprising the episulfide compound and a polymerization catalyst; and

It provides a method for producing an episulfide-based high refractive optical material, comprising the step of polymerizing the composition for an optical material.

Preparing the composition may further include any one or more of sulfur, a polythiol compound, and a polyisocyanate compound in the composition.

In the method for producing an episulfide compound for an optical material of the present invention, the reaction rate can be precisely controlled by directly generating hydrogen sulfide gas and injecting it into the process and adjusting the addition amounts of hydrochloric acid and epichlorohydrin at a constant temperature and pressure. have.

Accordingly, in the present invention, a compound with high purity and uniformity can be prepared in the process of reacting hydrogen sulfide gas, and an episulfide compound, which is a monomer capable of forming an optical material with high transparency and no fog during polymerization, can be prepared. have.

According to the method for producing an episulfide compound of the present invention, an episulfide compound having high transparency can be obtained in an economical manner because there is no haze during polymerization, and mass production is possible.

In the present invention, unless specifically limited, 'high refractive index' includes all of 1.67 or more to 1.71 or more, commonly referred to as ultra-high refractive index. Although not limited, the refractive index is usually in the range of 1.67 to 1.77.

episulfide Preparation of compounds

The method for producing an episulfide compound for an optical material of the present invention comprises the steps of generating hydrogen sulfide gas; reacting epichlorohydrin with hydrogen sulfide to prepare bis((3-chloro-2-hydroxypropyl)sulfide; and reacting bis((3-chloro-2-hydroxypropyl)sulfide with thiourea to produce epi It includes the step of preparing a sulfide compound, wherein the overall reaction progress is controlled and controlled by adjusting the input amounts of the hydrochloric acid and the epichlorohydrin. Hereinafter, each step will be described in detail.

1. Generation of hydrogen sulfide gas

Sulfide is put into the reactor (A) and acid is added to react to generate hydrogen sulfide gas. As the acid, preferably concentrated hydrochloric acid can be used. It is also possible to use dilute hydrochloric acid instead of concentrated hydrochloric acid, but since a relatively large amount of residual hydrogen sulfide gas remains in the reactor, there is a disadvantage in that the production is reduced.

The reactor (A) reacts with the sulfide and acid while maintaining the temperature 1 ℃ ~ 50 ℃, pressure 0.001kgf / cm ² ~ 10kgf / cm ² range, more preferably temperature 5 ℃ ~ 30 ℃, pressure 0.02kgf / cm ² ~ 5kgf / cm ^{2 The} reaction is maintained while maintaining. And particularly preferably a temperature 5 ℃ ~ 20 ℃, is allowed to react while maintaining the pressure ^{0.02kgf / cm 2 ~ 3kgf / cm} 2.

In this step, it is preferably reacted as shown in Scheme 1 below using concentrated hydrochloric acid. The generated hydrogen sulfide gas is fed to the reactor (B) in the next step for producing bis((3-chloro-2-hydroxypropyl)sulfide.

[Scheme 1]

2. Preparation of bis((3-chloro-2-hydroxypropyl)sulfide

Epichlorohydrin deurinreul into a reactor (B) while maintaining the reaction schemes below, the reactor (B) to a temperature 1 ℃ ~ 30 ℃, pressure ^{0.002kgf / cm 2 ~ 10kgf / cm} 2 range was added to the hydrogen sulfide gas generated in the step In the same reaction as in 2, 1-chloro-3-mercaptoporopan-2-ol is produced. At this point, and more preferably from maintaining the reactor (B) to a temperature 5 ℃ ~ 20 ℃, pressure ^{0.02kgf / cm 2 ~ 5kgf / cm} 2, particularly preferably at a temperature 5 ℃ ~ 15 ℃, 0.02kgf / cm 2 ~ 3kgf Keep it at /cm ^{2 .}

The reaction must be saturated with hydrogen sulfide, and the reaction can proceed at a constant rate by controlling the temperature and pressure. If the above conditions are not maintained, that is, if the temperature of the reactor rises to 30° C. or higher or the pressure exceeds the above range, the reaction proceeds irregularly and impurities are generated, affecting the episulfide compound, the product of the next step, and finally During polymerization, a haze phenomenon appears in the optical lens.

In this step, epichlorohydrin and hydrogen sulfide react to produce 1-chloro-3-mercaptoporopan-2-ol, and 1-chloro-3-mercaptoporopan-2-ol is again epichloroused. Reaction with hydrin gives bis((3-chloro-2-hydroxypropyl)sulfide.

In the hydrogen sulfide gas generation step and the bis((3-chloro-2-hydroxypropyl) sulfide production step, 1-chloro-3- To prepare mercaptophoropan-2-ol, at this time, hydrogen sulfide remaining in a saturated state in the reactor is reacted with epichlorohydrin to further produce 1-chloro-3-mercaptophoropan-2-ol As the hydrogen sulfide is consumed, the pressure drops and reaches the unpressurized atmospheric pressure.

[Scheme 2]

3. Preparation of Episulfide Compounds

The bis((3-chloro-2-hydroxypropyl)sulfide prepared in the above step is reacted with thiourea to prepare an episulfide compound as shown in Scheme 3 below.

[Scheme 3]

4. Reaction Control

In the above step, the overall reaction progress can be controlled by adjusting the amounts of acid and epichlorohydrin. That is, the amount of acid input to the reactor (A) in the hydrogen sulfide gas generation step and epichlorohydrin input to the reactor (B) in the production step of bis((3-chloro-2-hydroxypropyl)sulfide By adjusting the amount, the overall reaction progress can be controlled.

In a preferred embodiment, when epichlorohydrin is detected by GC analysis of the reaction product generated in the preparation step of the episulfide compound, hydrochloric acid is further added to the reactor (A), and 3-chloro-2-hydroxy- When propane-1-thiol is detected, epichlorohydrin is additionally added to the reactor (B) to control the reaction progress.

The starting material remaining without participating in the reaction may become an unintended impurity due to various reactions in the subsequent reaction system and may be incorporated into the final desired product. In the present invention, only by adjusting the amount of acid and epichlorohydrin input, the reaction progress can be precisely controlled to minimize the remaining starting materials and react almost completely, so that it is possible to produce a high-purity episulfide compound in a simple and easy way.

episulfide high refractive index Preparation of compositions for optical materials

The method for producing a composition for an episulfide-based high refractive optical material of the present invention,

Preparing an episulfide compound for an optical material represented by Chemical Formula 1 in the same manner as described above;

and preparing a composition comprising the episulfide compound and a polymerization catalyst.

In the preparing of the composition, any one or more of sulfur, a polythiol compound, and a polyisocyanate compound may be further included in the composition.

The episulfide compound is represented by Formula 1 above, for example, bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 1,3 and 1,4-bis(β). -epithiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2 Episulfide compounds having an alicyclic skeleton such as -bis[4-(β-epithiopropylthio)cyclohexyl]propane and bis[4-(β-epithiopropylthio)cyclohexyl]sulfide; 1,3 and 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropyl) Thio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfine, 4,4-bis(β-epithiopropylthio) ) episulfide compounds having an aromatic skeleton such as biphenyl; 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2,5- Epi having a dithiane chain skeleton such as bis(β-epithiopropylthioethyl)-1,4-dithiane and 2,3,5-tri(β-epithiopropylthioethyl)-1,4-dithiane sulfide compounds; 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropylthio)propane, 1,2-bis[(2-β-epithiopropylthioethyl)thio]- 3-(β-epithiopropylthio)propane, tetrakis(β-epithiopropylthiomethyl)methane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, bis-(β-epithio and an episulfide compound having an aliphatic skeleton such as propyl) sulfide. In addition, the episulfide compound may be a chlorine substituent of a compound having an episulfide group, a halogen substituent such as a bromine substituent, an alkyl substituent, an alkoxy substituent, a nitro substituent, or a prepolymer-type modified product with polythiol.

The episulfide compound represented by Formula 1 is preferably bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 1,3 and 1,4-bis(β-epi). thiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane; 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropyl thio) propane.

In addition to the episulfide compound represented by Formula 1, a 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound as in the product of Scheme 3 may be further included in the episulfide compound as a final product. The 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound increases the polymerizability of the composition to facilitate polymerization. Preferably, in the episulfide compound as the final product, the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound is contained in an amount of 0.3 to 15 wt%, more preferably 0.5 to 13 wt%. When the composition for an episulfide-based optical material of the present invention contains sulfur, the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound is particularly preferably used in an amount of 0.5 to 5% by weight in the episulfide compound. Included.

The polythiol compound is not particularly limited, and as long as it is a compound having at least one thiol group, one type or a mixture of two or more types may be used. Preferably, bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis(2-mercaptoethylthio)propane -1-thiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, tetrakis(mercaptomethyl)methane; 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2-(2,3-bis(2-mercaptoethylthio)propylthio)ethanethiol, bis(2,3-dimercapto Propanyl)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, bis(2-(2-mercaptoethylthio)-3 -Mercaptopropyl) disulfide, 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-mer) Capto-2-(2-mercaptoethylthio)-propylthio]ethylthio)ethylthio)propane-1-thiol, (4R,11S)-4,11-bis(mercaptomethyl)-3,6,9 ,12-tetrathiatetradecane-1,14-dithiol, (S)-3-((R-2,3-dimercaptopropyl)thio)propane-1,2-dithiol, (4R,14R) -4,14-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptane-1,17-dithiol, (S)-3-((R-3-mercapto-2- ((2-mercaptoethyl)thio)propyl)thio)propyl)thio)-2-((2-mercaptoethyl)thio)propane-1-thiol, 3,3'-dithiobis(propane-1,2 -dithiol), (7R,11S)-7,11-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)- 7,12-bis(mercaptomethyl)-3,6,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimer Capto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl- 1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol Ethritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hex Sakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4, At least one selected from 6-bis(mercaptomethylthio)-1,3-dithiane and 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiane may be used. In addition, as long as it is a compound having one or more thiol groups, one type or a mixture of two or more types may be used. In addition, a polymerization modified product obtained by prepolymerization with an isocyanate, an episulfide compound, a thietane compound, or a compound having an unsaturated bond as a resin modifier to the polythiol compound can also be used.

As the polythiol compound, particularly preferably, bis(2-mercaptoethyl)sulfide or 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane or another polythiol compound is added thereto to 1 It can be used by mixing more than one species.

The polythiol may preferably be included in the composition for an optical material in an amount of 1 to 15% by weight, more preferably 4 to 13% by weight, and still more preferably 5 to 11% by weight.

The polyisocyanate compound is not particularly limited, and a compound having at least one isocyanate group and/or an isothiocyanate group may be used. For example, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, hexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis(isocy aliphatic isocyanate compounds such as anatoethyl) carbonate and bis(isocyanatoethyl) ether; isophorone diisocyanate, 1,2-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane; alicyclic isocyanate compounds such as dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, and 2,2-dimethyldicyclohexylmethane isocyanate; Xylylene diisocyanate (XDI), bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis( Isocyanatomethyl) diphenyl ether, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene tri Isocyanate, diphenyl diisocyanate, toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate , bis(isocyanatophenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, etc. aromatic isocyanate compounds; bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide, bis(isocyanatohexyl)sulfide, bis(isocyanatomethyl)sulfone, bis(isocyanatomethyl)disulfide, Bis(isocyanatopropyl)disulfide, bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane, bis(isocyanatoethylthio)ethane, bis(isocyanatomethyl) sulfur-containing aliphatic isocyanate compounds such as thio)ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylthioether, bis(4-isocy Anatomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyldisulfide-5,5 '-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, 4,4'-dimethyldiphenyldisulfide Sulfur-containing aromatics such as -5,5'-diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, and 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate isocyanate compounds; 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl) Tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, 4,5-bis( One or two or more compounds selected from sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl)-2-methyl-1,3-dithiorane may be used. In addition, as long as it is a compound having at least one isocyanate group and/or isothiocyanate group, one type or a mixture of two or more types may be used. In addition, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents, polyhydric alcohols or thiols of these isocyanate compounds, carbodiimide modified products, urea modified products, and biuret modified products Alternatively, dimerization or trimerization reaction products may also be used.

As an isocyanate compound, Preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), norborane diisocyanate (NBDI), 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, 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane, 2 At least one selected from among ,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane may be used.

The isocyanate compound is included in an amount of 0.01 to 20% by weight of the composition for an optical material, and more preferably, may be included in an amount of 0.05 to 10% by weight.

The composition for an episulfide-based optical material may further include sulfur. When sulfur is included, the refractive index may be increased to an ultra-high refractive index of 1.71 or more. The sulfur included in the composition is preferably 98% or more pure. In the case of less than 98%, the transparency of the optical material may be deteriorated due to the influence of impurities. The purity of the sulfur is more preferably 99.0% or more, and particularly preferably 99.5% or more. Generally, commercially available sulfur is classified by differences in shape or refining method, and there are fine powder, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur, and the like. In the present invention, any sulfur can be used as long as the purity is 98% or more. Preferably, fine powder of fine particles that are easily dissolved may be used in the preparation of the composition for an optical material. In the composition for an optical material, sulfur is preferably contained in an amount of 1 to 40 wt%, more preferably 2 to 30 wt%, and most preferably 3 to 22 wt%.

The polymerization catalyst is preferably at least one selected from among amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. More preferably, at least one selected from a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound may be used. As the quaternary ammonium salt, for example, tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride, etc. can be used. . As a quaternary phosphonium salt, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, etc. can be used, for example. As the phosphine compound, triphenylphosphine or the like can be used. Particularly preferably, the polymerization catalyst is a quaternary phosphonium salt, and includes any one of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide. These polymerization catalysts can be used individually or in mixture of 2 or more types.

The composition for an episulfide-based optical material may further include a tin halogen compound as a polymerization regulator. The tin halogen compound is preferably any one of dibutyl tin dichloride and dimethyl tin dichloride, or one in which monomethyl tin trichloride is included in a small amount may be used. More preferably, monomethyl tin trichloride may be included in an amount of 0.1 to 3.5 wt%. When the composition for an episulfide-based optical material is polymerized and cured, the reaction proceeds rapidly, so that the viscosity of the composition may be rapidly increased. The polymerization regulator can suppress a sudden increase in viscosity by controlling the reaction rate. The polymerization regulator is preferably used in an amount of 0.01 to 5% by weight based on the total weight of the composition for an optical material. By using this polymerization regulator, the polymerization rate can be controlled to suppress a sudden increase in viscosity, and as a result, the polymerization yield is increased, and the generation of bubbles is also eliminated.

When sulfur is included in the composition for an episulfide-based optical material, it is preferable to polymerize after forming the prepolymer. have. Said alkylimidazole particularly preferably comprises 2-mercapto-1-methylimidazole. 2-Mercapto-1-methylimidazole is preferably used with a purity of 98% or more. The composition for an optical material may preferably contain 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, and still more preferably 0.15 to 1% by weight.

The composition for an optical material of the present invention may further include an internal release agent. Preferably, it may include a phosphate ester compound as an internal mold release agent. Phosphoric acid ester compound is _{prepared by adding 2 to 3 moles of an alcohol compound to phosphorus pentoxide (P 2} O ₅ ). At this time, various types of phosphoric acid ester compounds can be obtained depending on the type of alcohol used. Representative examples are types in which ethylene oxide or propylene oxide is added to an aliphatic alcohol or ethylene oxide or propylene oxide is added to a nonylphenol group or the like. When the phosphoric acid ester compound to which ethylene oxide or propylene oxide is added is included in the polymerizable composition of the present invention as an internal mold release agent, it is preferable to obtain an optical material having good mold release properties and excellent quality. The composition of the present invention is an internal mold release agent, preferably 4-PENPP [polyoxyethylene nonylphenol ether phosphate (5 wt% of ethylene oxide added by 5 moles, 80 wt% of 4 moles added, 3 moles added) 10 wt% of ethylene oxide, 5 wt% of added 1 mole)], 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 9 moles, 80 wt% of 8 moles added), 9 5 wt% of molar addition, 6 wt% of 7 molar addition, 6 wt% of 6 molar addition)], 12-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 13 moles) , 80 wt% of 12 moles added, 8 wt% of 11 moles added, 3 wt% of 9 moles added, 6 wt% of 4 moles added)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 17 moles, 79 wt% of added 16 moles, 10 wt% of 15 moles added, 4 wt% of 14 moles added, 4 wt% of 13 moles added)] , 20-PENPP [polyoxyethylene nonylphenol ether phosphate (6 wt% of ethylene oxide added by 21 moles, 76 wt% of 20 moles added, 7 wt% of 19 moles added, 6 wt% of 18 moles added) %, 17 mol added 5 wt %)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 mol propylene oxide added 5 wt %, 4 mol added 80 wt %, 3 mol added 10% by weight, 5% by weight added by 1 mole)], 8-PPNPP [Polyoxypropylene nonylphenol ether phosphate (3% by weight of propylene oxide added by 9 moles, 80% by weight added by 8 moles) 5% by weight added, 6% by weight added by 7 moles, 6% by weight added by 6 moles)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 weight% by adding 13 moles of propylene oxide) 80 wt% of 12 moles added, 8 wt% of 11 moles added, 3 wt% of 9 moles added, 6 wt% of 4 moles added)], 16-PPNPP [polyoxypropylene nonylphenol ether phosphate ( 3 wt% of propylene oxide added by 17 moles , 16 mol added 79 wt %, 15 mol added 10 wt %, 14 mol added 4 wt %, 13 mol added 4 wt %)], 20-PPNPP [polyoxypropylene nonylphenol ether phosphate (6 wt% of propylene oxide added by 21 moles, 76% by weight of 20 moles added, 7 wt% of 19 moles added, 6 wt% of 18 moles added, 5 wt% of 17 moles added)] and Zelec UN ^TM Use at least one selected from among. Various substituents including halogen compound substituents of these phosphoric acid ester compounds can also be used for the same purpose.

The composition for an optical material of the present invention may further include an olefin compound as a reactive resin modifier for the purpose of controlling impact resistance, specific gravity, monomer viscosity, etc. in order to improve optical properties of the optical material. Examples of the olefin compound that can be added as the resin modifier include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2 -Hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxy ethyl acrylate, phenoxy ethyl methacrylate, phenyl methacrylate, ethylene glycol di Acrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol Dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylic Late, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis(4-hydroxyethoxyphenyl)propane, 2,2-bis(4-methoxyethoxyphenyl)propane, 2, 2-bis(4-acroxydiethoxyphenyl)propane, 2,2-bis(4-methoxydiethoxyphenyl)propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis( 4-Acrythoxyphenyl)methane, 1,1-bis(4-methacrythoxyphenyl)methane, 1,1-bis(4-hydroxydiethoxyphenyl)methane, 1,1-bis(4 -Methoxydiethoxyphenyl) methane, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithioldiacrylate, (meth)acrylate compounds such as silylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl Allyl compounds such as tere, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate and diethylene glycol bisallyl carbonate and styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinyl and vinyl compounds such as benzene and 3,9-divinyl spirobi (m-dioxane), and the usable compounds are not limited to these exemplary compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

The composition for an optical material of the present invention may further include an ultraviolet absorber, if necessary. The ultraviolet absorber is used for improving the light resistance of the optical material and blocking ultraviolet rays, and a known ultraviolet absorber used for the optical material may be used without limitation. For example, ethyl-2-cyano-3,3-diphenylacrylate, 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-benzooxy-2-hydroxybenzophenone; 2,2',4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like may be used alone or in combination of two or more.

Preferably, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5 which has good ultraviolet absorption ability in the wavelength range of 400 nm or less and has good solubility in the composition of this invention -Chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, etc. can be used. Such a UV absorber can block 400 nm or more when used in an amount of 0.6 g or more with respect to 100 g of the composition for optical materials.

In addition, the composition for an optical material of the present invention may further include various additives such as a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a color inhibitor, an organic dye, a filler, and an adhesion improver, if necessary.

The composition for an optical material of the present invention composed as described above, after polymerization, has a solid-state refractive index (Ne) of 1.67 to 1.70 when sulfur is not included, and 1.71 to 1.77 when sulfur is included.

episulfide high refractive index Manufacturing of optical materials

The method for producing an episulfide-based high refractive optical material of the present invention,

preparing an episulfide compound for an optical material represented by Formula 1 in the same manner as described above;

preparing a composition for an optical material comprising the episulfide compound and a polymerization catalyst; and

and polymerizing the composition for an optical material.

That is, by polymerizing the composition for an optical material prepared as described above, an episulfide-based high refractive optical material can be obtained. A more detailed description is as follows. First, the polymerizable composition of the present invention is injected between the molding molds held by gaskets or tapes. At this time, in many cases, it is preferable to perform a degassing treatment under reduced pressure or a filtration treatment such as pressurization or reduced pressure depending on the physical properties required for the obtained optical material and if necessary. The polymerization conditions are not limited because conditions vary greatly depending on the polymerizable composition, the type and amount of catalyst used, the shape of the mold, and the like, but it is carried out at a temperature of about -50 to 130° C. for 1 to 50 hours. In some cases, it is preferable to maintain or gradually increase the temperature in a temperature range of 10 to 130° C. and harden in 1 to 48 hours.

The episulfide compound-based optical material obtained by curing may be subjected to treatment such as annealing, if necessary. The treatment temperature is usually 50 to 130°C, and preferably 90 to 120°C.

Since the optical material of the present invention can be obtained as a molded article having various shapes by changing the mold during casting polymerization, it can be used as various optical materials such as spectacle lenses, camera lenses, and light emitting diodes (LEDs). In particular, it is suitable as an optical material and an optical element, such as a spectacle lens, a camera lens, and a light emitting diode.

The episulfide-based high-refractive optical material obtained according to the present invention has excellent hard adhesion and can be hard coated without a primer, can be easily coated, and has excellent coating stability. In addition, the plastic optical lens obtained according to the present invention can be used by forming various coating layers on one side or both sides, if necessary. As the coating layer, a primer layer, a hard coating layer, an anti-reflection film layer, an anti-fogging coating film layer, an anti-fouling layer, a water-repellent layer, etc. are all possible, and these coating layers may be used alone or in multiple coating layers. In addition, when the coating layer is formed on both surfaces, it is possible to form the same coating layer on each surface or to form different coating layers.

Hereinafter, the present invention will be described in more detail through specific examples. However, these examples are only for explaining the present invention in more detail, and the scope of the present invention is not limited by these examples.

[ Synthesis example One]

Bis(3-chloro-2-hydroxypropyl)sulfide ( BCPS - 1) of synthesis

Epichlorohydrin (11126 g, 120.25 mol) and methanol (5000 g) were added to a GL reactor that can be used up to 12 kgf/cm ^{2 , and the reaction temperature was adjusted to 6 ° C. When the reaction temperature reached 6 ° C, caustic soda (50% (} aq), 10 g, 0.125 mol) was added. In another reactor usable up to 10 kgf/cm ² _{NaSH.xH 2} O (70% NaSH, 7320 g, 91.50 mol), methanol (4000 g) and water (2000 g) were added and stirred to dissolve completely, and 35.5% concentrated hydrochloric acid (9447 g) , 92.00 mol) was slowly added dropwise, and the generated hydrogen sulfide gas was directly added to the epichlorohydrin solution to obtain bis((3-chloro-2-hydroxypropyl)sulfide. The hydrogen sulfide gas reactor had an internal temperature of 8.2 ° C and an internal pressure of 0.03. kgf/cm ² was reacted while maintaining, and the reactor in which epichlorohydrin and hydrogen sulfide reacted was reacted while maintaining an internal temperature of 8.0 °C and an internal pressure of 0.02 kgf/cm ² . The completion of the reaction is the point at which epichlorohydrin and 3-chloro-2-hydroxy-propane-1-thiol compounds are completely eliminated by GC analysis of the final product, and bis(3-chloro-2-hydrocypropyl)sulfide is produced. was set to end the reaction. If 3-chloro-2-hydroxy-propane-thiol is present, bis(3-chloro-2-hydroxypropyl)sulfide ( BCPS- 1 ) was synthesized.

[ Synthesis example 2] to [ Synthesis example 10]

Bis(3-chloro-2-hydroxypropyl)sulfide ( BCPS -2 ~ BCPS - 10) of synthesis

In the same manner as in Synthesis Example 1 , compounds of BCPS -2 to BCPS -10 were prepared according to the pressures and conditions described in Table 1.

[ Comparative Synthesis Example One]

Bis(3-chloro-2-hydroxypropyl)sulfide ( BCPS - 11) of synthesis

Epichlorohydrin (11126 g, 120.25 mol) and methanol (5000 g) were added to a GL reactor that can be used up to 12 kgf/cm ^{2 , and the reaction temperature was adjusted to 6 ° C. When the reaction temperature reached 6 ° C, caustic soda (50% (} aq), 10 g, 0.125 mol) was added. In another reactor usable up to 10 kgf/cm ² _{NaSH.xH 2} O (70% NaSH, 7320 g, 91.50 mol), methanol (4000 g) and water (2000 g) were added and stirred to dissolve completely, and 35.5% concentrated hydrochloric acid (9447 g) , 92.00 mol) was slowly added dropwise, and hydrogen sulfide gas generated was added to the epichlorohydrin solution to obtain bis((3-chloro-2-hydroxypropyl)sulfide. The hydrogen sulfide gas reactor had an internal temperature of 10.0°C and an internal pressure of 0.00kgf. The reaction was carried out while maintaining /cm ² , and the reactor in which epichlorohydrin and hydrogen sulfide reacted was reacted while maintaining an internal temperature of 10.0° C. and an internal pressure of 0.00 kgf/cm ^{2. The} completion of the reaction was completed by GC analysis of the final product to be epichlorohydrin. The reaction was terminated at the point when the dry and 3-chloro-2-hydroxy-propane-1-thiol compounds were completely eliminated and bis(3-chloro-2-hydrocypropyl)sulfide was produced. In the presence of hydroxy-propane-thiol, bis(3-chloro-2-hydroxypropyl)sulfide ( BCPS - 11 ) was synthesized by adding more epichlorohydrin by calculating the relative integration ratio of GC analysis as the content.

[ Comparative Synthesis Example 2] ~ [ Comparative Synthesis Example 5]

Bis(3-chloro-2-hydroxypropyl)sulfide ( BCPS -12 ~ BCPS - 15) of synthesis

In the same manner as in Synthesis Example 1 and Comparative Synthesis Example 1 , compounds of BCPS- 12 to BCPS- 15 were prepared according to the pressures and conditions described in Table 1.

[ Synthesis example 11]

of bis (2,3-epithiopropyl) sulfide (BEPS-1) synthesis

BCPS- 1 (1070.48 g, 4.88 mol), 1300 g toluene, and 800 g of methanol were put in a 10 liter reaction vessel, and the external reaction temperature was adjusted to 30 °C while stirring. When it reached 25°C, NaOH (50% (aq), 783.08 g, 9.78 mol) was slowly added dropwise, and the reaction temperature was maintained at 25-30°C during the reaction. The dropwise addition was carried out within 1 hour, and the aging was carried out at 37° C. for 30 minutes. When the aging was completed, 2000 g of toluene was added, stirred for about 10 minutes, the layers were separated, the water layer was removed, and the organic solution as the supernatant was washed twice with water. Water was removed as much as possible, and 400 g of methanol was further added to the obtained solution and stirred. Thiourea (1117.65 g, 14.68 mol) and acetic anhydride (70 g) were added at a reaction temperature of 8° C., and the reaction was conducted at a reaction temperature of 18° C. for 18 hours. The completion of the reaction was confirmed by HPLC, and the starting material almost disappeared, and the reaction was terminated and stirring was stopped when the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound had an integral content of 8.6% in GC analysis. did. The organic layer obtained in the layer separation was washed with water 5 times, and the organic solvent was removed under reduced pressure to obtain a bis(2,3-epithiopropyl)sulfide compound BEPS- 1.

[ Synthesis example 12] to [ Synthesis example 20]

Bis(2,3-epithiopropyl)sulfide ( BEPS -2 ~ BEPS - 10) of synthesis

Episulfide compounds BEPS- 2 to BEPS- 10 were prepared using the starting materials BCPS- 2 to BCPS- 10 shown in Table 2 in the same manner as in Synthesis Example 1.

[ Comparative Synthesis Example 6]

of bis(2,3-epithiopropyl)sulfide (BEPS-11) synthesis

BCPS- 11 (1070.48g, 4.88 mol), 1300g toluene, and 800g methanol were put in a 10 liter reaction vessel, and the reaction temperature was adjusted to 30°C while stirring. When it reached 25°C, NaOH (50% (aq), 783.08 g, 9.78 mol) was slowly added dropwise, and the reaction temperature was maintained at 35-37°C during the reaction. The dropwise addition was carried out within 1 hour, and the aging was carried out at 37° C. for 30 minutes. When the aging was completed, 2000 g of toluene was added, stirred for about 10 minutes, the layers were separated, the water layer was removed, and the organic solution as the supernatant was washed twice with water. Water was removed as much as possible, and 400 g of methanol was further added to the obtained solution and stirred. Thiourea (1117.65 g, 14.68 mol) and acetic anhydride (70 g) were added at a reaction temperature of 8° C., and the reaction was conducted at a reaction temperature of 18° C. for 18 hours. The completion of the reaction was confirmed by HPLC, and when the starting material almost disappeared, the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound had an integral content of 9% in the GC analysis, the reaction was terminated and the stirring was stopped. did. The organic layer obtained in the layer separation was washed with water 5 times, and the organic solvent was removed under reduced pressure to obtain a bis(2,3-epithiopropyl)sulfide compound BEPS- 11.

[ Comparative Synthesis Example 7] to [ Comparative Synthesis Example 10]

Bis(2,3-epithiopropyl)sulfide ( BEPS -12 ~ BEPS - 15) of synthesis

In the same manner as in Synthesis Example 11 and Comparative Synthesis Example 6 , starting materials BCPS- 12 to BCPS - 15 described in Table 2 were used. Each of the episulfide compounds BEPS- 12 to BEPS - 15 were prepared.

Example One

Bis(2,3-epithiopropyl)sulfide ( BEPS- 1 ) 89g as thioepoxy compound, isophorone diisocyanate 5g as isocyanate compound, bis(2-mercaptoethyl)sulfide 6g as thiol compound, phosphate ester as internal mold release agent Phosphorus 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 9 moles, 80 wt% of 8 moles added, 5 wt% of 9 moles added, 6 wt% of 7 moles added) %, 6% by weight of 6 mol added)] 0.15 g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV absorber 2-(2'- 1.5 g of hydroxy-5'-t-octylphenyl)-2H-benzotriazole was mixed at 20 degreeC, and it was set as the homogeneous solution. This mixed solution was defoamed at 400 Pa for 1 hour. After that, it was filtered with a 1 μm PTFE filter, and injected into a mold made of a glass mold and a tape. This mold was put into a polymerization oven, and the temperature was gradually increased from 25°C to 130°C over 21 hours for polymerization. After completion of polymerization, the mold was taken out of the oven and demolded to obtain an optical lens. The releasability from the mold was good. The obtained optical lens was further annealed at 100°C for 4 hours. The obtained optical lens had a refractive index (nE) of 1.699 and an Abbe's number of 35. The melted state before injection into the mold was visually observed, and after demolding, physical properties and defects were checked.

Physical property test method

The physical properties of the optical lenses prepared in Examples were measured by the following experimental method, and the results are shown in Table 2 .

1) Refractive index and Abbe's number: It was measured using an Abbe refractometer, a DR-M4 model of Atago Corporation.

2) Transparency: Visually observe 100 lenses under a USHIO USH-10D Mercury Arc Lamp. If no lens turbidity is found, “◎” is indicated, and if 1 or 2 lenses are found, “○” ", and if three or more were found, it was marked with "x".

Example 2-10

An optical lens was manufactured with the composition shown in Table 2 in the same manner as in Example 1.

comparative example One

Bis(2,3-epithiopropyl)sulfide ( BEPS- 11 ) 89g as thioepoxy compound, isophorone diisocyanate 5g as isocyanate compound, bis(2-mercaptoethyl)sulfide 6g as thiol compound, phosphoric acid ester as internal mold release agent Phosphorus 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3 wt% of ethylene oxide added by 9 moles, 80 wt% of 8 moles added, 5 wt% of 9 moles added, 6 wt% of 7 moles added) %, 6% by weight of 6 mol added)] 0.15 g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV absorber 2-(2'- 1.5 g of hydroxy-5'-t-octylphenyl)-2H-benzotriazole was mixed at 20 degreeC, and it was set as the homogeneous solution. This mixed solution was defoamed at 400 Pa for 1 hour. After that, it was filtered with a 1 μm PTFE filter, and injected into a mold made of a glass mold and a tape. This mold was put into a polymerization oven, and the temperature was gradually increased from 25°C to 130°C over 21 hours for polymerization. After the polymerization was completed, the mold was taken out of the oven, and the releasability from the mold was good. The obtained lens was further annealed at 100 degreeC for 4 hours. The physical properties of the obtained lens were a refractive index (nE) of 1.699 and an Abbe's number of 35. The results of the physical properties are shown in Table 2 .

comparative example 2-5

Comparative Example 1 In the same manner, each of the episulfide compounds BEPS- 12 to BEPS - 15 described in Table 2 was used to prepare an optical lens, and the results are shown in Table 2.

Hydrogen Sulfide Generation Reactor
(Scheme 1) Hydrogen sulfide and epichlorohydrin reactor (Scheme 2) product Internal temperature (℃) pressure (kgf/cm ² ) Internal temperature (℃) pressure (kgf/cm ² ) Synthesis Example 1 8.2 0.03 8.0 0.02 BCPS-1 Synthesis Example 2 9.2 0.20 10.0 0.15 BCPS-2 Synthesis Example 3 10.0 0.40 6.5 0.35 BCPS-3 Synthesis Example 4 12.0 2.90 10.2 2.70 BCPS-4 Synthesis Example 5 12.0 0.85 7.6 0.77 BCPS-5 Synthesis Example 6 15.0 0.48 10.0 0.43 BCPS-6 Synthesis Example 7 19.0 0.92 13.0 0.84 BCPS-7 Synthesis Example 8 22.1 0.73 15.0 0.62 BCPS-8 Synthesis Example 9 15.0 1.34 8.5 1.22 BCPS-9 Synthesis Example 10 18.1 2.33 18.0 2.25 BCPS-10 Comparative Synthesis Example 1 10.0 0.00 10.0 0.00 BCPS-11 Comparative Synthesis Example 2 25.0 0.00 13.0 0.00 BCPS-12 Comparative Synthesis Example 3 10.0 11.0 10.0 10.5 BCPS-13 Comparative Synthesis Example 4 51.0 0.80 32.0 0.60 BCPS-14 Comparative Synthesis Example 5 0.7 3.40 0.5 3.20 BCPS -15

starting material, A episulfide compound, B Transparency Example One BCPS-1 Synthesis Example 1 BEPS-1 ◎ Example 2 BCPS-2 Synthesis Example 2 BEPS-2 ◎ Example 3 BCPS-3 Synthesis Example 3 BEPS-3 ◎ Example 4 BCPS-4 Synthesis Example 4 BEPS-4 ◎ Example 5 BCPS-5 Synthesis Example 5 BEPS-5 ◎ Example 6 BCPS-6 Synthesis Example 6 BEPS-6 ◎ Example 7 BCPS-7 Synthesis Example 7 BEPS-7 ◎ Example 8 BCPS-8 Synthesis Example 8 BEPS-8 ○ Example 9 BCPS-9 Synthesis Example 9 BEPS-9 ◎ Example 10 BCPS-10 Synthesis Example 10 BEPS-10 ○ comparative example One BCPS-11 Comparative Synthesis Example 1 BEPS-11 × comparative example 2 BCPS-12 Comparative Synthesis Example 2 BEPS-12 × comparative example 3 BCPS-13 Comparative Synthesis Example 3 BEPS-13 × comparative example 4 BCPS-14 Comparative Synthesis Example 4 BEPS-14 × comparative example 5 BCPS-15 Comparative Synthesis Example 5 BEPS-15 ×

<abbreviation>

A: bis(3-chloro-hydroxyphorophyl)sulfide

B: Bis (2,3-epithiopropyl) sulfide compound containing 8.5% of 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound

The method for producing an episulfide compound for an optical material of the present invention can produce a high-purity episulfide compound by precisely controlling the reaction progress in a simple way, so it can be used in various fields requiring an episulfide compound by replacing the existing production method In particular, it can be used in the field of high refractive optical materials requiring a high purity episulfide compound.

Since the episulfide-based high refractive optical material obtained according to the present invention has a good color and is clear and transparent, it can be usefully used for corrective sunglasses, fashion lenses, color-changing lenses, camera lenses, lenses for optical devices, and the like.

Claims (7)

(a) into a sulphide to the reactor (A) was added sikidoe an acid reaction, while maintaining the reactor (A) to a temperature 1 ℃ ~ 50 ℃, pressure ^{0.001kgf / cm 2 ~ 10kgf / cm} 2 range generation of hydrogen sulfide gas, All of the generated hydrogen sulfide gas is generated in the reactor (B) of the following step of generating hydrogen sulfide gas;
(b) epichlorohydrin deurinreul into a reactor (B) while maintaining the reactor (B) to a temperature 1 ℃ ~ 30 ℃, pressure ^{0.002kgf / cm 2 ~ 10kgf / cm} 2 In the range of the hydrogen sulfide gas generated in the step to prepare bis((3-chloro-2-hydroxypropyl)sulfide by the reaction shown in Scheme 2 below; and
(c) reacting the prepared bis((3-chloro-2-hydroxypropyl)sulfide with thiourea to prepare an episulfide compound represented by Formula 1 below,
A method for producing an episulfide compound for an optical material, characterized in that the reaction progress is controlled by controlling the input amount of the acid and the epichlorohydrin.
[Scheme 2]

[Formula 1]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.) According to claim 1,
Maintaining the reactor (A) at a temperature of 5 ℃ ~ 30 ℃, a pressure of 0.02kgf / cm ² ~ 5kgf / cm ^2,
The method for producing an episulfide compound for an optical material, characterized in that the reactor (B) ^{is maintained at a pressure of 0.02 kgf/cm 2} to 5 kgf/cm ^{2 .} According to claim 1,
The reaction progress control is,
In the reaction control step, when epichlorohydrin is detected by GC analysis of the reaction product of step (c), an acid is additionally added to the reactor (A), and 3-chloro-2-hydroxy-propane-1 - A method for producing an episulfide compound for an optical material, characterized in that when thiol is detected, epichlorohydrin is additionally added to the reactor (B). The method of any one of claims 1 to 3, comprising the steps of: preparing an episulfide compound for an optical material represented by Formula 1 below;
A method for producing a composition for an episulfide-based high refractive optical material, comprising the step of preparing a composition comprising the episulfide compound and a polymerization catalyst.
[Formula 1]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.) 5. The method of claim 4,
Preparing the composition comprises sulfur, a polythiol compound, and a polyisocyanate compound in the composition, characterized in that further comprising any one or more of an episulfide-based composition for a high refractive optical material. The method of any one of claims 1 to 3, comprising: preparing an episulfide compound for an optical material represented by the following Chemical Formula 1;
preparing a composition for an optical material comprising the episulfide compound and a polymerization catalyst; and
A method of producing an episulfide-based high refractive optical material, comprising the step of polymerizing the composition for an optical material.
[Formula 1]

(In the formula, m is an integer from 0 to 4, and n is an integer from 0 to 2.) 7. The method of claim 6,
Preparing the composition for an optical material is characterized in that the composition further comprises any one or more of sulfur, a polythiol compound, and a polyisocyanate compound.