KR102657702B1 - Composition for episulfide based optical material having high refractive index and method of preparing the optical material - Google Patents

Composition for episulfide based optical material having high refractive index and method of preparing the optical material Download PDF

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KR102657702B1
KR102657702B1 KR1020190034077A KR20190034077A KR102657702B1 KR 102657702 B1 KR102657702 B1 KR 102657702B1 KR 1020190034077 A KR1020190034077 A KR 1020190034077A KR 20190034077 A KR20190034077 A KR 20190034077A KR 102657702 B1 KR102657702 B1 KR 102657702B1
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weight
episulfide
refractive index
composition
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장동규
노수균
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미쓰이 가가쿠 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Abstract

본 발명은 에피설파이드계 고굴절 광학재료용 조성물과 이를 이용한 광학재료의 제조방법에 관한 것으로, 특히 할로겐화주석류과 같은 중합조절제를 사용하지 않고 황을 포함하면서도 색상 저하나 중합불균형이 없고 열안정성, 내광성, 이형성의 저하가 없는 굴절률 1.71에서 1.77 범위의 에피설파이드계 고굴절 광학재료용 조성물과 이를 이용한 광학재료의 제조방법에 관한 것이다. 본 발명에서는, 아래 화학식 1로 표시되는 에피설파이드 화합물 70~92중량%, 폴리티올 화합물 4~20중량%, 고체 황 2~9중량%, 이소시아네이트 화합물 0.01~5중량% 및 제4급 포스포늄염과 제3급 아민화합물 중에서 선택된 1종 이상의 중합촉매 0.05~2중량%를 포함하는, 굴절률 1.71~1.77의 에피설파이드계 고굴절 광학재료용 조성물이 제공된다.
[화학식 1]

(식 중에서 X는 O 또는 S이고, m은 0~4의 정수이며, n은 0~2의 정수이다.)The present invention relates to a composition for an episulfide-based high refractive index optical material and a method for manufacturing an optical material using the same. In particular, it does not use a polymerization regulator such as a halogenated tin, contains sulfur, but does not deteriorate in color or polymerization imbalance, and has thermal stability, light resistance, It relates to a composition for an episulfide-based high refractive index optical material with a refractive index in the range of 1.71 to 1.77 without deterioration in release properties, and a method for manufacturing an optical material using the same. In the present invention, 70 to 92% by weight of an episulfide compound represented by the formula 1 below, 4 to 20% by weight of a polythiol compound, 2 to 9% by weight of solid sulfur, 0.01 to 5% by weight of an isocyanate compound, and a quaternary phosphonium salt. A composition for an episulfide-based high refractive index optical material with a refractive index of 1.71 to 1.77 is provided, which includes 0.05 to 2% by weight of one or more polymerization catalysts selected from among tertiary amine compounds.
[Formula 1]

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

Description

에피설파이드계 고굴절 광학재료용 조성물과 이를 이용한 광학재료의 제조방법 {Composition for episulfide based optical material having high refractive index and method of preparing the optical material}Composition for episulfide-based high refractive optical material and method of manufacturing optical material using the same {Composition for episulfide based optical material having high refractive index and method of preparing the optical material}

본 발명은 에피설파이드계 고굴절 광학재료에 관한 것으로, 특히 할로겐화주석류과 같은 중합조절제를 사용하지 않고 황을 포함하면서도 색상 저하나 중합불균형이 없고 열안정성, 내광성, 이형성의 저하가 없는 굴절률 1.71에서 1.77 범위의 에피설파이드계 고굴절 광학재료용 조성물과 이를 이용한 광학재료의 제조방법에 관한 것이다. The present invention relates to an episulfide-based high refractive index optical material. In particular, it does not use polymerization regulators such as stannous halides, contains sulfur, but has a refractive index in the range of 1.71 to 1.77, without color deterioration or polymerization imbalance, and without deterioration of heat stability, light resistance, and release properties. It relates to a composition for an episulfide-based high refractive index optical material and a method of manufacturing an optical material using the same.

플라스틱 렌즈는 가볍고 내충격성이 좋고 착색이 용이하여, 근래 대부분의 안경렌즈에 플라스틱 렌즈가 사용되고 있다. 플라스틱 안경렌즈는 경량성, 고투명성, 낮은 황색도, 내열성, 내광성, 강도를 높이는 방향으로 발전되어 왔다. Plastic lenses are light, have good impact resistance, and are easy to tint, so plastic lenses are used in most spectacle lenses these days. Plastic eyeglass lenses have been developed to increase lightness, high transparency, low yellowness, heat resistance, light resistance, and strength.

한국등록특허 10-0681218호에서는 에피설파이드계 플라스틱 렌즈를 제안하고 있다. 에피설파이드계 렌즈는 고굴절률이면서도 고아베수를 갖는 우수한 성질이 있다. 또, 인장강도, 압축강도, 착색성, 하드 접착력, 생산성 등을 개선하기 위하여 에피설파이드 화합물과 폴리티올 화합물 또는 여기에 폴리이소시아네이트 화합물을 함께 공중합하는 방법이 한국등록특허 10-0417985호, 일본공개특허 평11-352302호 등에서 제안되었다. Korean Patent No. 10-0681218 proposes an episulfide-based plastic lens. Episulfide-based lenses have the excellent property of having a high refractive index and a high Babe number. In addition, in order to improve tensile strength, compressive strength, colorability, hard adhesion, productivity, etc., a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound together is disclosed in Korean Patent No. 10-0417985 and Japanese Patent Publication No. It was proposed in No. 11-352302, etc.

최근에는 에피설파이드 화합물을 포함하는 에피설파이드계 렌즈에서 굴절율을 더욱 높여 1.71 이상의 초고굴절률과 고아베수를 달성하기 위해, 에피설파이드 화합물에 황 원자나 셀레늄 원자 등의 무기 화합물을 배합하는 광학재료용 조성물이 제안되었다(일본 공개특허 2001-2783). 그러나 이렇게 무기 화합물을 배합하는 경우 종종 색상(투명성), 중합불균형, 열안정성, 내광성, 이형성 등에서 문제가 나타난다. 특히, 황 등의 무기화합물이 미반응물질로 남으면 렌즈의 색상, 중합불균형, 열안정성 등에 영향을 미치게 된다. 또, 최근에는 굴절률을 높이기 위해 황을 수지 중에 10% 이상 보통 15% 정도로 사용하는데, 이렇게 수지 중에 황 함유량이 높아지면 반응속도 조절을 위해 촉매와 별도로 주석할로겐 화합물을 사용하여야 하고, 황이 미반응물질로 남을 가능성도 높아진다. Recently, in order to further increase the refractive index in episulfide-based lenses containing episulfide compounds and achieve an ultra-high refractive index and high Abbe number of 1.71 or more, a composition for optical materials that mixes inorganic compounds such as sulfur atoms or selenium atoms with the episulfide compound. This was proposed (Japanese Patent Publication 2001-2783). However, when mixing inorganic compounds like this, problems often appear in color (transparency), polymerization imbalance, thermal stability, light resistance, release property, etc. In particular, if inorganic compounds such as sulfur remain as unreacted substances, they will affect the color, polymerization imbalance, and thermal stability of the lens. Also, recently, in order to increase the refractive index, sulfur is used in the resin from 10% to 15%, but when the sulfur content in the resin increases, a tin halogen compound must be used separately from the catalyst to control the reaction rate, and sulfur is an unreacted material. The likelihood that it will remain increases.

대한민국 등록특허공보 10-0417985Republic of Korea Patent Publication 10-0417985 일본 공개특허공보 특개평 11-352302Japanese Patent Publication No. 11-352302 일본 공개특허공보 2001-2783Japanese Patent Publication No. 2001-2783 대한민국 공개특허공보 10-2014-0122721Republic of Korea Patent Publication 10-2014-0122721

본 발명에서는 황을 포함하면서도 황으로 인한 색상, 중합불균형, 열안정성, 내광성, 이형성 저하의 문제가 없는 굴절률 1.71에서 1.77 범위의 에피설파이드계 고굴절 광학재료용 조성물을 제공하는 것을 목적으로 한다. The purpose of the present invention is to provide a composition for an episulfide-based high refractive index optical material with a refractive index in the range of 1.71 to 1.77 that contains sulfur and does not have problems with color, polymerization imbalance, thermal stability, light resistance, or deterioration of release properties due to sulfur.

특히 본 발명에서는 에피설파이드 화합물과 폴리티올 화합물을 포함하는 에피설파이드계 수지 조성물에 일정 함량의 황과 소량의 이소시아네이트 화합물 및 중합촉매로서 제4급 포스포늄염 등을 포함시켜, 미반응 황으로 인한 색상, 중합불균형, 열안정성, 내광성, 이형성 저하의 문제가 없는 1.71에서 1.77 범위의 에피설파이드계 고굴절 광학재료용 조성물을 제공하고자 한다. In particular, in the present invention, an episulfide-based resin composition containing an episulfide compound and a polythiol compound contains a certain amount of sulfur, a small amount of an isocyanate compound, and a quaternary phosphonium salt as a polymerization catalyst, thereby reducing color due to unreacted sulfur. The object is to provide a composition for an episulfide-based high refractive index optical material in the range of 1.71 to 1.77, which has no problems with polymerization imbalance, thermal stability, light resistance, or deterioration of release properties.

상기와 같은 목적을 달성하기 위하여, 본 발명에서는,In order to achieve the above object, in the present invention,

아래 화학식 1로 표시되는 에피설파이드 화합물 70~92중량%, 폴리티올 화합물 4~20중량%, 고체 황 2~9중량%, 이소시아네이트 화합물 0.01~5중량%, 그리고 제4급 포스포늄염과 제3급 아민화합물 중에서 선택된 1종 이상의 중합촉매 0.05~2중량%를 포함하는, 굴절률 1.71~1.77의 에피설파이드계 고굴절 광학재료용 조성물을 제공한다. 70 to 92% by weight of an episulfide compound represented by the formula 1 below, 4 to 20% by weight of a polythiol compound, 2 to 9% by weight of solid sulfur, 0.01 to 5% by weight of an isocyanate compound, and a quaternary phosphonium salt and a tertiary Provided is a composition for an episulfide-based high refractive index optical material with a refractive index of 1.71 to 1.77, comprising 0.05 to 2% by weight of one or more polymerization catalysts selected from secondary amine compounds.

[화학식 1][Formula 1]

(식 중에서 X는 O 또는 S이고, m은 0~4의 정수이며, n은 0~2의 정수이다.)(In the formula, X is O or S, m is an integer from 0 to 4, and n is an integer from 0 to 2.)

상기 조성물에서 제4급 포스포늄염은, 테트라-부틸포스포늄브로마이드, 테트라페닐포스포늄브로마이드 중 하나를 포함하는 것이 바람직하다. In the above composition, the quaternary phosphonium salt preferably includes one of tetra-butylphosphonium bromide and tetraphenylphosphonium bromide.

상기 조성물에서 제3급 아민화합물은, N,N-디메틸헥실아민， N-메틸디헥실아민， N,N-디메틸시클로헥실아민， N,N-디에틸시클로헥실아민， N-메틸디시클로헥실아민 중 하나를 포함하는 것이 바람직하다. In the composition, the tertiary amine compound is N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, N-methyldicyclohexyl It is preferred to include one of the amines.

상기 조성물에서 에피설파이드 화합물은, 비스(2,3-에피티오프로필)설파이드, 비스(2,3-에피티오프로필)디설파이드, 2,3-에폭시프로필(2,3-에피티오프로필)설파이드, 2,3-에폭시프로필(2,3-에피티오프로필)디설파이드, 비스(2,3-에티오프로필티오)메탄, 2,3-에폭시프로필티오(2', 3'-에피티오프로필티오)메탄, 1,3 및 1,4-비스(β-에피티오프로필티오)시클로헥산, 1,3 및 1,4-비스(β-에피티오프로필티오메틸)시클로헥산, 2,5-비스(β-에피티오프로필티오메틸)-1,4-디티안, 2,5-비스(β-에피티오프로필티오에틸티오메틸)-1,4-디티안, 2-(2-β-에피티오프로필티오에틸티오)-1,3-비스(β-에피티오프로필티오)프로판 중 하나를 포함하는 것이 바람직하다. In the composition, the episulfide compound is bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 2,3-epoxypropyl(2,3-epithiopropyl)sulfide, 2 , 3-epoxypropyl (2,3-epithiopropyl) disulfide, bis (2,3-ethiopropylthio) methane, 2,3-epoxypropylthio (2', 3'-epithiopropylthio) methane, 1,3 and 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epi) Thiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithian, 2-(2-β-epithiopropylthioethylthio )-1,3-bis(β-epithiopropylthio)propane is preferably included.

상기 조성물에서 폴리티올 화합물은, 비스(2-메르캅토에틸)설파이드, 비스(메르캅토메틸)설파이드, 비스(메르캅토메틸티오)메탄 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 중 하나를 포함하는 것이 바람직하다. In the composition, the polythiol compound is bis(2-mercaptoethyl)sulfide, bis(mercaptomethyl)sulfide, bis(mercaptomethylthio)methane 2,3-bis(2-mercaptoethylthio)propane-1 -It is preferred that it contains one of the thiols.

상기 조성물에서 이소시아네이트 화합물은, 이소포론디이소시아네이트(IPDI), 헥사메틸렌디이소시아네이트(HDI), 디사이클로헥실메탄디이소시아네이트(H12MDI), 자일릴렌디이소시아네이트(XDI), 노보란디이소시아네이트(NBDI), 3,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 3,9-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 4,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 2,5-비스(이소시아나토메틸)비시클로[2,2,1]헵탄, 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄 중 하나를 포함하는 것이 바람직하다. Isocyanate compounds in the composition include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), noborane 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, It is preferred that it contains one of 6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

또한, 본 발명에서는 상기 조성물을 중합시키는 것을 포함하는, 굴절률 1.71~1.77의 에피설파이드계 고굴절 광학재료의 제조방법을 제공한다. Additionally, the present invention provides a method for producing an episulfide-based high refractive index optical material with a refractive index of 1.71 to 1.77, which includes polymerizing the composition.

본 발명에서 제공하는 굴절률 1.71~1.77의 에피설파이드계 고굴절 광학재료용 조성물은, 황을 포함하면서도 황으로 인한 뿌연이 발생 등의 색상 저하나 중합불균형이 없고, 열안정성, 내광성, 이형성이 우수하다. The composition for episulfide-based high refractive index optical materials with a refractive index of 1.71 to 1.77 provided by the present invention does not cause color deterioration or polymerization imbalance, such as haze due to sulfur, even though it contains sulfur, and has excellent heat stability, light resistance, and release properties.

본 발명의 에피설파이드계 고굴절 광학재료용 조성물은, 굴절률 1.71~1.77의 고굴절률을 나타내며, 화학식 1로 표시되는 에피설파이드 화합물, 폴리티올 화합, 고체 황, 소량의 이소시아네이트 화합물 및 중합촉매로서 제4급 포스포늄염 및/또는 제3급 아민화합물을 포함한다.The composition for an episulfide-based high refractive index optical material of the present invention exhibits a high refractive index of 1.71 to 1.77, and contains an episulfide compound represented by Chemical Formula 1, a polythiol compound, solid sulfur, a small amount of isocyanate compound, and a quaternary polymerization catalyst. Contains phosphonium salts and/or tertiary amine compounds.

(식 중에서 X는 O 또는 S이고, m은 0~4의 정수이며, n은 0~2의 정수이다.)(In the formula, X is O or S, m is an integer from 0 to 4, and n is an integer from 0 to 2.)

상기 화학식 1로 표시되는 에피설파이드 화합물은 에피설파이드계 광학재료의 주성분이다. 상기 에피설파이드 화합물로, 바람직하게는, 비스(2,3-에피티오프로필)설파이드, 비스(2,3-에피티오프로필)디설파이드, 2,3-에폭시프로필(2,3-에피티오프로필)설파이드, 2,3-에폭시프로필(2,3-에피티오프로필)디설파이드, 비스(2,3-에티오프로필티오)메탄, 2,3-에폭시프로필티오(2', 3'-에피티오프로필티오)메탄, 1,3 및 1,4-비스(β-에피티오프로필티오)시클로헥산, 1,3 및 1,4-비스(β-에피티오프로필티오메틸)시클로헥산, 2,5-비스(β-에피티오프로필티오메틸)-1,4-디티안, 2,5-비스(β-에피티오프로필티오에틸티오메틸)-1,4-디티안, 2-(2-β-에피티오프로필티오에틸티오)-1,3-비스(β-에피티오프로필티오)프로판 중 1종 이상을 사용할 수 있다. The episulfide compound represented by Chemical Formula 1 is the main component of episulfide-based optical materials. The episulfide compound is preferably bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, and 2,3-epoxypropyl(2,3-epithiopropyl)sulfide. , 2,3-epoxypropyl (2,3-epithiopropyl) disulfide, bis (2,3-ethiopropylthio) methane, 2,3-epoxypropylthio (2', 3'-epithiopropylthio) Methane, 1,3 and 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β -Epitiopropylthiomethyl)-1,4-dithian, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithian, 2-(2-β-epithiopropylthio One or more types of ethylthio)-1,3-bis(β-epithiopropylthio)propane can be used.

에피설파이드 화합물은, 조성물 중에 70~92중량%로 포함되며, 보다 바람직하게는, 75~90중량%로 포함될 수 있다. The episulfide compound may be included in the composition at 70 to 92% by weight, and more preferably at 75 to 90% by weight.

상기 폴리티올화합물은, 특별히 한정되지 않고 최소한 1개 이상의 티올기를 가진 화합물이면 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 바람직하게는, 비스(2-메르캅토에틸)설파이드, 4-메르캅토메틸-1,8-디메르캅토-3,6-디티아옥탄, 2,3-비스(2-메르캅토에틸티오)프로판-1-티올, 2,2-비스(메르캅토메틸)-1,3-프로판디티올, 테트라키스(메르캅토메틸)메탄; 2-(2-메르캅토에틸티오)프로판-1,3-디티올, 2-(2,3-비스(2-메르캅토에틸티오)프로필티오)에탄티올, 비스(2,3-디메르캅토프로판닐)설파이드, 비스(2,3-디메르캅토프로판닐)디설파이드, 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판, 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)설파이드, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)디설파이드, 2-(2-메르캅토에틸티오)-3-2-메르캅토-3-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]프로필티오-프로판-1-티올, 2,2 -비스-(3-메르캅토-프로피오닐옥시메틸)-부틸 에스테르, 2-(2-메르캅토에틸티오)-3-(2-(2-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]에틸티오)에틸티오)프로판-1-티올, (4R,11S)-4,11-비스(메르캅토메틸)-3,6,9,12-테트라티아테트라데칸-1,14-디티올, (S)-3-((R-2,3-디메르캅토프로필)티오)프로판-1,2-디티올, (4R,14R)-4,14-비스(메르캅토메틸)-3,6,9,12,15-펜타티아헵탄-1,17-디티올, (S)-3-((R-3-메르캅토-2-((2-메르캅토에틸)티오)프로필)티오)프로필)티오)-2-((2-메르캅토에틸)티오)프로판-1-티올, 3,3'-디티오비스(프로판-1,2-디티올), (7R,11S)-7,11-비스(메르캅토메틸)-3,6,9,12,15-펜타티아헵타데칸-1,17-디티올, (7R,12S)-7,12-비스(메르캅토메틸)-3,6,9,10,13,16-헥사티아옥타데칸-1,18-디티올, 5,7-디메르캅토메틸-1,11-디메르캅토-3,6,9-트리티아운데칸, 4,7-디메르캅토메틸-1,11-디메르캅토-3,6,9-트리티아운데칸, 4,8-디메르캅토메틸-1,11-디메르캅토-3,6,9-트리티아운데칸, 펜타에리트리톨 테트라키스(3-메르캅토프로피오네이트), 트라이메틸올프로판 트리스(3-메르캅토프로피오네이트), 펜타에트리톨테트라키스(2-메르캅토아세테이트), 비스펜타에리트리톨-에테르-헥사키스(3-메르캅토프로피오네이트), 1,1,3,3-테트라키스(메르캅토메틸티오)프로판, 1,1,2,2-테트라키스(메르캅토메틸티오)에탄, 4,6-비스(메르캅토메틸티오)-1,3-디티안 및 2-(2,2-비스(메르캅토디메틸티오)에틸)-1,3-디티안 중에서 선택된 1종 이상을 사용할 수 있다. 이 밖에도 1개 이상의 티올기를 가진 화합물이면 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 또한, 폴리티올화합물에 이소시아네이트나 에피설파이드 화합물, 티에탄 화합물 또는 수지개질제로 불포화 결합을 가진 화합물과의 예비중합에서 얻어진 중합 변성체도 사용이 가능하다. The polythiol compound is not particularly limited, and any compound having at least one thiol group can be used alone or in a mixture of two or more types. Preferably, bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, 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-hexathioctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimer Capto-3,6,9-trithiaoundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecane, 4,8-dimercaptomethyl- 1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), penta Ethritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithian and 2-(2,2-bis(mercaptodimethylthio) )Ethyl)-1,3-dithiane can be used. In addition, any compound having one or more thiol groups can be used one type or a mixture of two or more types. In addition, polymerized modified products obtained by prepolymerization of a polythiol compound with an isocyanate compound, an episulfide compound, a thiethane compound, or a compound having an unsaturated bond as a resin modifier can also be used.

폴리티올화합물은, 특히 바람직하게는, 비스(2-메르캅토에틸)설파이드, 비스(메르캅토메틸)설파이드, 비스(메르캅토메틸티오)메탄 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 중 하나 이상을 포함하며, 또는 여기에 다른 폴리티올화합물을 1종 이상 혼합하여 사용할 수 있다. The polythiol compound is particularly preferably bis(2-mercaptoethyl)sulfide, bis(mercaptomethyl)sulfide, bis(mercaptomethylthio)methane 2,3-bis(2-mercaptoethylthio)propane. It contains one or more of -1-thiol, or it can be used in combination with one or more other polythiol compounds.

폴리티올은 조성물 중에 4~20중량%로 포함될 수 있으며, 보다 바람직하게는 5~15중량%로 포함될 수 있다. Polythiol may be included in the composition at 4 to 20% by weight, and more preferably at 5 to 15% by weight.

상기 고체 황은 바람직하게는 순도 98% 이상이다. 98% 미만의 경우, 불순물의 영향으로 광학재료의 투명도가 떨어질 수 있다. 황의 순도는 보다 바람직하게는 99.0% 이상이며, 특히 바람직하게는 99.5% 이상이다. 통상 상업적으로 입수 가능한 황은 형상이나 정제법의 차이에 의해 구분되는데, 미분황, 콜로이드황, 침강황, 결정황, 승화황 등이 있다. 본 발명에서는, 순도 98% 이상이면 어떤 황이나 사용 가능하다. 바람직하게는, 광학재료용 조성물 제조시 용해가 용이한 미세입자의 미분황을 사용할 수 있다. The solid sulfur preferably has a purity of 98% or more. If it is less than 98%, the transparency of the optical material may decrease due to the influence of impurities. The purity of 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 and purification method, and includes finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, and sublimated sulfur. In the present invention, any sulfur can be used as long as it has a purity of 98% or higher. Preferably, finely powdered sulfur of fine particles that are easily soluble can be used when producing a composition for optical materials.

황은 조성물의 굴절률을 높이는 역할을 하는데, 황을 10중량% 이상에서 15중량 정도로 많이 사용할 경우 굴절률 상승 면에서는 바람직하나, 중합속도 조절이 어려워 중합불균형 생기기 쉽고, 중합속도 조절을 위해 디부틸주석디클로라이드, 디메틸주석디클로라이드 같은 주석할로겐 화합물을 별도로 사용하여야 한다. 또, 미반응의 황이 남기 쉽고 그 결과 렌즈에 뿌연이를 발생시키는 등 투명성 저하를 가져오기 쉽다. 이러한 문제를 해결하기 위해 본 발명에서는 조성물 중 황의 함유량을 9중량% 이하로 하는 동시에 아래에 기술하는 바와 같이 소량의 이소시아네이트 화합물을 같이 사용하며, 중합촉매로 제4급 포스포늄염 및/또는 제3급 아민화합물만을 사용하고 별도로 주석할로겐 화합물을 사용하지 않는다. Sulfur plays a role in increasing the refractive index of the composition. When sulfur is used in large amounts, from 10% by weight to 15% by weight, it is desirable in terms of increasing the refractive index, but it is difficult to control the polymerization rate, so polymerization imbalance is easy to occur, and dibutyltin dichloride is used to control the polymerization rate. , tin halogen compounds such as dimethyltin dichloride must be used separately. In addition, unreacted sulfur is likely to remain, resulting in a decrease in transparency, such as causing haze in the lens. To solve this problem, in the present invention, the sulfur content in the composition is set to 9% by weight or less, and a small amount of isocyanate compound is used as described below, and quaternary phosphonium salt and/or tertiary phosphonium salt are used as polymerization catalysts. Only primary amine compounds are used and no tin halogen compounds are used separately.

상기 조성물 중 황은 2~9중량%로 포함되며, 보다 바람직하게는 3~7중량%로 포함된다. In the composition, sulfur is contained at 2 to 9% by weight, and more preferably at 3 to 7% by weight.

상기 이소시아네이트 화합물은 조성물 중에 소량 포함됨으로써 미반응의 황으로 인해 유발되는 광학재료의 투명성 저하 문제를 해소할 수 있다. 상기 폴리이소시아네이트 화합물은, 특별히 한정되지 않고 최소한 1개 이상의 이소시아네이트 기 및/또는 이소티오시아네이트 기를 가진 화합물이 사용될 수 있다. 예를 들어, 2,2-디메틸펜탄디이소시아네이트, 2,2,4-트리메틸헥산디이소시아네이트, 부텐디이소시아네이트, 1,3-부타디엔-1,4-디이소시아네이트, 헥사메틸렌디이소시아네이트, 2,4,4-트리메틸헥사메틸렌디이소시아네이트, 1,6,11-운데칸트리이소시아네이트, 1,3,6-헥사메틸렌트리이소시아네이트, 1,8-디이소시아네이트-4-이소시아네이토메틸옥탄, 비스(이소시아네이토에틸)카보네이트, 비스(이소시아네이토에틸)에테르 등의 지방족 이소시아네이트 화합물; 이소포론디이소시아네이트, 1,2-비스(이소시아네이토메틸)시클로헥산, 1,3-비스(이소시아네이토메틸)시클로헥산, 1,4-비스(이소시아네이토메틸)시클로헥산, 디시클로헥실메탄디이소시아네이트, 시클로헥산디이소시아네이트, 메틸시클로헥산디이소시아네이트, 디시클로헥실디메틸메탄이소시아네이트, 2,2-디메틸디시클로헥실메탄이소시아네이트 등의 지환족 이소시아네이트 화합물; 자일릴렌디이소시아네이트(XDI), 비스(이소시아네이토에틸)벤젠, 비스(이소시아네이토프로필)벤젠, 비스(이소시아네이토부틸)벤젠, 비스(이소시아네이토메틸)나프탈렌, 비스(이소시아네이토메틸)디페닐에테르, 페닐렌디이소시아네이트, 에틸페닐렌디이소시아네이트, 이소프로필페닐렌디이소시아네이트, 디메틸페닐렌디이소시아네이트, 디에틸페닐렌디이소시아네이트, 디이소프로필페닐렌디이소시아네이트, 트리메틸벤젠트리이소시아네이트, 벤젠트리이소시아네이트, 디페닐디이소시아네이트, 톨루이딘디이소시아네이트, 4,4'-디페닐메탄디이소시아네이트, 3,3'-디메틸디페닐메탄-4,4'-디이소시아네이트, 비벤질-4,4'-디이소시아네이트, 비스(이소시아네이토페닐)에틸렌, 3,3'-디메톡시비페닐-4,4'-디이소시아네이트, 헥사히드로벤젠디이소시아네이트, 헥사히드로디페닐메탄-4,4'-디이소시아네이트 등의 방향족 이소시아네이트 화합물; 비스(이소시아네이토에틸)설파이드, 비스(이소시아네이토프로필)설파이드, 비스(이소시아네이토헥실)설파이드, 비스(이소시아네이토메틸)설폰, 비스(이소시아네이토메틸)디설파이드, 비스(이소시아네이토프로필)디설파이드, 비스(이소시아네이토메틸티오)메탄, 비스(이소시아네이토에틸티오)메탄, 비스(이소시아네이토에틸티오)에탄, 비스(이소시아네이토메틸티오)에탄, 1,5-디이소시아네이토-2-이소시아네이토메틸-3-티아펜탄 등의 함황 지방족 이소시아네이트 화합물; 디페닐설파이드-2,4-디이소시아네이트, 디페닐설파이드-4,4'-디이소시아네이트, 3,3'-디메톡시-4,4'-디이소시아네이토디벤질티오에테르, 비스(4-이소시아네이토메틸벤젠)설파이드, 4,4-메톡시벤젠티오에틸렌글리콜-3,3-디이소시아네이트, 디페닐디설파이드-4,4'-디이소시아네이트, 2,2'-디메틸디페닐디설파이드-5,5'-디이소시아네이트, 3,3'-디메틸디페닐디설파이드-5,5'-디이소시아네이트, 3,3'-디메틸디페닐디설파이드-6,6'-디이소시아네이트, 4,4'-디메틸디페닐디설파이드-5,5'-디이소시아네이트, 3,3'-디메톡시디페닐디설파이드-4,4'-디이소시아네이트, 4,4'-디메톡시디페닐디설파이드-3,3'-디이소시아네이트 등의 함황 방향족 이소시아네이트 화합물; 2,5-디이소시아네이토티오펜, 2,5-비스(이소시아네이토메틸)티오펜, 2,5-디이소시아네이토테트라히드로티오펜, 2,5-비스(이소시아네이토메틸)테트라히드로티오펜, 3,4-비스(이소시아네이토메틸)테트라히드로티오펜, 2,5-디이소시아네이토-1,4-디티안, 2,5-비스(이소시아네이토메틸)-1,4-디티안, 4,5-디이소시아네이토-1,3-디티오란, 4,5-비스(이소시아네이토메틸)-1,3-디티오란, 4,5-비스(이소시아네이토메틸)-2-메틸-1,3-디티오란 등의 함황 복소환 이소시아네이트 화합물 중에서 선택된 1종 또는 2종 이상의 화합물이 사용될 수 있다. 이외에도 최소한 1개 이상의 이소시아네이트 기 및/또는 이소티오시아네이트 기를 가진 화합물이면 1종 또는 2종 이상을 혼합 사용할 수 있다. 또한, 이들 이소시아네이트 화합물의 염소 치환체, 브롬 치환체 등의 할로겐 치환체, 알킬 치환체, 알콕시 치환체, 니트로 치환체나, 다가 알코올 혹은 티올과의 프리폴리머형 변성체, 카르보디이미드 변성체, 우레아 변성체, 뷰렛 변성체 혹은 다이머화, 트라이머화 반응 생성물 등도 사용 가능하다.By including a small amount of the isocyanate compound in the composition, the problem of reduced transparency of optical materials caused by unreacted sulfur can be solved. The polyisocyanate compound is not particularly limited, and a compound having at least one isocyanate group and/or 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-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis(isocyanate) 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, hexahydrobenzened 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; Diphenyl sulfide-2,4-diisocyanate, diphenyl sulfide-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, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate, etc. 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-dithiorane, 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, any compound having at least one isocyanate group and/or isothiocyanate group can be used one type or a mixture of two or more types. In addition, halogen-substituted products such as chlorine-substituted products, bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, and biuret-modified products of these isocyanate compounds. Alternatively, dimerization or trimerization reaction products can also be used.

이소시아네이트 화합물로, 바람직하게는, 이소포론디이소시아네이트(IPDI), 헥사메틸렌디이소시아네이트(HDI), 디사이클로헥실메탄디이소시아네이트(H12MDI), 자일릴렌디이소시아네이트(XDI), 노보란디이소시아네이트(NBDI), 3,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 3,9-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 4,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 2,5-비스(이소시아나토메틸)비시클로[2,2,1]헵탄, 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄 중에서 선택된 1종 이상을 사용할 수 있다. The isocyanate compound is preferably isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), noborane 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 , 6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane can be used.

이소시아네이트 화합물은 조성물 중 0.01~5중량%로 포함되며, 보다 바람직하게는 0.05~3.5중량%로 포함될 수 있다. The isocyanate compound may be included in 0.01 to 5% by weight of the composition, and more preferably 0.05 to 3.5% by weight.

상기 조성물 중 중합촉매는 제4급 포스포늄염, 제3급 아민화합물 중에서 선택된 1종 이상이다. 제3급 아민 화합물은 특히 열경화가 잘 일어나지 않을 때 제4급 포스포늄염의 보조촉매로 동시에 사용하면 바람직하다. 조성물 중에 황을 2~9중량%로 포함함으로써 촉매로 제4급 포스포늄염 및/또는 제3급 아민화합물만을 사용해도 되고, 중합속도 조절을 위해 별도로 주석할로겐 화합물을 사용하지 않아도 된다. 주석할로겐 화합물을 사용하지 않기 때문에 위와 같이 이소시아네이트 화합물을 조성물 중에 포함할 수 있다. The polymerization catalyst in the composition is at least one selected from quaternary phosphonium salts and tertiary amine compounds. Tertiary amine compounds are preferably used simultaneously as cocatalysts for quaternary phosphonium salts, especially when thermal curing does not occur easily. By including 2 to 9% by weight of sulfur in the composition, only quaternary phosphonium salts and/or tertiary amine compounds can be used as catalysts, and there is no need to use a separate tin halogen compound to control the polymerization rate. Since tin halogen compounds are not used, isocyanate compounds can be included in the composition as above.

제4급 포스포늄염은 바람직하게는 테트라-부틸포스포늄브로마이드, 테트라페닐포스포늄브로마이드 중 어느 하나를 포함한다. The quaternary phosphonium salt preferably includes either tetra-butylphosphonium bromide or tetraphenylphosphonium bromide.

제3급 아민화합물은, 트리메틸아민， 트리에틸아민， 트리-n-프로필아민， 트리-iso-프로필아민， 트리-1,2-디메틸프로필아민， 트리-3-메톡시프로필아민， 트리-n-부틸아민， 트리-iso-부틸아민， 트리-sec-부틸아민， 트리펜틸아민， 트리-3-펜틸아민， 트리-n-헥실아민， 트리-n-옥틸아민， 트리-2-에틸헥실아민， 트리도데실아민， 트리라우릴아민， 디시클로헥실에틸아민， 시클로헥실디에틸아민， 트리시클로헥실아민， N,N-디메틸헥실아민， N-메틸디헥실아민， N,N-디메틸시클로헥실아민， N,N-디에틸시클로헥실아민， N-메틸디시클로헥실아민， N，N-디에틸에탄올아민， N，N-디메틸에탄올아민， N-에틸디에타놀아민， 트리에탄올아민， 트리벤질아민， N,N-디메틸벤질아민， 디에틸벤질아민， 트리페닐아민， N,N-디메틸아미노-p-크레졸， N,N-디메틸아미노메틸페놀， 2-(N,N-디메틸아미노메틸)페놀， N, N-디메틸아닐린， N,N-디에틸아닐린， N-메틸모르폴린, N-메틸피페리딘，2-(2-디메틸아미노에톡시)-4-메틸-1, 3, 2-디옥사보르난 등의 3급 아민 화합물 중에서 선택된 1종 또는 2종 이상의 화합물을 혼합하여 사용할 수 있다. 제3급 아민화합물은, 바람직하게는 N,N-디메틸헥실아민， N-메틸디헥실아민， N,N-디메틸시클로헥실아민， N,N-디에틸시클로헥실아민， N-메틸디시클로헥실아민 중 어느 하나를 포함한다. Tertiary amine compounds include trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, and tri-n. -Butylamine, tri-iso-butylamine, tri-sec-butylamine, tripentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine , Tridodecylamine, trilaurylamine, dicyclohexylethylamine, cyclohexyldiethylamine, tricyclohexylamine, N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexyl Amine, N, N-diethylcyclohexylamine, N-methyldicyclohexylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, N-ethyldiethanolamine, triethanolamine, tribenzylamine , N,N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N,N-dimethylamino-p-cresol, N,N-dimethylaminomethylphenol, 2-(N,N-dimethylaminomethyl)phenol , N, N-dimethylaniline, N, N-diethylaniline, N-methylmorpholine, N-methylpiperidine, 2-(2-dimethylaminoethoxy)-4-methyl-1, 3, 2- One or two or more compounds selected from tertiary amine compounds such as dioxabornane can be used in combination. The tertiary amine compound is preferably N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, N-methyldicyclohexyl Contains any one of amines.

중합촉매는 상기 조성물 중에 0.05~2중량%로 포함되며, 보다 바람직하게는 0.1~1.5중량%로 포함될 수 있다. 제3급 아민화합물을 제4급 포스포늄염의 보조촉매로 사용할 경우 중합촉매의 전체 함량 범위 내에서 사용하는 것이 바람직하며, 이때 제3급 아민화합물은 상기 조성물 중에 0.05~1중량%로 포함되는 것이 보다 바람직하다. The polymerization catalyst may be included in the composition in an amount of 0.05 to 2% by weight, and more preferably in an amount of 0.1 to 1.5% by weight. When using a tertiary amine compound as a cocatalyst for a quaternary phosphonium salt, it is preferable to use it within the total content range of the polymerization catalyst, and in this case, the tertiary amine compound is contained in 0.05 to 1% by weight in the composition. It is more desirable.

상기 조성물은 중합시 먼저 프리폴리머를 형성한 후 중합하는 것이 바람직한데, 이때 프리폴리머의 형성을 원활하게 하기 위해 바람직하게는 중합조절제로 알킬이미다졸을 더 포함할 수 있다. 상기 알킬이미다졸은 특히 바람직하게는 2-메르캅토-1-메틸이미다졸을 포함한다. 2-메르캅토-1-메틸이미다졸은 바람직하게는 순도 98% 이상의 것을 사용한다. 광학재료용 조성물 중에 바람직하게는 0.01~5중량% 포함될 수 있으며, 보다 바람직하게는 0.1~3중량%, 더욱 바람직하게는 0.15~1중량%가 포함될 수 있다.It is preferable that the composition first form a prepolymer and then polymerize it. In this case, to facilitate the formation of the prepolymer, an alkylimidazole may preferably be further included as a polymerization regulator. The alkylimidazole particularly preferably includes 2-mercapto-1-methylimidazole. 2-Mercapto-1-methylimidazole is preferably used with a purity of 98% or higher. The composition for optical materials may preferably contain 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, and even more preferably 0.15 to 1% by weight.

본 발명의 광학재료용 조성물은 내부이형제를 더 포함할 수 있다. 바람직하게는 내부이형제로 인산에스테르 화합물을 포함할 수 있다. 인산에스테르 화합물은 포스포러스펜톡사이드(P2O5)에 2~3몰의 알코올 화합물을 부가하여 제조하는데 이때 사용하는 알코올 종류에 따라 여러 가지 형태의 인산에스테르 화합물을 얻을 수 있다. 대표적인 것으로는 지방족 알코올에 에틸렌옥사이드 혹은 프로필렌 옥사이드가 부가되거나 노닐페놀기 등에 에틸렌 옥사이드 혹은 프로필렌 옥사이드가 부가된 종류들이다. 본 발명의 중합성 조성물에, 에틸렌 옥사이드 혹은 프로필렌 옥사이드가 부가된 인산에스테르화합물이 내부이형제로 포함될 경우, 이형성이 좋고 품질이 우수한 광학재료를 얻을 수 있어 바람직하다. 본 발명의 조성물은, 내부이형제로, 바람직하게는, 4-PENPP[폴리옥시에틸렌노닐페닐에테르포스페이트(에틸렌옥사이드가 5몰 부가된 것 5중량%, 4몰 부가된 것 80중량%, 3몰 부가된 것 10중량%, 1몰 부가된 것 5중량%)], 8-PENPP[폴리옥시에틸렌노닐페닐에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)], 12-PENPP[폴리옥시에틸렌노닐페닐에테르포스페이트(에틸렌옥사이드 13몰 부가된 것 3중량%, 12몰 부가된 것 80중량%, 11몰 부가된 것 8중량%, 9몰 부가된 것 3중량%, 4몰 부가된 것 6중량%)], 16-PENPP[폴리옥시에틸렌 노닐페닐에테르포스페이트(에틸렌옥사이드가 17몰 부가된 것 3중량%, 16몰 부가된 것 79중량%, 15몰 부가된 것 10중량%, 14몰 부가된 것 4중량%, 13몰 부가된 것 4중량%)], 20-PENPP[폴리옥시에틸렌노닐페닐에테르 포스페이트(에틸렌옥사이드가 21몰 부가된 것 6중량%, 20몰 부가된 것 76중량%, 19몰 부가된 것 7중량%, 18몰 부가된 것 6중량%, 17몰 부가된 것 5중량%)], 4-PPNPP[폴리옥시프로필렌노닐페닐에테르포스페이트(프로필렌옥사이드가 5몰 부가된 것 5중량%, 4몰 부가된 것 80중량%, 3몰 부가된 것 10중량%, 1몰 부가된 것 5중량%)], 8-PPNPP[폴리옥시프로필렌노닐페닐에테르포스페이트(프로필렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가 된 것 6중량%, 6몰 부가된 것 6중량%)], 12-PPNPP[폴리옥시프로필렌노닐페닐에테르포스페이트(프로필렌옥사이드 13몰 부가된 것 3중량%, 12몰 부가된 것 80중량%, 11몰 부가된 것 8중량%, 9몰 부가된 것 3중량%, 4몰 부가된 것 6중량%)], 16-PPNPP[폴리옥시프로필렌 노닐페닐에테르포스페이트(프로필렌옥사이드 17몰 부가된 것 3중량%, 16몰 부가된 것 79중량%, 15몰 부가된 것 10중량%, 14몰 부가된 것 4중량%, 13몰 부가된 것 4중량%)], 20-PPNPP[폴리옥시프로필렌노닐페닐에테르포스페이트(프로필렌옥사이드가 21몰 부가된 것 6중량%, 20몰 부가된 것 76중량%, 19몰 부가된 것 7중량%, 18몰 부가된 것 6중량%, 17몰 부가된 것 5중량%)] 및 Zelec UNTM 중에서 선택된 1종 이상을 사용한다. 이러한 인산에스테르화합물의 할로겐화합물 치환체를 비롯한 각종 치환체들도 같은 목적으로 사용이 가능하다.The composition for optical materials of the present invention may further include an internal mold release agent. Preferably, the internal mold release agent may include a phosphoric acid ester compound. Phosphate ester compounds are produced by adding 2 to 3 moles of alcohol compounds to phosphorus pentoxide (P 2 O 5 ), and various types of phosphoric acid ester compounds can be obtained depending on the type of alcohol used. Representative examples include those 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, etc. When a 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 release agent, it is preferable to obtain an optical material with good release properties and excellent quality. The composition of the present invention contains, as an internal release agent, preferably 4-PENPP [polyoxyethylene nonylphenyl ether phosphate (5% by weight of 5 moles of ethylene oxide added, 80% by weight of 4 moles added, 3 moles added) 10% by weight of those added, 5% by weight of those added by 1 mole)], 8-PENPP [polyoxyethylene nonylphenyl ether phosphate (3% by weight of those added by 9 moles of ethylene oxide, 80% by weight of those added by 8 moles, 9 5% by weight of those added by mole, 6% by weight of those added by 7 moles, 6% by weight of those added by 6 moles)], 12-PENPP [polyoxyethylene nonylphenyl ether phosphate (3% by weight of those added by 13 moles of ethylene oxide) , 80% by weight of those added by 12 moles, 8% by weight of those added by 11 moles, 3% by weight of those added by 9 moles, 6% by weight of those added by 4 moles)], 16-PENPP [polyoxyethylene nonylphenyl ether phosphate (3% by weight with 17 moles of ethylene oxide added, 79% by weight with 16 moles added, 10% by weight with 15 moles added, 4% by weight with 14 moles added, 4% by weight with 13 moles added)] , 20-PENPP [polyoxyethylene nonylphenyl ether phosphate (6% by weight with 21 moles of ethylene oxide added, 76% by weight with 20 moles added, 7% by weight with 19 moles added, 6% by weight with 18 moles added) %, 5% by weight of 17 moles added)], 4-PPNPP [polyoxypropylene nonylphenyl ether phosphate (5% by weight of 5 moles of propylene oxide added, 80% by weight of 4 moles added, 3 moles added) 10% by weight of that added, 5% by weight of 1 mole added)], 8-PPNPP [polyoxypropylene nonylphenyl ether phosphate (3% by weight of that added by 9 moles of propylene oxide, 80% by weight of 8 mole added, 9 moles) 5% by weight of those added, 6% by weight of those added by 7 moles, 6% by weight of those added by 6 moles)], 12-PPNPP [polyoxypropylene nonylphenyl ether phosphate (3% by weight of those with 13 moles of propylene oxide added, 80% by weight of those added by 12 moles, 8% by weight of those added by 11 moles, 3% by weight of those added by 9 moles, 6% by weight of those added by 4 moles)], 16-PPNPP [polyoxypropylene nonylphenyl ether phosphate ( 3% by weight of those with 17 moles of propylene oxide added, 79% by weight of those with 16 moles added, 10% by weight of those with 15 moles added, 4% by weight of those with 14 moles added, 4% by weight of those with 13 moles added)], 20 -PPNPP [polyoxypropylene nonylphenyl ether phosphate (6% by weight with 21 moles of propylene oxide added, 76% by weight with 20 moles added, 7% by weight with 19 moles added, 6% by weight with 18 moles added, 17 mol added (5% by weight)] and Zelec UN TM Use one or more types selected from among. Various substituents, including halogen compound substituents of these phosphoric acid ester compounds, can also be used for the same purpose.

본 발명의 광학재료용 조성물은, 광학재료의 광학적인 물성을 향상시키기 위해, 내충격성, 비중 및 모노머 점도 등을 조절하는 목적으로 올레핀 화합물을 반응성 수지개질제로 더 포함할 수 있다. 수지개질제로서 첨가할 수 있는 올레핀 화합물로는, 예를 들어, 벤질아크릴레이트, 벤질메타크릴레이트, 부톡시에틸아크릴레이트, 부톡시메틸메타크릴레이트, 시클로헥실아크릴레이트, 시클로헥실메타크릴레이트, 2-히드록시에틸아크릴레이트, 2-히드록시메틸메타크릴레이트, 글리시딜아크릴레이트, 글리시딜메타크릴레이트, 페녹시 에틸아크릴레이트, 페녹시에틸메타크릴레이트, 페닐메타크릴레이트, 에틸렌글리콜디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디아크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디아크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 폴리에틸렌글리콜디아크릴레이트, 폴리에틸렌글리콜디메타크릴레이트, 네오펜틸글리콜디아크릴레이트, 네오펜틸글리콜디메타크릴레이트, 에틸렌글리콜비스글리시딜아크릴레이트, 에틸렌글리콜비스글리시딜메타크릴레이트, 비스페놀 A 디아크릴레이트, 비스페놀 A 디메타크릴레이트, 2,2-비스(4-아크록시에톡시페닐)프로판, 2,2-비스(4-메타크록시에톡시페닐)프로판, 2,2-비스(4-아크록시디에톡시페닐)프로판, 2,2-비스(4-메타크록시디에톡시페닐)프로판, 비스페놀 F 디아크릴레이트, 비스페놀 F 디메타크릴레이트, 1,1-비스(4-아크록시에톡시페닐)메탄, 1,1-비스(4-메타크록시에톡시페닐)메탄, 1,1-비스(4-아크록시디에톡시페닐)메탄, 1,1-비스(4-메타크록시디에톡시페닐)메탄, 디메티롤트리시클로데칸디아크릴레이트, 트리메티롤프로판트리아크릴레이트, 트리메티롤프로판트리메타크릴레이트, 글리세롤디아크릴레이트, 글리세롤디메타크릴레이트, 펜타에리트리톨트리아크릴레이트, 펜타에리트리톨테트라크릴레이트, 펜타에리트리톨테트라메타크릴레이트, 메틸티오아크릴레이트, 메틸티오메타크릴레이트, 페닐티오아크릴레이트, 벤질티오메타크릴레이트, 크실리렌디티올디아크릴레이트, 크실리렌디티올디메타크릴레이트, 메르캅토에틸설파이드디아크릴레이트, 메르캅토에틸설파이드디메타크릴레이트 등의 (메타)아크릴레이트 화합물 및, 알릴글리시딜에테르, 디알릴프탈레이트, 디알릴테레프탈레이트, 디알릴이소프탈레이트, 디알릴카보네이트, 디에틸렌글리콜비스알릴카보네이트 등의 알릴 화합물 및 스티렌, 클로로스티렌, 메틸스티렌, 브로모스티렌, 디브로모스티렌, 디비닐벤젠, 3,9-디비닐스피로비(m-디옥산) 등의 비닐 화합물 등이 있으며, 사용 가능한 화합물이 이들 예시 화합물로 제한되는 것은 아니다. 이들 올레핀 화합물은 단독, 또는 2종류 이상을 혼합하여 사용해도 좋다.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 the optical properties of the optical material. Olefin compounds that can be added as a resin modifier include, for example, 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, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol dichloride. 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 methacrylate rate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis(4-acroxyethoxyphenyl)propane, 2,2-bis(4-methacroxyethoxyphenyl)propane, 2, 2-bis(4-acroxydiethoxyphenyl)propane, 2,2-bis(4-methacroxydiethoxyphenyl)propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis( 4-acroxyethoxyphenyl) methane, 1,1-bis (4-methacroxyethoxyphenyl) methane, 1,1-bis (4-acroxydiethoxyphenyl) methane, 1,1-bis (4 -Methacryloxydiethoxyphenyl) methane, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylene dithiol diacrylate, (meth)acrylate compounds such as silylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, di Allyl compounds such as allyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, and styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m -dioxane) and other vinyl compounds, and the compounds that can be used are not limited to these exemplary compounds. These olefin compounds may be used alone or in combination of two or more types.

본 발명의 광학재료용 조성물은 필요에 따라 자외선 흡수제를 더 포함할 수 있다. 자외선 흡수제는 광학재료의 내광성 향상 및 자외선 차단을 위하여 사용되는데, 광학재료에 사용되는 공지의 자외선 흡수제가 제한 없이 사용될 수 있다. 예를 들면, 에틸-2-시아노-3,3-디페닐아크릴레이트, 2-(2'-히드록시-5-메틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3'-t-부틸-5'-메틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-아밀페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-5'-t-부틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸; 2,4-디히드록시벤조페논; 2-히드록시-4-메톡시벤조페논; 2-히드록시-4-옥틸옥시벤조페논; 4-도데실옥시-2-히드록시벤조페논; 4-벤조록시-2-히드록시벤조페논; 2,2',4,4'-테트라히드록시벤조페논; 2,2'-디히드록시-4,4'-디메톡시벤조페논 등이 단독으로 또는 2종 이상 혼합 사용될 수 있다. The composition for optical materials of the present invention may further include an ultraviolet absorber, if necessary. Ultraviolet absorbers are used to improve the light resistance of optical materials and block ultraviolet rays. Known ultraviolet absorbers used in optical materials can 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-benzoloxy-2-hydroxybenzophenone; 2,2',4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc. may be used alone or in combination of two or more types.

바람직하게는, 400㎚ 이하의 파장역에서 양호한 자외선 흡수능을 가지고, 본 발명의 조성물에 양호한 용해성을 갖는, 2-(2'-히드록시-3'-t-부틸-5'-메틸페닐)-5-클로로-2H-벤조트리아졸과 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸 등을 사용할 수 있다. 이와 같은 자외선 흡수제는 광학재료용 조성물 100g에 대해 0.6g 이상으로 사용될 때 400nm 이상의 차단이 가능하다. 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 the present invention. -Chloro-2H-benzotriazole and 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole can be used. This type of ultraviolet absorber is capable of blocking 400 nm or more when used in an amount of 0.6 g or more per 100 g of the composition for optical materials.

본 발명의 광학재료용 조성물은 이 밖에도 필요에 따라 쇄연장제, 가교제, 광안정제, 산화방지제, 착색 방지제, 유기염료, 충전제, 밀착성 향상제 등의 여러 가지의 첨가제를 더 포함할 수 있다. In addition, the composition for optical materials of the present invention may further include various additives, such as chain extenders, cross-linking agents, light stabilizers, antioxidants, discoloration inhibitors, organic dyes, fillers, and adhesion improvers, as necessary.

위와 같이 조성된 본 발명의 광학재료용 조성물은, 바람직하게는 액상 점도가 500cps(20℃) 이하이며, 중합 후 고상굴절율(Ne)이 1.71~1.77 이다. The composition for optical materials of the present invention formulated as described above preferably has a liquid viscosity of 500 cps (20°C) or less, and a solid phase refractive index (Ne) of 1.71 to 1.77 after polymerization.

위와 같이 조성된 조성물을 주형 중합시키면 에피설파이드계 광학재료를 얻을 수 있다. 좀 더 자세히 설명하면 다음과 같다. 먼저, 개스켓 또는 테이프 등으로 유지된 성형 몰드 사이에, 본 발명의 중합성 조성물을 주입한다. 이때, 얻어지는 광학재료의 요구 물성에 따라, 또는 필요에 따라, 감압 하에서의 탈포처리나 가압, 감압 등의 여과처리 등을 실시하는 것이 바람직한 경우가 많다. 중합조건은, 중합성 조성물, 촉매의 종류와 사용량, 몰드의 형상 등에 의해서 크게 조건이 달라지기 때문에 한정되는 것은 아니지만, 약 -50~130℃의 온도에서 1~50시간에 걸쳐 실시된다. 경우에 따라서는, 10~130℃의 온도범위에서 유지 또는 서서히 승온하여, 1~48 시간에서 경화시키는 것이 바람직하다.By performing mold polymerization of the composition as described above, an episulfide-based optical material can be obtained. To explain in more detail, it is as follows. First, the polymerizable composition of the present invention is injected between molds held by gaskets or tapes. At this time, in many cases, it is desirable to perform degassing treatment under reduced pressure or filtration treatment such as pressurization or reduced pressure, depending on the required physical properties of the obtained optical material or as necessary. Polymerization conditions are not limited as they vary greatly depending on the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc., but are carried out at a temperature of about -50 to 130°C for 1 to 50 hours. In some cases, it is preferable to maintain the temperature in the range of 10 to 130°C or gradually increase the temperature to cure for 1 to 48 hours.

경화로 얻어진 에피설파이드계 광학재료는, 필요에 따라, 어닐링 등의 처리를 실시해도 좋다. 처리 온도는 통상 50~130℃의 사이에서 행해지며, 90~120℃에서 실시하는 것이 바람직하다.The episulfide-based optical material obtained through curing may be subjected to treatment such as annealing, if necessary. The treatment temperature is usually between 50 and 130°C, and is preferably between 90 and 120°C.

본 발명의 광학재료는, 주형 중합 시의 몰드를 바꾸는 것으로 여러 가지 형상의 성형체로 얻을 수 있으므로, 안경 렌즈, 카메라 렌즈, 발광다이오드(LED) 등의 각종 광학재료로 사용하는 것이 가능하다. 특히, 안경 렌즈, 카메라 렌즈, 발광다이오드 등의 광학재료나 광학소자로서 적합하다.Since the optical material of the present invention can be obtained as a molded body of various shapes by changing the mold during cast polymerization, it can be used in various optical materials such as spectacle lenses, camera lenses, and light-emitting diodes (LEDs). In particular, it is suitable as optical materials or optical elements such as spectacle lenses, camera lenses, and light-emitting diodes.

본 발명에 따라 얻어진 에피설파이드계 광학재료는 하드 접착성이 좋아 프라이머 없이도 하드 코팅이 가능하고, 코팅이 매우 용이하며, 코팅의 안정성 또한 매우 우수하다. 본 발명에 따라 얻어진 플라스틱 광학렌즈는 이 밖에도 필요에 따라, 단면 또는 양면에 다양한 코팅층을 형성하여 사용할 수 있다. 코팅층으로서는, 프라이머층, 하드코팅층, 반사방지막층, 방담코트막층, 방오염층, 발수층 등이 모두 가능하며, 이들 코팅층은 각각 단독으로 사용해도 좋고 복수의 코팅층을 다층화하여 사용해도 좋다. 또한, 양면에 코팅층을 형성하는 경우, 각각의 면에 동일한 코팅층을 형성하는 것이나 상이한 코팅층을 형성하는 것 모두 가능하다.The episulfide-based optical material obtained according to the present invention has good hard adhesion, allows hard coating without a primer, is very easy to coat, 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 or both sides as needed. As a coating layer, a primer layer, a hard coating layer, an anti-reflection layer, an anti-fog coating layer, an anti-fouling layer, a water-repellent layer, etc. can all be used, and these coating layers may be used individually or may be used in multiple layers. Additionally, when forming a coating layer on both sides, it is possible to form the same coating layer or different coating layers on each side.

[[ 실시예Example ]]

이하 구체적인 실시예를 통해 본 발명을 보다 상세히 설명한다. 그러나 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다. The present invention will be described in more detail below through specific examples. However, these examples are only for illustrating the present invention in more detail, and the scope of the present invention is not limited by these examples.

<< 실시예Example 1> 1>

반응기를 1.0 torr 이하로 감압하고, 외부온도를 54℃로 조절하였다. 이 반응기를 교반하면서 비스(2,3-에피티오프로필)설파이드 화합물 86g 및 2,3-에폭시프로필(2,3-에피티오프로필)설파이드 2g을 넣고, 연속하여 황 4g과 자외선 차단제 UV 31 0.8g을 첨가하고, 30분 동안 감압하여 탈포한 후에 2-메르캅토-1-메틸이미다졸 0.15g을 첨가하고 1시간 동안 교반하였다. 이후 30℃로 냉각하고 비스(2-메르캅토에틸)설파이드 2g, 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 6g, 테트라부틸포스포늄브로마이드 0.3g 및 내부이형제로 인산에스테르계인 8-PENPP[폴리옥시에티렌노닐페놀에스테르포스페이트(에틸렌옥사이드가 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%) 0.08g 을 반응기에 넣고, 광학렌즈용 수지 조성물을 만든 후 아래와 같은 방법으로 광학 렌즈를 제조하고 광학렌즈의 물성을 측정하였다.The reactor was reduced to 1.0 torr or less, and the external temperature was adjusted to 54°C. While stirring the reactor, 86g of bis(2,3-epithiopropyl)sulfide compound and 2g of 2,3-epoxypropyl(2,3-epithiopropyl)sulfide were added, followed by 4g of sulfur and 0.8g of UV blocker UV 31. was added and degassed under reduced pressure for 30 minutes, then 0.15 g of 2-mercapto-1-methylimidazole was added and stirred for 1 hour. After cooling to 30℃, 2g of bis(2-mercaptoethyl)sulfide, 6g of 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 0.3g of tetrabutylphosphonium bromide, and phosphoric acid ester as internal release agent. System 8-PENPP [polyoxyethylene nonyl phenol ester phosphate (3% by weight with 9 moles of ethylene oxide added, 80% by weight with 8 moles added, 5% by weight with 9 moles added, 6 with 7 moles added) 0.08g (% by weight, 6 moles added, 6% by weight) was placed in a reactor to prepare a resin composition for an optical lens, and then an optical lens was manufactured in the following manner and the physical properties of the optical lens were measured.

(1) 위와 같이 제조된 광학렌즈용 수지 조성물을 43℃에서 감압 하에 1시간 동안 교반하며 탈포하고, 30℃로 냉각하고 IPDI 0.1g 및 유기염료 HTAQ(88ppm) 및 PRD(30ppm)의 혼합용액을 첨가하고, 15분 동안 저어주고 여과한 다음, 감압탈포를 5분 동안 더 행하고, 폴리에스테르 점착테이프로 조립된 유리몰드에 주입하였다.(1) The resin composition for optical lenses prepared as above was degassed by stirring for 1 hour under reduced pressure at 43°C, cooled to 30°C, and mixed with 0.1 g of IPDI and the organic dyes HTAQ (88ppm) and PRD (30ppm). After addition, stirring for 15 minutes and filtering, degassing under reduced pressure was performed for an additional 5 minutes, and then injected into a glass mold assembled with polyester adhesive tape.

(2) 안경 렌즈용 수지조성물이 주입된 유리 몰드를 강제 순환식 오븐에서 30℃에서 110℃까지 20시간에 걸쳐서 가열 경화시킨 후, 70℃로 냉각하여 유리몰드를 탈착하여 렌즈를 얻었다. 얻어진 렌즈는 지름 72㎜로 가공한 후 알카리 수성 세척액에 초음파 세척한 다음, 100℃에서 2시간 어닐링 처리하였다. 아래와 같은 방법으로 물성을 측정하여 그 결과를 표 1에 나타내었다.(2) The glass mold into which the resin composition for spectacle lenses was injected was cured by heating in a forced circulation oven from 30°C to 110°C for 20 hours, then cooled to 70°C and the glass mold was detached to obtain a lens. The obtained lens was processed to a diameter of 72 mm, ultrasonic cleaned in an aqueous alkaline cleaning solution, and then annealed at 100°C for 2 hours. The physical properties were measured using the method below and the results are shown in Table 1 .

물성 실험방법Physical property test method

실시예에서 제조된 광학렌즈의 물성을 아래의 실험방법으로 측정하여 그 결과를 표 1에 기재하였다.The physical properties of the optical lenses manufactured in the examples were measured using the experimental method below, and the results are listed in Table 1 .

1) 굴절률 및 아베수: Atago 사의 DR-M4 모델인 아베 굴절계를 사용하여 측정하였다.1) Refractive index and Abbe number: Measured using Atago's DR-M4 model Abbe refractometer.

2) 투명성: 100매의 렌즈를 USHIO USH-10D인 수은 아크램프(Mercury Arc Lamp) 아래 육안으로 관찰하여, 렌즈의 탁함이 1개 이하가 발견되면 "◎"로 표시하고, 2~3개가 발견되면 "○"로 표시하고, 4개 이상이 발견되면 "×"로 표시하였다. 2) Transparency: Observe 100 lenses with the naked eye under the USHIO USH-10D Mercury Arc Lamp, and if less than 1 cloudiness of the lens is found, mark it as "◎", and if 2 to 3 cloudiness is found, If more than 4 were found, it was marked with "○", and if more than 4 were found, it was marked with "×".

3) 중합불균형: 100매의 안경렌즈를 USHIO USH-10D인 수은 아크램프(Mercury Arc Lamp) 아래 육안으로 관찰하고, 호상이 확인된 렌즈는 중합불균형이 있는 것으로 판정하여, 호상이 없는 것은 "◎"로 표시하고, 호상이 1~2개가 있는 것은 "○"로 표시하고, 호상이 3개 이상이 있는 것은 "×"로 표시하였다.3) Polymerization imbalance: 100 spectacle lenses were observed with the naked eye under a USHIO USH-10D mercury arc lamp, and lenses with confirmed polarization were judged to have polymerization imbalance, and those without polarization were judged to be "◎" ", those with 1 to 2 arcs are marked with "○", and those with 3 or more arcs are marked with "×".

4) 내광성: Q-Lab.사의 QUV/SE 모델 Accelerated Weathering Tester를 사용하였다. QUV 시험은 두께가 1.2㎜인 평판렌즈를 UVA-340 (340㎚), 광량 0.76W/㎡, 4시간 BPT(Black Panel Temperature)(60℃), 4시간 condensation (50℃) 조건하에서 24시간 동안 조사한 후, 색상변화의 측정에서 APHA 값이 0~2로 변하면 "◎"로 표시하고, APHA 값이 3~4으로 변하면 "○"로 표시하고, APHA 값이 4~6으로 변하면 "Δ"로 표시하고, APHA 값이 7 이상으로 변하면 "×"로 표시하였다.4) Light resistance: QUV/SE model Accelerated Weathering Tester from Q-Lab. was used. The QUV test is performed on a flat lens with a thickness of 1.2 mm for 24 hours under the conditions of UVA-340 (340 ㎚), light intensity of 0.76 W/㎡, 4 hours BPT (Black Panel Temperature) (60℃), and 4 hours of condensation (50℃). After irradiation, in the measurement of color change, if the APHA value changes from 0 to 2, it is marked as "◎", if the APHA value changes from 3 to 4, it is marked as "○", and if the APHA value changes from 4 to 6, it is marked as "Δ". Indicated, and when the APHA value changes to 7 or more, it is marked with “×”.

5) 열안정성: 경화된 광학렌즈를 100℃에서 3시간 동안 유지하고, 색상변화의 측정에서 APHA 값이 2 이하로 변하면 "◎"로 표시하고, APHA 값이 3~5으로 변하면 "○"로 표시하고, APHA 값이 6~8로 변하면 "Δ"으로 표시하고, APHA 값이 9 이상으로 변하면 "×"로 표시하였다.5) Thermal stability: The cured optical lens is maintained at 100℃ for 3 hours, and in the measurement of color change, if the APHA value changes to 2 or less, it is marked as "◎", and if the APHA value changes to 3 to 5, it is marked as "○". If the APHA value changes from 6 to 8, it is indicated as "Δ", and if the APHA value changes to 9 or more, it is indicated as "×".

6)이형성: 광학렌즈용 수지 조성물을 열경화시키고 70℃에서 탈형시 플라스틱렌즈와 몰드 사이가 쉽게 분리되어 100개의 유리몰드 중 하나도 깨지지 않으면 "◎"로 표시하였고, 100개의 유리몰드 중 1~2개가 깨지면 "○"로 표시하고, 쉽게 분리되지 않아 100개의 유리몰드 중 3개 이상이 깨지면 "×" 로 표시하였다. (균일한 평가를 위하여 -0.00 디옵타의 몰드를 이용하였다.).6) Release property: When the resin composition for optical lenses is heat-cured and demolded at 70°C, the plastic lens and the mold are easily separated and if none of the 100 glass molds are broken, it is marked with "◎", and 1 to 2 out of 100 glass molds If more than 3 of the 100 glass molds were broken because they were not easily separated, it was marked as "○". (For uniform evaluation, a mold of -0.00 diopter was used.)

<< 실시예Example 2~4> 2~4>

실시예 1과 같은 방법으로 표 1에 기재된 조성에 따라 광학렌즈를 제조하고, 그 물성을 측정하였으며, 결과는 표 1에 기재하였다.An optical lens was manufactured according to the composition shown in Table 1 in the same manner as in Example 1, and its physical properties were measured, and the results are shown in Table 1 .

<< 실시예Example 5> 5>

반응기를 1.0 torr 이하로 감압하고, 외부온도를 54℃로 조절하였다. 이 반응기를 교반하면서 비스(2,3-에피티오프로필티오)메탄 화합물 80g 및 2,3-에폭시프로필(2,3-에피티오프로필)설파이드 2g을 넣고, 연속하여 황 5g과 자외선 차단제 UV 31 0.8g을 첨가하고, 30분 동안 감압하여 탈포한 후에 2-메르캅토-1-메틸이미다졸 0.15g을 첨가하고 1시간 동안 교반하였다. 이후 30℃로 냉각하고 비스(메르캅토메틸)설파이드 4g, 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 9g, 테트라부틸포스포늄브로마이드 0.3g 및 내부이형제로 인산에스테르계인 8-PENPP[폴리옥시에티렌노닐페놀에스테르포스페이트(에틸렌옥사이드가 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%) 0.08g 을 반응기에 넣고, 광학렌즈용 수지 조성물을 만든 후 43℃에서 감압 하에 1시간 동안 교반하며 탈포하고, 30℃로 냉각하고 XDI 0.1g, 유기염료 HTAQ(88ppm) 및 PRD(30ppm)의 혼합용액을 첨가하였다. 수지 조성물을 15분 동안 저어주고, 20℃로 냉각하고 N,N-디메틸시클로헥실아민 0.2g을 천천히 첨가하고 15분 동안 교반하고 여과한 다음, 감압탈포를 5분 동안 더 행하고, 폴리에스테르 점착테이프로 조립된 유리몰드에 주입하여 실시예 1과 같은 방법으로 광학렌즈를 제조하고 그 물성을 측정하였다. 결과는 표 1에 나타내었다.The reactor was reduced to 1.0 torr or less, and the external temperature was adjusted to 54°C. While stirring the reactor, 80 g of bis(2,3-epithiopropylthio)methane compound and 2 g of 2,3-epoxypropyl(2,3-epithiopropyl)sulfide were added, followed by 5 g of sulfur and UV 31 0.8 UV blocker. g was added and degassed under reduced pressure for 30 minutes, then 0.15 g of 2-mercapto-1-methylimidazole was added and stirred for 1 hour. After cooling to 30℃, 4g of bis(mercaptomethyl)sulfide, 9g of 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 0.3g of tetrabutylphosphonium bromide, and phosphoric acid ester 8 as an internal release agent. -PENPP [polyoxyethylene nonyl phenol ester phosphate (3% by weight with 9 moles of ethylene oxide added, 80% by weight with 8 moles added, 5% by weight with 9 moles added, 6% by weight with 7 moles added) , 6 mol added (6% by weight) was placed in the reactor, a resin composition for optical lenses was prepared, and then stirred and degassed for 1 hour under reduced pressure at 43°C, cooled to 30°C, and 0.1g of XDI and organic dye HTAQ. A mixed solution of (88ppm) and PRD (30ppm) was added. Stir the resin composition for 15 minutes, cool to 20°C, slowly add 0.2 g of N,N-dimethylcyclohexylamine, stir for 15 minutes, filter, perform reduced pressure degassing for an additional 5 minutes, and polyester adhesive tape. An optical lens was manufactured in the same manner as in Example 1 by injecting it into a glass mold assembled, and its physical properties were measured. The results are shown in Table 1.

<< 실시예Example 6~8> 6~8>

실시예 1과 같은 방법으로 표 1에 기재된 조성에 따라 광학렌즈를 제조하고, 그 물성을 측정하였으며, 결과는 표 1에 기재하였다.An optical lens was manufactured according to the composition shown in Table 1 in the same manner as in Example 1, and its physical properties were measured, and the results are shown in Table 1 .

<< 비교예Comparative example 1> 1>

반응기를 1.0 torr 이하로 감압하고, 외부온도를 54℃로 조절하였다. 이 반응기를 교반하면서 비스(2,3-에피티오프로필)에피설파이드 화합물 86g 및 2,3-에폭시프로필(2,3-에피티오프로필)설파이드 2g을 넣고, 연속하여 황 4g과 자외선 차단제 UV 31 0.8g을 첨가하고, 30분 동안 감압하여 탈포한 후에 2-메르캅토-1-메틸이미다졸 0.15g을 첨가하고 1시간 동안 교반하였다. 이후 30℃로 냉각하고 비스(메르캅토메틸)설파이드 2g, 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 6g, 테트라부틸포스포늄브로마이드 0.3g 및 내부이형제로 인산에스테르계인 8-PENPP[폴리옥시에티렌노닐페놀에스테르포스페이트(에틸렌옥사이드가 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%) 0.08g 을 반응기에 넣고, 광학렌즈용 수지 조성물을 만든 후 43℃에서 감압 하에 1시간 동안 교반하며 탈포하고, 30℃로 냉각하고 유기염료 HTAQ(88ppm) 및 PRD(30ppm)의 혼합용액을 첨가하였다. 수지 조성물을 15분 동안 저어주고, 여과한 다음, 감압탈포를 5분 동안 더 행하고, 폴리에스테르 점착테이프로 조립된 유리몰드에 주입하여 실시예 1과 같은 방법으로 광학렌즈를 제조하고 그 물성을 측정하였으며, 결과를 표 2에 나타내었다.The reactor was reduced to 1.0 torr or less, and the external temperature was adjusted to 54°C. While stirring the reactor, 86 g of bis (2,3-epithiopropyl) episulfide compound and 2 g of 2,3-epoxypropyl (2,3-epithiopropyl) sulfide were added, followed by 4 g of sulfur and UV 31 0.8 UV blocker. g was added and degassed under reduced pressure for 30 minutes, then 0.15 g of 2-mercapto-1-methylimidazole was added and stirred for 1 hour. After cooling to 30℃, 2g of bis(mercaptomethyl)sulfide, 6g of 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 0.3g of tetrabutylphosphonium bromide, and phosphoric acid ester 8 as an internal release agent. -PENPP [polyoxyethylene nonyl phenol ester phosphate (3% by weight with 9 moles of ethylene oxide added, 80% by weight with 8 moles added, 5% by weight with 9 moles added, 6% by weight with 7 moles added) , 0.08 g (6% by weight of 6 mol added) was placed in the reactor, and a resin composition for optical lenses was prepared, then stirred and degassed for 1 hour under reduced pressure at 43°C, cooled to 30°C, and added organic dye HTAQ (88ppm) and A mixed solution of PRD (30ppm) was added. The resin composition was stirred for 15 minutes, filtered, degassed under reduced pressure for an additional 5 minutes, and then injected into a glass mold assembled with polyester adhesive tape to manufacture an optical lens in the same manner as in Example 1 and measure its physical properties. and the results are shown in Table 2 .

<< 비교예Comparative example 2~4> 2~4>

실시예 1과 같은 방법으로 표 2에 기재된 조성에 따라 광학렌즈를 제조하고, 그 물성을 측정하였으며, 결과는 표 2에 기재하였다.An optical lens was manufactured according to the composition shown in Table 2 in the same manner as in Example 1, and its physical properties were measured, and the results are shown in Table 2 .

<< 비교예Comparative example 5-6> 5-6>

실시예 5과 같은 방법으로 표 2에 기재된 수지에 따라 광학렌즈를 제조하고, 그 물성을 측정하였으며, 결과는 표 2에 기재하였다.An optical lens was manufactured according to the resin shown in Table 2 in the same manner as in Example 5, and its physical properties were measured, and the results are shown in Table 2 .

<< 비교예Comparative example 7> 7>

비교예 1과 같은 방법으로 표 2에 기재된 조성에 따라 광학렌즈를 제조하고, 그 물성을 측정하였으며, 결과는 표 2에 기재하였다.An optical lens was manufactured according to the composition shown in Table 2 in the same manner as in Comparative Example 1, and its physical properties were measured, and the results are shown in Table 2 .

구 분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4 Example 4 실시예 5Example 5 실시예 6Example 6 실시예 7Example 7 실시예 8Example 8 EPS(g)EPS(g) 8686 8686 8686 8686 22 EPDS(g)EPDS(g) 22 1010 EPTM(g)EPTM(g) 8080 8080 6666 8080 EPETS(g) EPETS(g) 22 22 22 22 22 22 22 황(g)Sulfur (g) 44 44 55 55 55 66 66 66 BMMS(g)BMMS(g) 44 44 44 MMTM(g)MMTM(g) 55 BMS(g)BMS(g) 22 22 22 22 22 GST(g)GST(g) 66 66 66 66 99 55 1010 88 IPDI(g)IPDI(g) 0.10.1 2.52.5 3.53.5 4.84.8 XDI(g)XDI(g) 4.04.0 NBDI(g)NBDI(g) 0.10.1 3.03.0 4.84.8 굴절률(Ne, 20℃)Refractive index (Ne, 20℃) 1.72131.7213 1.72081.7208 1.72001.7200 1.71871.7187 1.73561.7356 1.73661.7366 1.76011.7601 1.76101.7610 아베수Abesu 3434 3434 3434 3434 3232 3232 3030 2929 투명성transparency ◎◎ ◎◎ ◎◎ ○○ ◎◎ ◎◎ ◎◎ ○○ 중합불균형polymerization imbalance ◎◎ ◎◎ ◎◎ ◎◎ ◎◎ ◎◎ ◎◎ ◎◎ 내광성lightfastness ◎◎ ◎◎ ◎◎ ◎◎ ○○ ◎◎ ◎◎ ◎◎ 열안정성thermal stability ◎◎ ◎◎ ◎◎ ◎◎ ○○ ◎◎ ◎◎ ◎◎ 이형성Dysplasia ◎◎ ◎◎ ◎◎ ○○ ◎◎ ◎◎ ◎◎ ○○

구 분division 비교예Comparative example 1 One 비교예Comparative example 2 2 비교예Comparative example 3 3 비교예Comparative example 4 4 비교예Comparative example 5 5 비교예Comparative example 6 6 비교예Comparative example 7 7 EPS(g)EPS(g) 8686 8686 8686 8686 8080 EPDS(g)EPDS(g) 33 33 EPTM(g)EPTM(g) 8080 8080 EPETS(g) EPETS(g) 22 22 22 22 22 황(g)Sulfur (g) 44 44 44 44 33 33 33 BMMS(g)BMMS(g) 44 66 MMTM(g)MMTM(g) 44 BMS(g)BMS(g) 22 22 22 22 GST(g)GST(g) 66 66 66 66 1010 1010 77 IPDI(g)IPDI(g) 66 88 XDI(g)XDI(g) 66 NBDI(g)NBDI(g) 88 굴절률(Ne, 20℃)Refractive index (Ne, 20℃) 1.72151.7215 1.71701.7170 1.71761.7176 1.71731.7173 1.73121.7312 1.75701.7570 1.73701.7370 아베수Abesu 3434 3434 3434 3434 3333 3030 3232 투명성transparency ○○ ○○ ○○ ×× ○○ ×× ○○ 중합불균형polymerization imbalance ○○ ×× ×× ×× ○○ ×× ×× 내광성lightfastness ΔΔ ◎◎ ◎◎ ◎◎ ×× ○○ ΔΔ 열안정성thermal stability ×× ◎◎ ◎◎ ◎◎ ×× ○○ ΔΔ 이형성Dysplasia ◎◎ ×× ×× ×× ◎◎ ×× ◎◎

약어abbreviation

EPS: 비스(2,3-에피티오프로필)설파이드 (bis(2,3-epithiopropyl)sulfide)EPS: bis(2,3-epithiopropyl)sulfide

EPDS: 비스(2,3-에피티오프로필)디설파이드 (bis(2,3-epithiopropyl)disulfide)EPDS: bis(2,3-epithiopropyl)disulfide

EPTM: 비스(2,3-에피티오프로필티오)메탄 (bis(2,3-epithiopropylthio) methane)EPTM: bis(2,3-epithiopropylthio) methane

EPETS: 2,3-에폭시프로필(2,3-에피티오프로필)설파이드 (2,3-epoxypropyl(2,3-epithiopropyl)sulfide)EPETS: 2,3-epoxypropyl(2,3-epithiopropyl)sulfide

BMS: 비스(2-메르캅토에틸)설파이드 (bis(2-mercaptoethyl)sulfide)BMS: bis(2-mercaptoethyl)sulfide

BMMS: 비스(메르캅토메틸)설파이드 (bis(mercaptomethyl)sulfide)BMMS: bis(mercaptomethyl)sulfide

MMTM: 비스(메르캅토메틸티오)메탄 (bis(mercaptomethylthio)methane)MMTM: bis(mercaptomethylthio)methane

GST: 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 (2,3-bis(2-mercaptoethylthio)propane-1-thio)GST: 2,3-bis(2-mercaptoethylthio)propane-1-thio)

IPDI: 이소포론디이소시아네이트(isophorone diisocyanate)IPDI: isophorone diisocyanate

XDI: m-자일릴렌디이소시아네이트(m-xylylenediisocyanate)XDI: m-xylylenediisocyanate

NBDI: 노보란 디이소시아네이트(norbornane diisocyanate)NBDI: norbornane diisocyanate

본 발명에 따라 얻어진 에피설파이드계 광학재료는 황을 포함하여 굴절률이 1.71~1.77로 높은 고굴절률이면서도 황으로 인한 색상 저하나 중합불균형이 없고, 열안정성, 내광성, 이형성이 우수하므로, 고품질 렌즈로서 교정용 렌즈, 선글라스용 렌즈, 패션렌즈, 변색렌즈, 카메라렌즈, 광학 장치용 렌즈 등에 유용하게 이용될 수 있다. The episulfide-based optical material obtained according to the present invention contains sulfur and has a high refractive index of 1.71 to 1.77, but has no color deterioration or polymerization imbalance due to sulfur, and has excellent thermal stability, light resistance, and release properties, so it can be used as a high-quality corrective lens. It can be usefully used in lenses for sunglasses, fashion lenses, discolored lenses, camera lenses, and lenses for optical devices.

Claims (7)

아래 화학식 1로 표시되는 에피설파이드 화합물 75~90중량%, 폴리티올 화합물 5~15중량%, 고체 황 3~7중량%, 이소시아네이트 화합물 0.05~3.5중량%, 그리고 제4급 포스포늄염과 제3급 아민화합물 중에서 선택된 1종 이상의 중합촉매 0.05~2중량%를 포함하며,
상기 이소시아네이트 화합물은, 이소포론디이소시아네이트(IPDI), 헥사메틸렌디이소시아네이트(HDI), 디사이클로헥실메탄디이소시아네이트(H12MDI), 자일릴렌디이소시아네이트(XDI), 노보란디이소시아네이트(NBDI), 3,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 3,9-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 4,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 2,5-비스(이소시아나토메틸)비시클로[2,2,1]헵탄, 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄 중 적어도 하나를 포함하는, 굴절률 1.71~1.77의 에피설파이드계 고굴절 광학재료용 조성물.
[화학식 1]

(식 중에서 X는 O 또는 S이고, m은 0~4의 정수이며, n은 0~2의 정수이다.)75 to 90% by weight of an episulfide compound represented by the formula 1 below, 5 to 15% by weight of a polythiol compound, 3 to 7% by weight of solid sulfur, 0.05 to 3.5% by weight of an isocyanate compound, and a quaternary phosphonium salt and a tertiary Contains 0.05 to 2% by weight of one or more polymerization catalysts selected from secondary amine compounds,
The isocyanate compounds include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), noborane 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, 2,6- A composition for an episulfide-based high refractive index optical material with a refractive index of 1.71 to 1.77, comprising at least one of bis(isocyanatomethyl)bicyclo[2,2,1]heptane.
[Formula 1]

(In the formula, X is O or S, m is an integer from 0 to 4, and n is an integer from 0 to 2.) 제1항에 있어서,
상기 제4급 포스포늄염은, 테트라-부틸포스포늄브로마이드, 테트라페닐포스포늄브로마이드 중 하나를 포함하는 것을 특징으로 하는, 에피설파이드계 고굴절 광학재료용 조성물.According to paragraph 1,
A composition for an episulfide-based high refractive index optical material, wherein the quaternary phosphonium salt includes one of tetra-butylphosphonium bromide and tetraphenylphosphonium bromide. 제1항에 있어서,
상기 제3급 아민화합물은, N,N-디메틸헥실아민， N-메틸디헥실아민， N,N-디메틸시클로헥실아민， N,N-디에틸시클로헥실아민， N-메틸디시클로헥실아민 중 하나를 포함하는 것을 특징으로 하는, 에피설파이드계 고굴절 광학재료용 조성물.According to paragraph 1,
The tertiary amine compounds include N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, and N-methyldicyclohexylamine. A composition for an episulfide-based high refractive index optical material, characterized in that it contains one. 제1항에 있어서,
상기 에피설파이드 화합물은, 비스(2,3-에피티오프로필)설파이드, 비스(2,3-에피티오프로필)디설파이드, 2,3-에폭시프로필(2,3-에피티오프로필)설파이드, 2,3-에폭시프로필(2,3-에피티오프로필)디설파이드, 비스(2,3-에티오프로필티오)메탄, 2,3-에폭시프로필티오(2', 3'-에피티오프로필티오)메탄, 1,3 및 1,4-비스(β-에피티오프로필티오)시클로헥산, 1,3 및 1,4-비스(β-에피티오프로필티오메틸)시클로헥산, 2,5-비스(β-에피티오프로필티오메틸)-1,4-디티안, 2,5-비스(β-에피티오프로필티오에틸티오메틸)-1,4-디티안, 2-(2-β-에피티오프로필티오에틸티오)-1,3-비스(β-에피티오프로필티오)프로판 중 하나를 포함하는 것을 특징으로 하는, 에피설파이드계 고굴절 광학재료용 조성물.According to paragraph 1,
The episulfide compounds include bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 2,3-epoxypropyl(2,3-epithiopropyl)sulfide, 2,3 -Epoxypropyl(2,3-epithiopropyl)disulfide, bis(2,3-ethiopropylthio)methane, 2,3-epoxypropylthio(2', 3'-epithiopropylthio)methane, 1, 3 and 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3 and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epithiopropyl) thiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2-(2-β-epithiopropylthioethylthio)- A composition for an episulfide-based high refractive index optical material, characterized in that it contains one of 1,3-bis(β-epithiopropylthio)propane. 제1항에 있어서,
상기 폴리티올 화합물은, 비스(2-메르캅토에틸)설파이드, 비스(메르캅토메틸)설파이드, 비스(메르캅토메틸티오)메탄 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 중 하나를 포함하는 것을 특징으로 하는, 에피설파이드계 고굴절 광학재료용 조성물.According to paragraph 1,
The polythiol compound is bis(2-mercaptoethyl)sulfide, bis(mercaptomethyl)sulfide, bis(mercaptomethylthio)methane 2,3-bis(2-mercaptoethylthio)propane-1-thiol A composition for an episulfide-based high refractive index optical material, comprising one of the following: 삭제delete 제1항 내지 제5항 중 어느 한 항의 조성물을 중합시키는 것을 포함하는, 에피설파이드계 고굴절 광학재료의 제조방법.
A method for producing an episulfide-based high refractive index optical material, comprising polymerizing the composition of any one of claims 1 to 5.
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