KR20130086007A - Thioepoxy based copolymerizable composition and the method of preparing thioepoxy based optical material - Google Patents

Thioepoxy based copolymerizable composition and the method of preparing thioepoxy based optical material Download PDF

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KR20130086007A
KR20130086007A KR1020130006601A KR20130006601A KR20130086007A KR 20130086007 A KR20130086007 A KR 20130086007A KR 1020130006601 A KR1020130006601 A KR 1020130006601A KR 20130006601 A KR20130006601 A KR 20130006601A KR 20130086007 A KR20130086007 A KR 20130086007A
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bis
mercaptoethylthio
thioepoxy
propane
compound
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장동규
노수균
김종효
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주식회사 케이오씨솔루션
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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
    • 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
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/52—Polythioethers
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

PURPOSE: A thioepoxy-based copolymer composition and a production method of a thioepoxy-based optical material are provided to obtain a thioepoxy-based optical material with a high quality without striae and turbidity being transparent without deformation by controlling moist contents of a total composition along with moist content in a thioepoxy compound. CONSTITUTION: A thioepoxy-based copolymer composition contains thioepoxy compounds, polyisocyanate compounds, and polythiol compounds. Moist contents within the thioepoxy compound is 10-700 ppm. Moist contents of the composition is 10-800 ppm. A production method of a thioepoxy-based optical material includes following steps. A copolymer composition is polymerized in a mold and the copolymer composition includes thioepoxy compounds, polyisocyanate compounds, and polythiol compounds.

Description

티오에폭시계 공중합체 조성물과 티오에폭시계 광학재료의 제조방법 {Thioepoxy based copolymerizable composition and the method of preparing thioepoxy based optical material}Thioepoxy based copolymerizable composition and the method of preparing thioepoxy based optical material

본 발명은 티오에폭시화합물, 폴리이소시아네이트화합물, 폴리티올화합물로 이루어지는 공중합체 조성물과 이를 중합하는 티오에폭시계 광학재료에 관한 것으로, 특히 맥리, 백탁 및 기포를 발생시키지 않고, 무색 투명성이고 변형이 없는 고품질의 광학재료를 제조하는 방법에 관한 것이다. The present invention relates to a copolymer composition comprising a thioepoxy compound, a polyisocyanate compound, and a polythiol compound, and to a thioepoxy optical material for polymerizing the same. It relates to a method for producing the optical material of the.

종래 유리렌즈에 비해 플라스틱렌즈는 가볍고 내충격성이 좋고 착색이 용이하여 근래 안경렌즈에 대부분 플라스틱렌즈가 적용되고 있다. 그중에서도 대표적으로 디에틸렌글리콜비스알릴카보네이트(CR-39) 렌즈가 일반렌즈에 적용되어 왔다. 이 렌즈의 경우는 색수차가 적어 편안한 시야를 제공한다는 측면에서 유용하나 굴절율이 낮아 고굴절율이 요구되어왔다. 한국특허공고 1993-0006918호 및 1992-0005708호 등에서는 폴리티올 화합물과 폴리이소시아네이트 화합물을 반응시킨 티오우레탄계 렌즈를 제안하고 있다. 또한 한국등록특허 10-0681218호에서는 티오에폭시계 플라스틱 렌즈를 제안하고 있다.Compared to conventional glass lenses, plastic lenses are light, impact resistant and easy to color, and plastic lenses are mostly applied to eyeglass lenses in recent years. Among them, a typical diethylene glycol bisallylcarbonate (CR-39) lens has been applied to a general lens. This lens is useful for providing a comfortable field of view due to its low chromatic aberration, but a high refractive index has been required due to its low refractive index. Korean Patent Publication Nos. 1993-0006918, 1992-0005708 and the like propose a thiourethane lens in which a polythiol compound and a polyisocyanate compound are reacted. In addition, Korean Patent No. 10-0681218 proposes a thioepoxy plastic lens.

종래기술 중 티오우레탄계 렌즈는 고굴절이고 충격강도가 우수한 장점이 있으나 렌즈 표면이 무르다는 단점과 중심함몰 등의 문제가 있고 또한 굴절율이 높아지면 아베수가 급격히 낮아지는 문제점을 갖고 있다. 티오에폭시계 렌즈는 고굴절률이면서도 고아베수를 갖는 우수한 성질이 있으나 렌즈가 깨지기 쉽고 염색이 잘되지 않는 등의 문제점이 있다. 이런 문제점을 해결하기 위해 이들 두 종류의 서로 다른 성질의 수지를 공중합 하는 방법, 즉 티오에폭시화합물과 폴리티올화합물 및 폴리이소시아네이트 화합물을 공중합하는 방법이 한국특허 등록 10-0417985호, 일본특허 공개 평11-352302 등에서 제안되었다. 그런데 이런 공중합체 렌즈에서는 맥리, 백탁, 기포 등이 발생되는 경우가 있다. "맥리"란 조성의 차이 등으로 인해 주위의 정상 굴절율과 국소적으로 다르게 되는 현상을 말한다. "백탁"과 "백화"는 렌즈가 뿌옇게 되는 현상을 말하는데, 주로 "백탁"은 전체적으로 탁해지는 현상을 말하고 "백화"는 국소적인 현상을 말하나, 본 발명에서 "백탁"은 백화를 포함하는 의미이다. 맥리, 백탁, 기포는 광학재료의 품질과 성능에 나쁜 영향을 주고, 렌즈 수율을 낮춰 생산비를 상승시키는 요인이 된다. In the prior art, the thiourethane-based lens has advantages of high refractive index and excellent impact strength, but problems such as softness of the lens surface and center depression, and a problem in that Abbe's number is sharply lowered when the refractive index is increased. The thioepoxy lens has a high refractive index and an excellent characteristic of having a high Abbe number, but there are problems such as fragile lens and poor dyeing. In order to solve these problems, a method of copolymerizing these two kinds of resins, that is, a method of copolymerizing a thioepoxy compound, a polythiol compound, and a polyisocyanate compound, is disclosed in Korean Patent Registration No. 10-0417985, Japanese Patent Laid-Open No. 11 -352302 et al. By the way, such a copolymer lens may generate | occur | produce stria, haze, foam | bubble, etc. in some cases. "Stria" refers to a phenomenon that is locally different from the surrounding normal refractive index due to a difference in composition. The term "whitening" and "whitening" refers to a phenomenon in which the lens becomes cloudy, mainly "whitening" refers to a phenomenon of overall clouding, and "whitening" refers to a local phenomenon, but in the present invention, "whitening" is meant to include whitening. . Streaks, haze, and bubbles adversely affect the quality and performance of optical materials and increase the production cost by lowering lens yield.

대한민국 등록특허공보 10-0417985Republic of Korea Patent Publication 10-0417985 일본 공개특허공보 특개평 11-352302Japanese Laid-Open Patent Publication No. 11-352302

본 발명은 티오에폭시와 티오우레탄을 공중합하는 티오에폭시계 렌즈제조에 서 나타나는 맥리, 백탁, 기포를 발생시키지 않고 무색 투명한 고품질의 티오에폭시계 광학재료를 제공하는 것을 목적으로 한다. An object of the present invention is to provide a colorless, transparent, high quality thioepoxy optical material without generating striae, haze, and bubbles, which appear in the manufacture of thioepoxy lenses copolymerizing thioepoxy and thiourethane.

본 발명자들은 티오에폭시 화합물, 폴리이소시아네이트 화합물 및 폴리티올화합물로 이루어지는 공중합체 조성물의 수분 함량, 특히 티오에폭시 화합물 중의 수분 함량이 중합에 의해 제조된 광학재료의 맥리나 백탁, 기포에 직접 영향을 주는 것을 예기치 않게 알게 되었다. 조성물 중의 수분 함량이 중합체의 백탁이나 기포 발생과 관련이 있다는 종래에도 알려져 있었다. 그러나 수분이 맥리에 직접 영향을 미친다는 것은 그동안 알려져 있지 않았던 사실이다. 본 발명자들은 종래 컨트롤하기 어려웠던 맥리 현상이 티오에폭시 화합물 중의 수분함량과 조성물의 수분 함량을 일정 범위로 함으로써 제어될 수 있다는 것을 알게 되었다. 나아가 수분 함량을 일정범위로 유지함으로써 백탁과 기포까지 없는, 무색 투명하며 변형이 없는 고품질의 티오에폭시계 렌즈를 얻을 수 있었다. 본 발명자들은 이러한 사실을 확인하고, 본 발명을 완성하였다. The present inventors have found that the water content of the copolymer composition consisting of a thioepoxy compound, a polyisocyanate compound and a polythiol compound, in particular, the moisture content in the thioepoxy compound directly affects the stria, turbidity and bubbles of the optical material produced by polymerization. I learned unexpectedly. It has also been known previously that the water content in the composition is associated with the clouding or foaming of the polymer. However, it is not known that moisture directly affects striae. The present inventors have found that striae, which has been difficult to control in the past, can be controlled by keeping the water content of the thioepoxy compound and the water content of the composition within a certain range. Furthermore, by maintaining the water content in a certain range, it was possible to obtain a high-quality thioepoxy lens of colorless, transparent and free of deformation without white cloud and bubbles. The present inventors confirmed this fact and completed this invention.

본 발명에서는,In the present invention,

티오에폭시화합물과 폴리이소시아네이트화합물 및 폴리티올화합물을 포함하는 티오에폭시계 공중합체 조성물에 있어서, 상기 티오에폭시화합물 중의 수분 함유량이 10~700ppm이고, 상기 조성물 중의 수분 함유량이 10~800ppm인 것을 특징으로 하는 티오에폭시계 공중합체 조성물이 제공된다. A thioepoxy copolymer composition comprising a thioepoxy compound, a polyisocyanate compound, and a polythiol compound, wherein the water content in the thioepoxy compound is 10 to 700 ppm, and the water content in the composition is 10 to 800 ppm. A thioepoxy copolymer composition is provided.

또한, 본 발명에서는, 상기 공중합체 조성물을 주형중합하는 티오에폭시계 광학재료의 제조방법이 제공된다.Moreover, in this invention, the manufacturing method of the thio epoxy clock optical material which mold-polymerizes the said copolymer composition is provided.

또한, 본 발명에서는 상기 공중합체 조성물을 주형중합시켜 얻어지는 티오에폭시계 광학재료와 이 광학재료로 이루어진 광학렌즈가 제공된다. In addition, in the present invention, there is provided a thioepoxy optical material obtained by casting and polymerizing the copolymer composition and an optical lens made of the optical material.

본 발명에서는 티오에폭시화합물과 폴리이소시아네이트화합물 및 폴리티올화합물을 포함하는 공중합체 조성물에서 티오에폭시화합물 중의 수분 함량과 함께 전체 조성물의 수분 함량을 조절함으로써 맥리나 백탁이 없고 무색 투명하고 변형이 없는 고품질의 티오에폭시계 광학재료를 얻을 수 있다.
In the present invention, in the copolymer composition comprising a thioepoxy compound, a polyisocyanate compound, and a polythiol compound, by controlling the water content of the whole composition together with the water content of the thioepoxy compound, there is no muddy or white turbidity, colorless transparent, high quality without deformation. Thio epoxy clock optical material can be obtained.

본 발명의 공중합체 조성물은 티오에폭시화합물과 폴리이소시아네이트화합물 및 폴리티올화합물을 포함하며, 조성물에 포함된 티오에폭시화합물 중의 수분 함유량이 10~700ppm이고, 조성물 중의 수분 함유량이 10~800ppm이다. 이 공중합체 조성물을 중합하는 것에 의해 맥리, 백탁, 기포가 없는 티오에폭시계 광학재료를 제조할 수 있다. The copolymer composition of the present invention contains a thioepoxy compound, a polyisocyanate compound, and a polythiol compound, and has a water content of 10 to 700 ppm and a water content of 10 to 800 ppm in the composition. By polymerizing this copolymer composition, a thioepoxy optical material without striae, haze and bubbles can be produced.

상기 티오에폭시화합물은, 예를 들어, 비스(2,3-에피티오프로필)술피드, 비스(2,3-에피티오프로필)디술피드, 2,3-에피디티오프로필(2,3-에피티오프로필)디술피드, 2,3-에피디티오프로필(2,3-에피티오프로필)술피드, 1,3 및 1,4-비스(β-에피티오프로필티오)시클로헥산, 1,3 및 1,4-비스(β-에피티오프로필티오메틸)시클로헥산, 비스[4-(β-에피티오프로필티오)시클로헥실]메탄, 2,2-비스[4-(β-에피티오프로필티오)시클로헥실]프로판, 비스[4-(β-에피티오프로필티오)시클로헥실]술피드 등의 지환족골격을 갖는 에피술피드화합물; 1,3 및 1,4-비스(β-에피티오프로필티오메틸)벤젠, 비스[4-(β-에피티오프로필티오)페닐]메탄, 2,2-비스[4-(β-에피티오프로필티오)페닐]프로판, 비스[4-(β-에피티오프로필티오)페닐]술피드, 비스[4-(β-에피티오프로필티오)페닐]술핀, 4,4-비스(β-에피티오프로필티오)비페닐 등의 방향족골격을 갖는 에피술피드화합물; 2,5-비스(β-에피티오프로필티오메틸)-1,4-디티안, 2,5-비스(β-에피티오프로필티오에틸티오메틸)-1,4-디티안, 2,5-비스(β-에피티오프로필티오에틸)-1,4-디티안, 2,3,5-트리(β-에피티오프로필티오에틸)-1,4-디티안 등의 디티안사슬 골격을 갖는 에피술피드화합물; 2-(2-β-에피티오프로필티오에틸티오)-1,3-비스(β-에피티오프로필티오)프로판, 1,2-비스[(2-β-에피티오프로필티오에틸)티오]-3-(β-에피티오프로필티오)프로판, 테트라키스(β-에피티오프로필티오메틸)메탄, 1,1,1-트리스(β-에피티오프로필티오메틸)프로판, 비스-(β-에피티오프로필)술피드 등의 지방족 골격을 갖는 에피술피드화합물 등이 될 수 있다. 이외에도 티오에폭시화합물로 에피술피드기를 가진 화합물의 염소 치환체, 브롬 치환체 등의 할로겐 치환체, 알킬 치환체, 알콕시 치환체, 니트로 치환체나 폴리티올과의 프리폴리머형 변성체 등도 사용될 수 있다. The thioepoxy compound is, for example, bis (2,3- epithiopropyl) sulfide, bis (2, 3- epithiopropyl) disulfide, 2, 3- epidithiopropyl (2, 3- epi Thiopropyl) disulfide, 2,3-epidithiopropyl (2,3-ethiothiopropyl) sulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-ethiothiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) Episulfide compounds having an alicyclic skeleton such as cyclohexyl] propane and bis [4- (β-epithiopropylthio) cyclohexyl] sulfide; 1,3 and 1,4-bis (β-ethiothiopropylthiomethyl) benzene, bis [4- (β-ethiothiopropylthio) phenyl] methane, 2,2-bis [4- (β-ethiothiopropyl Thio) phenyl] propane, bis [4- (β-ethiothiopropylthio) phenyl] sulfide, bis [4- (β-ethiothiopropylthio) phenyl] sulphine, 4,4-bis (β-ethiothiopropyl Episulfide compounds having an aromatic skeleton such as thio) biphenyl; 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane, 2,5- Epi having a dithiane chain skeleton such as bis (β-ethiothiopropylthioethyl) -1,4-dithiane, 2,3,5-tri (β-ethiothiopropylthioethyl) -1,4-dithiane Sulfide compounds; 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane, 1,2-bis [(2-β-ethiothiopropylthioethyl) thio]- 3- (β-epithiopropylthio) propane, tetrakis (β-ethiothiopropylthiomethyl) methane, 1,1,1-tris (β-ethiothiopropylthiomethyl) propane, bis- (β-ethiothio Episulfide compounds having an aliphatic skeleton such as propyl) sulfide. In addition to the thioepoxy compound, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents and prepolymer-modified compounds with polythiol may be used.

티오에폭시 화합물로, 바람직하게는, 비스(2,3-에피티오프로필)술피드, 비스(2,3-에피티오프로필)디술피드, 2,3-에피디티오프로필(2,3-에피티오프로필)술피드, 2,3-에피디티오프로필(2,3-에피티오프로필)디술피드, 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. As a thioepoxy compound, Preferably, bis (2, 3- epithiopropyl) sulfide, bis (2, 3- epithiopropyl) disulfide, 2, 3- epidithiopropyl (2, 3- epithio Propyl) sulfide, 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1 , 4-bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthio One or more of ethylthiomethyl) -1,4-dithiane, 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane can be used.

이들 티오에폭시화합물 중의 수분 함유량은, 10~700ppm 범위이다.
The water content in these thioepoxy compounds is 10-700 ppm range.

상기 폴리이소시아네이트화합물은, 특별히 한정되지 않고 최소한 1개 이상의 이소시아네이트 및/또는 이소티오시아네이트 기를 가진 화합물이 사용될 수 있다. 예를 들어, 2,2-디메틸펜탄디이소시아네이트, 헥사메틸렌디이소시아네이트, 2,2,4-트리메틸헥산디이소시아네이트, 부텐디이소시아네이트, 1,3-부타디엔-1,4-디이소시아네이트, 2,4,4-트리메틸헥사메틸렌디이소시아네이트, 1,6,11-운데카트리이소시아네이트, 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, 비페닐디이소시아네이트, 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)술피드, 비스(이소시아네이토프로필)술피드, 비스(이소시아네이토헥실)술피드, 비스(이소시아네이토메틸)설폰, 비스(이소시아네이토메틸)디술피드, 비스(이소시아네이토프로필)디술피드, 비스(이소시아네이토메틸티오)메탄, 비스(이소시아네이토에틸티오)메탄, 비스(이소시아네이토에틸티오)에탄, 비스(이소시아네이토메틸티오)에탄, 1,5-디이소시아네이토-2-이소시아네이토메틸-3-티아펜탄 등의 함황 지방족 이소시아네이트 화합물; 디페닐술피드-2,4-디이소시아네이트, 디페닐술피드-4,4-디이소시아네이트, 3,3-디메톡시-4,4-디이소시아네이토디벤질티오에테르, 비스(4-이소시아네이토메틸벤젠)술피드, 4,4-메톡시벤젠티오에틸렌글리콜-3,3-디이소시아네이트, 디페닐디술피드-4,4-디이소시아네이트, 2,2-디메틸디페닐디술피드-5,5-디이소시아네이트, 3,3-디메틸디페닐디술피드-5,5-디이소시아네이트, 3,3-디메틸디페닐디술피드-6,6-디이소시아네이트, 4,4-디메틸디페닐디술피드-5,5-디이소시아네이트, 3,3-디메톡시 디페닐디술피드-4,4-디이소시아네이트, 4,4-디메톡시디페닐디술피드-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 이상이 사용될 수 있다. 이외에도 최소한 1개 이상의 이소시아네이트 및/또는 이소티오시아네이트 기를 가진 화합물이면 1종 또는 2종 이상을 사용할 수 있으며, 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 사용할 수 있다. The polyisocyanate compound is not particularly limited and a compound having at least one isocyanate and / or isothiocyanate group can be used. For example, 2,2-dimethylpentane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6,11-undectriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocyane Aliphatic isocyanate compounds such as itoethyl) 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 dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane isocyanate and 2,2-dimethyldicyclohexyl methane 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, trimethylbenzenetriisocyanate, benzene tree Isocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (iso Cyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzenediisocyanate, hexa Aromatic isocyanate compounds such as hydrodiphenylmethane-4,4-diisocyanate; 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 ( Sulfur-containing aliphatic isocyanate compounds such as isocyanatomethylthio) 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-isocyane Itomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5 -Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4-dimethyldiphenyldisulfide-5, Sulfur-containing aromatic isocyanate compounds such as 5-diisocyanate, 3,3-dimethoxy diphenyldisulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyldisulfide-3,3-diisocyanate; 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-dithiorane, 4,5-bis ( One or two or more selected from sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl) -2-methyl-1,3-dithiolan can be used. In addition, as long as it is a compound having at least one isocyanate and / or isothiocyanate group, one kind or two or more kinds can be used, and also halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents and nitros of these isocyanate compounds. Substituents, prepolymer-modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, biuret-modified or dimerized, trimerized reaction products, and the like can also be used.

폴리이소시아네이트화합물로, 바람직하게는, 이소포론디이소시아네이트(IPDI), 헥사메틸렌디이소시아네이트(HDI), 디사이클로헥실메탄디이소시아네이트(H12MDI), 자일릴렌디이소시아네이트(XDI), 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 사용한다.
As polyisocyanate compound, Preferably, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H12MDI), xylylene diisocyanate (XDI), 3,8-bis (iso Cyanatomethyl) 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 (iso One or more selected from cyanatomethyl) bicyclo [2,2,1] heptane is used.

폴리티올화합물은, 특별히 한정되지 않고 최소한 1개 이상의 티올기를 가진 화합물이면 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 바람직하게는, 비스(2-메르캅토에틸)술피드, 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)술피드, 비스(2,3-디메르캅토프로판닐)디술피드, 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판, 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)술피드, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)디술피드, 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. 이외에도 1개 이상의 티올기를 가진 화합물이면 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 또한 폴리티올화합물에 이소시아네이트나 티오에폭시 화합물, 티에탄 화합물 또는 수지개질제로 불포화 결합을 가진 화합물과의 예비중합에서 얻어진 중합 변성체도 사용이 가능하다. The polythiol compound is not particularly limited and may be used alone or in combination of two or more thereof as long as it is a compound having at least one thiol group. 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 Propaneyl) 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-mercapto-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 Pentathiaheptan-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-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaeryte Lithol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaery Lithol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) At least one selected from ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane Can be used. In addition, if it is a compound which has one or more thiol groups, it can use 1 type or in mixture of 2 or more types. Furthermore, the polymerization modified body obtained by prepolymerization with an isocyanate, a thioepoxy compound, a ethane compound, or the compound which has an unsaturated bond as a resin modifier to a polythiol compound can also be used.

폴리티올화합물로, 특히 바람직하게는, 비스(2-메르캅토에틸)술피드 또는 비스(2-메르캅토에틸)술피드에 다른 폴리티올화합물을 1종 이상 혼합하여 사용할 수 있다.
As the polythiol compound, particularly preferably, one or more other polythiol compounds may be mixed with bis (2-mercaptoethyl) sulfide or bis (2-mercaptoethyl) sulfide.

본 발명의 공중합체 조성물은 내부이형제를 포함할 수 있으며, 바람직하게는 내부이형제로 인산에스테르화합물을 포함한다. 인산에스테르는 포스포러스펜톡사이드(P2O5)에 2~3몰의 알코올 화합물을 부가하여 제조하는데 이때 사용하는 알코올 종류에 따라 여러 가지 형태의 인산에스테르화합물이 있을 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[폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드가 5몰 부가된 것 5중량%, 4몰 부가된 것 80중량%, 3몰 부가된 것 10중량%, 1몰 부가된 것 5중량%)], 8-PENPP[폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)], 12-PENPP[폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드 13몰 부가된 것 3중량%, 12몰 부가된 것 80중량%, 11몰 부가된 것 8중량%, 9몰 부가된 것 3중량%, 4몰 부가된 것 6중량%)], 16-PENPP[폴리옥시에틸렌 노닐페놀에테르포스페이트(에틸렌옥사이드가 17몰 부가된 것 3중량%, 16몰 부가된 것 79중량%, 15몰 부가된 것 10중량%, 14몰 부가된 것 4중량%, 13몰 부가된 것 4중량%)], 20-PENPP[폴리옥시에틸렌노닐페놀에테르 포스페이트(에틸렌옥사이드가 21몰 부가된 것 5중량%, 20몰 부가된 것 76중량%, 19몰 부가된 것 7중량%, 18몰 부가된 것 6중량%, 17몰 부가된 것 4중량%)], 4-PPNPP[폴리옥시프로필렌노닐페놀에테르포스페이트(프로필렌옥사이드가 5몰 부가된 것 5중량%, 4몰 부가된 것 80중량%, 3몰 부가된 것 10중량%, 1몰 부가된 것 5중량%)], 8-PPNPP[폴리옥시프로필렌노닐페놀에테르포스페이트(프로필렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가 된 것 6중량%, 6몰 부가된 것 6중량%)], 12-PPNPP[폴리옥시프로필렌노닐페놀에테르포스페이트(프로필렌옥사이드 13몰 부가된 것 3중량%, 12몰 부가된 것 80중량%, 11몰 부가된 것 8중량%, 9몰 부가된 것 3중량%, 4몰 부가된 것 6중량%)], 16-PPNPP[폴리옥시프로필렌 노닐페놀에테르포스페이트(프로필렌옥사이드 17몰 부가된 것 3중량%, 16몰 부가된 것 79중량%, 15몰 부가된 것 10중량%, 14몰 부가된 것 4중량%, 13몰 부가된 것 4중량%)], 20-PPNPP[폴리옥시프로필렌노닐페놀에테르포스페이트(프로필렌옥사이드가 21몰 부가된 것 5중량%, 20몰 부가된 것 76중량%, 19몰 부가된 것 7중량%, 18몰 부가된 것 6중량%, 17몰 부가된 것 4중량%)] 및 Zelec UNTM 중에서 선택된 1종 이상을 사용한다. 이러한 인산에스테르화합물의 할로겐화합물 치환체를 비롯한 각종 치환체들도 같은 목적으로 사용이 가능하다.
The copolymer composition of the present invention may include an internal mold release agent, and preferably include a phosphate ester compound as the internal mold release agent. Phosphate ester is prepared by adding 2-3 moles of alcohol compound to phosphorus pentoside (P 2 O 5 ). There may be various types of phosphate ester compounds depending on the type of alcohol used. Typical examples include those in which ethylene oxide or propylene oxide is added to the aliphatic alcohol, or ethylene oxide or propylene oxide is added to the nonylphenol group. In the polymerizable composition of the present invention, when the phosphate ester compound added with ethylene oxide or propylene oxide is included as an internal mold release agent, an optical material having good release property and excellent quality can be obtained. The composition of the present invention is an internal mold release agent, preferably 4-PENPP [polyoxyethylene nonyl phenol ether phosphate (5% by weight 5 mol ethylene oxide, 80% by weight 4 mol added ethylene oxide, 3 mol addition 10% by weight, 1 mole added 5% by weight)], 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3% by weight 9 mole of ethylene oxide added, 80% by weight 8 mole added, 9 Mole added 5% by weight, 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PENPP [polyoxyethylenenonylphenoletherphosphate (13 mole added by ethylene oxide 3% by weight) , 12 mole added 80%, 11 mole added 8%, 9 mole added 3%, 4 mole added 6% by weight)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (3% by weight of 17 moles of ethylene oxide added, 79% by weight of 16 moles added, 10% by weight of 15 moles added, 4% by weight of 14 moles added, 4% by weight of 13 moles added)] 20-PENPP [polyoxyethylenenonylphenolether phosphate (21% addition of 5% by weight of ethylene oxide, 20% addition of 76% by weight, 19% addition by 7% by weight, 18 parts by weight of 6% by weight) %, 17 mole added 4% by weight)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 mole added with 5 mole of propylene oxide, 80% by weight added with 4 mole added, 3 mole added) 10 wt%, 1 mol added 5 wt%)], 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (9 mol added propylene oxide 3 wt%, 8 mol added 80 wt%, 9 mol 5 wt% added, 7 mol added 6 wt%, 6 mol added 6 wt%)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13 wt% propylene oxide added, 12 mole added 80% by weight, 11 mole added 8% by weight, 9 mole added 3% by weight, 4 mole added 6% by weight)], 16-PPNPP [polyoxypropylene nonylphenol Ether phosphate (3% by weight of 17 mole added propylene oxide, 79% by weight added 16 mole, 15% added 10%, 14 mole added 4%, 13 mole added 4% by weight) 20-PPNPP [Polyoxypropylenenonylphenol ether phosphate (5% by weight of 21 mol of propylene oxide, 76% by weight of 20 mol of added, 7% by weight of 19 mol of added, 18 mol of added 6) Wt%, 17 mol added 4 wt%)] and Zelec UN ™ Use at least one selected from. Various substituents including the halogen compound substituents of such phosphate ester compounds may be used for the same purpose.

본 발명의 공중합체 조성물은, 공중합체 광학수지(광학재료)의 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, 메르캅토에틸술피드디아크릴레이트, 메르캅토에틸술피드디메타크릴레이트 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.
In order to improve the optical properties of the copolymer optical resin (optical material), the copolymer composition of the present invention may further include an olefin compound as a reactive resin modifier for the purpose of controlling impact resistance, specific gravity and monomer viscosity. . As an olefin compound which can be added as a resin modifier, 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, 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 Dimethac Latex, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2 , 2-bis (4-hydroxyethoxyphenyl) propane, 2,2-bis (4-methoxyethoxyphenyl) propane, 2,2-bis (4-hydroxydiethoxyphenyl) propane, 2, 2-bis (4-methoxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-hydroxyethoxyphenyl) methane, 1,1-bis ( 4-Methoxyethoxyphenyl) methane, 1,1-bis (4-acryoxydiethoxyphenyl) methane, 1,1-bis (4-methoxydiethoxyphenyl) methane, dimethyloltricyclodecane Acrylate, trimetholpropane triacrylate, trimetholpropane trimethacrylate, glycerol diacrylate, Liserol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, (Meth) acrylate compounds, such as xylene dithiol diacrylate, xylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, and mercaptoethyl sulfide dimethacrylate, and allyl glycidyl ether , Allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, and diethylene glycol bisallylcarbonate, and styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, and divinylbenzene , Vinyl compounds such as 3,9-divinylspirobi (m-dioxane), and the like, It is not limited to these exemplary compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

본 발명의 광학재료는 바람직하게는 주형 중합을 통해 얻게 된다. 즉, 개스켓 또는 테이프 등으로 유지된 성형 몰드 사이에, 본 발명의 공중합체 조성물을 주입한다. 이때, 얻어지는 광학재료에 요구되는 물성에 따라, 또 필요에 따라, 감압 하에서의 탈포처리나 가압, 감압 등의 여과처리 등을 실시하는 것이 바람직한 경우가 많다. 중합조건은, 공중합체 조성물, 촉매의 종류와 사용량, 몰드의 형상 등에 의해서 크게 조건이 달라지기 때문에 한정되는 것은 아니지만, 약 -50~150℃의 온도에서 1~50시간에 걸쳐 실시된다. 경우에 따라서는, 10~150℃의 온도범위에서 유지 또는 서서히 승온하여, 1~48 시간에서 경화시키는 것이 바람직하다.The optical material of the present invention is preferably obtained through mold polymerization. That is, the copolymer composition of this invention is inject | poured between the shaping | molding mold hold | maintained with the gasket or the tape. Under the present circumstances, it is preferable to perform the defoaming process under reduced pressure, the filtration process, such as pressurization and reduced pressure, etc. according to the physical property calculated | required at the time of the obtained optical material in many cases. The polymerization conditions are not limited because the conditions vary greatly depending on the copolymer composition, the type and amount of the catalyst used, the shape of the mold, and the like, but are carried out over a period of 1 to 50 hours at a temperature of about -50 to 150 ° C. In some cases, it is preferable to maintain or gradually raise the temperature in a temperature range of 10 to 150 ° C. and to cure in 1 to 48 hours.

경화로 얻어진 광학재료는, 필요에 따라, 어닐링 등의 처리를 실시해도 좋다. 처리 온도는 통상 50~150℃의 사이에서 행해지며, 90~140℃에서 실시하는 것이 바람직하다.The optical material obtained by hardening may process annealing etc. as needed. Treatment temperature is normally performed between 50-150 degreeC, and it is preferable to carry out at 90-140 degreeC.

본 발명의 조성물은 바람직하게는, 내부이형제로 인산에스테르화합물을 첨가하여 주형 중합시킨다. 인산에스테르화합물에 대한 설명은 위와 동일하다. 또한, 중합 시 목적에 따라 공지의 성형법과 마찬가지로 쇄연장제, 가교제, 광안정제, 자외선 흡수제, 산화방지제, 착색 방지제, 유용염료, 충전제, 밀착성 향상제 등의 여러 가지의 첨가제를 가해도 좋다. 특히 사용되는 촉매가 중요한 역활을 하는데, 그 촉매의 종류는 에폭시 경화제들이 주로 사용되나, 강한 아민류는 이소시아네이트 반응을 격렬하게 하므로 그 사용에 주의를 요한다. 본 발명에서는 주로 아민의산염류, 포스포늄염류, 포스핀류 및 전자흡인기를 지니지 않는 3차아민류, 루이스산류, 라디칼개시제등이 주로 사용되며, 촉매의 종류와 량은 경우에 따라 달라질 수 있다.The composition of the present invention is preferably polymerized by adding a phosphate ester compound as an internal mold release agent. Description of the phosphate ester compound is the same as above. Moreover, according to the objective at the time of superposition | polymerization, you may add various additives, such as a chain extender, a crosslinking agent, a light stabilizer, a ultraviolet absorber, antioxidant, a coloring inhibitor, a useful dye, a filler, and an adhesive improvement agent. Particularly, the catalyst used plays an important role. Epoxy hardeners are mainly used as the catalysts, but strong amines cause intense isocyanate reaction, so use thereof is necessary. In the present invention, amine salts, phosphonium salts, phosphines and tertiary amines having no electron withdrawing groups, Lewis acids, radical initiators and the like are mainly used, and the type and amount of the catalyst may vary depending on the case.

본 발명의 광학재료는, 주형 중합 시의 몰드를 바꾸는 것으로 여러 가지의 형상의 성형체로 얻을 수 있어, 안경 렌즈, 카메라 렌즈, 발광다이오드(LED) 등의 각종 광학재료로 사용하는 것이 가능하다. 특히, 안경 렌즈, 카메라 렌즈, 발광다이오드 등의 광학재료, 광학소자로서 적합하다.The optical material of this invention can be obtained by the molded object of various shapes by changing the mold at the time of casting polymerization, and can be used with various optical materials, such as an eyeglass lens, a camera lens, and a light emitting diode (LED). In particular, it is suitable as optical materials, such as an eyeglass lens, a camera lens, a light emitting diode, and an optical element.

본 발명의 광학재료로 이루어진 렌즈는 필요에 따라, 단면 또는 양면에 코팅층을 실시하여 사용해도 좋다. 코팅층으로서는, 프라이머층, 하드코트층, 반사방지막층, 방담코트막층, 방오염층, 발수층 등을 들 수 있다. 이들 코팅층은 각각 단독으로 사용하는 것도 복수의 코팅층을 다층화하여 사용해도 좋다. 양면에 코팅층을 실시하는 경우, 각각의 면에 동일한 코팅층을 실시해도, 상이한 코팅층을 실시해도 좋다.
The lens made of the optical material of the present invention may be used by providing a coating layer on one or both surfaces as necessary. Examples of the coating layer include a primer layer, a hard coat layer, an antireflection film layer, an antifogging coat film layer, an antifouling layer, and a water repellent layer. These coating layers may be used alone, or may be used by multilayering a plurality of coating layers. When providing a coating layer on both surfaces, you may give the same coating layer to each surface, or may give a different coating layer.

[[ 실시예Example ]]

실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.
The examples are only for explaining the present invention more specifically, but the scope of the present invention is not limited by these examples.

시험 및 평가방법Test and evaluation method

공중합체 조성물 중의 수분 함유량, 테이프백화, 맥리 및 기포 발생률을 다음과 같은 방법으로 평가하였다.The water content, tape whitening, striae, and bubble incidence in the copolymer composition were evaluated in the following manner.

수분 함유량: Metrohm사 수분측정기에 860KF thermoprep의 수분기화장치가 정착된 자동수분측정에 의해 칼 피셔 용액으로 수분 함유량을 측정하였다.Moisture content: The moisture content was measured by Karl Fischer's solution by automatic moisture measurement in which a 860 KF thermoprep water branching device was installed on a Metrohm moisture meter.

테이프백화: 중합 후 탈형한 다음 면가공하지 않은 상태로 조도 1800LUX 이상으로 조사하여 뿌연 현상이 육안관찰되는 수량을 백분율로 산출하였다.Tape whitening: demolding after polymerization, irradiated with roughness of 1800LUX or more without surface processing, and the amount of visual observation of the cloudy phenomenon was calculated as a percentage.

기포: 중합 탈형후 형광등 빛에 조사하여 누액으로 인한 것이 아니라 기포현상이 발생한 수량을 백분율로 산출하였다.Bubbles: After polymerization demolding, irradiation with fluorescent light was performed to calculate the percentage of bubbles generated, not due to leakage.

맥리: 100매의 렌즈를 USHIO USH-10D인 수은 아크램프(Mercury Arc Lamp) 아래 육안으로 관찰하고, 호상이 확인된 렌즈는 맥리가 있는 것으로 판정하여, 맥리 발생율을 산출하였다. Streaks: 100 lenses were visually observed under a Mercury Arc Lamp, which is a USHIO USH-10D, and it was determined that a lens having an arc shape had a stria, and a stria occurrence rate was calculated.

[실시예 1]Example 1

티오에폭시화합물로서 비스(2,3-에피티오프로필)술피드(BEPS-1) 89g, 이소시아네이트화합물로서 이소포론디이소시아네이트 5g, 티올화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 인산에스테르인 8-PENPP [폴리옥시에티렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g을 20℃에서 혼합하여, 균일용액으로 했다. 티오에폭시화합물의 수분함량은 80ppm이었고, 이를 포함한 전체 수지조성물의 수분함량은 112ppm이었다. 이 혼합용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1μm PTFE 필터로 여과를 실시하고, 유리 몰드와 테이프로 이뤄진 몰드형에 주입하였다. 이 몰드형를 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합하였다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈고, 몰드형으로부터 이형하여 렌즈를 얻었다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 이와 같이 하여 렌즈를 100매 제작하고, 테이프백화 현상, 기포현상 및 맥리현상을 확인하여 백분율을 산출하였고, 결과를 아래 표 1에 나타내었다.
89 g of bis (2,3-epithiopropyl) sulfide (BEPS-1) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, as an internal release agent Phosphoric acid ester 8-PENPP [Polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 8% of added moles 8% by weight, 5% by weight 9 moles added, 7 moles added) 6 wt%, 6 mol added 6 wt%)] 0.15 g, tetrabutylphosphonium bromide 0.2 g, triphenylphosphine 0.1 g, organic dyes HTAQ (20 ppm) and PRD (10 ppm), UV absorber HOPBT 1.5 g It mixed at 20 degreeC and set it as the homogeneous solution. The water content of the thioepoxy compound was 80 ppm, and the water content of the entire resin composition including this was 112 ppm. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the percentages were calculated by checking the tape whitening, bubble development, and striae, and the results are shown in Table 1 below.

[실시예 2][Example 2]

티오에폭시화합물로서 비스(2,3-에피티오프로필)술피드(BEPS-1) 89g, 이소시아네이트화합물로서 이소포론디이소시아네이트 5g, 티올화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 인산에스테르인 8-PENPP [폴리옥시에티렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g을 20℃에서 혼합하여, 균일용액으로 했다. 티오에폭시화합물의 수분함량은 150ppm이었고, 이를 포함한 전체 수지조성물의 수분함량은 212ppm이었다. 이 혼합용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1μm PTFE 필터로 여과를 실시하고, 유리 몰드와 테이프로 이뤄진 몰드형에 주입하였다. 이 몰드형를 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합하였다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈고, 몰드형으로부터 이형하여 렌즈를 얻었다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 이와 같이 하여 렌즈를 100매 제작하고, 테이프백화 현상 기포현상 및 맥리현상을 확인하여 백분율을 산출하였고, 결과를 아래 표 1에 나타내었다.
89 g of bis (2,3-epithiopropyl) sulfide (BEPS-1) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, as an internal release agent Phosphoric acid ester 8-PENPP [Polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 8% of added moles 8% by weight, 5% by weight 9 moles added, 7 moles added) 6 wt%, 6 mol added 6 wt%)] 0.15 g, tetrabutylphosphonium bromide 0.2 g, triphenylphosphine 0.1 g, organic dyes HTAQ (20 ppm) and PRD (10 ppm), UV absorber HOPBT 1.5 g It mixed at 20 degreeC and set it as the homogeneous solution. The water content of the thioepoxy compound was 150 ppm, and the water content of the entire resin composition including this was 212 ppm. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the percentages were calculated by checking the bubble whitening and the striae phenomenon, and the results are shown in Table 1 below.

[실시예 3][Example 3]

티오에폭시화합물로서 비스(2,3-에피티오프로필)술피드(BEPS-1) 89g, 이소시아네이트화합물로서 이소포론디이소시아네이트 5g, 티올화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 인산에스테르인 8-PENPP [폴리옥시에티렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g을 20℃에서 혼합하여, 균일용액으로 했다. 티오에폭시화합물의 수분함량은 387ppm이었고, 이를 포함한 전체 수지조성물의 수분은 450ppm이었다. 이 혼합용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1μm PTFE 필터로 여과를 실시하고, 유리 몰드와 테이프로 이뤄진 몰드형에 주입하였다. 이 몰드형를 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합하였다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈고, 몰드형으로부터 이형하여 렌즈를 얻었다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 이와 같이 하여 렌즈를 100매 제작하고, 테이프백화 현상, 기포현상 및 맥리현상을 확인하여 백분율을 산출하였고, 결과를 아래 표 1에 나타내었다.
89 g of bis (2,3-epithiopropyl) sulfide (BEPS-1) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, as an internal release agent Phosphoric acid ester 8-PENPP [Polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide added, 8% of added moles 8% by weight, 5% by weight 9 moles added, 7 moles added) 6 wt%, 6 mol added 6 wt%)] 0.15 g, tetrabutylphosphonium bromide 0.2 g, triphenylphosphine 0.1 g, organic dyes HTAQ (20 ppm) and PRD (10 ppm), UV absorber HOPBT 1.5 g It mixed at 20 degreeC and set it as the homogeneous solution. The water content of the thioepoxy compound was 387 ppm, and the water content of the entire resin composition including the same was 450 ppm. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the percentages were calculated by checking the tape whitening, bubble development, and striae, and the results are shown in Table 1 below.

[실시예 4]Example 4

티오에폭시화합물로서 비스(2,3-에피티오프로필)술피드(BEPS) 89g, 이소시아네이트화합물로서 이소포론디이소시아네이트 5g, 티올화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 인산에스테르인 8-PENPP [폴리옥시에티렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g을 20℃에서 혼합하여, 균일용액으로 했다. 티오에폭시화합물의 수분함량은 519ppm이었고, 이를 포함한 전체 수지조성물의 수분은 600ppm이었다. 이 혼합용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1μm PTFE 필터로 여과를 실시하고, 유리 몰드와 테이프로 이뤄진 몰드형에 주입하였다. 이 몰드형를 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합하였다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈고, 몰드형으로부터 이형하여 렌즈를 얻었다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 이와 같이 하여 렌즈를 100매 제작하고, 테이프백화 현상, 기포현상 및 맥리현상을 확인하여 백분율을 산출하였고, 결과를 아래 표 1에 나타내었다.
89 g of bis (2,3-epithiopropyl) sulfide (BEPS) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, phosphate ester as an internal release agent Phosphorus 8-PENPP [Polyoxyethylenenonylphenoletherphosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 7 parts of added moles) %, 6 mol added 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dyes HTAQ (20ppm) and PRD (10ppm), UV absorber HOPBT 1.5g 20 ℃ The mixture was mixed to obtain a homogeneous solution. The water content of the thioepoxy compound was 519 ppm, and the water content of the total resin composition including this was 600 ppm. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the percentages were calculated by checking the tape whitening, bubble development, and striae, and the results are shown in Table 1 below.

[실시예 5][Example 5]

티오에폭시화합물로서 비스(2,3-에피티오프로필)디술피드(BEPDS) 91g, 이소시아네이트화합물로서 이소포론디이소시아네이트 4g, 티올화합물로서 비스(2-메르캅토에틸)술피드 5g, 내부이형제로 인산에스테르인 8-PENPP [폴리옥시에티렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g을 20℃에서 혼합하여, 균일용액으로 했다. 티오에폭시화합물의 수분함량은 83ppm이었고, 이를 포함한 전체 수지조성물의 수분은 154ppm이었다. 이 혼합용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1μm PTFE 필터로 여과를 실시하고, 유리 몰드와 테이프로 이뤄진 몰드형에 주입하였다. 이 몰드형를 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합하였다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈고, 몰드형으로부터 이형하여 렌즈를 얻었다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 이와 같이 하여 렌즈를 100매 제작하고, 테이프백화 현상, 기포현상 및 맥리현상을 확인하여 백분율을 산출하였고, 결과를 아래 표 1에 나타내었다.
91 g of bis (2,3-epithiopropyl) disulfide (BEPDS) as a thioepoxy compound, 4 g of isophorone diisocyanate as an isocyanate compound, 5 g of bis (2-mercaptoethyl) sulfide as a thiol compound, a phosphate ester as an internal release agent Phosphorus 8-PENPP [Polyoxyethylenenonylphenoletherphosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 7 parts of added moles) %, 6 mol added 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dyes HTAQ (20ppm) and PRD (10ppm), UV absorber HOPBT 1.5g 20 ℃ The mixture was mixed to obtain a homogeneous solution. The water content of the thioepoxy compound was 83 ppm, and the water content of the entire resin composition including this was 154 ppm. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the percentages were calculated by checking the tape whitening, bubble development, and striae, and the results are shown in Table 1 below.

[비교예 1]Comparative Example 1

티오에폭시화합물로서 비스(2,3-에피티오프로필)술피드(BEPS) 89g, 이소시아네이트화합물로서 이소포론디이소시아네이트 5g, 티올화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 인산에스테르인 8-PENPP [폴리옥시에티렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g을 20℃에서 혼합하여, 균일용액으로 했다. 티오에폭시화합물의 수분함량은 821ppm이었고, 이를 포함한 전체 수지조성물의 수분은 900ppm이었다. 이 혼합용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1μm PTFE 필터로 여과를 실시하고, 유리 몰드와 테이프로 이뤄진 몰드형에 주입하였다. 이 몰드형를 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합하였다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈고, 몰드형으로부터 이형하여 렌즈를 얻었다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 이와 같이 하여 렌즈를 100매 제작하고, 테이프백화 현상, 기포현상 및 맥리현상을 확인하여 백분율을 산출하였고, 결과를 아래 표 1에 나타내었다.
89 g of bis (2,3-epithiopropyl) sulfide (BEPS) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, phosphate ester as an internal release agent Phosphorus 8-PENPP [Polyoxyethylenenonylphenoletherphosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 7 parts of added moles) %, 6 mol added 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dyes HTAQ (20ppm) and PRD (10ppm), UV absorber HOPBT 1.5g 20 ℃ The mixture was mixed to obtain a homogeneous solution. The water content of the thioepoxy compound was 821 ppm, and the water content of the total resin composition including the same was 900 ppm. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the percentages were calculated by checking the tape whitening, bubble development, and striae, and the results are shown in Table 1 below.

[비교예 2]Comparative Example 2

티오에폭시화합물로서 비스(2,3-에피티오프로필)술피드(BEPS) 89g, 이소시아네이트화합물로서 이소포론디이소시아네이트 5g, 티올화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 인산에스테르인 8-PENPP [폴리옥시에티렌노닐페놀에테르포스페이트(에틸렌옥사이드 9몰 부가된 것 3중량%, 8몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g을 20℃에서 혼합하여, 균일용액으로 했다. 티오에폭시화합물의 수분함량은 1404ppm이었고, 이를 포함한 전체 수지조성물의 수분은 1500ppm이었다. 이 혼합용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1μm PTFE 필터로 여과를 실시하고, 유리 몰드와 테이프로 이뤄진 몰드형에 주입하였다. 이 몰드형를 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합하였다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈고, 몰드형으로부터 이형하여 렌즈를 얻었다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 이와 같이 하여 렌즈를 100매 제작하고, 테이프백화 현상, 기포현상 및 맥리현상을 확인하여 백분율을 산출하였고, 결과를 아래 표 1에 나타내었다.89 g of bis (2,3-epithiopropyl) sulfide (BEPS) as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, 6 g of bis (2-mercaptoethyl) sulfide as a thiol compound, phosphate ester as an internal release agent Phosphorus 8-PENPP [Polyoxyethylenenonylphenoletherphosphate (3% by weight of 9 moles of ethylene oxide added, 80% by weight of 8 moles added, 5% by weight of 9 moles added, 7 parts of added moles) %, 6 mol added 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dyes HTAQ (20ppm) and PRD (10ppm), UV absorber HOPBT 1.5g 20 ℃ The mixture was mixed to obtain a homogeneous solution. The water content of the thioepoxy compound was 1404 ppm, and the water content of the entire resin composition including the same was 1500 ppm. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered by the 1 micrometer PTFE filter, and injected into the mold mold which consists of a glass mold and a tape. This mold was charged into a polymerization oven, and gradually heated to 25 ° C to 130 ° C over 21 hours to polymerize. After the completion of the polymerization, the mold was removed from the oven, and the mold was released from the mold to obtain a lens. The obtained resin was further annealed at 130 ° C. for 4 hours. In this way, 100 lenses were prepared, and the percentages were calculated by checking the tape whitening, bubble development, and striae, and the results are shown in Table 1 below.

Figure pat00001
Figure pat00001

<약어> <Abbreviation>

모노머Monomer

BEPS: 비스(2,3-에피티오프로필)술피드(bis(2,3-epithiopropyl)sulfide)BEPS: bis (2,3-epithiopropyl) sulfide

BEPDS: 비스(2,3-에피티오프로필)디술피드(bis(2,3-epithiopropyl)sulfide)BEPDS: bis (2,3-epithiopropyl) disulfide

BMES: 비스(2-메르캅토에틸)술피드(bis(2-메르캅토에틸)sulfide)BMES: bis (2-mercaptoethyl) sulfide (bis (2-mercaptoethyl) sulfide)

IPDI: 이소포론디이소시아네이트(isophorone diisocyanate)IPDI: isophorone diisocyanate

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

TBPB: 테트라부틸포스포늄브로마이드(tetrabutylphosphonium bromide)TBPB: tetrabutylphosphonium bromide

HTQA: 1-히드록시-4-(p-톨루딘)-엔트로퀴논(1-hydroxy-4-(p-toluidine)anthraquinone)HTQA: 1-hydroxy-4- (p-tolludine) -entroquinone (1-hydroxy-4- (p-toluidine) anthraquinone)

PRD: 퍼리논 염료(perinone dye)PRD: Perinone dye

Claims (10)

티오에폭시화합물과 폴리이소시아네이트화합물 및 폴리티올화합물을 포함하는 티오에폭시계 공중합체 조성물에 있어서, 상기 티오에폭시화합물 중의 수분 함유량이 10~700ppm이고, 상기 조성물 중의 수분 함유량이 10~800ppm인 것을 특징으로 하는 티오에폭시계 공중합체 조성물.A thioepoxy copolymer composition comprising a thioepoxy compound, a polyisocyanate compound, and a polythiol compound, wherein the water content in the thioepoxy compound is 10 to 700 ppm, and the water content in the composition is 10 to 800 ppm. Thioepoxy copolymer composition. 제1항에 있어서, 상기 티오에폭시화합물은 비스(2,3-에피티오프로필)술피드, 비스(2,3-에피티오프로필)디술피드, 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 중에서 선택된 1종 이상인 것을 특징으로 하는 공중합체 조성물.The method of claim 1, wherein the thioepoxy compound is bis (2,3-ethiothio) sulfide, bis (2,3-ethiothio) disulfide, 1,3 and 1,4-bis (β-epi). Thiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2- (2-β-ethiothiopropylthioethylthio) -1,3-bis (β-ethiothiopropyl Copolymer composition, characterized in that at least one selected from thio) propane. 제1항에 있어서, 상기 폴리이소시아네이트화합물이 이소포론디이소시아네이트, 헥사메틸렌디이소시아네이트, 디사이클로헥실메탄디이소시아네이트, 자일릴렌디이소시아네이트, 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, 및 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄 중에서 선택된 1종 이상인 것을 특징으로 하는 공중합체 조성물.The polyisocyanate compound according to claim 1, wherein the polyisocyanate compound is isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, xylylene diisocyanate, 3,8-bis (isocyanatomethyl) tricyclo [5,2 , 1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5 , 2,1,02,6] decane, 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, and 2,6-bis (isocyanatomethyl) bicyclo [2, 2,1] copolymer composition, characterized in that at least one selected from heptane. 제1항에 있어서, 상기 폴리티올 화합물이, 비스(2-메르캅토에틸)술피드, 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)술피드, 비스(2,3-디메르캅토프로판닐)디술피드, 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판, 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)술피드, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)디술피드, 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 이상인 것을 특징으로 하는 공중합체 조성물.The polythiol compound according to claim 1, wherein the polythiol compound is 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 Propaneyl) 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-mercapto-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 -Pentathiaheptan-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-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaeryte Lithol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaery Lithol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) At least one selected from ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane The copolymer composition characterized by the above-mentioned. 티오에폭시화합물과 폴리이소시아네이트화합물 및 폴리티올화합물을 포함하는 공중합체 조성물을 주형중합하는 티오에폭시계 광학재료의 제조방법에 있어서,
상기 티오에폭시화합물 중의 수분 함유량이 10~700ppm이고, 상기 조성물 중의 수분의 함유량이 10~800ppm인 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법.In the manufacturing method of the thioepoxy optical material which mold-polymerizes the copolymer composition containing a thioepoxy compound, a polyisocyanate compound, and a polythiol compound,
A water content in the thioepoxy compound is 10 to 700 ppm, and a water content in the composition is 10 to 800 ppm. 제5항에 있어서, 상기 티오에폭시화합물은 비스(2,3-에피티오프로필)술피드, 비스(2,3-에피티오프로필)디술피드, 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 중에서 선택된 1종 이상인 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법.The method of claim 5, wherein the thioepoxy compound is 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-ethiothiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2- (2-β-ethiothiopropylthioethylthio) -1,3-bis (β-ethiothiopropyl A method for producing a thioepoxy clock optical material, characterized in that at least one selected from thio) propane. 제5항에 있어서, 상기 폴리이소시아네이트화합물이 이소포론디이소시아네이트, 헥사메틸렌디이소시아네이트, 디사이클로헥실메탄디이소시아네이트, 자일릴렌디이소시아네이트, 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, 및 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄 중에서 선택된 1종 이상인 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법.The polyisocyanate compound according to claim 5, wherein the polyisocyanate compound is isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, xylylene diisocyanate, 3,8-bis (isocyanatomethyl) tricyclo [5,2 , 1,02,6] decane, 3,9-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5 , 2,1,02,6] decane, 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, and 2,6-bis (isocyanatomethyl) bicyclo [2, 2,1] a method for producing a thioepoxy optical material, characterized in that at least one selected from heptane. 제5항에 있어서, 상기 폴리티올 화합물이, 비스(2-메르캅토에틸)술피드, 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)술피드, 비스(2,3-디메르캅토프로판닐)디술피드, 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판, 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)술피드, 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)디술피드, 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 이상인 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법.The polythiol compound according to claim 5, wherein the polythiol compound is 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 Propaneyl) 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-mercapto-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 -Pentathiaheptan-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-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaeryte Lithol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaery Lithol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) At least one selected from ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane A method for producing a thioepoxy clock optical material characterized by the above-mentioned. 제1항의 공중합체 조성물을 주형중합시켜 얻어지는 티오에폭시계 광학재료.The thioepoxy clock optical material obtained by casting-polymerizing the copolymer composition of Claim 1. 제9항의 광학재료로 이루어진 광학렌즈. An optical lens made of the optical material of claim 9.
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