KR20130081257A - Polymerizable composition for thioepoxy based optical material and method of preparing the optical material - Google Patents

Polymerizable composition for thioepoxy based optical material and method of preparing the optical material Download PDF

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KR20130081257A
KR20130081257A KR1020130001720A KR20130001720A KR20130081257A KR 20130081257 A KR20130081257 A KR 20130081257A KR 1020130001720 A KR1020130001720 A KR 1020130001720A KR 20130001720 A KR20130001720 A KR 20130001720A KR 20130081257 A KR20130081257 A KR 20130081257A
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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
    • 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
    • C08K5/378—Thiols containing heterocyclic rings
    • 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
    • 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
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/405—Thioureas; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Eyeglasses (AREA)

Abstract

PURPOSE: A production method of a thio epoxy based optical material is provided to easily obtain the thio epoxy based optical material which is clear, transparent, and has high quality. CONSTITUTION: A thio epoxy based polymerizable composition contains a thio epoxy compound containing less than 1wt% of epithio chlorohydrine. The thio epoxy based polymerizable composition additionally contains a polyisocyanate compound, and a polythiol compound.

Description

티오에폭시계 광학재료용 중합성 조성물과 티오에폭시계 광학재료의 제조방법 {Polymerizable composition for thioepoxy based optical material and method of preparing the optical material}Polymerizable composition for thioepoxy based optical material and method of preparing the optical material

본 발명은 티오에폭시계 광학재료용 중합성 조성물과 티오에폭시계 광학재료의 제조방법에 관한 것으로, 특히 티오에폭시계 광학재료에서 나타나는 색상 불안정 문제를 해결하여 맑고 투명한 고품질의 티오에폭시계 광학재료를 제공하는 것에 관한 것이다.The present invention relates to a polymerizable composition for a thioepoxy clock optical material and a method for producing a thioepoxy optical material, and in particular, to solve the color instability problem in the thioepoxy optical material, to provide a clear and transparent high quality thioepoxy optical material. It's about doing.

대한민국 특허공고공보 1993-0006918호 및 1992-0005708호 등에서는 폴리티올 화합물과 폴리이소시아네이트 화합물을 반응시킨 티오우레탄계 렌즈를 제안하고 있다. 대한민국 등록특허공보 10-0681218호에는 티오에폭시계 플라스틱 렌즈를 제안하고 있다. 티오우레탄계 렌즈는 고굴절이고 충격강도가 우수한 장점이 있으나 렌즈 표면이 무르다는 단점과 중심함몰 등의 문제가 있고, 또한 굴절율이 높아지면서 아베수가 급격히 낮아지는 문제점이 있다. 티오에폭시계 렌즈는 고굴절률이면서도 고아베수를 갖는 장점이 있으나 렌즈가 깨지기 쉽고 염색이 잘되지 않는 등의 문제점이 있다. 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. Korean Patent Publication No. 10-0681218 proposes a thioepoxy watch plastic lens. The thiourethane-based lens has the advantages of high refractive index and excellent impact strength, but there are disadvantages such as softness of the lens surface and central depression, and also a problem in that Abbe's number decreases rapidly as the refractive index increases. The thioepoxy lens has the advantage of having a high refractive index and a high Abbe number, but there are problems such as fragile lens and poor dyeing.

티오우레탄계 렌즈와 티오에폭시계 렌즈가 갖는 문제점을 해결하기 위하여, 이들 두 종류의 서로 다른 성질의 수지를 공중합 하는 방법, 즉 티오에폭시 화합물과 폴리티올 화합물 및 폴리이소시아네이트 화합물을 공중합하는 방법이 대한민국 등록특허공보 10-0417985호, 일본 특허공개공보 특개평 11-292950 및 특개평 11-352302 등에서 제안되었다. In order to solve the problems of the thiourethane lens and the thioepoxy lens, 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, has been proposed. Patent Documents No. 10-0417985, Japanese Patent Laid-Open No. Hei 11-292950, and Japanese Patent Laid-Open No. Hei 11-352302 have been proposed.

그러나 티오에폭시 화합물을 포함하는 티오에폭시계 렌즈에서는 여전히 렌즈의 색상이 불안정한 경우가 있다. 대한민국 등록특허공보 10-0681218호에서는 티오에폭시 화합물의 제조 과정에서 에폭시 화합물이 티오에폭시 화합물로 변환되는 과정의 순도, 즉 변환되는 과정에서 부반응으로 발생하는 불순물 티오에폭시 화합물의 함유량이 렌즈의 색상에 영향을 미치는 원인임을 밝히고, 이러한 불순물 티오에폭시 화합물의 함유량을 줄인 중합성 조성물과 줄이는 방법을 개시하고 있다. However, in thioepoxy lenses containing a thioepoxy compound, the color of the lens may still be unstable. In Korean Patent Application Publication No. 10-0681218, the purity of the process of converting an epoxy compound to a thioepoxy compound in the manufacturing process of the thioepoxy compound, that is, the content of impurity thioepoxy compound generated as a side reaction in the process of converting affects the color of the lens. The present invention discloses a polymerizable composition having a reduced content of such impurity thioepoxy compound and a method of reducing the same.

대한민국 등록특허공보 10-0417985Republic of Korea Patent Publication 10-0417985 일본 공개특허공보 특개평 11-292950Japanese Laid-Open Patent Publication No. 11-292950 일본 공개특허공보 특개평 11-352302Japanese Laid-Open Patent Publication No. 11-352302 대한민국 등록특허공보 10-0681218Republic of Korea Patent Registration 10-0681218

본 발명에서는 티오에폭시계 광학재료에서 색상에 영향을 미치는 보다 결정적인 원인을 찾아내고 이를 제어함으로써 티오에폭시계 광학재료에서 색상 불안정의 문제를 해결하고자 한다. 특히, 본 발명은 보다 제어가 쉬운 색상 불안정의 원인 규명을 통해 맑고 투명한 고품질의 티오에폭시계 광학재료를 용이하게 제조하는 방법과 그 중합성 조성물을 제공하는 것을 목적으로 한다. The present invention seeks to solve the problem of color instability in thioepoxy optical materials by finding and controlling more critical causes affecting color in thioepoxy optical materials. In particular, it is an object of the present invention to provide a method for easily preparing a clear and high quality thioepoxy optical material through the identification of the cause of color instability that is more controllable, and a polymerizable composition thereof.

본 발명자들은 티오에폭시계 광학재료에서 색상에 영향을 미치는 주요한 인자가, 출발 물질로 사용하는 에피클로로히드린이 반응계에 계속 잔존하여 에피티오클로로히드린으로 변환되는 데 있는 것임을 예기치 않게 알게 되었다. 즉, 출발 물질로 사용하는 에피클로로히드린이 반응계에 계속 잔존함으로써 티오우레아를 넣고 에피술피드화 하는 과정에서 에피티오클로로히드린으로 바뀌게 되고 이 에피티오클로로히드린이 광학재료의 색상에 결정적인 영향을 미치게 된다. 또한, 이 에피티오클로로히드린은 렌즈의 색상을 나쁘게 할 뿐만 아니라 이형 분리를 저해하는 것도 확인할 수 있었다. 또한, 본 발명자들은 티오에폭시 화합물의 제조과정에서 부반응으로 발생하는 불순물 티오에폭시 화합물의 함유량을 따로 제어하지 않더라도 출발 물질 중의 에피클로로히드린과 티오에폭시 화합물 중의 에피티오클로로히드린의 함유량을 제어함으로써 티오에폭시계 광학재료의 색상 문제를 해결할 수 있음을 확인하였다. The inventors unexpectedly found that the main factor affecting color in thioepoxy optical materials is that epichlorohydrin used as starting material remains in the reaction system and is converted to epithiochlorohydrin. In other words, the epichlorohydrin used as the starting material remains in the reaction system and is changed to epithiochlorohydrin in the process of adding thiourea and episulfide, and this epithiochlorohydrin is critical to the color of the optical material. Get mad. In addition, it was confirmed that the epithiochlorohydrin not only degraded the color of the lens but also inhibited the heterogeneous separation. Further, the present inventors have found that, even if the content of the impurity thioepoxy compound generated as a side reaction during the production of the thioepoxy compound is not controlled, the content of epichlorohydrin in the starting material and the content of epithiochlorohydrin in the thioepoxy compound are controlled, It was confirmed that the color problem of the epoxy based optical material can be solved.

본 발명에서는, In the present invention,

티오에폭시 화합물을 포함하는 티오에폭시계 중합성 조성물에 있어서, 상기 티오에폭시 화합물의 에피티오클로로히드린 함유량이 1중량% 이하인 것을 특징으로 하는 티오에폭시계 중합성 조성물이 제공된다. 중합성 조성물은, 폴리이소시아네이트 화합물 및/또는 폴리티올 화합물을 더 포함할 수 있다. In the thioepoxy polymerizable composition comprising a thioepoxy compound, the thioepoxy polymerizable composition is characterized in that the epithiochlorohydrin content of the thioepoxy compound is 1% by weight or less. The polymerizable composition may further include a polyisocyanate compound and / or a polythiol compound.

바람직하게는, 상기 티오에폭시 화합물은 에피클로로히드린 함유량이 1중량% 이하인 술피드 화합물과 티오우레아를 반응시켜 에피술피드화하는 단계를 포함하는 방법으로 합성될 수 있다.Preferably, the thioepoxy compound may be synthesized by a method comprising episulfidation by reacting a sulfide compound having an epichlorohydrin content of 1% by weight or less with thiourea.

또한, 본 발명에서는 상기 중합성 조성물을 중합시키는 티오에폭시계 광학재료의 제조방법이 제공된다.Moreover, in this invention, the manufacturing method of the thio epoxy clock optical material which superposes | polymerizes the said polymeric composition is provided.

또한, 본 발명에서는 상기 제조방법으로 얻어지는 티오에폭시계 광학재료와 이 광학재료로 이루어진 광학렌즈가 제공된다.Further, in the present invention, a thioepoxy optical material obtained by the above production method and an optical lens made of the optical material are provided.

본 발명에서 "티오에폭시계 광학재료"는 특별히 한정하지 않는 한, 티오에폭시 화합물을 중합한 광학재료와, 티오에폭시와 티오우레탄을 공중합한 광학재료를 모두 포함하는 의미이다. In the present invention, "thioepoxy optical material" is meant to include both optical materials obtained by polymerizing thioepoxy compounds and optical materials copolymerized with thioepoxy and thiourethane, unless otherwise specified.

본 발명에서는 티오에폭시 화합물을 합성하는 출발물질 중의 에피클로로히드린 함유량 또는 티오에폭시 화합물 중의 에피티오클로로히드린 함유량을 제어함으로써 용이한 방법으로 티오에폭시계 광학재료에서 나타나는 색상 불안정의 문제를 해결할 수 있다. 본 발명에 따르면 맑고 투명한 고품질의 티오에폭시계 렌즈를 높은 수율로 용이하게 제조할 수 있다.
In the present invention, by controlling the epichlorohydrin content in the starting material for synthesizing the thioepoxy compound or the epithiochlorohydrin content in the thioepoxy compound, the problem of color instability appearing in the thioepoxy optical material can be solved in an easy way. . According to the present invention, a clear and high quality thioepoxy lens can be easily manufactured in high yield.

본 발명의 중합성 조성물에 포함되는 티오에폭시 화합물은, 한 개 이상의 티오에폭시기를 갖는 화합물이다. 에피티오클로로히드린의 함유량이 1중량% 이하인 티오에폭시 화합물은, 여러 가지 방법으로 제조될 수 있다. 바람직하게는, 티오에폭시 화합물은 에피클로로히드린 함유량이 1중량% 이하인 술피드 화합물과 티오우레아를 반응시켜 에피술피드화하는 단계를 거쳐 합성한다. 예를 들어, 에피클로로 히드린과 황화수소가스를 부가하여 1-클로로-3-메르캅토-2-프로판올을 제조한 후 다시 에피클로로 히드린과 부가 반응을 진행하거나 1-클로로-3-메르캅토-2-프로판올을 제조한 후 자체 디술피드화 반응을 진행한 후 에폭시 화합물을 제조하게 된다. 이 과정에서 에피클로로 히드린을 완전히 제거하기가 쉽지 않으나 그 잔존량이 1중량% 이하, 바람직하게는 0.5중량% 이하가 되게 더 반응을 진행하여 티오에폭시 화합물로 제조한다. 이렇게 제조된 티오에폭시 화합물은 광학재료의 색상을 최적화할 수 있다. The thioepoxy compound contained in the polymerizable composition of the present invention is a compound having one or more thioepoxy groups. The thioepoxy compound whose content of epithiochlorohydrin is 1 weight% or less can be manufactured by various methods. Preferably, the thioepoxy compound is synthesized by reacting a sulfide compound having an epichlorohydrin content of 1% by weight or less with thiourea to episulfide. For example, epichlorohydrin and hydrogen sulfide gas are added to prepare 1-chloro-3-mercapto-2-propanol, followed by addition reaction with epichlorohydrin, or 1-chloro-3-mercapto- After preparing 2-propanol and proceeding with its own disulfide reaction, an epoxy compound is prepared. In this process, it is not easy to completely remove epichlorohydrin, but the reaction is further carried out so that the remaining amount is 1% by weight or less, preferably 0.5% by weight or less, to prepare a thioepoxy compound. The thioepoxy compound thus prepared can optimize the color of the optical material.

티오에폭시 화합물은, 예를 들면, 비스(2,3-에피티오프로필)디술피드, 비스(2,3-에피티오프로필)술피드, 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-에피티오프로 필티오)시클로헥실]메탄, 2,2-비스[4-(β-에피티오프로필티오)시클로헥실]프로판, 비스[4-(β-에피티오프로필티오)시클로헥실]술피드 등의 지환족골격을 갖는 에피술피드 화합물; 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)비페닐등 방향족골격을 갖는 에피술피드 화합물; 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 에피술피드 화합물; 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 에피술피드 화합물 등이다. 이외에도 티오에폭시 화합물로 에피술피드기를 가진 화합물의 염소 치환체, 브롬 치환체 등의 할로겐 치환체, 알킬 치환체, 알콕시 치환체, 니트로 치환체나 폴리티올과의 프리폴리머형 변성체 등도 사용 가능하다.The thioepoxy compound is, for example, bis (2,3-ethiothio) disulfide, bis (2,3-ethiothio) sulfide, 2,3-epidithiopropyl (2,3-epithio Propyl) disulfide, 2,3- epidithiopropyl (2,3- epithiopropyl) sulfide, 1,3 and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3 and 1 , 4-bis (β-ethiothiopropylthiomethyl) 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, as 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, 및 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 and 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-ethiothiopropylthio) propane may be used. .

본 발명의 중합성 조성물은 폴리이소시아네이트 화합물을 더 포함할 수 있다. 폴리이소시아네이트 화합물은, 특별히 한정되지 않고 최소한 1개 이상의 이시아소네이트 기 및/또는 이소티오시아네이트 기를 가진 화합물이 사용될 수 있다. 예를 들어, 헥사메틸렌디이소시아네이트, 2,2-디메틸펜탄디이소시아네이트, 2,2,4-트리메틸헥산디이소시아네이트, 부텐디이소시아네이트, 1,3-부타디엔-1,4-디이소시아네이트, 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; 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, 톨릴렌디이소시아네이트, 자일릴렌디이소시아네이트, 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'-디메톡시디페닐디술피드-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 이상의 화합물이 사용될 수 있다. 이외에도 최소한 1개 이상의 이소네이트 기 및/또는 이소티오시아네이트 기를 가진 화합물이면 1종 또는 2종 이상을 혼합 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 사용 가능하다. 폴리이소시아네이트 화합물로, 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.
The polymerizable composition of the present invention may further include a polyisocyanate compound. The polyisocyanate compound is not particularly limited and a compound having at least one isocyanate group and / or isothiocyanate group can be used. For example, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexanediisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocy Aliphatic isocyanate compounds such as anatoethyl) carbonate and bis (isocyanatoethyl) ether; Isophorone diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, Alicyclic isocyanate compounds such as dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane isocyanate and 2,2-dimethyldicyclohexyl methane isocyanate; 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, benzenetriisocyanate, diphenyldiisocyanate, toluidine Diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-di Isocyanate, bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, hexahydro Aromatic diisocyanate compounds such as jendi isocyanate, hexahydro-diphenylmethane-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- Isocyanatomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide Feed-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, 4, 4'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3 Sulfur-containing aromatic isocyanate compounds such as 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 compounds selected from sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl) -2-methyl-1,3-dithiolane can be used. In addition, as long as it is a compound having at least one or more isonate groups and / or isothiocyanate groups, one or two or more kinds thereof may be used, and halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents and alkoxy of these isocyanate compounds. Substituents, nitro substituents, prepolymer-modified products with polyhydric alcohols or thiols, carbodiimide-modified products, urea-modified products, biuret-modified or dimerized products, and trimerized reaction products can also be used. As a 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.

본 발명의 중합성 조성물은 폴리티올 화합물을 더 포함할 수 있다. 폴리티올 화합물은, 특별히 한정되지 않고 최소한 1개 이상의 티올기를 가진 화합물이면 1종 또는 2종 이상을 혼합하여 사용될 수 있다. 예를 들어, 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)-부틸에스테르, 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, 펜타에리트리톨테트라키스(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, 2-(2,2-비스(메르캅토디메틸티오)에틸)-1,3-디티안 등을 사용할 수 있다. 이외에도 1개 이상의 티올기를 가진 화합물이면 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 또한 폴리티올 화합물에 이소시아네이트나 티오에폭시 화합물, 티에탄 화합물 또는 수지개질제로 불포화 결합을 가진 화합물과의 예비중합에서 얻어진 중합 변성체도 사용이 가능하다. 폴리티올 화합물로, 바람직하게는, 비스(2-메르캅토에틸)술피드 또는 비스(2-메르캅토에틸)술피드에 다른 폴리티올 화합물을 1종 이상 혼합하여 사용할 수 있다.
The polymerizable composition of the present invention may further include a polythiol compound. 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. For example, 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) -butylester, 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-trithiaundane, 4,7-dimercaptomethyl- 1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaerythritol Tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaeryte Tol-ether-hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) Ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane and the like 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. Moreover, the polymerization modified body obtained by the 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. As a polythiol compound, Preferably, 1 or more types of other polythiol compounds can be mixed and used by bis (2-mercaptoethyl) sulfide or bis (2-mercaptoethyl) sulfide.

본 발명의 중합성 조성물은 내부이형제를 포함할 수 있으며, 바람직하게는 내부이형제로 산성인산에스테르 화합물을 포함한다. 산성인산 에스테르는 포스포러스펜톡사이드(P2O5)에 2~3몰의 알콜 화합물을 부가하여 제조하는데 이때 사용하는 알콜 종류에 따라 여러 가지 형태의 인산에스테르 화합물이 있을 수 있다. 대표적인 것으로는 지방족 알콜에 에틸렌옥사이드 혹은 프로필렌 옥사이드가 부가되거나 노닐페놀기등에 에틸렌 옥사이드 혹은 프로필렌 옥사이드가 부가된 종류들이다. 본 발명의 중합성 조성물에, 에틸렌 옥사이드 혹은 프로필렌 옥사이드가 부가된 인산에스테르 화합물이 내부이형제로 포함될 경우, 이형성이 좋고 품질이 우수한 광학재료를 얻을 수 있어 바람직하였다. 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 부가 된 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(프로필렌옥사이드가 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%)], Zelec UNTM 중에서 선택된 1종 이상의 인산에스테르 화합물을 사용한다. 이러한 인산에스테르 화합물의 할로겐 화합물 치환체를 비롯한 각종 치환체들도 같은 목적으로 사용이 가능하다.The polymerizable composition of the present invention may include an internal mold release agent, and preferably includes an acidic phosphoric acid ester compound as the internal mold release agent. Acidic phosphate ester is prepared by adding 2-3 moles of alcohol compound to phosphorus pentoxide (P 2 O 5 ), and there may be various types of phosphate ester compounds depending on the type of alcohol used. Typical examples are those in which ethylene oxide or propylene oxide is added to aliphatic alcohol or ethylene oxide or propylene oxide is added to 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. As the internal mold release agent, preferably, 4-PENPP [polyoxyethylenenonylphenol ether phosphate (5% by weight of 5 mol of ethylene oxide added, 80% by weight of 4 mol added, 10% by weight of 3 mol added, 1 mole added 5% by weight)], 8-PENPP [Polyoxyethylenenonylphenol ether phosphate (3% by weight, 9 moles of ethylene oxide added, 80% by weight, 8 moles added, 5 parts of 9 moles added) %, 7 mol added 6 wt%, 6 mol added 6 wt%)], 12-PENPP [polyoxyethylenenonylphenol ether phosphate (13 mol added ethylene oxide 3 wt%, 12 mol added 80 wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PENPP [polyoxyethylene nonylphenol ether phosphate (17 mol ethylene oxide) 3 weight percent added, 16 mol added 79 weight percent, 15 mol added 10 weight percent, 14 mol added 4 weight percent, 13 mol added 4 weight percent)], 20-PENPP [poly Oxie Lennonylphenol ether phosphate (with 21 moles of ethylene oxide added 5% by weight, 20 moles added 76% by weight, 19 moles added 7% by weight, 18 moles added 6% by weight, 17 moles added 4 wt%)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 wt% of propylene oxide added, 80 wt% of 4 mol added, 10 wt% of 3 mol added, 1 mol) 5 wt% added)], 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (3 wt% of 9 mol added propylene oxide, 80 wt% added 8 mol, 5 wt% added 9 mol, 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13 mole added propylene oxide 3% by weight, 12 mole added 80% by weight) %, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PPNPP [polyoxypropylene nonylphenol ether phosphate ( 3 mol% of 17 mol added, 17 mol added 79 weight percent, 15 mol added 10 weight percent, 14 mol added 4 weight percent, 13 mol added 4 weight percent) , 20-PPNPP [polyoxypropylene nonylphenol ether phosphate (5% by weight of 21 mol of propylene oxide, 76% by weight of 20 mol added, 7% by weight of 19 mol added, 18 weight added %, 17 mol added 4% by weight)], at least one phosphate ester compound selected from Zelec UN ™ . Various substituents including halogen compound substituents of such phosphate ester compounds can be used for the same purpose.

본 발명의 중합성 조성물은, 광학재료의 광학적인 물성을 향상시키기 위해, 내충격성, 비중 및 모노머 점도 등을 조절하기 위한 목적으로 올레핀 화합물을 반응성 수지개질제로서 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, 에틸렌글리콜 디아크릴레이트, 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; 알릴글리시딜에테르, 디알릴프탈레이트, 디알릴테레프탈레이트, 디알릴이소프탈레이트, 디알릴카보네이트, 디에틸렌글리콜비스알릴카보네이트 등의 알릴 화합물; 그리고 스티렌, 클로로스티렌, 메틸스티렌, 브로모스티렌, 디브로모스티렌, 디비닐벤젠, 3,9-디비닐스피로비(m-디옥산) 등의 비닐 화합물 등이 있다. 그러나 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 optical material, the polymerizable 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, monomer viscosity, and the like. 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; Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, and diethylene glycol bisallyl carbonate; And vinyl compounds such as styrene, chlorostyrene, methyl styrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobiby (m-dioxane). However, the compounds that can be used are not limited to these exemplary compounds. You may use these olefin compounds individually or in mixture of 2 or more types.

본 발명의 광학재료는 주형 중합을 통해 얻게 된다. 즉, 개스켓 또는 테이프 등으로 유지된 성형 몰드 사이에, 본 발명의 중합성 조성물을 주입한다. 이때, 얻어지는 플라스틱 렌즈에 요구되는 물성에 따라, 또 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 -50~150℃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 obtained through mold polymerization. That is, the polymeric 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 of pressurization, reduced pressure, etc. according to the physical property calculated | required at the time of the plastic lens obtained, etc. in many cases. The polymerization conditions are not limited because the conditions largely vary depending on the polymerizable composition, the type and amount of the catalyst, 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 티오에폭시 화합물과 이소시아네이트 화합물 및 티올 화합물 공중합체는, 필요에 따라, 어닐링 등의 처리를 실시해도 좋다. 처리 온도는 통상 50~150℃의 사이에서 행해지며, 90~140℃에서 실시하는 것이 바람직하다.The thioepoxy compound, isocyanate compound, and thiol compound copolymer obtained by hardening may perform 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 산성 인산에스테르 화합물을 첨가하여 주형 중합시킨다. 산성 인산에스테르 화합물에 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 an acidic phosphate ester compound as an internal mold release agent. Description of the acidic 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 공중합체 수지는, 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, 본 발명의 수지는 맑고 투명하므로, 교정용렌즈, 썬글라스용렌즈, 패션렌즈, 변색렌즈, 카메라렌즈, 광학 장치용 렌즈 등에 적합하다.The copolymer resin 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 for various optical materials, such as an eyeglass lens, a camera lens, and a light emitting diode (LED). In particular, since the resin of the present invention is clear and transparent, it is suitable for lenses for correction, lenses for sunglasses, fashion lenses, discoloration lenses, camera lenses, optical devices, and the like.

본 발명의 공중합체 수지를 사용한 플라스틱 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 형성하거나 복수의 코팅층을 다층으로 형성하여 사용해도 좋다. 양면에 코팅층을 실시하는 경우, 각각의 면에 동일한 코팅층을 실시해도, 상이한 코팅층을 실시해도 좋다.
You may use the plastic lens using the copolymer resin of this invention, giving a coating layer to single side | surface or both surfaces as needed. 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 formed alone, or a plurality of coating layers may be formed in multiple 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.

[실시예][Example]

이하 구체적인 실시예를 통해 본 발명을 보다 상세히 설명한다. 그러나 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these embodiments.

시험 및 평가방법Test and evaluation method

색상 : 색차계로 측정한 수지의 YI값이 에피티오클로로히드린 함량이 0.01중량%인 실시예 1의 중합성 조성물을 경화 시켰을 때의 값보다 ±1이상 차가 있는 경우에는 '×', 그 미만의 경우에는 '○'로 표시하였다.Color: When the YI value of the resin measured by the color difference meter is ± 1 or more different from the value when the polymerizable composition of Example 1 having an epithiochlorohydrin content of 0.01% by weight is cured, In the case, it is indicated as '○'.

굴절률(nE), 아베수 : Atago 사의 IT 및 DR-M4 모델인 아베굴절계를 이용하여 20℃에서 측정했다.Refractive index (nE), Abbe number: It measured at 20 degreeC using the Abe refractometer of the Atago company IT and DR-M4 model.

[합성예 1] 비스(3-클로로-2-히드록시프로필)술피드(BCP-1)의 합성Synthesis Example 1 Synthesis of Bis (3-chloro-2-hydroxypropyl) sulfide (BCP-1)

10리터의 반응기에 에피클로로히드린 (5563g, 60.12 mol) 및 메탄올 (2500g)를 첨가하고 반응온도를 6에 맞추고 반응온도가 6에 도달했을 때 가성소다 (50% aq, 5g)을 첨가한다. 또 다른 10리터의 반응기에 NaSH.xH2O(70% NaSH, 3660g, 45.75 mol), 메탄올(1000g) 및 물(500g)을 첨가하고 교반하여 완전히 녹이고, 염산을 천천히 적가하여 발생한 황화수소 가스를 에피클로로히드린 용액에 첨가하여 비스(3-클로로-2-히드록시프로필)술피드를 얻는다. 반응의 종결은 최종생성물을 GC로 확인하여 에피클로로히드린과 3-클로로-2-히드록시-프로판-1-티올 화합물이 완전히 없어지고 비스(3-클로로-2-히드록시프로필)술피드가 생성되는 시점을 반응의 종결로 하였다. 과량으로 존재하는 3-클로로-2-히드록시-프로판-1-티올을 제거하기 위하여 GC로 상대적인 적분비의 함량을 계산하여 에피클로로히드린을 첨가하였다. GC 분석에서 에피클로로히드린 함량이 2.2%인 비스(3-클로로-2-히드록시프로필)술피드(BCP-1) (6388.73g, 58.31mol 97%)를 합성하였다.
Epichlorohydrin (5563 g, 60.12 mol) and methanol (2500 g) are added to a 10 liter reactor, caustic soda (50% aq, 5 g) is added when the reaction temperature reaches 6. In another 10 liter reactor, NaSH.xH 2 O (70% NaSH, 3660 g, 45.75 mol), methanol (1000 g) and water (500 g) were added and stirred to dissolve completely, and hydrochloric acid was slowly added dropwise to epidemic hydrogen sulfide gas generated. It is added to the chlorohydrin solution to obtain bis (3-chloro-2-hydroxypropyl) sulfide. Termination of the reaction confirmed the final product by GC, epichlorohydrin and 3-chloro-2-hydroxy-propane-1-thiol compound completely disappeared and bis (3-chloro-2-hydroxypropyl) sulfide The time point produced was the end of the reaction. Epichlorohydrin was added by calculating the relative integral content in GC to remove excess 3-chloro-2-hydroxy-propane-1-thiol. Bis (3-chloro-2-hydroxypropyl) sulfide (BCP-1) (6388.73 g, 58.31 mol 97%) having an epichlorohydrin content of 2.2% was synthesized by GC analysis.

[합성예 2] 비스(3-클로로-2-히드록시프로필)술피드(BCP-2)의 합성Synthesis Example 2 Synthesis of Bis (3-Chloro-2-hydroxypropyl) sulfide (BCP-2)

10리터의 반응기에 에피클로로히드린 (5563g, 60.12 mol) 및 메탄올 (2500g)를 첨가하고 반응온도를 6에 맞추고 반응온도가 6에 도달했을 때 가성소다 (50% aq, 5g)를 첨가한다. 또 다른 10리터의 반응기에 NaSH.xH2O(70% NaSH, 3660g, 45.75 mol), 메탄올(1000g) 및 물(500g)을 첨가하고 교반하여 완전히 녹이고, 염산을 천천히 적가하여 발생한 황화수소 가스를 에피클로로히드린 용액에 첨가하여 비스(3-클로로-2-히드록시프로필)술피드를 얻는다. 에피클로로히드린 함량이 2.2중량%인 비스(3-클로로-2-히드록시프로필)술피드 화합물에 황화수소가스를 첨가하여 GC 분석에서 에피클로로히드린 함량이 0.2중량%인 비스(3-클로로-2-히드록시프로필)술피드 화합물(BCP-2)(6456.11g, 58.92mol, 98%)을 합성하였다.
Epichlorohydrin (5563 g, 60.12 mol) and methanol (2500 g) are added to a 10 liter reactor, caustic soda (50% aq, 5 g) is added when the reaction temperature reaches 6. In another 10 liter reactor, NaSH.xH 2 O (70% NaSH, 3660 g, 45.75 mol), methanol (1000 g) and water (500 g) were added and stirred to dissolve completely, and hydrochloric acid was slowly added dropwise to epidemic hydrogen sulfide gas generated. It is added to the chlorohydrin solution to obtain bis (3-chloro-2-hydroxypropyl) sulfide. Hydrogen sulfide gas was added to a bis (3-chloro-2-hydroxypropyl) sulfide compound having an epichlorohydrin content of 2.2% by weight and bis (3-chloro- with an epichlorohydrin content of 0.2% by weight in GC analysis. 2-hydroxypropyl) sulfide compound (BCP-2) (6456.11 g, 58.92 mol, 98%) was synthesized.

[합성예 3] 비스(3-클로로-2-히드록시프로필)술피드(BCP-3)의 합성Synthesis Example 3 Synthesis of Bis (3-chloro-2-hydroxypropyl) sulfide (BCP-3)

10리터의 반응기에 에피클로로히드린 (5563g, 60.12 mol) 및 메탄올 (2500g)를 첨가하고 반응온도를 6에 맞추고 반응온도가 6에 도달했을 때 가성소다 (50% aq, 5g)을 첨가한다. 또 다른 10리터의 반응기에 NaSH.xH2O(70% NaSH, 3660g, 45.75 mol), 메탄올(1000g) 및 물(500g)을 첨가하고 교반하여 완전히 녹이고, 염산을 천천히 적가하여 발생한 황화수소 가스를 에피클로로히드린 용액에 첨가하여 비스(3-클로로-2-히드록시프로필)술피드를 얻는다. 반응의 종결은 최종생성물을 GC로 확인하여 과량의 3-클로로-2-히드록시-프로판-1-티올이 존재하면 GC로 상대적인 적분비를 계산하고 에피클로로히드린을 첨가하여 함량이 0.7중량%인 비스(3-클로로-2-히드록시프로필)술피드(BCPS-3)(6455g, 58.91mol, 98%)를 합성하였다.
Epichlorohydrin (5563 g, 60.12 mol) and methanol (2500 g) are added to a 10 liter reactor, caustic soda (50% aq, 5 g) is added when the reaction temperature reaches 6. In another 10 liter reactor, NaSH.xH 2 O (70% NaSH, 3660 g, 45.75 mol), methanol (1000 g) and water (500 g) were added and stirred to dissolve completely, and hydrochloric acid was slowly added dropwise to epidemic hydrogen sulfide gas generated. It is added to the chlorohydrin solution to obtain bis (3-chloro-2-hydroxypropyl) sulfide. The reaction was terminated by checking the final product with GC to calculate the relative integral ratio by GC when excess 3-chloro-2-hydroxy-propane-1-thiol was present and adding 0.7% by weight of epichlorohydrin. Phosphorous bis (3-chloro-2-hydroxypropyl) sulfide (BCPS-3) (6455 g, 58.91 mol, 98%) was synthesized.

[합성예 4] 비스(3-클로로-2-히드록시프로필)술피드(BCP-4)의 합성Synthesis Example 4 Synthesis of Bis (3-chloro-2-hydroxypropyl) sulfide (BCP-4)

10리터의 반응기에 에피클로로히드린 (5563g, 60.12 mol) 및 메탄올 (2500g)를 첨가하고 반응온도를 6에 맞추고 반응온도가 6에 도달했을 때 가성소다 (50% aq, 5g)를 첨가한다. 또 다른 10리터의 반응기에 NaSH.xH2O(70% NaSH, 3660g, 45.75 mol), 메탄올(1000g) 및 물(500g)을 첨가하고 교반하여 완전히 녹이고, 염산을 천천히 적가하여 발생한 황화수소 가스를 에피클로로히드린 용액에 첨가하여 비스(3-클로로-2-히드록시프로필)술피드를 얻는다. 에피클로로히드린 함량이 2.2중량%인 비스(3-클로로-2-히드록시프로필)술피드 화합물에 황화수소가스를 첨가하여 에피클로로히드린 함량이 0.5중량%인 비스(3-클로로-2-히드록시프로필)술피드 화합물(BCP-4)(6521.11g, 59.51mol, 99%)을 합성하였다.
Epichlorohydrin (5563 g, 60.12 mol) and methanol (2500 g) are added to a 10 liter reactor, caustic soda (50% aq, 5 g) is added when the reaction temperature reaches 6. In another 10 liter reactor, NaSH.xH 2 O (70% NaSH, 3660 g, 45.75 mol), methanol (1000 g) and water (500 g) were added and stirred to dissolve completely, and hydrochloric acid was slowly added dropwise to epidemic hydrogen sulfide gas generated. It is added to the chlorohydrin solution to obtain bis (3-chloro-2-hydroxypropyl) sulfide. Hydrogen sulfide was added to a bis (3-chloro-2-hydroxypropyl) sulfide compound having an epichlorohydrin content of 2.2% by weight, thereby making a bis (3-chloro-2-hydride having a content of 0.5% by weight of epichlorohydrin. Roxypropyl) sulfide compound (BCP-4) (6521.11 g, 59.51 mol, 99%) was synthesized.

[합성예 5] 비스(2,3-에피티오프로필)술피드(EPS-1)의 합성Synthesis Example 5 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (EPS-1)

10리터의 반응용기에, 합성예 2에서 합성한 에피클로로히드린 함량이 0.2중량%인 비스(3-클로로-2-히드록시-프로필)술피드(BCP-2)(1072.48g, 4.89 mol), 톨루엔 1300g, 메탄올 800g을 넣고 교반하면서 반응온도를 30에 맞춘다. 25에서 도달했을 때 NaOH(50% aq., 783.08g, 9.78 mol)를 적가하고 적가시 반응온도는 35~37에서 행하고, 온도를 유지하면서 반응시킨다. 적가는 1시간 이내로 하며 숙성은 37에서 약 30분 동안 행하고 숙성이 끝나면 톨루엔 2000g를 첨가하여 약 10분간 교반하고 층분리하여 상층액인 유기층을 물로 2회 세척하고 물을 최대한 제거하고 유기층인 유기용액을 메탄올 400g를 더 첨가하여 교반하고 반응온도 8에서 티오우레아(1117.65g, 14.30 mol) 및 무수초산(70g)을 첨가하고 반응온도를 18에 올려 18시간 동안 반응시킨다. 반응의 종결은 HPLC로 확인 출발물질이 사라지고 생성물이 더 이상 변화가 없을 때 한다. 반응이 종결되면 교반을 중지하고 층분리에서 얻은 유기층을 물로 세 번 세척하고, 유기용매를 제거하여 에피티오클로로히드린의 함량이 0.2중량%인 비스(2,3-에피티오프로필)술피드 화합물(EPS-1)(593g, 3.32mol, 68%)을 얻었다. 굴절률 (nD, 20)은 1.614 이었다.
Bis (3-chloro-2-hydroxy-propyl) sulfide (BCP-2) (1072.48 g, 4.89 mol) having a content of 0.2% by weight of epichlorohydrin synthesized in Synthesis Example 2 in a 10 liter reaction vessel 1300 g of toluene and 800 g of methanol were added and the reaction temperature was adjusted to 30 with stirring. When it reaches 25, NaOH (50% aq., 783.08 g, 9.78 mol) is added dropwise and the reaction temperature is added at 35 to 37 at the dropwise reaction. The dropping time is within 1 hour. After aging, the fermentation is carried out at 37 to 30 minutes. After aging, 2000 g of toluene is added and stirred for about 10 minutes. 400 g of methanol was further added and stirred, thiourea (1117.65 g, 14.30 mol) and acetic anhydride (70 g) were added at the reaction temperature 8, and the reaction temperature was raised to 18 and reacted for 18 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. When the reaction is complete, the stirring is stopped, the organic layer obtained in the layer separation is washed three times with water, and the organic solvent is removed to remove the bis (2,3-ethiothiopropyl) sulfide compound having 0.2% by weight of epithiochlorohydrin. (EPS-1) (593 g, 3.32 mol, 68%) was obtained. The refractive index (nD, 20) was 1.614.

[합성예 6] 비스(2,3-에피티오프로필)술피드(EPS-2)의 합성Synthesis Example 6 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (EPS-2)

10리터의 반응용기에, 합성예 4에서 합성한 에피클로로히드린 함량이 0.5중량%인 비스(3-클로로-2-히드록시-프로필)술피드(BCP-4)(1072.48g, 4.89 mol), 톨루엔 1300g, 메탄올 800g을 넣고 교반하면서 반응온도를 30에 맞춘다. 25에서 도달했을 때 NaOH(50% aq., 783.08g, 9.78 mol)를 적가하고 적가시 반응온도는 35~37에서 행하고, 온도를 유지하면서 반응시킨다. 적가는 1시간 이내로 하며 숙성은 37에서 약 30분 동안 행하고 숙성이 끝나면 톨루엔 2000g를 첨가하여 약 10분간 교반하고 층분리하여 상층액인 유기층을 물로 2회 세척하고 물을 최대한 제거하고 유기층인 유기용액을 메탄올 400g를 더 첨가하여 교반하고 반응온도 8에서 티오우레아(1117.65g, 14.30 mol) 및 무수초산(70g)을 첨가하고 반응온도를 18에 올려 18시간 동안 반응시킨다. 반응의 종결은 HPLC로 확인 출발물질이 사라지고 생성물이 더 이상 변화가 없을 때 한다. 반응이 종결되면 교반을 중지하고 층분리에서 얻은 유기층을 물로 세 번 세척하고, 유기용매를 제거하여 에피티오클로로히드린이 0.41중량% 함유된 비스(2,3-에피티오프로필)술피드 화합물(EPS-2)(593.01g, 3.32mol, 68%)을 얻었다. 굴절률 (nD, 20)은 1.614 이었다.
Bis (3-chloro-2-hydroxy-propyl) sulfide (BCP-4) (1072.48 g, 4.89 mol) having a content of 0.5% by weight of epichlorohydrin synthesized in Synthesis Example 4 in a 10 liter reaction vessel 1300 g of toluene and 800 g of methanol were added and the reaction temperature was adjusted to 30 with stirring. When it reaches 25, NaOH (50% aq., 783.08 g, 9.78 mol) is added dropwise and the reaction temperature is added at 35 to 37 at the dropwise reaction. The dropping time is within 1 hour. After aging, the fermentation is carried out at 37 to 30 minutes. After aging, 2000 g of toluene is added and stirred for about 10 minutes. 400 g of methanol was further added and stirred, thiourea (1117.65 g, 14.30 mol) and acetic anhydride (70 g) were added at the reaction temperature 8, and the reaction temperature was raised to 18 and reacted for 18 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. At the end of the reaction, stirring was stopped and the organic layer obtained in the layer separation was washed three times with water, and the organic solvent was removed to remove bis (2,3-ethiothio) sulfide compound containing 0.41% by weight of epithiochlorohydrin. EPS-2) (593.01 g, 3.32 mol, 68%) were obtained. The refractive index (nD, 20) was 1.614.

[합성예 7] 비스(2,3-에피티오프로필)술피드(EPS-3)의 합성Synthesis Example 7 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (EPS-3)

10리터의 반응용기에, 합성예 3에서 합성한 에피클로로히드린 함량이 0.7중량%인 비스(3-클로로-2-히드록시-프로필)술피드(BCP-3)(1072.48g, 4.89 mol), 톨루엔 1300g, 메탄올 800g을 넣고 교반하면서 반응온도를 30에 맞춘다. 25에서 도달했을 때 NaOH(50% aq., 783.08g, 9.78 mol)를 적가하고 적가시 반응온도는 35~37에서 행하고, 온도를 유지하면서 반응시킨다. 적가는 1시간 이내로 하며 숙성은 37에서 약 30분 동안 행하고 숙성이 끝나면 톨루엔 2000g를 첨가하여 약 10분간 교반하고 층분리하여 상층액인 유기층을 물로 2회 세척하고 물을 최대한 제거하고 유기층인 유기용액을 메탄올 400g를 더 첨가하여 교반하고 반응온도 8에서 티오우레아(1117.65g, 14.30 mol) 및 무수초산(70g)을 첨가하고 반응온도를 18에 올려 18시간 동안 반응시킨다. 반응의 종결은 HPLC로 확인 출발물질이 사라지고 생성물이 더 이상 변화가 없을 때 한다. 반응이 종결되면 교반을 중지하고 층분리에서 얻은 유기층을 물로 세 번 세척하고, 유기용매를 제거하여 에피티오클로로히드린이 0.57중량% 함유된 비스(2,3-에피티오프로필)술피드 화합물(EPS-3)(587.23g, 3.29mol, 67%)을 얻었다. 굴절률 (nD, 20)은 1.614 이었다.
Bis (3-chloro-2-hydroxy-propyl) sulfide (BCP-3) (1072.48 g, 4.89 mol) having a content of 0.7% by weight of epichlorohydrin synthesized in Synthesis Example 3 in a 10 liter reaction vessel 1300 g of toluene and 800 g of methanol were added and the reaction temperature was adjusted to 30 with stirring. When it reaches 25, NaOH (50% aq., 783.08 g, 9.78 mol) is added dropwise and the reaction temperature is added at 35 to 37 at the dropwise reaction. The dropping time is within 1 hour. After aging, the fermentation is carried out at 37 to 30 minutes. After aging, 2000 g of toluene is added and stirred for about 10 minutes. 400 g of methanol was further added and stirred, thiourea (1117.65 g, 14.30 mol) and acetic anhydride (70 g) were added at the reaction temperature 8, and the reaction temperature was raised to 18 and reacted for 18 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. At the end of the reaction, stirring was stopped and the organic layer obtained from the layer separation was washed three times with water, and the organic solvent was removed to remove bis (2,3-ethiothio) sulfide compound containing 0.57% by weight of epithiochlorohydrin. EPS-3) (587.23 g, 3.29 mol, 67%). The refractive index (nD, 20) was 1.614.

[합성예 8] 비스(2,3-에피티오프로필)술피드(EPS-4)의 합성Synthesis Example 8 Synthesis of Bis (2,3-Ethiothiopropyl) Sulfide (EPS-4)

10리터의 반응용기에, 합성예 1에서 합성한 에피클로로히드린 함량이 2.2중량%인 비스(3-클로로-2-히드록시-프로필)술피드(BCP-1)(1072.48g, 4.89 mol), 톨루엔 1300g, 메탄올 800g을 넣고 교반하면서 반응온도를 30에 맞춘다. 25에서 도달했을 때 NaOH(50% aq., 783.08g, 9.78 mol)를 적가하고 적가시 반응온도는 35~37에서 행하고, 온도를 유지하면서 반응시킨다. 적가는 1시간 이내로 하며 숙성은 37에서 약 30분 동안 행하고 숙성이 끝나면 톨루엔 2000g를 첨가하여 약 10분간 교반하고 층분리하여 상층액인 유기층을 물로 2회 세척하고 물을 최대한 제거하고 유기층인 유기용액을 메탄올 400g를 더 첨가하여 교반하고 반응온도 8에서 티오우레아(1117.65g, 14.30 mol) 및 무수초산(70g)을 첨가하고 반응온도를 18에 올려 18시간 동안 반응시킨다. 반응의 종결은 HPLC로 확인 출발물질이 사라지고 생성물이 더 이상 변화가 없을 때 한다. 반응이 종결되면 교반을 중지하고 층분리에서 얻은 유기층을 물로 세 번 세척하고, 유기용매를 제거하여 에피티오클로로히드린이 1.89중량% 함유된 비스(2,3-에피티오프로필)술피드 화합물(EPS-4)(584.95g, 3.28 mol, 67%)을 얻었다. 굴절률 (nD, 20)은 1.614 이었다.
Bis (3-chloro-2-hydroxy-propyl) sulfide (BCP-1) (1072.48 g, 4.89 mol) having an epichlorohydrin content of 2.2 wt% synthesized in Synthesis Example 1 in a 10 liter reaction vessel 1300 g of toluene and 800 g of methanol were added and the reaction temperature was adjusted to 30 with stirring. When it reaches 25, NaOH (50% aq., 783.08 g, 9.78 mol) is added dropwise and the reaction temperature is added at 35 to 37 at the dropwise reaction. The dropping time is within 1 hour. After aging, the fermentation is carried out at 37 to 30 minutes. After aging, 2000 g of toluene is added and stirred for about 10 minutes. 400 g of methanol was further added and stirred, thiourea (1117.65 g, 14.30 mol) and acetic anhydride (70 g) were added at the reaction temperature 8, and the reaction temperature was raised to 18 and reacted for 18 hours. Termination of the reaction is confirmed by HPLC when the starting material disappears and the product no longer changes. When the reaction was completed, the stirring was stopped and the organic layer obtained in the layer separation was washed three times with water, and the organic solvent was removed to contain bis (2,3-ethiothio) sulfide compound containing 1.89% by weight of epithiochlorohydrin. EPS-4) (584.95 g, 3.28 mol, 67%) was obtained. The refractive index (nD, 20) was 1.614.

[실시예 1]Example 1

티오에폭시 화합물로서 에피티오클로로히드린 함량이 0.2중량%인 합성예 5의 비스(2,3-에피티오프로필)술피드(EPS-1) 89g, 이소시아네이트 화합물로서 이소포론디이소시아네이트 5g, 티올 화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 산성인산에스테르인 8-PENPP[폴리옥시에티렌노닐페놀에테프소프페이트(에틸렌옥사이드 9몰부가된것 3중량%, 8몰 부가된것 80중량%, 9몰 부가된것 5중량%, 7몰부가 된것 6중량%, 6몰부가된것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g, 20℃에서 혼합 용해하여, 균일 용액으로 했다. 이 혼합 용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1㎛ PTFE제 필터로 여과를 실시하고, 유리 몰드와 테이프로 이루어지는 몰드형에 주입했다. 이 몰드형을 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합했다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈다. 몰드형으로부터의 이형성은 양호했다. 얻어진 수지를 130℃에서 4시간 더 어닐링처리를 실시했다. 얻어진 수지의 물성은, 굴절률(nE) 1.697, 아베수 35 이었다. 몰드형에 주입전 용해된 상태를 육안으로 관찰하였고, 탈형 후 표면 링 불량 여부를 확인한 결과 이상이 없었고, 백화는 보이지 않았으며, YI값은 1.8 이었고, 안정한 품질의 수지가 얻어졌다.
89 g of bis (2,3- epithiopropyl) sulfide (EPS-1) of Synthesis Example 5 having an epithiochlorohydrin content of 0.2% by weight as a thioepoxy compound, 5 g of isophorone diisocyanate as a isocyanate compound and a thiol compound Bis (2-mercaptoethyl) sulfide 6g, 8-PENPP [polyoxyethylenenonyl phenolic phosphate (9 mol part of ethylene oxide, 3 weight%, 8 mol addition) which is an acidic phosphate ester as an internal mold release agent 80% by weight, 9% by weight 5% by weight, 7% by weight 6% by weight, 6% by weight 6% by weight)] 0.15g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic The dye HTAQ (20 ppm), PRD (10 ppm), and the ultraviolet absorber HOPBT 1.5g, 20 degreeC were mixed and melt | dissolved, and it was set as the uniform solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with 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 end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.697 and Abbe number 35. The state dissolved before injection into the mold was visually observed. After demolding, it was confirmed that there was no surface ring defect. There was no abnormality, no whitening was observed, the YI value was 1.8, and a resin of stable quality was obtained.

[실시예 2][Example 2]

티오에폭시 화합물로서 에피티오클로로히드린 함량이 0.41중량%인 합성예 6의 EPS-2을 사용한 것 외에는 실시예 1과 동일하게 수지 조성물을 제조하고, 이 혼합 용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1㎛ PTFE제 필터로 여과를 실시하고, 유리 몰드와 테이프로 이루어지는 몰드형에 주입했다. 이 몰드형을 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합했다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈다. 몰드형으로부터의 이형성은 양호했다. 얻어진 수지를 더 130℃에서 4시간 어닐링처리를 실시했다. 얻어진 수지의 물성은, 굴절률(nE) 1.697, 아베수 35이였다. 몰드형에 주입전 용해된 상태를 육안으로 관찰하였고, 탈형 후 표면 링 불량 여부를 확인한 결과 이상이 없었고, 백화는 보이지 않았으며, YI값은 2.1 이었고, 안정한 품질의 수지가 얻어졌다.
A resin composition was prepared in the same manner as in Example 1 except that EPS-2 of Synthesis Example 6 having an epithiochlorohydrin content of 0.41% by weight was used as the thioepoxy compound, and the mixed solution was defoamed at 400 Pa for 1 hour. . Then, it filtered with 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 end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.697 and Abbe number 35. The state dissolved before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, the YI value was 2.1, and a resin of stable quality was obtained.

[실시예 3][Example 3]

티오에폭시 화합물로서 에피티오클로로히드린 함량이 0.57중량%인 합성예 7의 EPS-3을 사용한 것 외에는 실시예 1과 동일하게 수지 조성물을 제조하고, 이 혼합 용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1㎛ PTFE제 필터로 여과를 실시하고, 유리 몰드와 테이프로 이루어지는 몰드형에 주입했다. 이 몰드형을 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합했다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈다. 몰드형으로부터의 이형성은 양호했다. 얻어진 수지를 더 130℃에서 4시간 어닐링처리를 실시했다. 얻어진 수지의 물성은, 굴절률(nE) 1.697, 아베수 35이였다. 몰드형에 주입전 용해된 상태를 육안으로 관찰하였고, 탈형 후 표면 링 불량 여부를 확인한 결과 이상이 없었고, 백화는 보이지 않았으며, YI값은 2.3 이었고, 안정한 품질의 수지가 얻어졌다.
A resin composition was prepared in the same manner as in Example 1 except that EPS-3 of Synthesis Example 7 having an epithiochlorohydrin content of 0.57 wt% was used as the thioepoxy compound, and the mixed solution was defoamed at 400 Pa for 1 hour. . Then, it filtered with 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 end of the polymerization, the mold was taken out of the oven. Release property from the mold was good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.697 and Abbe number 35. The state dissolved before injection into the mold was visually observed, and after demolding, it was confirmed that there was no surface ring defect, no abnormality, no whitening was observed, the YI value was 2.3, and a resin of stable quality was obtained.

[비교예 1]Comparative Example 1

티오에폭시 화합물로서 에피티오클로로히드린 함량이 1.89중량%인 합성예 8의 비스(2,3-에피티오프로필)술피드 89g, 이소시아네이트 화합물로서 이소포론디이소시아네이트 5g, 티올 화합물로서 비스(2-메르캅토에틸)술피드 6g, 내부이형제로 산성인산에스테르인 8-PENPP[폴리옥시에티렌노닐페놀에테프소프페이트(에틸렌옥사이드 9몰부가된것 3중량%, 8몰 부가된것 80중량%, 9몰 부가된것 5중량%, 7몰부가 된것 6중량%, 6몰부가된것 6중량%)] 0.15g, 테트라부틸포스포늄브로마이드 0.2g, 트리페닐포스핀 0.1g, 유기염료 HTAQ(20ppm) 및 PRD(10ppm), 자외선 흡수제 HOPBT 1.5g, 20℃에서 혼합 용해하여, 균일 용액으로 했다. 이 혼합 용액을 400Pa에서 1시간 탈포를 실시했다. 그 후, 1㎛ PTFE제 필터로 여과를 실시하고, 유리 몰드와 테이프로 이루어지는 몰드형에 주입했다. 이 몰드형을 중합 오븐에 투입, 25℃~130℃까지 21시간에 걸쳐 서서히 승온하여 중합했다. 중합종료 후, 오븐으로부터 몰드형을 꺼냈다. 몰드형으로부터의 이형성이 매우 좋지 않았다. 얻어진 수지를 더 130℃에서 4시간 어닐링처리를 실시했다. 얻어진 수지의 물성은, 굴절률(nE) 1.697, 아베수 35이었다. 몰드형에 주입전 용해된 상태를 육안으로 관찰하였고, 탈형후 표면 링 불량 여부를 확인한 결과 이상이 없었고 백화는 보이지 않았으며, YI값은 3.2 이었다.
89 g of bis (2,3- epithiopropyl) sulfide of Synthesis Example 8 having an epithiochlorohydrin content of 1.89% by weight as a thioepoxy compound, 5 g of isophorone diisocyanate as an isocyanate compound, and a bis (2-mer as a thiol compound Captoethyl) sulfide 6g, 8-PENPP [polyoxyethylenenonylphenol ethofate (acidic phosphoric acid ester) 3% by weight, 8% added 80% by weight, 9 5% by weight, 7% by weight 6% by weight, 6% by weight 6% by weight)] 0.15 g, tetrabutylphosphonium bromide 0.2 g, triphenylphosphine 0.1 g, organic dye HTAQ (20 ppm) And PRD (10 ppm), ultraviolet absorber HOPBT 1.5 g, and 20 degreeC were mixed and melt | dissolved, and it was set as the uniform solution. The mixed solution was defoamed at 400 Pa for 1 hour. Then, it filtered with 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 end of the polymerization, the mold was taken out of the oven. The release property from the mold was not very good. The obtained resin was further annealed at 130 ° C. for 4 hours. The physical properties of the obtained resin were refractive index (nE) 1.697 and Abbe number 35. The state of dissolution before injection into the mold was visually observed. After demolding, it was confirmed that there was no surface ring defect and there was no abnormality, no whitening was observed, and the YI value was 3.2.

상기 실시예 및 비교예의 수지 조성 및 결과를 아래 표 1에 정리하였다.
The resin composition and the result of the said Example and a comparative example are put together in Table 1 below.

Figure pat00001
Figure pat00001

- 약어- - Abbreviation-

EPS : 비스(2,3-에피티오프로필)술피드EPS: bis (2,3-ethiothiopropyl) sulfide

IPDI : 이소포론디이소시아네이트(isophorondiisocyanate)IPDI: isophorondiisocyanate

BMES : 비스(2,3-에피티오프로필)술파이드(bis-(2,3-epithiopropyl)sulfide)BMES: bis (2,3-epithiopropyl) sulfide

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)

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

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

본 발명에 따르면 티오에폭시계 광학재료에서 나타나는 색상 불안정의 문제를 용이하게 해결하여 맑고 투명한 고품질의 티오에폭시계 렌즈를 높은 수율로 제조할 수 있다. 본 발명에 따라 제조된 맑고 투명한 티오에폭시계 광학재료는 기존 광학재료를 대체하여 다양한 분야에서 널리 이용될 수 있다. 구체적으로 플라스틱 안경렌즈, 안경렌즈에 편광필름을 장착한 3D 편광렌즈, 카메라 렌즈 등으로 이용될 수 있으며, 이외에도 프리즘, 광섬유, 광디스크 등에 사용되는 기록 매체기판이나 착색필터와 자외선 흡수 필터 등의 다양한 광학제품에 이용될 수 있다. According to the present invention, it is possible to easily solve the problem of color instability in the thioepoxy optical material, thereby producing a clear and high quality thioepoxy lens with high yield. The clear and transparent thioepoxy optical material prepared according to the present invention can be widely used in various fields in place of the existing optical material. Specifically, it can be used as a plastic glasses lens, a 3D polarizing lens equipped with a polarizing film on the spectacle lens, a camera lens, etc. In addition to a variety of optical, such as recording media substrates, color filters and ultraviolet absorption filters used in prisms, optical fibers, optical disks, etc. Can be used in the product.

Claims (15)

티오에폭시 화합물을 포함하는 티오에폭시계 중합성 조성물에 있어서, 상기 티오에폭시 화합물의 에피티오클로로히드린 함유량이 1중량% 이하인 것을 특징으로 하는 티오에폭시계 중합성 조성물. A thioepoxy polymerizable composition comprising a thioepoxy compound, wherein the epithiochlorohydrin content of the thioepoxy compound is 1% by weight or less. 제1항에 있어서, 폴리이소시아네이트 화합물을 더 포함하는 티오에폭시계 중합성 조성물. The thioepoxy polymerizable composition according to claim 1, further comprising a polyisocyanate compound. 제1항에 있어서, 폴리티올 화합물을 더 포함하는 티오에폭시계 중합성 조성물. The thioepoxy polymerizable composition according to claim 1, further comprising a polythiol compound. 제2항에 있어서, 폴리티올 화합물을 더 포함하는 티오에폭시계 중합성 조성물. The thioepoxy polymerizable composition according to claim 2, further comprising a polythiol compound. 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 티오에폭시 화합물은 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, 및 2-(2-β-에피티오프로필티오에틸티오)-1,3-비스(β-에피티오프로필티오)프로판으로 구성된 군으로부터 선택된 1종 이상인 것을 특징으로 하는 티오에폭시계 중합성 조성물. The compound according to any one of claims 1 to 4, wherein the thioepoxy compound is bis (2,3-ethiothio) sulfide, bis (2,3-ethiothio) disulfide, 1,3- and 1,4-bis (β-ethiothiopropylthio) cyclohexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthio Methyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane, and 2- (2-β-ethiothiopropylthioethylthio)- A thioepoxy polymerizable composition, characterized in that at least one member selected from the group consisting of 1,3-bis (β-epithiopropylthio) propane. 제2항 또는 제4항에 있어서, 상기 폴리이소시아네이트 화합물이 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, 및 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄으로 구성된 군으로부터 선택된 1종 이상인 것을 특징으로 하는 티오에폭시계 중합성 조성물. The polyisocyanate compound according to claim 2 or 4, wherein the polyisocyanate compound is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H12MDI), xylylene diisocyanate (XDI), 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 A thioepoxy polymerizable composition, characterized in that at least one member selected from the group consisting of 2,6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane. 제1항 내지 제4항 중 어느 한 항에 있어서, 반응성 수지개질제로 올레핀 화합물을 더 포함하는 티오에폭시계 중합성 조성물. The thioepoxy polymerizable composition according to any one of claims 1 to 4, further comprising an olefin compound as a reactive resin modifier. 제1항 내지 제4항 중 어느 한 항에 있어서, 내부이형제로, 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 부가 된 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(프로필렌옥사이드가 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 으로 구성된 군으로부터 선택된 1종 이상의 인산에스테르 화합물을 더 포함하는 티오에폭시계 중합성 조성물. The internal release agent according to any one of claims 1 to 4, wherein 4-PENPP [polyoxyethylene nonyl phenol ether phosphate (5% by weight of 5 mole of ethylene oxide added, 80% by weight of 4 mole added) , 3 mol added 10 wt%, 1 mol added 5 wt%)], 8-PENPP [polyoxyethylene nonylphenol ether phosphate (3 mol% added 9 mol ethylene oxide, 8 mol added 80) Wt%, 9 mol added 5 wt%, 7 mol added 6 wt%, 6 mol added 6 wt%)], 12-PENPP [polyoxyethylenenonylphenoletherphosphate (13 mol added ethylene oxide added) 3 wt%, 12 mol added 80 wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 16-PENPP [polyoxyethylene Nonylphenol ether phosphate (added 17 mol of ethylene oxide 3 weight percent, 16 mol added 79 weight percent, 15 mol added 10 weight percent, 14 mol added 4 weight percent, 13 mol added 4 Wt%)], 20-PENPP [polyoxyethylenenonylphenolether phosphate (5 wt% with 21 mol of ethylene oxide, 76 wt% with 20 mol, 7 wt% with 19 mol, 18 mol addition 6 weight percent, 17 mol added 4 weight percent)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 weight percent added with 5 mol of propylene oxide, 80 weight percent added with 4 mol, 3 mole added 10% by weight, 1 mole added 5% by weight)], 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (3% by weight of 9 moles of propylene oxide, 80% by weight added) %, 9 mol added 5 wt%, 7 mol added 6 wt%, 6 mol added 6 wt%)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13 mol added propylene oxide) 3 weight%, 12 mol added 80 weight%, 11 mol added 8 weight%, 9 mol added 3 weight%, 4 mol added 6 weight%)], 16-PPNPP [polyoxypropylene furnace Nylphenol ether phosphate (3% by weight of 17 moles of propylene oxide added, 79% by weight of 16 moles added, 10% by weight of 15 moles added, 4% by weight, 14 moles added, 13 moles added 4 Wt%)], 20-PPNPP [polyoxypropylenenonylphenoletherphosphate (5 wt% with 21 mol of propylene oxide, 76 wt% with 20 mol, 7 wt% with 19 mol, 18 mol addition 6 wt%, 17 mol added 4 wt%)], and Zelec UN ™ further comprising at least one phosphate ester compound selected from the group consisting of. 제1항 내지 제4항 중 어느 한 항의 중합성 조성물을 주형 중합시키는 티오에폭시계 광학재료의 제조방법. The manufacturing method of the thio epoxy clock optical material which mold-polymerizes the polymeric composition of any one of Claims 1-4. 제9항에 있어서, 상기 티오에폭시 화합물은 에피클로로히드린 함유량이 1중량% 이하인 에폭시 화합물과 티오우레아를 반응시켜 에피술피드화하는 단계를 포함하는 방법으로 합성되는 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법. The thioepoxy optical compound according to claim 9, wherein the thioepoxy compound is synthesized by a method including episulfidation by reacting an thiourea with an epoxy compound having an epichlorohydrin content of 1% by weight or less. Method of manufacturing the material. 제9항에 있어서, 상기 티오에폭시 화합물은 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, 및 2-(2-β-에피티오프로필티오에틸티오)-1,3-비스(β-에피티오프로필티오)프로판으로 구성된 군으로부터 선택된 1종 이상인 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법. The compound of claim 9, wherein the thioepoxy compound is bis (2,3-ethiothiopropyl) sulfide, bis (2,3-ethiothio) disulfide, 1,3- and 1,4-bis (β- Epithiopropylthio) cyclohexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, 2,5-bis (β-ethiothiopropylthiomethyl) -1,4-diti An, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, and 2- (2-β-ethiothiopropylthioethylthio) -1,3-bis (β- A method for producing a thioepoxy clock optical material, characterized in that at least one member selected from the group consisting of epithiopropylthio) propane. 제9항에 있어서, 상기 중합성 조성물은, 반응성 수지개질제로 올레핀 화합물을 더 포함하는 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법. The method of manufacturing a thioepoxy optical material according to claim 9, wherein the polymerizable composition further comprises an olefin compound as a reactive resin modifier. 제9항에 있어서, 상기 중합성 조성물은, 내부이형제로, 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 부가 된 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(프로필렌옥사이드가 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 으로 구성된 군으로부터 선택된 1종 이상의 인산에스테르 화합물을 더 포함하는 것을 특징으로 하는 티오에폭시계 광학재료의 제조방법. 10. The method of claim 9, wherein the polymerizable composition, 4-PENPP [polyoxyethylene nonyl phenol ether phosphate (5% by weight, 5% by weight of ethylene oxide added, 80% by weight, 3 mol added) as an internal mold release agent Mole added 10% by weight, 1 mole added 5% by weight)], 8-PENPP [polyoxyethylenenonylphenol ether phosphate (3% by weight of 9 moles of ethylene oxide, 80% by weight added) , 9 mole added 5% by weight, 7 mole added 6% by weight, 6 mole added 6% by weight)], 12-PENPP [polyoxyethylenenonylphenol ether phosphate (13 mole added, ethylene oxide 3) Wt%, 12 mol added 80 wt%, 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol added 6 wt%)], 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, 14 moles added, 14 moles added % By weight)], 20-PENPP [polyoxyethylenenonylphenolether phosphate (5% by weight of 21 mole of ethylene oxide, 76% by weight of 20 mole added, 7% by weight of 19 mole added, 18 mole added) 6 weight percent, 17 mol added 4 weight percent)], 4-PPNPP [polyoxypropylene nonylphenol ether phosphate (5 weight percent added with 5 mol of propylene oxide, 80 weight percent added with 4 mol, 3 mole added 10% by weight, 1 mole added 5% by weight)], 8-PPNPP [polyoxypropylene nonylphenol ether phosphate (3% by weight of 9 moles of propylene oxide, 80% by weight added) %, 9 mol added 5 wt%, 7 mol added 6 wt%, 6 mol added 6 wt%)], 12-PPNPP [polyoxypropylene nonylphenol ether phosphate (13 mol added propylene oxide) 3 weight%, 12 mol added 80 weight%, 11 mol added 8 weight%, 9 mol added 3 weight%, 4 mol added 6 weight%)], 16-PPNPP [polyoxypropylene nonyl Phenol ether phosphate (3% by weight of 17 moles of propylene oxide added, 79% by weight of 16 moles added, 10% by weight of 15 moles added, 4% by weight of 14 moles added, 4 parts by weight of 13 moles added %)], 20-PPNPP [polyoxypropylene nonylphenol ether phosphate (5% by weight of 21 mol propylene oxide, 76% by weight 20 mol added, 7% by weight 19 mol added, 18 mol added 6 wt%, 17 mol added 4 wt%)], and Zelec UN ™ are at least one phosphate ester compound selected from the group consisting of. 제9항의 제조방법으로 얻어지는 티오에폭시계 광학재료.A thioepoxy clock optical material obtained by the manufacturing method of claim 9. 제15항의 광학재료로 이루어진 티오에폭시계 광학렌즈. A thiopepoxy optical lens comprising the optical material of claim 15.
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