KR20100077847A - Resin composition using new thiol compound for optical lens having light weight and high refractive index, and the optical lens using it - Google Patents

Resin composition using new thiol compound for optical lens having light weight and high refractive index, and the optical lens using it Download PDF

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KR20100077847A
KR20100077847A KR1020080135911A KR20080135911A KR20100077847A KR 20100077847 A KR20100077847 A KR 20100077847A KR 1020080135911 A KR1020080135911 A KR 1020080135911A KR 20080135911 A KR20080135911 A KR 20080135911A KR 20100077847 A KR20100077847 A KR 20100077847A
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resin composition
optical lens
hydroxy
compound
benzotriazole
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KR1020080135911A
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KR101074450B1 (en
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장동규
노수균
김종효
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주식회사 케이오씨솔루션
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Priority to KR1020080135911A priority Critical patent/KR101074450B1/en
Priority to PCT/KR2009/005604 priority patent/WO2010076942A1/en
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    • 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
    • G02B1/041—Lenses
    • 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
    • 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
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

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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)
  • Eyeglasses (AREA)

Abstract

PURPOSE: An optical resin composition and an optical lens are provided to have high refractive index and light weight, to obtain excellent optical properties including impact resistance, heat resistance, moldability, light transmission rate, and Abbe's number, and to be used for manufacturing a glasses lens with strong prescriptions. CONSTITUTION: A resin composition for an optical lens includes a reaction mixture in which a thiol compound of a chemical formula 1 and an isocyanate compound are mixed. The reaction mixture includes a thiol compound which is selected from a group comprising 2-(2-mercaptoethylthio)propane-1,3-dithiol and 2-(2-mercaptoethylthio)-3-2-[3-mercapto-2(2-mercaptoethylthio)-propylthio]-ethylthio-propane-1-thiol.

Description

신규 티올 화합물을 이용한 광학렌즈용 경량성 고굴절 수지 조성물 및 이를 이용한 광학렌즈 {Resin Composition Using New Thiol Compound for Optical Lens Having Light Weight and High Refractive Index, and the Optical Lens Using It} Resin Composition Using New Thiol Compound for Optical Lens Having Light Weight and High Refractive Index, and the Optical Lens Using It}

본 발명은 플라스틱 광학렌즈용 수지 조성물에 관한 것으로, 특히 신규 티올 화합물을 이용한 광학렌즈용 경량성 고굴절 수지 조성물 및 이를 이용한 광학렌즈에 관한 것이다. The present invention relates to a resin composition for plastic optical lenses, and more particularly to a lightweight high refractive resin composition for optical lenses using a novel thiol compound and an optical lens using the same.

플라스틱 렌즈는 경량이면서도 내 충격성이 우수할 뿐만 아니라, 유리렌즈에 비하여 염색이 용이하기 때문에 오늘날 각종 광학렌즈의 생산에 사용되고 있다. 플라스틱 광학렌즈의 재료로 통상 폴리에틸렌글리콜비스알릴카르보네이트, 폴리메틸메타아크릴레이트(PMMA), 변성디아릴프탈레이트와 에틸렌글리콜비스알릴카르보네이트의 혼합물 등이 사용되었다. 그러나 이러한 플라스틱 렌즈 재료들은 굴절률이 1.50∼1.55 정도로 낮기 때문에 돗수를 높이기 위해서는 렌즈의 두께가 두꺼워지는 문제점이 있다. 따라서 렌즈의 미관이 나빠지는 불리함이 있고, 이는 플라스틱 렌즈가 갖는 경량성 등의 우수성을 상쇄시키게 된다. 특히, 디아릴프탈레이트와 에틸렌글리콜비스알릴카르보네이트의 혼합물로 만든 근시렌즈의 경우는 돗수가 높을 경우 플라스틱 렌즈의 가장자리 두께가 두꺼워지는 미관상의 문제뿐만 아니라, 복굴절 및 색수차가 발생하는 문제점까지 있다. 따라서 비중이 낮은 플라스틱 렌즈의 장점을 최대한 살리면서도 굴절률이 높아 렌즈의 두께를 감소시킬 수 있고, 색수차가 낮으며, 저분산을 나타낼 수 있는 플라스틱 렌즈 재료가 요구된다. Plastic lenses are used in the production of various optical lenses today because they are lightweight and have excellent impact resistance, and are easy to dye as compared to glass lenses. As a material of a plastic optical lens, polyethyleneglycol bisallyl carbonate, polymethyl methacrylate (PMMA), a mixture of modified diaryl phthalate and ethylene glycol bisallyl carbonate, etc. have been generally used. However, since these plastic lens materials have a low refractive index of about 1.50 to 1.55, the thickness of the lens is increased in order to increase the number of tap water. Therefore, there is a disadvantage that the aesthetics of the lens worsens, which cancels the superiority such as light weight of the plastic lens. In particular, the myopia lens made of a mixture of diaryl phthalate and ethylene glycol bisallyl carbonate has a problem that birefringence and chromatic aberration occur, as well as aesthetic problems in which the edge thickness of the plastic lens becomes thick when the tap water is high. Accordingly, there is a need for a plastic lens material that can reduce the thickness of the lens due to its high refractive index and to reduce the chromatic aberration and exhibit low dispersion while making the most of the advantages of the low specific gravity plastic lens.

한국특허 공고 특1992-0005708호에서는 굴절률 1.65 이상으로 렌즈의 가장자리 두께를 얇게 제조할 수 있는 플라스틱 렌즈 재료를 제공하고 있으나, 높은 색수차와 낮은 내열성 문제가 있고, 고상 비중 또한 1.33∼1.36으로 높아 렌즈가 무거워지는 문제점이 있다. Korean Patent Publication No. 1992-0005708 provides a plastic lens material capable of producing a thin lens thickness with a refractive index of 1.65 or more, but has high chromatic aberration and low heat resistance problems, and has a high specific gravity of 1.33 to 1.36. There is a problem that becomes heavy.

한국특허 특1987-0008928에서는 자일렌디이소시아네이트 0.05M과 펜타에리트리톨테트라키스메르캅토프로피오네이트 0.025M을 열경화시켜 투명성, 인장 강도가 우수하고, 분산치가 낮은 우레탄계 플라스틱 광학렌즈를 제조하고 있다. 그러나, 상기 광학렌즈는 1.593의 고굴절률을 갖고 있으나 내열성이 낮아 렌즈 표면에 하드 및 멀티코팅시 렌즈 중심 부분이 변형되는 문제점이 있고, 고상 비중이 1.30∼1.34로 높아 렌즈가 무겁다는 단점이 있다.In Korean Patent 1987-0008928, 0.05M xylene diisocyanate and 0.025M pentaerythritol tetrakismercaptopropionate are thermally cured to produce urethane plastic optical lenses having excellent transparency and tensile strength and low dispersion. However, the optical lens has a high refractive index of 1.593, but the heat resistance is low, there is a problem that the lens center portion is deformed during the hard and multi-coating on the lens surface, there is a disadvantage that the lens is heavy due to the high specific gravity of 1.30 ~ 1.34.

또한, 한국특허 공고 특1993-0006918에서는 지환족 이소시아네이트 화합물과 펜타에리트리롤테트라키스메르캅토피오피네이트 혹은 1,2-비스[(2-메르캅토에틸)티오]-3-메르캅토프로판을 열경화시켜서, 굴절률 1.593의 고굴절 우레탄계 플라스틱 광학렌즈를 제조하고 있으나, 이와 같이 제조된 광학렌즈는 고상 비중이 1.30∼1.34로 높아 렌즈가 무겁다는 문제점이 있다.In addition, Korean Patent Publication No. 1993-0006918 discloses an alicyclic isocyanate compound and a pentaerythritol tetrakismercaptopiopinate or 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane. By curing, a high refractive index urethane-based plastic optical lens having a refractive index of 1.593 is manufactured, but the optical lens manufactured as described above has a problem that the lens is heavy due to its high specific gravity of 1.30 to 1.34.

본 발명자들은 본 발명에 앞서 가볍고 충격에 강한 플라스틱 렌즈의 장점을 그대로 보유하면서 고굴절률을 가질 수 있는 광학렌즈용 수지에 관한 발명인 “광학렌즈용 경량성 고굴절 수지 및 이를 이용한 광학렌즈”를 특허출원 제10-2007-0077515호 출원한 바 있다. 본 발명에서는 이러한 특성을 더욱 발전시켜 비중은 더 낮으면서도 원재료비가 낮고 수율이 높아 생산비를 크게 낮출 수 있는 신규의 폴리티올 화합물을 포함하는 광학렌즈용 수지조성물을 제공하고자 한다. Prior to the present invention, the inventors have filed a patent application entitled “Lightweight high refractive resin for an optical lens and an optical lens using the same” which is an invention for an optical lens resin that can have a high refractive index while retaining the advantages of a light and impact resistant plastic lens. 10-2007-0077515 has been filed. The present invention further develops these properties to provide a resin composition for an optical lens including a novel polythiol compound which can lower the specific cost, but also lower the raw material cost and high yield, thereby greatly reducing the production cost.

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

하기 화학식 1로 표시되는 티올 화합물과 이소시아네이트 화합물을 혼합한 반응 혼합물을 포함하는 광학렌즈용 수지 조성물이 제공된다.There is provided a resin composition for an optical lens comprising a reaction mixture of a thiol compound represented by the following formula (1) and an isocyanate compound.

Figure 112008090048801-PAT00001
Figure 112008090048801-PAT00001

또한, 본 발명에서는 상기 광학렌즈용 수지 조성물을 열경화시켜서 얻은 플라스틱 안경렌즈가 제공된다.Moreover, in this invention, the plastic spectacle lens obtained by thermosetting the said resin composition for optical lenses is provided.

본 발명에서 얻어진 광학 수지 조성물 및 광학렌즈는 고굴절이면서도 비중이 낮아 가볍고 내충격성, 내열성, 성형성, 염색성, 광투과률, 아베수 등의 광학특성이 우수하다. 따라서 높은 돗수에서도 렌즈의 가장자리 두께를 얇게 할 수 있고 동시에 경량성이므로 높은 돗수의 안경렌즈 제조에 유용하게 이용될 수 있다. 특히 본 출원인의 선출원 발명인 “광학렌즈용 경량성 고굴절 수지 및 이를 이용한 광학렌즈”(특허출원 제10-2007-0077515호)에 따라 제조된 수지 조성물에 비해서도 비중이 낮아 더 가벼우며, 열변형온도는 더 높아 내열성이 더 우수한 반면, 원재료비가 낮고 수율이 높아 생산비를 30∼40% 정도로 크게 낮출 수 있다. The optical resin composition and the optical lens obtained in the present invention have high refractive index and low specific gravity, and are light and excellent in optical properties such as impact resistance, heat resistance, moldability, dyeing property, light transmittance and Abbe's number. Therefore, the edge thickness of the lens can be made thin even at high degrees of water, and at the same time, it can be usefully used for manufacturing glasses of high degree of water because of its light weight. In particular, compared to the resin composition prepared according to the applicant's prior application of "lightweight high refractive resin for optical lenses and optical lenses using the same" (Patent Application No. 10-2007-0077515), the specific gravity is lighter and heat distortion temperature is Its higher heat resistance makes it possible to reduce production costs by 30-40% due to lower raw material costs and higher yields.

본 발명의 광학렌즈용 경량성 고굴절 수지 조성물은 상기 화학식 1로 표시되는 신규 티올 화합물과 이소시아네이트 화합물을 혼합한 반응 혼합물을 포함한다. The lightweight high refractive resin composition for an optical lens of the present invention includes a reaction mixture obtained by mixing a novel thiol compound and an isocyanate compound represented by Chemical Formula 1.

상기 반응 혼합물은 2,3-비스(2-메르캅토에틸티오)프로판-1-티올; 2-(2-메르캅토에틸티오)-3-2-[3-메르캅토-2(2-메르캅토에틸티오)-프로필티오]-에틸티오-프로판-1-티올; 및 2-(2-메르캅토에틸티오)프로판-1,3-디티올로 구성된 군으로부터 선택된 1종 또는 2종 이상의 티올 화합물을 더 포함할 수 있다. The reaction mixture comprises 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2-mercaptoethylthio) -3-2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethylthio-propane-1-thiol; And 2- (2-mercaptoethylthio) propane-1,3-dithiol, and may further include one or two or more thiol compounds selected from the group consisting of.

상기 이소시아네이트 화합물은 바람직하게는 이소프론디이소시아네이트; 1,6-헥사메틸렌디소시아네아네이트; 및 시클로헥실메탄디이소시아네이트(H12MDI)로 구성된 군으로부터 1종 또는 2종 이상 선택된다. The isocyanate compound is preferably isoprone diisocyanate; 1,6-hexamethylenedisocyananeate; And cyclohexyl methane diisocyanate (H12MDI) is selected from the group consisting of one or two or more.

또, 상기 반응 혼합물은 반응물질로 활성화 수소화합물을 더 포함할 수 있다. 본 명세서에서 “활성화 수소화합물”은 펜타에리트리톨테트라키스머캅토프로 피오네이트; 펜타에리트리톨테트라키스머캅토아세테이트; 에틸렌글리콜; 디에틸렌글리콜; 프로필렌글리콜; 디프로필렌글리콜; 부틸렌글리콜; 네오펜틸글리콜; 글리세린; 트리메틸롤에탄; 부탄트리올; 1,2-메틸클로라이드; 펜타에리트리톨; 디펜타에리트리톨; 트리펜타에리트리톨; 소르비톨; 에틸렌글리콜; 트레이톨리비톨(트레이톨, 리비톨); 아라비니톨; 자일리톨; 알리톨; 마니톨; 돌시톨; 히데이톨; 글리콜; 이노시톨; 헥산트리올; 트리글리세롤; 디글리세롤; 트리에틸렌글리콜; 폴리에틸렌글리콜; 트리스(2-히드록시에틸)이소시아누레이트; 시클로부탄디올; 시클로펜탄디올; 시클로헥산디올; 시클로헵탄디올; 시클로옥탄디올; 시클로헥산디메탄올; 히드록시프로필시클로헥산올; 디히드록시나프탈렌; 트리히드록시나프탈렌; 테트라히드록시나프탈렌; 디히드록시벤젠; 벤젠트리올; 디페닐테트라올; 피로갈올; (히드록시나프틸)피로갈올; 트리히드록시페난트렌; 비스페놀A-테트라브롬; 비스페놀A-비스(2-히드록시에틸에테르); 1,3-비스(2,히드록시에틸티오에틸)-시클로헥산 등의 유황원자를 함유한 폴리올; 1,2-에탄디티올; 1,1-프로판디티올; 1,2-프로판디티올; 1,3-프로판디티올; 2,2-프로판디티올; 1,6-헥산디티올; 1,2,3-프로판트리티올 및 하기 화학식 2로 표시되는 화합물로 구성된 군으로부터 선택된 1종 또는 2종 이상의 화합물을 의미한다. 활성화 수소화합물로는 바람직하게는 펜타에리트리톨테트라키스머캅토프로피오네이트; 펜타에리트리톨테트라키스메캅토아세테이트; 및 하기 화학식 2로 표시되는 화합물이 각각 단독으로 또는 2종 이상 함께 사용될 수 있다.In addition, the reaction mixture may further include an activated hydrogen compound as a reactant. As used herein, “activated hydrogen compound” includes pentaerythritol tetrakismercaptopropionate; Pentaerythritol tetrakismercaptoacetate; Ethylene glycol; Diethylene glycol; Propylene glycol; Dipropylene glycol; Butylene glycol; Neopentyl glycol; glycerin; Trimethylol ethane; Butanetriol; 1,2-methylchloride; Pentaerythritol; Dipentaerythritol; Tripentaerythritol; Sorbitol; Ethylene glycol; Thritol libitol (Treitol, Ribitol); Arabinitol; Xylitol; Alitol; Mannitol; Dolitol; Hydritol; Glycol; Inositol; Hexanetriol; Triglycerol; Diglycerol; Triethylene glycol; Polyethylene glycol; Tris (2-hydroxyethyl) isocyanurate; Cyclobutanediol; Cyclopentanediol; Cyclohexanediol; Cycloheptanediol; Cyclooctanediol; Cyclohexanedimethanol; Hydroxypropylcyclohexanol; Dihydroxynaphthalene; Trihydroxynaphthalene; Tetrahydroxynaphthalene; Dihydroxybenzene; Benzenetriol; Diphenyltetraol; Pyrogalol; (Hydroxynaphthyl) pyrogalol; Trihydroxyphenanthrene; Bisphenol A-tetrabrom; Bisphenol A-bis (2-hydroxyethyl ether); Polyols containing sulfur atoms such as 1,3-bis (2, hydroxyethylthioethyl) -cyclohexane; 1,2-ethanedithiol; 1,1-propanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 2,2-propanedithiol; 1,6-hexanedithiol; It means one or two or more compounds selected from the group consisting of 1,2,3-propanetriol and the compound represented by the following formula (2). As an activating hydrogen compound, Preferably, pentaerythritol tetrakismercaptopropionate; Pentaerythritol tetrakismecaptoacetate; And compounds represented by the following Chemical Formula 2 may be used alone or in combination of two or more thereof.

Figure 112008090048801-PAT00002
Figure 112008090048801-PAT00002

상기 화학식 1로 표시되는 티올 화합물과 상기 활성수소 화합물을 합친 혼합물에 대한 이소시아네이트 화합물의 사용 비율은 (NCO)/(OH+SH)의 관능기 몰비가 통상 0.5∼3.0의 범위이며, 바람직하게는 0.5∼1.5이다. The molar ratio of the functional group of the isocyanate compound to the mixture of the thiol compound represented by the formula (1) and the active hydrogen compound is (NCO) / (OH + SH) is usually in the range of 0.5 to 3.0, preferably 0.5 to 3.0. 1.5.

상기 티올 화합물 30∼70 중량%와 이소시아네이트 화합물 30∼70 중량%를 반응시켜 얻어진 본 발명의 수지 조성물은 고상 굴절률(nD, 20℃) 1.572∼1.632, 액상 굴절률 1.520∼1.570, 고상 비중 1.15∼1.25, 고상 수지의 아베수 32∼50, 액상 점도(20℃) 5∼800cps를 갖는다.The resin composition of the present invention obtained by reacting the thiol compound 30 to 70 wt% with the isocyanate compound 30 to 70 wt% has a solid phase refractive index (nD, 20 ° C) of 1.572 to 1.632, a liquid phase refractive index of 1.520 to 1.570, a solid phase specific gravity of 1.15 to 1.25, It has Abbe's number 32-50 of liquid resin, and 5-800 cps of liquidus viscosity (20 degreeC).

본 발명의 수지 조성물은 제조된 수지의 광 안정성을 향상시키기 위하여 상기 반응 혼합물 전체 중량에 대하여 자외선 흡수제 0.0007∼9 중량%를 포함할 수 있으며, 바람직하게는 0.5∼3 중량%로 포함할 수 있다. 자외선 흡수제를 상기 범위보다 소량으로 사용할 경우에는 눈에 유해한 자외선을 효과적으로 차단하기 어렵고, 이 범위를 넘어 사용할 경우에는 광학렌즈 조성물에 녹이기도 어렵고 경화한 광학렌즈의 표면에 점무늬가 발생하거나 광학렌즈의 투명도가 떨어지는 문제점이 발생할 수 있다. 자외선 흡수제로는, 광학렌즈에 사용 가능한 공지의 자외선 흡수 제면 제한 없이 사용될 수 있다. 예를 들면, 에틸-2-시아노-3,3-디페닐아크릴레이트; 2-(2'-히드록시-5-메틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3'-t-부틸-5'-메틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-아밀페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-5'-t-부틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸; 2,4-디히드록시벤조페논; 2-히드록시-4-메톡시벤조페논; 2-히드록시-4-옥틸옥시벤조페논; 4-도데실옥시-2-히드록시벤조페논; 4-벤족시-2-히드록시벤조페논; 2,2',4,4'-테트라히드록시벤조페논; 2,2'-디히드록시-4,4'-디메톡시벤조페논 등이 단독으로 또는 2종 이상 혼합 사용될 수 있다. 바람직하게는, 400㎚ 이하의 파장역에서 양호한 자외선 흡수능을 가지고, 본 발명의 조성물에 양호한 용해성을 갖는 2-(2'-히드록시-5-메틸페닐)-2H-벤조트리아졸, 2-히드록시-4-메톡시벤조페논; 에틸-2-시아노-3,3-디페닐아크릴레이트; 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸; 2,2'-디히드록시-4,4'-디메톡시벤조페논; 2-(2'-히드록시-3',5'-디-t-아밀페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3,5'-디-t-부틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3'-t-부틸-5'-메틸페닐)-5-클로로-2H-벤조트리아졸 및 2,2-디히드록시-4,4'-디메톡시벤조페논 등이 단독으로 또는 2종 이상 같이 사용될 수 있다.The resin composition of the present invention may include 0.0007 to 9% by weight of the ultraviolet absorber, and preferably 0.5 to 3% by weight, based on the total weight of the reaction mixture in order to improve the light stability of the prepared resin. If the UV absorber is used in a smaller amount than the above range, it is difficult to effectively block ultraviolet rays harmful to the eyes, and when it is used beyond this range, it is difficult to dissolve in the optical lens composition, and spot patterns appear on the surface of the cured optical lens or transparency of the optical lens. Problem may occur. As the ultraviolet absorbent, it can be used without any known ultraviolet absorbent surface limitation that can be used for the optical lens. For example, ethyl-2-cyano-3,3-diphenyl acrylate; 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzoxoxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,2'- dihydroxy-4,4'- dimethoxy benzophenone etc. can be used individually or in mixture of 2 or more types. Preferably, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, 2-hydroxy having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention. -4-methoxybenzophenone; Ethyl-2-cyano-3,3-diphenylacrylate; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3,5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole and 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like These may be used alone or in combination of two or more.

본 발명의 광학렌즈용 경량성 수지는 렌즈의 초기 색상 개선 및 소비자의 기호도 만족 등을 위해 공지의 유기염료를 포함할 수 있다. 본 발명의 실시예에서는 1-히드록시-4-(파라-톨루이딘)안트라퀴논[1-hydroxy-4-(p-toluidin) -anthraquinone], 페리논 염료(perinone dye) 등을 광학렌즈용 조성물 1㎏ 당 0.001∼10,000ppm, 바람직하게는 0.005∼1,000ppm 첨가함으로써 자외선 흡수제 첨가에 의하여 광학렌즈가 노란색을 띠는 것을 방지할 수 있다.The lightweight resin for an optical lens of the present invention may include a known organic dye for improving the initial color of the lens and satisfying consumer's preference. In the embodiment of the present invention 1-hydroxy-4- (para- toluidine) anthraquinone [1-hydroxy-4- (p-toluidin) -anthraquinone], perinone dye (perinone dye) and the like for an optical lens composition 1 By adding 0.001 to 10,000 ppm, preferably 0.005 to 1,000 ppm per kg, it is possible to prevent the optical lens from becoming yellow by the addition of an ultraviolet absorber.

또, 본 발명의 수지 조성물은 내부이형제를 더 포함할 수 있다. 내부 이형제로는, 퍼플루오르알킬기, 히드록시알킬기 또는 인산에스테르기를 지닌 불소계 비이온계면활성제; 디메틸폴리실록산기, 히드록시알킬기 또는 인산에스테르기를 가진 실리콘계 비이온계면활성제; 알킬제 4급 암모늄염 즉, 트리메틸세틸 암모늄염, 트리메틸스테아릴, 디메틸에틸세틸 암모늄염, 트리에틸도데실 암모늄염, 트리옥틸메틸 암모늄염, 디에틸시클로헥사도데실 암모늄염; 산성 인산에스테르 중에서 선택된 성분이 단독으로 혹은 2종 이상 함께 사용될 수 있다. 바람직하게는 산성 인산에스테르를 사용하며, 산성 인산에스테르로는, 이소프로필산포스페이트; 디이소프로필산포스페이트; 부틸산포스페이트; 옥틸산포스페이트; 디옥틸산포스페이트; 이소데실산 포스페이트; 디이소데실산포스페이트; 트리데칸올산포스페이트; 비스(트리데칸올산)포스페이트 등이 단독으로 또는 2종 이상 혼합 사용될 수 있다. 본 발명의 실시예에서는 산성 인산에스테르계인 ZELEC UN™(DUPONT 사)이 경화 후 몰드를 렌즈에서 탈형시킬 때의 탈형성이 가장 좋은 것으로 나타났다. 내부이형제는 상기 반응 혼합물 전체 중량에 대하여 0.0001∼10 중량%로 사용할 수 있으나, 바람직하게는 0.005∼2 중량%로 사용하는 것이 렌즈에서 몰드의 탈형성이 좋고 중합 수율 또한 높았다. 이형제의 첨가량이 0.005% 이하이면 성형된 광학렌즈를 유리 몰드에서 분리시 유리몰드 표면에 렌즈가 부착되어 일어나는 현상이 발생할 수 있고, 2 중량% 이상이면 주형 중합 중 렌즈가 유리 몰드에서 분리되어 렌즈의 표면에 얼룩이 발생할 수 있는 문제점이 있다.In addition, the resin composition of the present invention may further include an internal mold release agent. Examples of the internal mold release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group; Silicone nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; The component selected from the acidic phosphate ester can be used individually or in combination of 2 or more types. Preferably, acidic phosphate ester is used, and as acidic phosphate ester, isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof. In the embodiment of the present invention, ZELEC UN ™ (DUPONT, Inc.), which is an acidic phosphate ester, showed the best demolding when demolding the mold from the lens after curing. The internal mold release agent may be used in an amount of 0.0001 to 10% by weight based on the total weight of the reaction mixture. Preferably, 0.005 to 2% by weight of the mold release agent is good in the lens and the polymerization yield is high. If the amount of the release agent is less than 0.005%, a phenomenon may occur in which the lens adheres to the surface of the glass mold when the molded optical lens is separated from the glass mold, and if more than 2% by weight, the lens is separated from the glass mold during the polymerization of the mold. There is a problem that may cause stains on the surface.

상기 티올 화합물과 이소시아네이트 화합물을 반응시키는데 사용되는 중합 개시제로는 아민계 혹은 주석계 화합물 등이 사용될 수 있다. 주석계 화합물로는, 부틸틴디라우레이트; 디부틸틴디클로라이드; 디부틸틴디아세테이트; 옥칠산제1주석; 디라우르산디부틸주석; 테트라플루오르주석; 테트라클로로주석; 테트라브로모주석; 테트라아이도주석; 메틸주석트리클로라이드; 부틸주석트리클로라이드; 디메틸주석디클로라이드; 디부틸주석디클로라이드; 트리메틸주석클로라이드; 트리부틸주석클로라이드; 트리페닐주석클로라이드; 디부틸주석술피드; 디(2-에틸섹실)주석옥사이드 등이 단독으로 또는 2종 이상 함께 사용될 수 있다. 이러한 주석계 화합물을 사용하면 중합 수율이 높고 기포의 발생이 없었다. 사용량은 상기 반응 혼합물 전체 중량에 대하여 0.0001∼10 중량% 가 바람직하다.As the polymerization initiator used to react the thiol compound and the isocyanate compound, an amine or tin compound may be used. As a tin type compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous oxide; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraidotin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; Triphenyltin chloride; Dibutyltin sulfide; Di (2-ethylsecyl) tin oxide and the like may be used alone or in combination of two or more thereof. When such a tin compound was used, the polymerization yield was high and there was no bubble generation. The amount of use is preferably 0.0001 to 10% by weight based on the total weight of the reaction mixture.

본 발명의 광학렌즈용 수지 조성물을 열경화시키면 플라스틱 광학렌즈가 얻어진다. 이러한 플라스틱 광학렌즈에는 특히 안경렌즈가 포함된다. 본 발명의 조성물을 열경화시켜 안경렌즈를 제조하는 바람직한 실시예는 다음과 같다. 우선, 본 발명의 수지를 구성하는 조성물에 마지막으로 중합개시제를 첨가하고, 질소로 치환하여 배합통(반응기) 내에 공기를 제거한 후 2∼5시간 동안 감압교반하고, 교반을 정지한 다음 감압 탈포하여 몰드에 주입한다. 이때 몰드는 바람직하게는, 폴리에스테르나 폴리프로필렌 점착테이프, 또는 플라스틱 가스켓으로 고정된 유리 몰 드나 금속제 몰드를 사용한다. 혼합물이 주입된 유리몰드를 강제 순환식 오븐에 넣고, 33∼37℃에서 2시간 유지, 38∼42℃로 3시간 승온, 80∼90℃로 10시간 승온, 120∼140℃로 2∼4시간 승온, 120∼140℃로 2시간 유지, 60∼80℃로 2시간에 걸쳐서 냉각시킨 후 몰드로부터 고형물을 이형시켜 광학렌즈를 얻는다. 이렇게 얻은 광학렌즈를 120∼140℃의 온도에서 1∼4시간 아닐닝(annealing)처리하여 최종 목적하는 플라스틱 광학렌즈를 얻는다. When the resin composition for optical lenses of the present invention is thermoset, a plastic optical lens is obtained. Such plastic optical lenses include eyeglass lenses in particular. Preferred embodiments for preparing the spectacle lens by thermal curing the composition of the present invention are as follows. First, the polymerization initiator is finally added to the composition constituting the resin of the present invention, substituted with nitrogen to remove air in the mixing vessel (reactor), and then stirred under reduced pressure for 2 to 5 hours, and the stirring is stopped, followed by degassing under reduced pressure. Inject into the mold. The mold is preferably a glass mold or a metal mold fixed with polyester or polypropylene adhesive tape or plastic gasket. The glass mold injected with the mixture was placed in a forced circulation oven, held at 33 to 37 ° C. for 2 hours, heated to 38 to 42 ° C. for 3 hours, heated to 80 to 90 ° C. for 10 hours, and 120 to 140 ° C. for 2 to 4 hours. After raising the temperature at 120 to 140 ° C. for 2 hours and cooling at 60 to 80 ° C. for 2 hours, the solid is released from the mold to obtain an optical lens. The optical lens thus obtained is annealed at a temperature of 120 to 140 ° C. for 1 to 4 hours to obtain a final desired plastic optical lens.

또, 상기 방법으로 얻어진 광학렌즈에, 광학특성을 높이기 위하여 하드코팅 및 멀티코팅 처리를 할 수 있다. 하드코팅층의 형성은 에폭시기, 알콕시기, 비닐기 등의 관능기를 가지는 적어도 하나의 실란화합물과 산화규산, 산화티탄, 산화안티몬, 산화주석, 산화텅스텐, 산화알루미늄 등의 적어도 하나 이상의 금속산화물 콜로이드를 주성분으로 하는 코팅조성물에 렌즈를 함침하거나 혹은 스핀코팅법으로 광학렌즈 표면에 두께 0.5∼10㎛로 코팅층을 형성한 후, 가열 또는 UV 경화하여 코팅막을 완성한다. In addition, the optical lens obtained by the above method can be subjected to hard coating and multi-coating treatment in order to increase the optical characteristics. The hard coat layer may be formed of at least one silane compound having functional groups such as an epoxy group, an alkoxy group, a vinyl group, and at least one metal oxide colloid such as silicic acid oxide, titanium oxide, antimony oxide, tin oxide, tungsten oxide, and aluminum oxide. After impregnating the lens into the coating composition or by spin coating to form a coating layer with a thickness of 0.5 to 10㎛ on the surface of the optical lens, the coating film is completed by heating or UV curing.

멀티코팅층, 즉, 반사방지코팅 층은 산화규소, 불화마그네슘, 산화알루미늄, 산화지르코늄, 산화티탄늄, 산화탄탈, 산화이트륨 등의 금속산화물을 진공증착 또는 스퍼트링(sputtering)하는 방법에 의하여 형성할 수 있다. 가장 바람직하게는 렌즈의 양면 하드코팅막 위에 산화규소와 산화지르코늄 막을 교대로 3회 이상 반복 진공 증착한 후 마지막으로 산화규소막을 진공 증착한다. 또한, 필요에 따라 마지막 산화규소와 산화지르코늄 막 사이에 수막층으로서 ITO(Indium Tin Oxide)층을 더 둘 수도 있다. 본 발명의 광학렌즈는 필요에 따라 하드액에 분산염료 혹은 광 변색염료를 첨가하여 착색 처리한 후 사용할 수도 있다.The multi-coating layer, that is, the anti-reflective coating layer, may be formed by vacuum deposition or sputtering metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide, and yttrium oxide. Can be. Most preferably, the silicon oxide film and the zirconium oxide film are alternately vacuum-deposited three times or more on both surfaces of the hard coating film of the lens, and finally, the silicon oxide film is vacuum deposited. In addition, an indium tin oxide (ITO) layer may be further provided as a water film layer between the final silicon oxide and the zirconium oxide film as necessary. The optical lens of the present invention may be used after coloring by adding a disperse dye or a photochromic dye to the hard liquid, if necessary.

본 발명의 경량성 고굴절 수지 조성물로 제조된 광학렌즈는 비중이 낮아서 렌즈가 매우 가볍다. 특히 본 출원인의 선출원 발명인 “광학렌즈용 경량성 고굴절 수지 및 이를 이용한 광학렌즈”(특허출원 제10-2007-0077515호)에 따라 제조된 GST(2,3-비스(2-메르캅토에틸티오)프로판-1-티올), ETS4(2-(2-메르캅토에틸티오)-3-2-[3-메르캅토-2(2-메르캅토에틸티오)-프로필티오]-에틸티오-프로판-1-티올), GMT(2-(2-메르캅토에틸티오)프로판-1,3-디티올), MMPPT(2-(2-메르캅토에틸티오)-3-2-[3-메르캅토-2(2-메르캅토에틸티오)-프로필티오]-에톡시-프로판-1-티올)에 비해서도 비중이 낮아 더 가벼우며, 열변형온도는 더 높아 내열성이 보다 우수하다. 또한 원재료비가 30% 정도 낮고 제조시 반응기의 VOLUME 수율이 27% 정도 높아 전체적인 생산비가 30∼40% 정도로 크게 낮아지게 된다. The optical lens made of the light weight high refractive resin composition of the present invention has a low specific gravity, so that the lens is very light. In particular, GST (2,3-bis (2-mercaptoethylthio) prepared according to the applicant's prior application "Lightweight high refractive resin for optical lenses and optical lenses using the same" (Patent Application No. 10-2007-0077515) Propane-1-thiol), ETS4 (2- (2-mercaptoethylthio) -3-2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethylthio-propane-1 -Thiol), GMT (2- (2-mercaptoethylthio) propane-1,3-dithiol), MMPPT (2- (2-mercaptoethylthio) -3-2- [3-mercapto-2 Compared to (2-mercaptoethylthio) -propylthio] -ethoxy-propane-1-thiol), the specific gravity is lower and lighter, and the heat distortion temperature is higher, so that the heat resistance is better. In addition, the raw material cost is about 30% lower and the VOLUME yield of the reactor during manufacturing is about 27%, resulting in a significant reduction in the overall production cost of about 30-40%.

[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 examples are only for illustrating the present invention in more detail, the scope of the present invention is not limited by these examples.

실시예 1Example 1

신규 폴리 티올 화합물 Y1S4,(2-mercapto-ethylthio)-3-[4-(1-4-Novel polythiol compound Y1S4, (2-mercapto-ethylthio) -3- [4- (1-4-

[3-mercapto-2-(2-mercapto-ethylthio)-propyl]-phenyl-1-methyl-ethyl)- phenoxy]-propane-propane-1-thiol의 제조Preparation of [3-mercapto-2- (2-mercapto-ethylthio) -propyl] -phenyl-1-methyl-ethyl) -phenoxy] -propane-propane-1-thiol

1.5L 플라스크에 비스페놀A디글리시딜에테르 200g(0.535mol, 에폭시당량 187) 및 NaOH 수용액(NaOH 0.5g에 물 5㎖를 녹인 용액)을 첨가하고 2-메르캅토에탄올 83.56g(1.07mol)을 50∼60℃ 범위에서 천천히 적가하고 적가가 끝난 후 약 1시간 동안 60℃에서 숙성시켜 중간체를 얻는다. 반응용액을 30℃로 냉각시키고 티오우레아 195.33g(2.577 mol) 및 36% 진한 염산 278.92 ㎖(3.208 mol)를 첨가하고 110℃에서 3시간 30분간 환류를 시킨다. 반응이 완결된 후 반응용액을 냉각시키고 25% 암모니아수 240.18㎖를 30℃가 넘지 않게 천천히 적가한다. 다음 톨루엔 400㎖를 첨가하고 80℃에서 1시간 30분간 가수분해하고 냉각시킨 다음 분액 깔대기로 유기층을 분리하여 36% 진한 염산 150㎖으로 세척하고 탈 이온 수 150㎖으로 세척한다. 분리하여 얻은 유기층에서 물을 제거하면 원하는 폴리티올 화합물 Y1S4(화합물 I) 286.1g, 16.6%의 수율을 얻었다. To a 1.5 L flask, 200 g (0.535 mol, epoxy equivalent 187) of bisphenol A diglycidyl ether and an aqueous NaOH solution (solution dissolved in 5 ml of water in 0.5 g of NaOH) were added, and 83.56 g (1.07 mol) of 2-mercaptoethanol was added. It is slowly added dropwise in the range of 50-60 ° C. and aged at 60 ° C. for about 1 hour after the dropwise addition is completed to obtain an intermediate. The reaction solution was cooled to 30 ° C., 195.33 g (2.577 mol) of thiourea and 278.92 mL (3.208 mol) of 36% concentrated hydrochloric acid were added, and the mixture was refluxed at 110 ° C. for 3 hours 30 minutes. After the reaction was completed, the reaction solution was cooled and 240.18 ml of 25% aqueous ammonia was slowly added dropwise not to exceed 30 ° C. Next, 400 ml of toluene was added, hydrolyzed at 80 ° C. for 1 hour and 30 minutes, cooled, and the organic layer was separated with a separating funnel, washed with 150 ml of 36% concentrated hydrochloric acid, and washed with 150 ml of deionized water. Removal of water from the organic layer obtained by separation gave the yield of 286.1 g of the desired polythiol compound Y1S4 (Compound I), 16.6%.

Figure 112008090048801-PAT00003
Figure 112008090048801-PAT00003

화합물 I          Compound I

실시예 2Example 2

광학렌즈의 제조Manufacture of Optical Lens

상기 실시예 1에서 제조한 화합물Ⅰ 56.39g; 이소포론디이소시아네이트 19.82g; 헥사메틸렌디이소시아네이트 23.79g; 자외선 흡수제로 2-(2'-히드록시-5-메틸페닐)-2H-벤조트리아졸 1.50g; 이형제로 폴리옥시에틸렌노닐페닐포스페이트 1.0g; 유기염료로 1-히드록시-4-(파라-톨루이딘)안트라퀴논(Blue) 70ppm, 페리논 염료 30ppm, 중합 개시제로 디부틸틴디클로라이드 0.1g;을 교반기가 장착된 배합통에 넣고, 질소로 치환하여 배합통 내에 있는 공기를 제거한 후 감압 교반을 2시간 행하고, 교반을 정지한 다음 감압탈포하여 폴리에스테르 점착테이프로 고정된 유리몰드(디옵타-5.00, 중심 두께 1.2㎜)에 질소가스를 이용하여 혼합물을 주입하였다. 혼합물이 주입된 유리몰드를 강제순환식 오븐에 넣고 33℃에서 2시간 유지, 33℃에서 40℃까지 3시간 승온, 40℃에서 90℃까지 10시간 승온, 90℃에서 130℃로 4시간 승온, 130℃로 2시간 유지, 130℃에서 70℃까지 2시간 냉각 후, 유리몰드를 탈착하여 플라스틱 광학렌즈를 얻었다. 56.39 g of Compound I prepared in Example 1; 19.82 g of isophorone diisocyanate; 23.79 g of hexamethylene diisocyanate; 1.50 g of 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole as an ultraviolet absorber; 1.0 g of polyoxyethylene nonylphenyl phosphate as a releasing agent; 70 ppm of 1-hydroxy-4- (para-toluidine) anthraquinone (Blue) as organic dye, 30 ppm of perinone dye, 0.1 g of dibutyltin dichloride as a polymerization initiator; was placed in a mixing vessel equipped with a stirrer and replaced with nitrogen. After removing the air in the mixing vessel, stirring under reduced pressure was carried out for 2 hours, the stirring was stopped, and degassing under reduced pressure was carried out using nitrogen gas in a glass mold (diopta-5.00, center thickness 1.2 mm) fixed with polyester adhesive tape. The mixture was injected. The glass mold injected with the mixture was placed in a forced circulation oven, maintained at 33 ° C. for 2 hours, heated at 33 ° C. to 40 ° C. for 3 hours, heated at 40 ° C. to 90 ° C. for 10 hours, and heated at 90 ° C. to 130 ° C. for 4 hours, After holding for 2 hours at 130 ° C and cooling for 2 hours at 130 ° C to 70 ° C, the glass mold was detached to obtain a plastic optical lens.

제조된 렌즈는 아래와 같은 방법으로 물성평가를 하여 그 결과를 표 1에 같이 나타내었다. 평가 결과, 표 1에 나타난 바와 같이 제조된 렌즈는 굴절률(nD)이 1.588으로 높고, 아베수도 38로 높았으며, 내충격성, 내광성, 투명성과 같은 광학 특성도 우수하고, 비중은 1.21으로 낮았다.The manufactured lens was evaluated for physical properties in the following manner and the results are shown in Table 1. As a result of the evaluation, the lens manufactured as shown in Table 1 had a high refractive index (nD) of 1.588, an Abbe number of 38, high optical properties such as impact resistance, light resistance, and transparency, and low specific gravity of 1.21.

물성평가Property evaluation

(1) 굴절률 및 아베수: 아타코사의 아베굴절계(1T 모델)를 사용하여 측정하 였다.(1) Refractive index and Abbe's number: It was measured using the Abe refractometer (1T model) of the company.

(2) 비중: 수중치환법을 사용하여 광학렌즈의 부피와 무게를 측정하여 계산하였다.(2) Specific gravity: It was calculated by measuring the volume and weight of the optical lens using an underwater substitution method.

(3) 열변형온도(Tg):Thermomechanical analyer(TMA)를 사용하여 측정하였다.(3) Heat deflection temperature (Tg): Measured using thermomechanical analyer (TMA).

실시예 3∼9Examples 3-9

광학렌즈의 제조Manufacture of Optical Lens

표 1에 기재된 조성으로 하는 것 외에는 실시예 2와 동일하게 실시하여 광학렌즈를 제조하였다. 제조된 렌즈의 물성 또한 동일한 방법으로 평가하여 표 1에 함께 나타내었다. Except having set it as the composition of Table 1, it carried out similarly to Example 2, and manufactured the optical lens. The physical properties of the prepared lens were also evaluated in the same manner and shown in Table 1 together.

비교예 1∼7Comparative Examples 1 to 7

광학렌즈의 제조Manufacture of Optical Lens

하기 표 2에 기재된 조성으로 하는 것 외에는 실시예 2와 동일하게 실시하여 광학렌즈를 제조하였다. 제조된 렌즈의 물성 또한 동일한 방법으로 평가하여 표 2에 함께 나타내었다. An optical lens was manufactured in the same manner as in Example 2 except that the composition shown in Table 2 was used. The physical properties of the prepared lens were also evaluated and shown in Table 2 together.

Figure 112008090048801-PAT00004
Figure 112008090048801-PAT00004

Figure 112008090048801-PAT00005
Figure 112008090048801-PAT00005

표 1∼2의 약자 표시Abbreviation of Tables 1-2

[모노머] [Monomer]

ETS4: 2-(2-메르캅토에틸티오)-3-2-[3-메르캅토-2(2-메르캅토에틸티오)-프로필티오]-에틸티오-프로판-1-티올ETS4: 2- (2-mercaptoethylthio) -3-2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethylthio-propane-1-thiol

GST: 2,3-비스(2-메르캅토에틸티오)프로판-1-티올GST: 2,3-bis (2-mercaptoethylthio) propane-1-thiol

GMT: 2-(2-메르캅토에틸티오)프로판-1,3-디티올GMT: 2- (2-mercaptoethylthio) propane-1,3-dithiol

PETMP: 펜타에리트리톨테트라키스메르캅토프로피오네이트 PETMP: pentaerythritol tetrakismercaptopropionate

(pentaerythritol tetrakis(3-mercaptopropionate))  (pentaerythritol tetrakis (3-mercaptopropionate))

MMPPT:2-(2-메르캅토에틸티오)-3-2-[3-메르캅토-2(2-메르캅토에틸티오)-프로필티오]-에톡시-프로판-1-티올MMPPT: 2- (2-mercaptoethylthio) -3-2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethoxy-propane-1-thiol

IPDI: 이소프론디이소시아네이트 IPDI: isopron diisocyanate

HDI: 1,6-헥사메틸렌디소시아네아네이트 HDI: 1,6-hexamethylenedisocyananeate

H12MDI: 시클로헥실메탄디이소시아네이트H12MDI: cyclohexyl methane diisocyanate

[유기염료][Organic Dyes]

HTAQ: 1-히드록시-4-(p-톨루이딘)안트라퀴논HTAQ: 1-hydroxy-4- (p-toluidine) anthraquinone

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

PRD: 페리논 염료(perinone dye)PRD: perinone dye

[이형제][Release agent]

POEP:폴리옥시에틸렌노닐페닐포스페이트POEP: Polyoxyethylene nonyl phenyl phosphate

[자외선흡수제][UV absorber]

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

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

[중합개시제][Polymerization Initiator]

BTC: 디부틸틴디클로라이드(dibutyltin dichloride)BTC: dibutyltin dichloride

본 발명의 수지 조성물은 고굴절이면서 경량성이고 생산비용이 저렴하여 다양한 광학렌즈 분야에서 유용하게 이용될 수 있다. 본 발명의 수지 조성물은 특히 높은 도수에서도 렌즈의 가장자리 두께를 얇게 할 수 있고 가벼운데다 생산비를 기존 렌즈에 비해 30% 이상 크게 낮출 수 있으므로, 안경렌즈 분야에서 종래 사용되던 플라스틱 렌즈를 대체하여 크게 활용될 것으로 기대된다. The resin composition of the present invention can be usefully used in various optical lenses because of its high refractive index, light weight, and low production cost. In particular, the resin composition of the present invention can thin the edge thickness of the lens even at a high degree of power and can reduce the production cost by 30% or more significantly compared to the existing lens. It is expected to be.

Claims (12)

하기 화학식 1로 표시되는 티올 화합물과 이소시아네이트 화합물을 혼합한 반응 혼합물을 포함하는 광학렌즈용 수지 조성물.Resin composition for an optical lens comprising a reaction mixture of a thiol compound and an isocyanate compound represented by the formula (1). [화학식 1] [Formula 1]
Figure 112008090048801-PAT00006
Figure 112008090048801-PAT00006
 청구항 1에 있어서, 상기 반응 혼합물은 2,3-비스(2-메르캅토에틸티오)프로판-1-티올; 2-(2-메르캅토에틸티오)-3-2-[3-메르캅토-2(2-메르캅토에틸티오)-프로필티오]-에틸티오-프로판-1-티올; 및 2-(2-메르캅토에틸티오)프로판-1,3-디티올로 구성된 군으로부터 선택된 1종 또는 2종 이상의 티올 화합물을 더 포함하는 것을 특징으로 하는 광학렌즈용 수지 조성물.The method of claim 1, wherein the reaction mixture comprises 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2-mercaptoethylthio) -3-2- [3-mercapto-2 (2-mercaptoethylthio) -propylthio] -ethylthio-propane-1-thiol; And one or two or more thiol compounds selected from the group consisting of 2- (2-mercaptoethylthio) propane-1,3-dithiol. 청구항 1에 있어서, 상기 이소시아네이트 화합물은 이소프론디이소시아네이트; 1,6-헥사메틸렌디소시아네이트; 및 시클로헥실메탄디이소시아네이트(H12MDI)로 구성된 군으로부터 1종 또는 2종 이상 선택되는 것을 특징으로 하는 광학렌즈용 수지 조성물.The method according to claim 1, wherein the isocyanate compound is isopron diisocyanate; 1,6-hexamethylenedisocyanate; And cyclohexyl methane diisocyanate (H12MDI) is selected from the group consisting of one or two or more resin compositions for optical lenses. 청구항 1에 있어서, 상기 반응 혼합물은 활성화 수소화합물을 더 포함하며, 상기 티올 화합물과 활성화 수소화합물을 합친 혼합물에 대한 이소시아네이트 화합물의 사용 비율은 (NCO)/(OH+SH)의 관능기 몰비가 0.5∼3.0의 범위인 것을 특징으로 하는 광학렌즈용 수지 조성물.The method of claim 1, wherein the reaction mixture further comprises an activating hydrogen compound, the ratio of use of the isocyanate compound to the mixture of the thiol compound and the activating hydrogen compound is 0.5 to functional group molar ratio of (NCO) / (OH + SH) It is the range of 3.0, The resin composition for optical lenses. 청구항 4에 있어서, 상기 활성화 수소화합물은 펜타에리트리톨테트라키스머캅토프로피오네이트; 펜타에리트리톨테트라키스메캅토아세테이트; 트리메틸올프로판트리스(메르캅토프로피오네이트); 트리메틸올에탄트리스(메르캅토프로피오네이트)및 하기 화학식 2로 표시되는 화합물로 구성된 군으로부터 1종 또는 2종 이상 선택되는 것을 특징으로 하는 광학렌즈용 수지 조성물.The method according to claim 4, wherein the activated hydrogen compound is pentaerythritol tetrakismercaptopropionate; Pentaerythritol tetrakismecaptoacetate; Trimethylolpropane tris (mercaptopropionate); A resin composition for optical lenses, characterized in that at least one selected from the group consisting of trimethylol ethane tris (mercaptopropionate) and a compound represented by the following formula (2). [화학식 2] [Formula 2]
Figure 112008090048801-PAT00007
Figure 112008090048801-PAT00007
 청구항 1 내지 5 중 어느 한 항에 있어서, 티올 화합물 30∼70 중량%와 이소시아네이트 화합물 30∼70 중량%를 반응시켜 얻어진 고상 굴절률(nD, 20℃) 1.572∼1.632, 액상 굴절률 1.520∼1.570, 고상 비중 1.15∼1.25, 고상 수지의 아베수 32∼50, 액상 점도(20℃) 5∼800cps의 광학렌즈용 수지 조성물.Solid phase refractive index (nD, 20 degreeC) 1.572-1.632, liquid phase refractive index 1.520-1.570, solid specific gravity in any one of Claims 1-5 obtained by making 30-70 weight% of thiol compounds react with 30-70 weight% of isocyanate compounds. The resin composition for optical lenses of 1.15-1.25, Abbe number 32-50 of solid resin, and liquid viscosity (20 degreeC) 5-800 cps. 청구항 6에 있어서, 상기 반응 혼합물 전체 중량에 대하여 자외선 흡수제 0.0007∼9 중량%; 내부이형제 0.0001∼10 중량% 및 중합개시제 0.0001∼10 중량%를 더 포함하는 것을 특징으로 하는 광학렌즈용 수지 조성물.The method according to claim 6, 0.0007 to 9% by weight of the ultraviolet absorbent based on the total weight of the reaction mixture; A resin composition for an optical lens, further comprising 0.0001 to 10% by weight of an internal mold release agent and 0.0001 to 10% by weight of a polymerization initiator. 청구항 7에 있어서, 상기 자외선 흡수제는 2-(2'-히드록시-5-메틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3'-t-부틸-5'-메틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-아밀페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐) -2H-벤조트리아졸; 2-(2'-히드록시-5'-t-부틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸; 2,4-디히드록시벤조페논; 2-히드록시-4-메톡시벤조페논; 2-히드록시-4-옥틸옥시벤조페논; 4-도데실옥시-2-히드록시벤조페논; 4-벤조록시-2-히드록시벤조페논; 2,2',4,4'-테트라히드록시벤조페논; 및 2,2'-디히드록시-4,4'-디메톡시벤조페논로 구성된 군으로부터 1종 또는 2종 이상 선택되는 것을 특징으로 하는 광학렌즈용 수지 조성물.The method according to claim 7, wherein the ultraviolet absorber is 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzooxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; And 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. The resin composition for an optical lens according to claim 1 or 2 or more. 청구항 7에 있어서, 상기 내부이형제로 이소프로필산포스페이트; 디이소프로필산포스페이트; 부틸산포스페이트; 옥틸산포스페이트; 디옥틸산포스페이트; 이소데실산포스페이트; 디이소데실산포스페이트; 트리데칸올산포스페이트; 및 비스(트리데칸올산)포스페이트로 구성된 군으로부터 1종 또는 2종 이상 선택된 산성 인산 에스테르를 사용하는 것을 특징으로 하는 광학렌즈용 수지 조성물.The method according to claim 7, wherein the internal mold release agent isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; And an acidic phosphate ester selected from the group consisting of bis (tridecanoic acid) phosphates and a resin composition for an optical lens. 청구항 7에 있어서, 상기 중합개시제로 주석계 또는 아민계 화합물을 사용하는 것을 특징으로 하는 광학렌즈용 수지 조성물.The resin composition for an optical lens according to claim 7, wherein a tin-based or amine-based compound is used as the polymerization initiator. 청구항 10에 있어서, 상기 주석계 화합물은, 부틸틴디라우레이트; 디부틸틴디클로라이드; 디부틸틴디아세테이트; 옥칠산 제1주석; 디라우르산디부틸주석; 테트라플루오르주석; 테트라클로로주석; 테트라브로모주석; 테트라아이오드주석; 메틸주석트리클로라이드; 부틸주석트리클로라이드; 디메틸주석디클로라이드; 디부틸주석디클로라이드; 트리메틸주석클로라이드; 트리부틸주석클로라이드; 트리페닐주석클로라이드; 디부틸주석술피드; 및 디(2-에틸섹실)주석옥사이드로 구성된 군으로부터 1종 또는 2종 이상 선택되는 것을 특징으로 하는 광학렌즈용 수지 조성물.The method of claim 10, wherein the tin-based compound, Butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Oxalic acid stannous; Dibutyl dilaurate; Tetrafluorotin; Tetrachlorotin; Tetrabromotin; Tetraiodine tin; Methyl tin trichloride; Butyltin trichloride; Dimethyltin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; Triphenyltin chloride; Dibutyltin sulfide; And di (2-ethylsecyl) tin oxide. The resin composition for an optical lens of claim 1 or 2 or more. 청구항 1의 광학렌즈용 수지 조성물을 열경화시켜 얻은 플라스틱 안경렌즈.A plastic spectacle lens obtained by thermosetting the resin composition for optical lenses of claim 1.
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