WO2014035120A1 - Polymerization composition for epoxy acrylic optical material having enhanced storage stability and method for manufacturing epoxy acrylic optical material - Google Patents

Polymerization composition for epoxy acrylic optical material having enhanced storage stability and method for manufacturing epoxy acrylic optical material Download PDF

Info

Publication number
WO2014035120A1
WO2014035120A1 PCT/KR2013/007683 KR2013007683W WO2014035120A1 WO 2014035120 A1 WO2014035120 A1 WO 2014035120A1 KR 2013007683 W KR2013007683 W KR 2013007683W WO 2014035120 A1 WO2014035120 A1 WO 2014035120A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphate
phosphite
acid phosphate
optical material
epoxy acrylic
Prior art date
Application number
PCT/KR2013/007683
Other languages
French (fr)
Korean (ko)
Inventor
장동규
노수균
김종효
Original Assignee
주식회사 케이오씨솔루션
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 케이오씨솔루션 filed Critical 주식회사 케이오씨솔루션
Priority to CN201380045139.1A priority Critical patent/CN104583250B/en
Publication of WO2014035120A1 publication Critical patent/WO2014035120A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • C08K5/49—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

Definitions

  • the present invention relates to a polymerizable composition for an epoxy acrylic optical material and a method for producing an epoxy acrylic optical material, and in particular, a polymerizable composition for an epoxy acrylic optical material and an optically improved storage stability that can prevent color change during long-term storage at room temperature. It relates to a method for producing a material.
  • Plastic optical lenses were introduced as a replacement for the high specific gravity and low impact of glass lenses.
  • Representative examples thereof include polyethylene glycol bisallylcarbonate, polymethyl methacrylate, diallyl phthalate, and the like.
  • optical lenses made of these polymers are excellent in physical properties such as moldability, dyeability, hard coat coating adhesion, impact resistance, etc., but the refractive index is about 1.50 (nD) and 1.55 (nD), resulting in a problem of thickening the lens. . Therefore, various attempts have been made to develop optical materials having high refractive indexes to reduce the thickness of lenses.
  • a polyisocyanate compound and a polythiol compound are thermally cured to obtain a thiourethane optical lens.
  • the thiourethane-based optical lens has excellent optical properties such as dyeability, impact resistance, and transparency, but has a problem in that the Abbe number decreases as the refractive index increases.
  • the manufacturing process of the lens is expensive because the material is expensive and sensitive to moisture. It is difficult and there is a problem of the center deformation of the lens due to moisture in the air even when the lens is stored.
  • Korean Patent Nos. 10-0496911, 10-0498896, etc. unlike such thiourethane-based lenses, have high refractive index and high optical properties such as transparency, light weight, and heat resistance, and have a high refractive index.
  • the composition for this is disclosed.
  • Such an epoxy acrylic optical material can produce a lens without requiring separate management of moisture in the air even in a high temperature and high humidity region, and there is no central deformation of the lens due to moisture in the air when the lens is stored.
  • such an epoxy acrylic optical material has a problem of color change when stored for a long time at room temperature. This storage stability is not only a problem in the storage and distribution process after manufacturing the lens, but also a problem in the process of finally purchasing the spectacle lens and using it.
  • phosphorus thermal stabilizers have been used for epoxy acrylic optical materials (Korea Patent 10-0498896).
  • Examples of such phosphorus thermal stabilizers include triphenyl phosphite, diphenyldecyl phosphite, phenyl diddecyl phosphite, diphenyl dodecyl phosphite, trinolyl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite and tripropyl
  • One or two or more compounds selected from phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite) and tris (monophenyl) phosphite were used.
  • the conventional thermal stabilizer was intended to prevent deformation such as discoloration in the lens at high temperature during hard coating or multi-coating, and
  • Korean Patent No. 10-0897407 discloses a lens composition using a phosphate ester compound to prevent yellowing of the lens caused by heat during annealing during lens manufacturing in an epoxy acrylic optical material.
  • a phosphate ester compound isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyric acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, dioctyl acid phosphate, trioctylic acid phosphate , Isodecyl phosphate, diisodecyl phosphate, triisodecyl phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, dimethyl acid phosphate, trimethyl acid phosphate, diethyl acid phosphate, triethyl acid phosphate Propyl acid ester, tripropyl acid
  • Patent Document 1 Republic of Korea Patent Publication 10-0496911
  • Patent Document 2 Republic of Korea Patent Registration 10-0498896
  • Patent Document 3 Republic of Korea Registered Patent Publication 10-0897407
  • the present inventors unexpectedly found that when the diphenyldodecyl phosphite and the phosphate ester compound in the phosphorus thermal stabilizer are used together in the epoxy acrylic polymerizable composition, the storage stability of the optical material can be significantly improved.
  • the present invention has confirmed and completed the present invention, and an object of the present invention is to provide a polymerizable composition for epoxy acrylic optical materials having greatly improved storage stability by including diphenyldodecyl phosphite and a phosphate ester compound together in the polymerizable composition. .
  • the polymerizable composition for epoxy acrylic optical materials containing the compound represented by following formula (1), a diphenyldodecyl phosphite, and a phosphate ester compound is provided.
  • the polymerizable composition for an epoxy acrylic optical material of the present invention may further include a compound represented by Formula 2 below.
  • Epoxy acrylic optical including polymerizing by adding a diphenyldodecyl phosphite and a phosphate ester compound to improve storage stability when casting a polymerizable composition comprising the epoxy acrylate compound represented by the formula (1)
  • a method of making a material is provided.
  • the polymerizable composition may further include a compound represented by Chemical Formula 2.
  • the optical material obtained by casting-polymerizing the said polymeric composition and the optical lens which consists of this optical material are provided.
  • the optical lens in particular comprises an spectacle lens or a polarizing lens.
  • the storage stability of the epoxy acrylic optical material can be greatly improved by including diphenyldodecyl phosphite and a phosphate ester compound in the composition.
  • the optical material manufactured according to the present invention has a high refractive index, high Abbe number, excellent optical properties such as transparency, light weight, heat resistance, and the like, and is stored for a long time at room temperature while having the advantages of an epoxy acrylic optical material having low manufacturing cost. Even when used, high quality epoxy acrylic optical materials without discoloration can be easily obtained.
  • the polymerizable composition for epoxy acrylic optical materials of the present invention comprises an epoxy acrylate compound represented by the following formula (1), a diphenyldodecyl phosphite and a phosphate ester compound, preferably represented by the following formula (2) It may further comprise a compound.
  • N is 0 to 15, R 1 is H or CH 3 , and R 2 is H or Br.
  • n is 0-10, More preferably, it is 0-5.
  • diphenyldodecylphosphite together with the phosphate ester compound, imparts a storage stability to the composition such that the polymerized lens does not discolor even when stored for a long time at room temperature. This is different from the role as a heat stabilizer to prevent discoloration in the manufacturing process involving high temperature such as hard coating or multi-coating.
  • the amount of diphenyldodecyl phosphite is appropriately 0.5 to 8% by weight of the total composition. If the amount is less than 0.5 wt%, the effect is insignificant. If it is more than 8 wt%, thermal stability and storage stability are found to be reduced, and adversely affect the physical properties of the lens. More preferably, 1 to 5 weight% is good.
  • the phosphate ester compound is isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyric acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, dioctyl acid phosphate , Trioctylic acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, triisodecyl acid phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, dimethyl acid phosphate, trimethyl acid phosphate, diethyl acid phosphate, tri Ethyl acid phosphate, dipropyl acid ester, tripropyl acid ester, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, benzyl phosphate, dibenzyl phosphate, dibenzyl
  • the polymerizable composition of the present invention may further include a reactive diluent.
  • reactive diluents include, for example, styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrenedimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzylmaleate, dibenzyl maleate, monobenzyl Fumarate, dibenzyl fumarate, methylbenzyl malate, dimethyl malate, diethyl malate, dibutyl malate, dibutyl fumarate, monobutyl malate, monopentyl malate, dipentyl malate, monopentyl fumarate , Dipentyl fumarate, diethylene glycol bisaryl carbonate, and the like may be used alone or in combination of two or more thereof.
  • the ratio of the total reactive diluent to 100 parts by weight of the total epoxy acrylate compound further comprising the compound represented by Formula 1 or represented by Formula 2 is preferably 30 to 300. Parts by weight.
  • the reactive diluent is used at less than 30 parts by weight, the moldability is difficult due to the high viscosity, and when it is used in excess of 300 parts by weight, the viscosity is so low that the polymerizable composition flows out of the mold when injected into a glass mold assembled with a gasket. Can come out.
  • the polymerizable composition of the present invention may further include an internal mold release agent, a heat stabilizer, an ultraviolet absorber, an organic dye, an inorganic pigment, an anti-coloring agent, an antioxidant, a light stabilizer, a catalyst, and the like according to a conventional method.
  • phosphate ester compounds silicone-based surfactants, fluorine-based surfactants, and the like may be used alone or in combination of two or more thereof, and may be included in the polymerizable composition at 0.001 to 10% by weight.
  • the internal mold release agent it is preferable to use other phosphate ester compounds in addition to the phosphate ester.
  • phosphoric acid ester compounds used as internal release agents include, for example, polyoxyethylene nonylphenol ether phosphate (5% by weight of 5 mole of ethylene oxide, 80% by weight of 4 mole, 10% by weight of 3 mole, 1 mole added 5% by weight), polyoxyethylene nonylphenyl phosphate (9 mole added by 9 moles of ethylene oxide, 8 mole added by 8 moles of ethylene oxide, 7 mole added by ethylene oxide 10 % By weight, up to 6 moles of ethylene oxide added 5% by weight), polyoxyethylene nonylphenol ether phosphate (with 11 moles of ethylene oxide added 3% by weight, 10 moles added 80% by weight, 9 moles added) 5 weight%, 7 mol added 6 weight%, 6 mol added 6 weight%), polyoxyethylene nonyl phenol ether phosphate (13 mol added ethylene oxide 3 weight%, 12 mol added 80 weight% , 11 moles added 8% by weight, 9 moles added 3% by weight, 4 moles Added
  • the heat stabilizer may be included in the composition, preferably 0.01 to 5.00% by weight.
  • the thermal stabilizer is used at 0.01 wt% or less, the thermal stability effect is weak.
  • the thermal stabilizer is used at 5.00 wt% or more, the polymerization failure rate during curing is high and the thermal stability of the cured product is lowered.
  • the thermal stabilizer include calcium stearate, barium stearate, zinc stearate, cadmium stearate, lead stearate, magnesium stearate, aluminum stearate, potassium stearate and zinc octoate, which are metal fatty acid salts.
  • One or two or more compounds selected from the compounds can be used.
  • triphenyl phosphite diphenyldecyl phosphite, phenyl diddecyl phosphite, trinoyl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite, tripropyl phosphite, triethyl phosphite 1 type, or 2 or more types of compound chosen from the trimethyl phosphite, the tris (monodecyl phosphite), and the tris (monophenyl) phosphite can be used.
  • heat stabilizers from which the series differs among the heat stabilizers illustrated above.
  • a phosphorus-based heat stabilizer not only the initial color of the molded lens but also the thermal stability of the optical lens can be greatly improved without deteriorating optical properties such as transparency, impact strength, heat resistance, and polymerization yield.
  • the method for producing an epoxy acrylic optical material of the present invention is diphenyldodecyl phosphite and phosphate ester when the polymer polymerization of the epoxy acrylate compound represented by the formula (1) or further comprising a compound represented by the formula (2) After the compound is added and mixed, the mold is polymerized.
  • the purity of all raw materials is checked prior to preparation to purify low purity compounds and use high purity compounds without purification.
  • high purity compounds up to 70-99.99% purity are used.
  • the epoxy acrylate compound, the diphenyldodecyl phosphite, the phosphate ester compound and the reactive diluent are mixed, then the reaction catalyst is added and stirred, and then the polymerizable composition is injected into the mold via vacuum degassing.
  • the mold into which the polymerizable composition was injected is placed in a forced circulation oven and gradually heat-cured from 30 ° C. to 100 ° C., and then cooled to about 70 ⁇ 10 ° C. to detach and remove the mold to obtain a lens.
  • Component (I) compound is represented by the formula (3).
  • a compound having an equivalent weight of 259 was prepared by adding acrylic acid to the YD-128 epoxy resin of Kukdo Chemical having an equivalent weight of 187 (prepared by reacting at 105 ° C. for 20 hours), and having an average molecular weight of 518.
  • Component (II) compound is represented by the formula (4).
  • Methacrylic acid was added to an epoxy resin having an equivalent weight of 187 and acrylated (prepared by reacting at 105 DEG C for 20 hours) to prepare a compound having an equivalent weight of 273, which was a mixture having an average molecular weight of 546.
  • Component (III) compound is represented by the formula (5).
  • a compound having an equivalent weight of 472 was prepared by adding acrylic acid to the YDB-400 epoxy resin of Kukdo Chemical, which had an equivalent weight of 400, and reacting it at 20O < 0 > C for 20 hours, and a mixture having an average molecular weight of 944.
  • Component (IV) compound is represented by the formula (6).
  • Methacrylic acid was added to the epoxy resin having an equivalent weight of 400 to prepare an acrylate compound (prepared by reacting at 105 DEG C for 20 hours) to prepare a compound having an equivalent weight of 486, and a mixture having an average molecular weight of 972.
  • Acrylic acid was added to an alcohol having ethylene oxide added to bisphenol A having an equivalent weight of 175, and then acrylated (prepared by reacting at 105 DEG C for 20 hours) to prepare a compound having an equivalent weight of 229.
  • the mixture has an average molecular weight of 458, and the structural formula is shown in Chemical Formula 7 below.
  • Methacrylic acid was added to an alcohol having ethylene oxide added to bisphenol A having an equivalent weight of 175 to acrylate (prepared by reacting at 105 ° C. for 20 hours) to prepare a compound having an equivalent weight of 243.
  • the mixture has an average molecular weight of 486, and the structural formula is shown in Chemical Formula 8 below.
  • the polymerizable composition for optical lenses thus prepared was stirred for 1 hour, degassed under reduced pressure for 10 minutes, filtered, and then injected into a glass mold assembled with a polyester adhesive tape.
  • the glass mold in which the polymerizable composition was injected was heat-cured in a forced circulation oven from 35 ° C. to 110 ° C. over 20 hours, and then cooled to 70 ° C. to remove the glass mold to obtain a lens.
  • the resulting lens was processed to a diameter of 72 mm and then ultrasonically washed with an alkaline aqueous washing solution, followed by annealing at 120 ⁇ for 2 hours. Measure the physical properties with the following method Table 1 Shown in
  • Refractive index and Abbe number It was measured using an Abbe refractometer, a DR-M4 model of Atago.
  • the cured optical lens is annealed at 120 ° C. for 2 hours, stored at 20 ° C. for 30 days, and when the APHA value of the measured color change is changed to less than 1, it is “ ⁇ ” and is 1 or more and less than 2 When it changed, it represented by "(circle)" and when it changed more than 2, it represented by "x".
  • Example 2 In the same manner as in Example 1, according to the composition shown in Table 1 , the composition and the optical lens were prepared and tested for physical properties, respectively, and the results are shown in Table 1 .
  • component (I), 29.4 g of component (IV), and 8 g of component (VI) contained 40 g of styrene, 5 g of alpha-methylstyrene, 2 g of methylstyrene dimer, 0.3 g of DPDP, 0.3 g of TDP and DPP. 2 g was added and stirred for about 30 minutes. Thereafter, the resultant was filtered with a filter paper of 0.45 ⁇ m or less, and thereto was added 0.05g of G65 and 0.13g of 3-M as a catalyst, and 8-PENPP 0.1g and 12-PENPP 0.1g were mixed as an internal release agent to prepare a resin composition for an optical lens. After the preparation, an optical lens was manufactured by the following method, and the physical properties of the lens were measured. A lens was manufactured and the physical properties of the lens were measured, and the results are shown in Table 1 .
  • TDP Tridecanol acid phosphate
  • V65 2,2'-azobis (2,4-dimethylbarrenonitrile) (2,2'-azobis (2,4-dimethylvaleronitrile)
  • 4-PENPP polyoxyethylene nonylphenyl phosphate (5% by weight of 5 mol of ethylene oxide added, 80% by weight of 4 mol of ethylene oxide added, 10% by weight of 3 mol of ethylene oxide added, 5% by weight of 1 mol of ethylene oxide added)
  • 8-PENPP polyoxyethylene nonylphenyl phosphate (5% by weight of 9 mol of ethylene oxide added, 80% by weight of 8 mol of ethylene oxide, 10% by weight of 7 mol of ethylene oxide, ethylene oxide 5 mole% added by 6 mol or less)
  • 12-PENPP polyoxyethylene nonyl phenol ether phosphate (3% by weight of 13 mol of ethylene oxide added, 80% by weight of 12 mol added, 8% by weight of 11 mol added, 3% by weight 9 mol added , 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) , 13 mol added 4 wt%)
  • the present invention has high refractive index and excellent Abbe's number, and has the advantages of epoxy acrylic optical material having excellent optical properties such as transparency, light weight, heat resistance and low manufacturing cost, and no discoloration even when stored or used for a long time at room temperature.
  • High quality epoxy acrylic optical materials can be easily obtained.
  • the epoxy acrylic optical material manufactured according to the present invention may be widely used in various fields in place of the existing optical material, and in particular, may be used as an eyeglass lens or a camera lens.
  • the optical material of the present invention can be used as a plastic spectacle lens, a 3D polarizing lens equipped with a polarizing film on the spectacle lens, and the like, as well as recording media substrates, color filters, and ultraviolet absorbers used in prisms, optical fibers, optical disks, and the like It can be used for various optical products such as a filter.

Abstract

The present invention relates to a polymerization composition for an epoxy acrylic optical material and a method for manufacturing an epoxy acrylic optical material, and more specifically, to a polymerization composition for an epoxy acrylic optical material having enhanced storage stability that can prevent discoloration when stored at room temperature for a long time, and to a method for manufacturing an optical material. The present invention provides the polymerization composition for the epoxy acrylic optical material, comprising an epoxy acrylate-based compound, diphenyl dodecyl phosphate, and a phosphoric acid ester compound. According to the present invention, a high-quality epoxy acrylic optical material having the advantages of a high refractive rate, an excellent Abbe value, and superior optical properties including transparency, lightness, and heat resistance, and which is not subject to discoloration even when storing or using at room temperature for a long time, can be easily obtained. The epoxy acrylic optical material according to the present invention can replace existing optical materials and be widely used in a variety of industries.

Description

저장 안정성이 향상된 에폭시 아크릴계 광학재료용 중합성 조성물 및 에폭시 아크릴계 광학재료의 제조방법Polymeric composition for epoxy acrylic optical material with improved storage stability and method for producing epoxy acrylic optical material
본 발명은 에폭시 아크릴계 광학재료용 중합성 조성물 및 에폭시 아크릴계 광학재료의 제조방법에 관한 것으로, 특히 실온에서 장시간 보관시의 색상변화를 막을 수 있는 저장안정성이 향상된 에폭시 아크릴계 광학재료용 중합성 조성물과 광학재료의 제조방법에 관한 것이다.The present invention relates to a polymerizable composition for an epoxy acrylic optical material and a method for producing an epoxy acrylic optical material, and in particular, a polymerizable composition for an epoxy acrylic optical material and an optically improved storage stability that can prevent color change during long-term storage at room temperature. It relates to a method for producing a material.
플라스틱 광학렌즈는 유리렌즈의 문제점인 높은 비중과 낮은 충격성을 보완한 대체품으로 소개되었다. 그 대표적인 것으로 폴리에틸렌글리콜 비스알릴카르보네이트, 폴리메틸메타아크릴레이트, 디알릴프탈레이트 등이 있다. 하지만, 이들 중합체로 제조된 광학렌즈는 주형성, 염색성, 하드코트피막 밀착성, 내충격성 등의 물성 면에서는 우수하나, 굴절률이 1.50(nD)과 1.55(nD) 정도로 낮아서 렌즈가 두꺼워지는 문제점이 있었다. 이에 렌즈의 두께를 줄이기 위해 굴절률이 높은 광학재료의 개발이 여러 가지로 시도되었다. Plastic optical lenses were introduced as a replacement for the high specific gravity and low impact of glass lenses. Representative examples thereof include polyethylene glycol bisallylcarbonate, polymethyl methacrylate, diallyl phthalate, and the like. However, optical lenses made of these polymers are excellent in physical properties such as moldability, dyeability, hard coat coating adhesion, impact resistance, etc., but the refractive index is about 1.50 (nD) and 1.55 (nD), resulting in a problem of thickening the lens. . Therefore, various attempts have been made to develop optical materials having high refractive indexes to reduce the thickness of lenses.
대한민국 등록특허 10-0136698, 10-0051275, 10-0051939, 10-0056025, 10-0040546, 10-0113627 등에서는, 폴리이소시아네이트 화합물과 폴리티올 화합물을 열 경화하여 티오우레탄계 광학렌즈를 얻고 있다. 티오우레탄계 광학렌즈는 염색성, 내충격성, 투명성 등의 광학특성은 우수하나, 굴절률이 높아지면서 아베수가 낮아지는 문제점이 있고, 또한 재료의 가격이 비싸고, 습기에 민감하게 반응하기 때문에 렌즈의 제조 공정이 까다로우며, 렌즈의 보관 시에도 공기 중 수분에 의한 렌즈의 중심변형 문제가 있다. In Korean Patent Nos. 10-0136698, 10-0051275, 10-0051939, 10-0056025, 10-0040546, 10-0113627, and the like, a polyisocyanate compound and a polythiol compound are thermally cured to obtain a thiourethane optical lens. The thiourethane-based optical lens has excellent optical properties such as dyeability, impact resistance, and transparency, but has a problem in that the Abbe number decreases as the refractive index increases. In addition, the manufacturing process of the lens is expensive because the material is expensive and sensitive to moisture. It is difficult and there is a problem of the center deformation of the lens due to moisture in the air even when the lens is stored.
대한민국 등록특허 10-0496911, 10-0498896 등에서는 이러한 티오우레탄계 렌즈와 달리 높은 굴절률을 가지면서도 아베수가 높고, 투명성, 경량성, 내열성 등의 광학 특성이 우수하며, 재료의 가격이 저렴한 에폭시 아크릴계 광학재료용 조성물을 개시하고 있다. 이러한 에폭시 아크릴계 광학재료는 고온 다습한 지역에서도 공기 중 수분 관리를 별도로 요하지 않고 렌즈의 생산이 가능하며, 렌즈의 보관시 공기 중 수분에 의한 렌즈의 중심변형이 없다. 그러나 이러한 에폭시 아크릴계 광학재료는 상온에서 장시간 보관시 색상변화가 일어나는 문제가 있다. 이러한 저장 안정성은 렌즈 제조 후 보관, 유통 과정에서 문제가 될 뿐만 아니라 최종적으로 소비자가 안경 렌즈를 구입한 후 이를 사용하는 과정에서도 문제가 된다. Korean Patent Nos. 10-0496911, 10-0498896, etc., unlike such thiourethane-based lenses, have high refractive index and high optical properties such as transparency, light weight, and heat resistance, and have a high refractive index. The composition for this is disclosed. Such an epoxy acrylic optical material can produce a lens without requiring separate management of moisture in the air even in a high temperature and high humidity region, and there is no central deformation of the lens due to moisture in the air when the lens is stored. However, such an epoxy acrylic optical material has a problem of color change when stored for a long time at room temperature. This storage stability is not only a problem in the storage and distribution process after manufacturing the lens, but also a problem in the process of finally purchasing the spectacle lens and using it.
종래에 에폭시 아크릴계 광학재료에 인계 열안정제가 사용되었다(대한민국 등록특허 10-0498896). 이러한 인계 열안정제에는, 트리페닐 포스파이트, 디페닐데실포스파이트, 페닐디데실포스파이트, 디페닐도데실포스파이트, 트리노릴페닐포스파이트, 디페닐이소옥틸포스파이트, 트리부틸포스파이트, 트리프로필포스파이트, 트리에틸포스파이트, 트리메틸포스파이트, 트리스(모노데실포스파이트), 트리스(모노페닐)포스파이트 중에서 선택된 1종 혹은 2종 이상의 화합물이 사용되었다. 그러나 종래 열안정제는 하드코팅이나 멀티코팅 시의 고온에서 렌즈에 변색 등의 변형이 발생하는 것을 막기 위한 것이었으며, 이와 같은 고온에서의 열안정성과 상온에서의 저장안정성은 비례관계에 있지 않다. Conventionally, phosphorus thermal stabilizers have been used for epoxy acrylic optical materials (Korea Patent 10-0498896). Examples of such phosphorus thermal stabilizers include triphenyl phosphite, diphenyldecyl phosphite, phenyl diddecyl phosphite, diphenyl dodecyl phosphite, trinolyl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite and tripropyl One or two or more compounds selected from phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite) and tris (monophenyl) phosphite were used. However, the conventional thermal stabilizer was intended to prevent deformation such as discoloration in the lens at high temperature during hard coating or multi-coating, and such thermal stability at high temperature and storage stability at room temperature are not in proportion.
또한, 대한민국 등록특허 10-0897407에서는, 에폭시 아크릴계 광학재료에서 렌즈 제조시 아닐링 과정에서 열에 의해 발생하는 렌즈의 황변현상을 막기 위해 인산 에스테르 화합물을 사용하는 렌즈 조성물을 개시하고 있다. 이러한 인산 에스테르 화합물로는, 이소프로필산 포스페이트, 디이소프로필산 포스페이트, 트리이소프로필산 포스페이트, 부틸산 포스페이트, 디부틸산 포스페이트, 트리부틸산 포스페이트, 옥틸산 포스페이트, 디옥틸산 포스페이트, 트리옥틸산 포스페이트, 이소데실산 포스페이트, 디이소데실산 포스페이트, 트리이소데실산 포스페이트, 트리데칸올산 포스페이트, 비스(트리데칸올산)포스페이트, 디메틸산 포스페이트, 트리메틸산 포스페이트, 디에틸산 포스페이트, 트리에틸산 포스페이트, 디프로필산 에스테르, 트리프로필산 에스테르, 메틸산 포스페이트, 에틸산 포스페이트, 프로필산 포스페이트, 벤질산 포스페이트, 디벤질산 포스페이트, 트리벤질산 포스페이트, 폴리옥시에틸렌 노닐 페놀에테르 포스페이트, 트리 폴리옥시에틸렌 노닐 페놀에테르 포스페이트, 에틸렌글리콜 모노에틸 포스페이트, 디에틸렌글리콜 모노에틸 포스페이트, 트리에틸렌글리콜 모노에틸 포스페이트, 디에틸렌글리콜 모노부틸 트리포스페이트, 디에틸렌글리콜 모노부틸 디포스페이트, 디에틸렌글리콜 모노부틸 포스페이트, 이소프로필렌글리콜 모노에틸 포스페이트, 디이소프로필렌글리콜 모노에틸 포스페이트, 트리이소프로필렌글리콜 모노에틸 포스페이트 등이 1종 또는 2종 이상 혼합 사용된다. 그러나 이 또한 열 경화후 아닐링 시 촉매에 의하여 유기 또는 무기안료가 산화되어 심한 황변현상이 발생하게 되는 문제점, 즉 고온에서 촉매에 의해 촉발되는 변색을 해결하기 위한 것으로서, 인산 에스테르 화합물도 상온에서의 저장안정성 문제를 해결하지는 못하고 있다. In addition, Korean Patent No. 10-0897407 discloses a lens composition using a phosphate ester compound to prevent yellowing of the lens caused by heat during annealing during lens manufacturing in an epoxy acrylic optical material. As such a phosphate ester compound, isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyric acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, dioctyl acid phosphate, trioctylic acid phosphate , Isodecyl phosphate, diisodecyl phosphate, triisodecyl phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, dimethyl acid phosphate, trimethyl acid phosphate, diethyl acid phosphate, triethyl acid phosphate Propyl acid ester, tripropyl acid ester, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, benzyl acid phosphate, dibenzyl acid phosphate, tribenzyl acid phosphate, polyoxyethylene nonyl phenolether phosphate, tri polyoxyethylene nonyl phenol Ter phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethyl phosphate, triethylene glycol monoethyl phosphate, diethylene glycol monobutyl triphosphate, diethylene glycol monobutyl diphosphate, diethylene glycol monobutyl phosphate, isopropylene glycol mono Ethyl phosphate, diisopropylene glycol monoethyl phosphate, triisopropylene glycol monoethyl phosphate, and the like are used alone or in combination of two or more thereof. However, this is also to solve the problem of severe yellowing phenomenon caused by oxidation of organic or inorganic pigments by catalyst during annealing after thermal curing, that is, discoloration triggered by catalyst at high temperature. It does not solve the storage stability problem.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 대한민국 등록특허공보 10-0496911(Patent Document 1) Republic of Korea Patent Publication 10-0496911
(특허문헌 2) 대한민국 등록특허공보 10-0498896(Patent Document 2) Republic of Korea Patent Registration 10-0498896
(특허문헌 3) 대한민국 등록특허공보 10-0897407(Patent Document 3) Republic of Korea Registered Patent Publication 10-0897407
본 발명자들은, 에폭시 아크릴계 중합성 조성물에 인계 열안정제 중 디페닐도데실포스파이트와 인산 에스테르 화합물을 함께 사용할 경우 광학재료의 저장안정성을 획기적으로 향상시킬 수 있음을 예기치 않게 알게 되었다. 본 발명은 이를 확인하고 완성한 것으로서, 본 발명에서는 디페닐도데실포스파이트와 인산 에스테르 화합물을 중합성 조성물에 함께 포함시켜 저장안정성이 크게 향상된 에폭시 아크릴계 광학재료용 중합성 조성물을 제공하는 것을 목적으로 한다.The present inventors unexpectedly found that when the diphenyldodecyl phosphite and the phosphate ester compound in the phosphorus thermal stabilizer are used together in the epoxy acrylic polymerizable composition, the storage stability of the optical material can be significantly improved. The present invention has confirmed and completed the present invention, and an object of the present invention is to provide a polymerizable composition for epoxy acrylic optical materials having greatly improved storage stability by including diphenyldodecyl phosphite and a phosphate ester compound together in the polymerizable composition. .
본 발명에서는,In the present invention,
아래 화학식 1로 표시되는 화합물과, 디페닐도데실포스파이트와, 인산 에스테르 화합물을 포함하는 에폭시 아크릴계 광학재료용 중합성 조성물이 제공된다. 본 발명의 에폭시 아크릴계 광학재료용 중합성 조성물은 아래 화학식 2로 표시되는 화합물을 더 포함할 수 있다.The polymerizable composition for epoxy acrylic optical materials containing the compound represented by following formula (1), a diphenyldodecyl phosphite, and a phosphate ester compound is provided. The polymerizable composition for an epoxy acrylic optical material of the present invention may further include a compound represented by Formula 2 below.
[화학식 1][Formula 1]
Figure PCTKR2013007683-appb-I000001
Figure PCTKR2013007683-appb-I000001
(여기서 n = 0~15 이고, R1은 H 또는 CH3이며, R2는 H 혹은 Br이다.)(Where n = 0-15, R 1 is H or CH 3 and R 2 is H or Br)
[화학식 2][Formula 2]
Figure PCTKR2013007683-appb-I000002
Figure PCTKR2013007683-appb-I000002
(여기서 R은 H 또는 CH3이고, m = 0~5, n = 0~5 이고, m과 n은 동시에 0 이 아니며, m+n = 1~10 이다.)(Where R is H or CH 3 , m = 0-5, n = 0-5, m and n are not zero at the same time, m + n = 1-10)
또한, 본 발명에서는, In the present invention,
상기 화학식 1로 표시되는 에폭시 아크릴레이트계 화합물을 포함하는 중합성 조성물을 주형중합할 때에, 저장안정성을 향상시키기 위해 디페닐도데실포스파이트와 인산 에스테르 화합물을 첨가하여 중합시키는 것을 포함하는 에폭시 아크릴계 광학재료의 제조방법이 제공된다. 이때 중합성 조성물은 바람직하게는 상기 화학식 2로 표시되는 화합물을 더 포함할 수 있다.Epoxy acrylic optical, including polymerizing by adding a diphenyldodecyl phosphite and a phosphate ester compound to improve storage stability when casting a polymerizable composition comprising the epoxy acrylate compound represented by the formula (1) A method of making a material is provided. In this case, the polymerizable composition may further include a compound represented by Chemical Formula 2.
또한, 본 발명에서는, 상기 중합성 조성물을 주형중합하여 얻은 광학재료와 이 광학재료로 이루어진 광학렌즈가 제공된다. 상기 광학렌즈는 특히 안경렌즈 또는 편광렌즈를 포함한다.Moreover, in this invention, the optical material obtained by casting-polymerizing the said polymeric composition and the optical lens which consists of this optical material are provided. The optical lens in particular comprises an spectacle lens or a polarizing lens.
본 발명에서는, 디페닐도데실포스파이트와 인산 에스테르 화합물을 조성물에 포함시킴으로써 에폭시 아크릴계 광학재료의 저장안정성을 크게 향상시킬 수 있다. 본 발명에 따라 제조된 광학재료는, 높은 굴절률을 가지면서도 아베수가 높고, 투명성, 경량성, 내열성 등의 광학 특성이 우수하고 제조비용이 저렴한 에폭시 아크릴계 광학재료의 장점을 지니면서 상온에서 오랜 시간 보관하거나 사용해도 변색이 없는 고품질의 에폭시 아크릴계 광학재료를 용이하게 얻을 수 있다.In the present invention, the storage stability of the epoxy acrylic optical material can be greatly improved by including diphenyldodecyl phosphite and a phosphate ester compound in the composition. The optical material manufactured according to the present invention has a high refractive index, high Abbe number, excellent optical properties such as transparency, light weight, heat resistance, and the like, and is stored for a long time at room temperature while having the advantages of an epoxy acrylic optical material having low manufacturing cost. Even when used, high quality epoxy acrylic optical materials without discoloration can be easily obtained.
본 발명의 에폭시 아크릴계 광학재료용 중합성 조성물은, 아래 화학식 1로 표시되는 에폭시 아크릴레이트계 화합물과, 디페닐도데실포스파이트와, 인산 에스테르 화합물을 포함하며, 바람직하게는 아래 화학식 2로 표시되는 화합물을 더 포함할 수 있다. The polymerizable composition for epoxy acrylic optical materials of the present invention comprises an epoxy acrylate compound represented by the following formula (1), a diphenyldodecyl phosphite and a phosphate ester compound, preferably represented by the following formula (2) It may further comprise a compound.
[화학식 1][Formula 1]
Figure PCTKR2013007683-appb-I000003
Figure PCTKR2013007683-appb-I000003
여기서 n은 0~15 이고, R1은 H 또는 CH3이며, R2는 H 혹은 Br이다. 바람직하게는 n은 0~10이며, 더욱 바람직하게는 0~5이다. N is 0 to 15, R 1 is H or CH 3 , and R 2 is H or Br. Preferably n is 0-10, More preferably, it is 0-5.
[화학식 2][Formula 2]
Figure PCTKR2013007683-appb-I000004
Figure PCTKR2013007683-appb-I000004
(여기서 R은 H 또는 CH3이고, m = 0~5, n = 0~5 이고, m과 n은 동시에 0 이 아니며, m+n = 1~10 이다.)(Where R is H or CH 3 , m = 0-5, n = 0-5, m and n are not zero at the same time, m + n = 1-10)
본 발명의 중합성 조성물에서 디페닐도데실포스파이트는, 인산 에스테르 화합물과 함께, 중합된 렌즈가 상온에서 장시간 보관 시에도 변색되지 않도록 하는 저장 안정성을 조성물에 부여한다. 이는 하드코팅이나 멀티코팅 등과 같은 고온이 수반되는 제조과정에서의 변색을 막는 열안정제로서의 역할과는 다른 것이다. 디페닐도데실포스파이트의 사용량은 전체 조성물 중 0.5~8 중량%가 적절하다. 0.5 중량% 미만이면 효과가 미미하며, 8 중량%를 넘으면 오히려 열안정 및 저장안정성이 감소하는 것으로 나타났으며, 렌즈의 물성에도 좋지 않은 영향을 미쳤다. 보다 바람직하게는 1~5 중량%가 좋았다. In the polymerizable composition of the present invention, diphenyldodecylphosphite, together with the phosphate ester compound, imparts a storage stability to the composition such that the polymerized lens does not discolor even when stored for a long time at room temperature. This is different from the role as a heat stabilizer to prevent discoloration in the manufacturing process involving high temperature such as hard coating or multi-coating. The amount of diphenyldodecyl phosphite is appropriately 0.5 to 8% by weight of the total composition. If the amount is less than 0.5 wt%, the effect is insignificant. If it is more than 8 wt%, thermal stability and storage stability are found to be reduced, and adversely affect the physical properties of the lens. More preferably, 1 to 5 weight% is good.
본 발명의 중합성 조성물에서, 인산 에스테르 화합물은 이소프로필산 포스페이트, 디이소프로필산 포스페이트, 트리이소프로필산 포스페이트, 부틸산 포스페이트, 디부틸산 포스페이트, 트리부틸산 포스페이트, 옥틸산 포스페이트, 디옥틸산 포스페이트, 트리옥틸산 포스페이트, 이소데실산 포스페이트, 디이소데실산 포스페이트, 트리이소데실산 포스페이트, 트리데칸올산 포스페이트, 비스(트리데칸올산)포스페이트, 디메틸산 포스페이트, 트리메틸산 포스페이트, 디에틸산 포스페이트, 트리에틸산 포스페이트, 디프로필산 에스테르, 트리프로필산 에스테르, 메틸산 포스페이트, 에틸산 포스페이트, 프로필산 포스페이트, 벤질산 포스페이트, 디벤질산 포스페이트, 트리벤질산 포스페이트, 폴리옥시에틸렌 노닐 페놀에테르 포스페이트, 트리 폴리옥시에틸렌 노닐 페놀에테르 포스페이트, 에틸렌글리콜 모노에틸 포스페이트, 디에틸렌글리콜 모노에틸 포스페이트, 트리에틸렌글리콜 모노에틸 포스페이트, 디에틸렌글리콜 모노부틸 트리포스페이트, 디에틸렌글리콜 모노부틸 디포스페이트, 디에틸렌글리콜 모노부틸 포스페이트, 이소프로필렌글리콜 모노에틸 포스페이트, 디이소프로필렌글리콜 모노에틸 포스페이트, 트리이소프로필렌글리콜 모노에틸 포스페이트, 젤렉유엔TM(Zelec UNTM) 등이 단독으로 또는 2종 이상 함께 사용될 수 있다. In the polymerizable composition of the present invention, the phosphate ester compound is isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyric acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, dioctyl acid phosphate , Trioctylic acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, triisodecyl acid phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, dimethyl acid phosphate, trimethyl acid phosphate, diethyl acid phosphate, tri Ethyl acid phosphate, dipropyl acid ester, tripropyl acid ester, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, benzyl phosphate, dibenzyl acid phosphate, tribenzyl acid phosphate, polyoxyethylene nonyl phenolether phosphate, tripoly jade Ethylene nonyl phenolether phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethyl phosphate, triethylene glycol monoethyl phosphate, diethylene glycol monobutyl triphosphate, diethylene glycol monobutyl diphosphate, diethylene glycol monobutyl phosphate, iso propylene glycol monomethyl phosphate, di-isopropylene glycol mono ethyl phosphate, tri-iso-propylene glycol mono-ethyl phosphate, jelrek UN TM (Zelec UN TM) may be used alone or in combination with two or more of them.
본 발명의 중합성 조성물은, 반응성 희석제를 더 포함할 수 있다. 다른 반응성 희석제로는, 예컨대 스틸렌, 디비닐벤젠, 알파메틸스틸렌, 알파메틸스틸렌다이머, 벤질메타아크릴레이트, 클로로스틸렌, 브로모스틸렌, 메톡시스틸렌, 모노벤질말레이트, 디벤질말레이트, 모노벤질푸말레이트, 디벤질푸말레이트, 메틸벤질말레이트, 디메틸말레이트, 디에틸말레이트, 디부틸말레이트, 디부틸푸말레이트, 모노부틸말레이트, 모노펜틸말레이트, 디펜틸말레이트, 모노펜틸푸말레이트, 디펜틸푸말레이트, 디에틸렌글리콜 비스아릴카르보네이트 등이 단독으로 또는 2종 이상 함께 사용될 수 있다. 본 발명의 중합성 조성물 중 상기 화학식 1로 표시되는 또는 여기에 화학식 2로 표시되는 화합물을 더 포함하는 총 에폭시 아크릴레이트계 화합물 100 중량부에 대해 총 반응성 희석제의 비율은, 바람직하게는 30~300 중량부이다. 반응성 희석제를 30 중량부 미만으로 사용할 경우 점도가 높아 몰드 주입이 어려워 작업성이 떨어지며, 300 중량부를 초과하여 사용할 경우에는 점도가 너무 낮아 가스켓으로 조립된 유리몰드에 주입 시 중합성 조성물이 몰드 밖으로 흘러나올 수 있다. The polymerizable composition of the present invention may further include a reactive diluent. Other reactive diluents include, for example, styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrenedimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzylmaleate, dibenzyl maleate, monobenzyl Fumarate, dibenzyl fumarate, methylbenzyl malate, dimethyl malate, diethyl malate, dibutyl malate, dibutyl fumarate, monobutyl malate, monopentyl malate, dipentyl malate, monopentyl fumarate , Dipentyl fumarate, diethylene glycol bisaryl carbonate, and the like may be used alone or in combination of two or more thereof. In the polymerizable composition of the present invention, the ratio of the total reactive diluent to 100 parts by weight of the total epoxy acrylate compound further comprising the compound represented by Formula 1 or represented by Formula 2 is preferably 30 to 300. Parts by weight. When the reactive diluent is used at less than 30 parts by weight, the moldability is difficult due to the high viscosity, and when it is used in excess of 300 parts by weight, the viscosity is so low that the polymerizable composition flows out of the mold when injected into a glass mold assembled with a gasket. Can come out.
본 발명의 중합성 조성물은 이밖에 내부이형제, 열안정제, 자외선 흡수제, 유기염료, 무기안료, 착색방지제, 산화방지제, 광안정제, 촉매 등을 통상의 방법에 따라 더 포함할 수 있다. In addition, the polymerizable composition of the present invention may further include an internal mold release agent, a heat stabilizer, an ultraviolet absorber, an organic dye, an inorganic pigment, an anti-coloring agent, an antioxidant, a light stabilizer, a catalyst, and the like according to a conventional method.
내부 이형제로는 상기 인산 에스테르 외에 다른 인산 에스테르 화합물, 실리콘계 계면활성제, 불소계 계면활성제 등이 각각 단독으로 또는 2종 이상 함께 사용될 수 있으며, 바람직하게는 중합성 조성물 중에 0.001~10 중량%로 포함될 수 있다. 내부이형제로, 바람직하게는, 상기 인산 에스테르 외에 다른 인산 에스테르 화합물을 사용할 수 있다. 내부이형제로 사용되는 다른 인산 에스테르 화합물은, 예컨대 폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드가 5몰 부가된 것 5중량%, 4몰 부가된 것 80중량%, 3몰 부가된 것 10중량%, 1몰 부가된 것 5중량%), 폴리옥시에틸렌노닐페닐포스페이트(에틸렌옥사이드가 9몰 부가된 것 5 중량%, 에틸렌옥사이드가 8몰 부가된 것 80 중량%, 에틸렌옥사이드가 7몰 부가된 것 10 중량%, 에틸렌옥사이드가 6몰 이하 부가된 것 5 중량%), 폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드 11몰 부가된 것 3중량%, 10몰 부가된 것 80중량%, 9몰 부가된 것 5중량%, 7몰 부가된 것 6중량%, 6몰 부가된 것 6중량%), 폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드 13몰 부가된 것 3중량%, 12몰 부가된 것 80중량%, 11몰 부가된 것 8중량%, 9몰 부가된 것 3중량%, 4몰 부가된 것 6중량%), 폴리옥시에틸렌 노닐페놀에테르포스페이트(에틸렌옥사이드가 17몰 부가된 것 3중량%, 16몰 부가된 것이 79중량%, 15몰 부가된 것 10중량%, 14몰 부가된 것 4중량%, 13몰 부가된 것 4중량%), 폴리옥시에틸렌노닐페놀에테르 포스페이트(에틸렌옥사이드가 21몰 부가된 것 5중량%, 20몰 부가된 것 78중량%, 19몰 부가된 것 7중량%, 18몰 부가된 것 6중량%, 17몰 부가된 것 4중량%) 등이 단독으로 또는 2종 이상 함께 사용될 수 있다. As the internal release agent, other phosphate ester compounds, silicone-based surfactants, fluorine-based surfactants, and the like may be used alone or in combination of two or more thereof, and may be included in the polymerizable composition at 0.001 to 10% by weight. . As the internal mold release agent, it is preferable to use other phosphate ester compounds in addition to the phosphate ester. Other phosphoric acid ester compounds used as internal release agents include, for example, polyoxyethylene nonylphenol ether phosphate (5% by weight of 5 mole of ethylene oxide, 80% by weight of 4 mole, 10% by weight of 3 mole, 1 mole added 5% by weight), polyoxyethylene nonylphenyl phosphate (9 mole added by 9 moles of ethylene oxide, 8 mole added by 8 moles of ethylene oxide, 7 mole added by ethylene oxide 10 % By weight, up to 6 moles of ethylene oxide added 5% by weight), polyoxyethylene nonylphenol ether phosphate (with 11 moles of ethylene oxide added 3% by weight, 10 moles added 80% by weight, 9 moles added) 5 weight%, 7 mol added 6 weight%, 6 mol added 6 weight%), polyoxyethylene nonyl phenol ether phosphate (13 mol added ethylene oxide 3 weight%, 12 mol added 80 weight% , 11 moles added 8% by weight, 9 moles added 3% by weight, 4 moles Added 6% by weight), polyoxyethylene nonylphenol ether phosphate (added 17 moles of ethylene oxide 3%, 16 moles added 79%, 15 moles added 10%, 14 moles added 4 weight%, 13 mol added 4 weight%), polyoxyethylene nonylphenol ether phosphate (5 weight% with 21 mol ethylene oxide added, 78 weight% with 20 mol added, 19 mol added 7 Weight percent, 18 mol added 6 weight percent, 17 mol added 4 weight percent) and the like may be used alone or in combination of two or more thereof.
열안정제는, 바람직하게는 조성물 중에 0.01~5.00 중량%로 포함될 수 있다. 열안정제를 0.01 중량% 이하로 사용할 때에는 열안정성 효과가 약하며, 5.00 중량% 이상으로 사용할 때에는 경화시 중합불량률이 높고 경화물의 열안정성이 도리어 낮아지는 문제점이 있다. 열안정제로는, 예를 들면, 금속 지방산염계인 칼슘 스테아레이트, 바륨 스테아레이트, 아연 스테아레이트, 카드뮴 스테아레이트, 납 스테아레이트, 마그네슘 스테아레이트, 알루미늄 스테아레이트, 칼륨스테아레이트, 아연 옥토에이트 등의 화합물 중에서 선택된 1종 혹은 2종 이상의 화합물을 사용할 수 있다. 바람직하게는, 인계인 트리페닐포스파이트, 디페닐데실포스파이트, 페닐디데실포스파이트, 트리노릴페닐포스파이트, 디페닐이소옥틸포스파이트, 트리부틸포스파이트, 트리프로필포스파이트, 트리에틸포스파이트, 트리메틸포스파이트, 트리스(모노데실포스파이트), 트리스(모노페닐)포스파이트 중에서 선택된 1종 혹은 2종 이상의 화합물을 사용할 수 있다. 또한, 납계인 3PbO.PbSO4.4H2O, 2PbO.Pb(C8H4O4), 3PbO.Pb(C4H2O4).H2O 등의 화합물 중에서 선택된 1종 혹은 2종 이상도 사용 가능하며, 유기주석계인 디부틸틴 디아우레이트, 디부틸틴말리에이트, 디부틸틴 비스(이소옥틸말리에이트), 디옥틸말리에이트, 디부틸틴 비스(모노메틸말리에이트), 디부틸틴 비스(라우릴메르캅티드), 디부틸 비스(이소옥실메르캅토아세테이트), 모노부틸틴 트리스(이소옥틸메르캅토아세테이트), 디메틸틴비스(이소옥틸메르캅토아세테이트), 트리스(이소옥틸메르캅토아세테이트), 비옥틸틴비스(이소옥틸메르캅토아세테이트), 디부틸틴 비스(2-메르캅토에틸로레이트), 모노부틸틴트리스(2-메르캅토에티로레이트), 디메틸틴 비스(2-메르캅토에틸로레이트), 모노메틸틴 트리스(2-메르캅토에틸로레이트) 등의 화합물 중에서 선택된 1종 혹은 2종 이상도 사용 가능하다. 또한, 상기 예시한 열안정제 중 계열이 다른 열안정제를 2종 이상 혼합하여 사용하는 것도 가능하다. 가장 바람직하게는, 인계의 열안정제를 사용함으로써 성형된 렌즈의 초기 색상뿐만 아니라 투명성, 충격강도, 내열성 및 중합수율 등의 광학특성의 저하 없이 광학렌즈의 열안정성을 크게 향상시킬 수 있었다. The heat stabilizer may be included in the composition, preferably 0.01 to 5.00% by weight. When the thermal stabilizer is used at 0.01 wt% or less, the thermal stability effect is weak. When the thermal stabilizer is used at 5.00 wt% or more, the polymerization failure rate during curing is high and the thermal stability of the cured product is lowered. Examples of the thermal stabilizer include calcium stearate, barium stearate, zinc stearate, cadmium stearate, lead stearate, magnesium stearate, aluminum stearate, potassium stearate and zinc octoate, which are metal fatty acid salts. One or two or more compounds selected from the compounds can be used. Preferably, triphenyl phosphite, diphenyldecyl phosphite, phenyl diddecyl phosphite, trinoyl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite, tripropyl phosphite, triethyl phosphite 1 type, or 2 or more types of compound chosen from the trimethyl phosphite, the tris (monodecyl phosphite), and the tris (monophenyl) phosphite can be used. In addition, one or two or more selected from compounds such as lead-based 3PbO.PbSO4.4H 2 O, 2PbO.Pb (C 8 H 4 O 4 ), 3PbO.Pb (C 4 H 2 O 4 ) .H 2 O and the like Dibutyltin diaurate, dibutyltin maleate, dibutyltin bis (isooctyl maleate), dioctyl maleate, dibutyltin bis (monomethyl maleate), dibutyltin Bis (lauryl mercaptide), dibutyl bis (isooxyl mercaptoacetate), monobutyl tin tris (isooctyl mercaptoacetate), dimethyl tin bis (isooctyl mercaptoacetate), tris (isooctyl mercaptoacetate ), Dioctyl tin bis (isooctyl mercaptoacetate), dibutyl tin bis (2-mercapto ethyl laurate), monobutyl tin tris (2- mercapto ethyl laurate), dimethyl tin bis (2- mercapto 1 type selected from compounds such as ethyl laurate) and monomethyl tin tris (2-mercaptoethyl laurate) Or two or more kinds can be used. Moreover, it is also possible to mix and use 2 or more types of heat stabilizers from which the series differs among the heat stabilizers illustrated above. Most preferably, by using a phosphorus-based heat stabilizer, not only the initial color of the molded lens but also the thermal stability of the optical lens can be greatly improved without deteriorating optical properties such as transparency, impact strength, heat resistance, and polymerization yield.
본 발명의 에폭시 아크릴계 광학재료의 제조방법은 상기 화학식 1로 표시되는 또는 여기에 화학식 2로 표시되는 화합물을 더 포함하는 에폭시 아크릴레이트계 화합물을 주형중합할 때에, 디페닐도데실포스파이트와 인산 에스테르 화합물을 첨가, 혼합한 후 주형중합한다. 바람직한 실시예에 따르면, 제조하기에 앞서 모든 원재료의 순도를 확인하여 순도가 낮은 화합물은 정제하고 순도가 높은 화합물은 정제 없이 사용한다. 바람직하게는, 순도 70~99.99% 까지의 고순도 화합물을 사용한다. 바람직한 실시예에 따르면, 에폭시 아크릴레이트 화합물과 디페닐도데실포스파이트, 인산 에스테르 화합물 및 반응성 희석제를 혼합한 후 반응 촉매를 첨가하고 교반한 다음 감압탈포를 거쳐 중합성 조성물을 몰드에 주입한다. 중합성 조성물이 주입된 몰드를 강제순환식 오븐에 넣고 30℃에서 100℃까지 서서히 가열경화시킨 후, 70±10℃ 정도로 냉각하여 몰드를 탈착하여 렌즈를 얻는다. The method for producing an epoxy acrylic optical material of the present invention is diphenyldodecyl phosphite and phosphate ester when the polymer polymerization of the epoxy acrylate compound represented by the formula (1) or further comprising a compound represented by the formula (2) After the compound is added and mixed, the mold is polymerized. According to a preferred embodiment, the purity of all raw materials is checked prior to preparation to purify low purity compounds and use high purity compounds without purification. Preferably, high purity compounds up to 70-99.99% purity are used. According to a preferred embodiment, the epoxy acrylate compound, the diphenyldodecyl phosphite, the phosphate ester compound and the reactive diluent are mixed, then the reaction catalyst is added and stirred, and then the polymerizable composition is injected into the mold via vacuum degassing. The mold into which the polymerizable composition was injected is placed in a forced circulation oven and gradually heat-cured from 30 ° C. to 100 ° C., and then cooled to about 70 ± 10 ° C. to detach and remove the mold to obtain a lens.
[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.
에폭시 아크릴레이트계 화합물Epoxy acrylate compound
1) 성분(I) 화합물의 합성1) Synthesis of Component (I) Compound
성분(I) 화합물은 화학식 3과 같다. 당량이 187인 국도화학의 YD-128 에폭시 수지에 아크릴산을 첨가하여 아크릴레이트화하여(105℃에서 20시간 반응시켜서 제조함) 당량 259인 화합물을 제조하였으며, 평균 분자량이 518인 혼합물이다. Component (I) compound is represented by the formula (3). A compound having an equivalent weight of 259 was prepared by adding acrylic acid to the YD-128 epoxy resin of Kukdo Chemical having an equivalent weight of 187 (prepared by reacting at 105 ° C. for 20 hours), and having an average molecular weight of 518.
[화학식 3][Formula 3]
Figure PCTKR2013007683-appb-I000005
Figure PCTKR2013007683-appb-I000005
(n = 0~15)(n = 0-15)
2) 성분(Ⅱ) 화합물2) Component (II) Compound
성분(Ⅱ) 화합물은 화학식 4와 같다. 당량이 187인 에폭시 수지에 메타아크릴산을 첨가하여 아크릴레이트화하여(105℃에서 20시간 반응시켜서 제조함) 당량 273인 화합물을 제조하였으며, 평균 분자량이 546인 혼합물이다. Component (II) compound is represented by the formula (4). Methacrylic acid was added to an epoxy resin having an equivalent weight of 187 and acrylated (prepared by reacting at 105 DEG C for 20 hours) to prepare a compound having an equivalent weight of 273, which was a mixture having an average molecular weight of 546.
[화학식 4] [Formula 4]
Figure PCTKR2013007683-appb-I000006
Figure PCTKR2013007683-appb-I000006
(n = 0 ~ 15)(n = 0 to 15)
3) 성분(Ⅲ) 화합물3) Component (III) Compound
성분(Ⅲ) 화합물은 화학식 5와 같다. 당량이 400인 국도화학의 YDB-400 에폭시 수지에 아크릴산을 첨가하여 아크릴레이트화하여(105℃에서 20시간 반응시켜서 제조함) 당량 472인 화합물을 제조하였으며, 평균 분자량이 944인 혼합물이다. Component (III) compound is represented by the formula (5). A compound having an equivalent weight of 472 was prepared by adding acrylic acid to the YDB-400 epoxy resin of Kukdo Chemical, which had an equivalent weight of 400, and reacting it at 20O < 0 > C for 20 hours, and a mixture having an average molecular weight of 944.
[화학식 5][Formula 5]
Figure PCTKR2013007683-appb-I000007
Figure PCTKR2013007683-appb-I000007
(n = 0 ~ 15)(n = 0 to 15)
4) 성분(Ⅳ) 화합물4) Component (IV) Compound
성분(Ⅳ) 화합물은 화학식 6과 같다. 당량이 400인 에폭시 수지에 메타아크릴산을 첨가하여 아크릴레이트화하여(105℃에서 20시간 반응시켜서 제조함) 당량 486인 화합물을 제조하였으며, 평균 분자량이 972인 혼합물이다. Component (IV) compound is represented by the formula (6). Methacrylic acid was added to the epoxy resin having an equivalent weight of 400 to prepare an acrylate compound (prepared by reacting at 105 DEG C for 20 hours) to prepare a compound having an equivalent weight of 486, and a mixture having an average molecular weight of 972.
[화학식 6][Formula 6]
Figure PCTKR2013007683-appb-I000008
Figure PCTKR2013007683-appb-I000008
(n = 0 ~ 15)(n = 0 to 15)
5) 성분(Ⅴ) 화합물5) Component (V) Compound
당량이 175인 비스페놀 A에 에틸렌옥사이드가 첨가된 알코올에 아크릴산을 첨가하여 아크릴레이트화 (105℃에서 20시간 반응시켜서 제조함)하여 당량 229인 화합물을 제조하였다. 평균 분자량이 458인 혼합물이고, 구조식은 아래 화학식 7과 같다. Acrylic acid was added to an alcohol having ethylene oxide added to bisphenol A having an equivalent weight of 175, and then acrylated (prepared by reacting at 105 DEG C for 20 hours) to prepare a compound having an equivalent weight of 229. The mixture has an average molecular weight of 458, and the structural formula is shown in Chemical Formula 7 below.
[화학식 7] [Formula 7]
Figure PCTKR2013007683-appb-I000009
Figure PCTKR2013007683-appb-I000009
(m = 0~5, n = 0~5 이고, m과 n은 동시에 0 이 아니며, m+n = 1~10 이다.)(m = 0 ~ 5, n = 0 ~ 5, m and n are not 0 at the same time, m + n = 1 ~ 10)
6) 성분(Ⅵ) 화합물6) Component (VI) Compound
당량이 175인 비스페놀 A에 에틸렌옥사이드가 첨가된 알코올에 메타아크릴산을 첨가하여 아크릴레이트화 (105℃에서 20시간 반응시켜서 제조함)하여 당량 243인 화합물을 제조하였다. 평균 분자량이 486인 혼합물이고, 구조식은 아래 화학식 8과 같다. Methacrylic acid was added to an alcohol having ethylene oxide added to bisphenol A having an equivalent weight of 175 to acrylate (prepared by reacting at 105 ° C. for 20 hours) to prepare a compound having an equivalent weight of 243. The mixture has an average molecular weight of 486, and the structural formula is shown in Chemical Formula 8 below.
[화학식 8] [Formula 8]
Figure PCTKR2013007683-appb-I000010
Figure PCTKR2013007683-appb-I000010
(m = 0~5, n = 0~5 이고, m과 n은 동시에 0 이 아니며, m+n = 1~10 이다.)(m = 0 ~ 5, n = 0 ~ 5, m and n are not 0 at the same time, m + n = 1 ~ 10)
실시예 1Example 1
위에서 얻은 에폭시 아크릴레이트계 화합물 중 성분(I) 15g, 성분(Ⅲ) 30g 및 성분(V) 10g에 스틸렌 40g, 메틸스틸렌다이머 2g, DPDP 2g, DOP 1g 및 DBTM 2g를 첨가하고, 약 30분간 교반하였다. 이후 0.45㎛이하의 여과지로 여과하고, 여기에 촉매로 V65 0.05g 및 3-M 0.12g을 첨가하고, 내부 이형제로 4-PENPP 0.05g 및 8-PENPP 0.2g을 혼합하여 광학렌즈용 중합성 조성물을 만들었다. 이렇게 제조된 광학렌즈용 중합성 조성물을 1 시간 교반한 후, 10분간 감압탈포하고 여과한 다음, 폴리에스테르 점착테이프로 조립된 유리몰드에 주입하였다. 중합성 조성물이 주입된 유리 몰드를 강제 순환식 오븐에서 35℃에서 110℃까지 20시간에 걸쳐서 가열 경화시킨 후, 70℃로 냉각하여 유리몰드를 탈착하여 렌즈를 얻었다. 얻어진 렌즈는 지름 72㎜로 가공한 후 알카리 수성 세척액에 초음파 세척한 다음, 120℃에서 2시간 어닐링 처리하였다. 아래와 같은 방법으로 물성을 측정하여 그 결과를 표 1에 나타내었다.15 g of component (I), 30 g of component (III) and component (V) of the epoxy acrylate compound obtained above To 10 g, 40 g of styrene, 2 g of methylstyrene dimer, 2 g of DPDP, 1 g of DOP, and 2 g of DBTM were added and stirred for about 30 minutes. Thereafter, the resultant was filtered with a filter paper of 0.45 μm or less, and thereto was added 0.05 g of V65 and 0.12 g of 3-M as a catalyst, and 4-PENPP 0.05 g and 8-PENPP 0.2 g were mixed with an internal mold release agent to form a polymerizable composition for an optical lens. Made. The polymerizable composition for optical lenses thus prepared was stirred for 1 hour, degassed under reduced pressure for 10 minutes, filtered, and then injected into a glass mold assembled with a polyester adhesive tape. The glass mold in which the polymerizable composition was injected was heat-cured in a forced circulation oven from 35 ° C. to 110 ° C. over 20 hours, and then cooled to 70 ° C. to remove the glass mold to obtain a lens. The resulting lens was processed to a diameter of 72 mm and then ultrasonically washed with an alkaline aqueous washing solution, followed by annealing at 120 캜 for 2 hours. Measure the physical properties with the following methodTable 1Shown in
물성 실험방법Property test method
이하의 물성 실험방법으로 제조된 광학렌즈의 물성을 측정하여 그 결과를 아래 표 1에 기록하였다.The physical properties of the optical lenses manufactured by the following physical property test methods were measured and the results are reported in Table 1 below.
1) 굴절률 및 아베수 : Atago 사의 DR-M4 모델인 아베 굴절계를 사용하여 측정하였다.1) Refractive index and Abbe number: It was measured using an Abbe refractometer, a DR-M4 model of Atago.
2) 비중: 분석저울을 이용하고, 수중치환법에 의해 측정하였다.2) Specific gravity: It was measured by an underwater substitution method using an analytical balance.
3) 이형성: 광학렌즈 제조시 에폭시 아크릴계 수지 조성물을 열경화시키고 70℃에서 탈형시 광학렌즈와 몰드의 분리시 렌즈 혹은 몰드의 파손에 따라 "○" 및 "×"로 표시하였다. "○"는 100개의 광학렌즈와 몰드의 분리과정에서 렌즈 혹은 몰드가 전혀 파손되지 않거나 1개가 파손된 경우, "×"는 100개의 광학렌즈와 몰드의 분리과정에서 렌즈 혹은 몰드가 4개 이상이 파손된 경우로 나타내었다.3) Release property: The epoxy acrylic resin composition was thermally cured when the optical lens was manufactured, and was marked with “○” and “×” according to the breakage of the lens or the mold when the optical lens and the mold were separated when demolded at 70 ° C. "○" means that the lens or mold is not broken at all or one is broken during the separation of 100 optical lenses and the mold, and "x" means that 4 or more lenses or molds are removed during the separation of 100 optical lenses and the mold. It is shown as a broken case.
4) 열안정성: 경화된 광학렌즈를 100℃에서 10시간 동안 유지하고, 색상변화의 측정에서 APHA 값이 1 미만으로 변하면 "◎"로 표시하였고, 1 이상 2 미만으로 변하면 "○"로, 2 이상 변하면 "×"로 표시하였다. APHA는 Hunterlab사의 ColorQuest XE를 이용하였고 플라스틱 렌즈를 넣고 직접 측정하였다. 이는 이미 백금과 코발트의 시약을 용해하여 조제한 표준액의 농도를 데이터화하여 내장된 프로그램과 시료 액의 비교에서 얻어진 APHA 값을 측정치로 하였다. 측정한 값이 작을수록 색상이 양호하다.4) Thermal Stability: The cured optical lens was kept at 100 ° C. for 10 hours, and when the APHA value changed to less than 1 in the measurement of color change, “◎” was displayed. If abnormal, the change was indicated by "x". APHA was used by Hunterlab's ColorQuest XE and measured directly with a plastic lens. This data was obtained by measuring the concentration of the standard solution prepared by dissolving the reagents of platinum and cobalt, and measuring the APHA value obtained by comparing the built-in program with the sample solution. The smaller the measured value, the better the color.
5) 저정안정성: 경화된 광학렌즈를 120℃에서 2시간 아닐링하고, 20℃에서 30일 동안 보관하고, 측정한 색상변화의 APHA 값이 1 미만으로 변하면 "◎"로, 1 이상 2 미만으로 변하면 "○"로, 2 이상 변하면 "×"로 표시하였다. 5) Low Stability: The cured optical lens is annealed at 120 ° C. for 2 hours, stored at 20 ° C. for 30 days, and when the APHA value of the measured color change is changed to less than 1, it is “◎” and is 1 or more and less than 2 When it changed, it represented by "(circle)" and when it changed more than 2, it represented by "x".
6) 중합불균형: 공정에서 얻어진 렌즈 100개를 육안 및 USH10 USH-102D인 수은아크 램프(Mercury Arc Lamp)로 관찰하여 광학 왜곡이 3개 이상이 나타나면 "×"로, 광학왜곡이 3개 이하이면 "○"으로 표기하였다. 6) Polymerization imbalance: 100 lenses obtained in the process were observed with the naked eye and a Mercury Arc Lamp (USH10 USH-102D), and if 3 or more optical distortions appeared, it was "x". If the optical distortion was 3 or less, "○" was written.
7) 색상: 경화된 광학렌즈의 색상이 무색이면 "○"으로 표시하였고, 색상을 띠면 "×"로 표시하였다.7) Color: When the color of the cured optical lens is colorless, "○" is displayed. When the color is colored, "×" is indicated.
실시예 2~6Examples 2-6
실시예 1과 같은 방법으로 표 1에 기재된 조성에 따라 각각 조성물 및 광학렌즈를 제조하고 물성을 실험하였으며, 그 결과를 표 1에 기재하였다.In the same manner as in Example 1, according to the composition shown in Table 1 , the composition and the optical lens were prepared and tested for physical properties, respectively, and the results are shown in Table 1 .
비교예 1Comparative Example 1
위에서 얻은 에폭시 아크릴레이트계 화합물 중 성분(I) 15g, 성분(Ⅳ) 29.4g 및 성분(Ⅵ) 8g에 스틸렌 40g, 알파-메틸스틸렌 5g, 메틸스틸렌다이머 2g, DPDP 0.3g, TDP 0.3g 및 DPP 2g 를 첨가하고, 약 30분간 교반하였다. 이후 0.45㎛이하의 여과지로 여과하고, 여기에 촉매로 V65 0.05g 및 3-M 0.13g을 첨가하고, 내부 이형제로 8-PENPP 0.1g 및 12-PENPP 0.1g을 혼합하여 광학렌즈용 수지 조성물을 만든 후, 아래와 같은 방법으로 광학 렌즈를 제조하고, 렌즈의 물성을 측정하였다. 렌즈를 제조하고 렌즈의 물성을 측정하여, 그 결과를 표 1에 나타내었다.In the epoxy acrylate compound obtained above, 15 g of component (I), 29.4 g of component (IV), and 8 g of component (VI) contained 40 g of styrene, 5 g of alpha-methylstyrene, 2 g of methylstyrene dimer, 0.3 g of DPDP, 0.3 g of TDP and DPP. 2 g was added and stirred for about 30 minutes. Thereafter, the resultant was filtered with a filter paper of 0.45 µm or less, and thereto was added 0.05g of G65 and 0.13g of 3-M as a catalyst, and 8-PENPP 0.1g and 12-PENPP 0.1g were mixed as an internal release agent to prepare a resin composition for an optical lens. After the preparation, an optical lens was manufactured by the following method, and the physical properties of the lens were measured. A lens was manufactured and the physical properties of the lens were measured, and the results are shown in Table 1 .
비교예 2~3Comparative Examples 2-3
비교예 1과 같은 방법으로 표 1에 기재된 조성에 따라 각각 조성물 및 광학렌즈를 제조하고 물성을 실험하였으며, 그 결과를 표 1에 기재하였다.According to the composition shown in Table 1 in the same manner as in Comparative Example 1, the composition and the optical lens were prepared and tested for physical properties, and the results are shown in Table 1 .
[표 1]TABLE 1
Figure PCTKR2013007683-appb-I000011
Figure PCTKR2013007683-appb-I000011
[약어][Abbreviation]
저장안정제Storage stabilizer
DPDP: 디페닐도데실포스파이트(diphenyldodecyl phosphate)DPDP: diphenyldodecyl phosphate
인산에스테르화합물Phosphate Ester Compound
DOP: 디옥틸산 포스페이트(dioctyl acid phosphate)DOP: dioctyl acid phosphate
TDP: 트리데칸올산 포스페이트(Tridecanol acid phosphate)TDP: Tridecanol acid phosphate
열안정제Heat stabilizer
DBTM: 디부틸틴말리에이트(dibutyltinmaleate)DBTM: dibutyltinmaleate
TPP: 트리페닐포스파이트(triphenylphosphite)TPP: triphenylphosphite
DPP: 디페닐이소데실포스파이트(diphenylisodecylphosphite)DPP: diphenylisodecylphosphite
중합개시제Polymerization initiator
V65: 2,2'-아조비스(2,4-디메틸바레노니트릴) (2,2'-azobis(2,4-dimethylvaleronitrile)V65: 2,2'-azobis (2,4-dimethylbarrenonitrile) (2,2'-azobis (2,4-dimethylvaleronitrile)
3-M: 1,1-비스(t-부틸퍼록시)-3,3-5-트리메틸 사이클로헥산, (1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane)3-M: 1,1-bis (t-butylperoxy) -3,3-5-trimethyl cyclohexane, (1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane)
내부이형제Internal release agent
4-PENPP: 폴리옥시에틸렌노닐페닐포스페이트(에틸렌옥사이드가 5몰 부가된 것 5 중량%, 에틸렌옥사이드가 4몰 부가된 것 80중량%, 에틸렌옥사이드가 3몰 부가된 것 10중량%, 에틸렌옥사이드가 1몰 부가된 것 5 중량%)4-PENPP: polyoxyethylene nonylphenyl phosphate (5% by weight of 5 mol of ethylene oxide added, 80% by weight of 4 mol of ethylene oxide added, 10% by weight of 3 mol of ethylene oxide added, 5% by weight of 1 mol of ethylene oxide added)
8-PENPP: 폴리옥시에틸렌노닐페닐포스페이트(에틸렌옥사이드가 9몰 부가된 것 5 중량%, 에틸렌옥사이드가 8몰 부가된 것 80 중량%, 에틸렌옥사이드가 7몰 부가된 것 10 중량%, 에틸렌옥사이드가 6몰 이하 부가된 것 5 중량%)8-PENPP: polyoxyethylene nonylphenyl phosphate (5% by weight of 9 mol of ethylene oxide added, 80% by weight of 8 mol of ethylene oxide, 10% by weight of 7 mol of ethylene oxide, ethylene oxide 5 mole% added by 6 mol or less)
12-PENPP: 폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드가 13몰 부가된 것 3 중량%, 12몰 부가된 것 80 중량%, 11몰 부가된 것 8 중량%, 9몰 부가된 것 3 중량%, 4몰 부가된 것 6 중량%)12-PENPP: polyoxyethylene nonyl phenol ether phosphate (3% by weight of 13 mol of ethylene oxide added, 80% by weight of 12 mol added, 8% by weight of 11 mol added, 3% by weight 9 mol added , 4 mol added 6 wt%)
16-PENPP: 폴리옥시에틸렌노닐페놀에테르포스페이트(에틸렌옥사이드가 17몰 부가된 것 3 중량%, 16몰 부가된 것 79 중량%, 15몰 부가된 것 10 중량%, 14몰 부가된 것 4 중량%, 13몰 부가된 것 4 중량%)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) , 13 mol added 4 wt%)
본 발명에 따르면, 높은 굴절률과 우수한 아베수에, 투명성, 경량성, 내열성 등의 광학 특성이 우수하고 제조비용이 저렴한 에폭시 아크릴계 광학재료의 장점을 지니면서 상온에서 오랜 시간 보관하거나 사용해도 변색이 없는 고품질의 에폭시 아크릴계 광학재료를 용이하게 얻을 수 있다. 본 발명에 따라 제조된 에폭시 아크릴계 광학재료는 기존의 광학재료를 대체하여 다양한 분야에서 널리 이용될 수 있으며, 특히 안경렌즈나 카메라 렌즈 등으로 사용될 수 있다. 본 발명의 광학재료는, 구체적으로, 플라스틱 안경렌즈, 안경렌즈에 편광필름을 장착한 3D 편광렌즈 등으로 이용될 수 있고, 이외에도 프리즘, 광섬유, 광디스크 등에 사용되는 기록 매체기판이나 착색필터와 자외선 흡수 필터 등의 다양한 광학제품에 이용될 수 있다. According to the present invention, it has high refractive index and excellent Abbe's number, and has the advantages of epoxy acrylic optical material having excellent optical properties such as transparency, light weight, heat resistance and low manufacturing cost, and no discoloration even when stored or used for a long time at room temperature. High quality epoxy acrylic optical materials can be easily obtained. The epoxy acrylic optical material manufactured according to the present invention may be widely used in various fields in place of the existing optical material, and in particular, may be used as an eyeglass lens or a camera lens. Specifically, the optical material of the present invention can be used as a plastic spectacle lens, a 3D polarizing lens equipped with a polarizing film on the spectacle lens, and the like, as well as recording media substrates, color filters, and ultraviolet absorbers used in prisms, optical fibers, optical disks, and the like It can be used for various optical products such as a filter.

Claims (13)

  1. 아래 화학식 1로 표시되는 화합물과, 디페닐도데실포스파이트와, 인산 에스테르 화합물을 포함하는 에폭시 아크릴계 광학재료용 중합성 조성물. The polymerizable composition for epoxy acrylic optical materials containing the compound represented by following General formula (1), a diphenyldodecyl phosphite, and a phosphate ester compound.
    [화학식 1][Formula 1]
    Figure PCTKR2013007683-appb-I000012
    Figure PCTKR2013007683-appb-I000012
    (여기서 n = 0~15 이고, R1은 H 또는 CH3이며, R2는 H 혹은 Br이다.)(Where n = 0-15, R 1 is H or CH 3 and R 2 is H or Br)
  2. 제1항에 있어서, 아래 화학식 2로 표시되는 화합물을 더 포함하는 에폭시 아크릴계 광학재료용 중합성 조성물. The polymerizable composition for an epoxy acrylic optical material according to claim 1, further comprising a compound represented by the following Chemical Formula 2.
    [화학식 2][Formula 2]
    Figure PCTKR2013007683-appb-I000013
    Figure PCTKR2013007683-appb-I000013
    (여기서 R은 H 또는 CH3이고, m = 0~5, n = 0~5 이고, m과 n은 동시에 0 이 아니며, m+n = 1~10 이다.)(Where R is H or CH 3 , m = 0-5, n = 0-5, m and n are not zero at the same time, m + n = 1-10)
  3. 제1항 또는 제2항에 있어서, 상기 디페닐도데실포스파이트와 인산 에스테르 화합물은 상기 중합성 조성물 중에 각각 0.5~8 중량% 및 0.5~3 중량%로 포함되는 것을 특징으로 하는 에폭시 아크릴계 광학재료용 중합성 조성물. The epoxy acrylic optical material according to claim 1 or 2, wherein the diphenyldodecyl phosphite and the phosphate ester compound are contained in the polymerizable composition at 0.5 to 8% by weight and 0.5 to 3% by weight, respectively. Polymerizable composition for.
  4. 제1항 또는 제2항에 있어서, 상기 인산 에스테르 화합물은 이소프로필산 포스페이트, 디이소프로필산 포스페이트, 트리이소프로필산 포스페이트, 부틸산 포스페이트, 디부틸산 포스페이트, 트리부틸산 포스페이트, 옥틸산 포스페이트, 디옥틸산 포스페이트, 트리옥틸산 포스페이트, 이소데실산 포스페이트, 디이소데실산 포스페이트, 트리이소데실산 포스페이트, 트리데칸올산 포스페이트, 비스(트리데칸올산)포스페이트, 디메틸산 포스페이트, 트리메틸산 포스페이트, 디에틸산 포스페이트, 트리에틸산 포스페이트, 디프로필산 에스테르, 트리프로필산 에스테르, 메틸산 포스페이트, 에틸산 포스페이트, 프로필산 포스페이트, 벤질산 포스페이트, 디벤질산 포스페이트, 트리벤질산 포스페이트, 폴리옥시에틸렌 노닐 페놀에테르 포스페이트, 트리 폴리옥시에틸렌 노닐 페놀에테르 포스페이트, 에틸렌글리콜 모노에틸 포스페이트, 디에틸렌글리콜 모노에틸 포스페이트, 트리에틸렌글리콜 모노에틸 포스페이트, 디에틸렌글리콜 모노부틸 트리포스페이트, 디에틸렌글리콜 모노부틸 디포스페이트, 디에틸렌글리콜 모노부틸 포스페이트, 이소프로필렌글리콜 모노에틸 포스페이트, 디이소프로필렌글리콜 모노에틸 포스페이트, 트리이소프로필렌글리콜 모노에틸 포스페이트 및 젤렉유엔TM(Zelec UNTM)으로 구성된 군으로부터 선택된 1종 또는 2종 이상인 것을 특징으로 하는 에폭시 아크릴계 광학재료용 중합성 조성물. According to claim 1 or 2, wherein the phosphate ester compound is isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyric acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, Dioctylic Acid Phosphate, Trioctyl Acid Phosphate, Isodecyl Acid Phosphate, Diisodecyl Acid Phosphate, Triisodecyl Acid Phosphate, Tridecanoic Acid Phosphate, Bis (tridecanoic Acid) Phosphate, Dimethyl Acid Phosphate, Trimethyl Acid Phosphate, Diethyl Acid Phosphate, Triethyl Acid Phosphate, Dipropyl Acid Ester, Tripropyl Acid Ester, Methyl Phosphate, Ethyl Acid Phosphate, Propyl Acid Phosphate, Benzyl Acid Phosphate, Dibenzyl Acid Phosphate, Tribenzyl Acid Phosphate, Polyoxyethylene Nonyl Phenol Ether Phosphate Tri-poly Cyethylene nonyl phenolether phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethyl phosphate, triethylene glycol monoethyl phosphate, diethylene glycol monobutyl triphosphate, diethylene glycol monobutyl diphosphate, diethylene glycol monobutyl phosphate, isopropylene glycol monoethyl phosphate, di-isopropylene glycol monoethyl phosphate, tri isopropylene glycol monoethyl phosphate and jelrek UN TM (Zelec UN TM) epoxy acrylic optical material, characterized in that at least one or two selected from the group consisting of Polymerizable composition for.
  5. 제1항 또는 제2항에 있어서, 반응성 희석제로 스틸렌, 디비닐벤젠, 알파메틸스틸렌, 알파메틸스틸렌다이머, 벤질메타아크릴레이트, 클로로스틸렌, 브로모스틸렌, 메톡시스틸렌, 모노벤질말레이트, 디벤질말레이트, 모노벤질푸말레이트, 디벤질푸말레이트, 메틸벤질말레이트, 디메틸말레이트, 디에틸말레이트, 디부틸말레이트, 디부틸푸말레이트, 모노부틸말레이트, 모노펜틸말레이트, 디펜틸말레이트, 모노펜틸푸말레이트, 디펜틸푸말레이트 및 디에틸렌글리콜 비스아릴카르보네이트로 구성된 군으로부터 선택된 1종 혹은 2종 이상의 화합물을 더 포함하는 에폭시 아크릴계 광학재료용 중합성 조성물. The styrene, divinylbenzene, alphamethyl styrene, alphamethyl styrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxy styrene, monobenzyl maleate, di, as a reactive diluent Benzyl maleate, monobenzyl fumarate, dibenzyl fumarate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, monopentyl maleate, dipentyl malate A polymerizable composition for epoxy acrylic optical materials further comprising one or two or more compounds selected from the group consisting of latex, monopentyl fumarate, dipentyl fumarate and diethylene glycol bisaryl carbonate.
  6. 제5항에 있어서, 열안정제로 트리페닐 포스파이트, 디페닐데실포스파이트, 페닐디데실포스파이트, 트리노릴페닐포스파이트, 디페닐이소옥틸포스파이트, 트리부틸포스파이트, 트리프로필포스파이트, 트리에틸포스파이트, 트리메틸포스파이트, 트리스(모노데실포스파이트) 및 트리스(모노페닐)포스파이트로 구성된 군으로부터 선택된 1종 혹은 2종 이상의 화합물을 더 포함하는 에폭시 아크릴계 광학재료용 중합성 조성물. The method of claim 5, wherein the thermal stabilizer is triphenyl phosphite, diphenyldecyl phosphite, phenyl diddecyl phosphite, trinoyl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite, tripropyl phosphite, tri A polymerizable composition for an epoxy acrylic optical material further comprising one or two or more compounds selected from the group consisting of ethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite) and tris (monophenyl) phosphite.
  7. 제4항에 있어서, 내부이형제로 다른 인산 에스테르 화합물을 더 포함하는 에폭시 아크릴계 광학재료용 중합성 조성물. The polymerizable composition for epoxy acrylic optical material according to claim 4, further comprising another phosphate ester compound as an internal release agent.
  8. 아래 화학식 1로 표시되는 에폭시 아크릴레이트계 화합물을 포함하는 중합성 조성물을 주형중합할 때에, 저장안정성을 향상시키기 위해 디페닐도데실포스파이트와 인산 에스테르 화합물을 첨가하여 중합시키는 것을 포함하는 에폭시 아크릴계 광학재료의 제조방법.Epoxy acrylic optical, including polymerizing by adding a diphenyldodecyl phosphite and a phosphate ester compound to improve storage stability when casting a polymerizable composition comprising an epoxy acrylate compound represented by Formula 1 below Method of manufacturing the material.
    [화학식 1][Formula 1]
    Figure PCTKR2013007683-appb-I000014
    Figure PCTKR2013007683-appb-I000014
    (여기서 n = 0~15 이고, R1은 H 또는 CH3이며, R2는 H 혹은 Br이다.)(Where n = 0-15, R 1 is H or CH 3 and R 2 is H or Br)
  9. 제8항에 있어서, 상기 중합성 조성물은 아래 화학식 2로 표시되는 화합물을 더 포함하는 것을 특징으로 하는 에폭시 아크릴계 광학재료의 제조방법.The method of claim 8, wherein the polymerizable composition further comprises a compound represented by Chemical Formula 2 below.
    [화학식 2][Formula 2]
    Figure PCTKR2013007683-appb-I000015
    Figure PCTKR2013007683-appb-I000015
    (여기서 R은 H 또는 CH3이고, m = 0~5, n = 0~5 이고, m과 n은 동시에 0 이 아니며, m+n = 1~10 이다.)(Where R is H or CH 3 , m = 0-5, n = 0-5, m and n are not zero at the same time, m + n = 1-10)
  10. 제8항 또는 제9항에 있어서, 상기 디페닐도데실포스파이트와 인산 에스테르 화합물은 상기 중합성 조성물 전체 중량 중 각각 0.5~ 8 중량% 및 0.5~3 중량%로 첨가되는 것을 특징으로 하는 에폭시 아크릴계 광학재료의 제조방법.The epoxy acrylic type according to claim 8 or 9, wherein the diphenyldodecyl phosphite and the phosphate ester compound are added at 0.5 to 8 wt% and 0.5 to 3 wt%, respectively, in the total weight of the polymerizable composition. Method for producing optical material.
  11. 제1항 또는 제2항의 중합성 조성물을 주형중합하여 얻은 광학재료.The optical material obtained by casting-polymerizing the polymerizable composition of Claim 1 or 2.
  12. 제11항의 광학재료로 이루어진 광학렌즈.An optical lens made of the optical material of claim 11.
  13. 제12항에 있어서, 상기 광학렌즈는 안경렌즈 또는 편광렌즈인 광학렌즈.The optical lens of claim 12, wherein the optical lens is an eyeglass lens or a polarizing lens.
PCT/KR2013/007683 2012-08-27 2013-08-27 Polymerization composition for epoxy acrylic optical material having enhanced storage stability and method for manufacturing epoxy acrylic optical material WO2014035120A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201380045139.1A CN104583250B (en) 2012-08-27 2013-08-27 Propylene oxide acids polymerizable composition for optical material and the preparation method of propylene oxide acids optical material that storage stability is improved

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20120093890 2012-08-27
KR10-2012-0093890 2012-08-27

Publications (1)

Publication Number Publication Date
WO2014035120A1 true WO2014035120A1 (en) 2014-03-06

Family

ID=50183866

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/007683 WO2014035120A1 (en) 2012-08-27 2013-08-27 Polymerization composition for epoxy acrylic optical material having enhanced storage stability and method for manufacturing epoxy acrylic optical material

Country Status (3)

Country Link
KR (1) KR102097174B1 (en)
CN (1) CN104583250B (en)
WO (1) WO2014035120A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109627399B (en) * 2018-12-13 2022-03-25 山东鲁源化工科技有限公司 High-refractive-index optical resin monomer and preparation method thereof
KR102647150B1 (en) * 2019-01-31 2024-03-14 다이킨 고교 가부시키가이샤 Brother Lee
CN112175493A (en) * 2020-09-30 2021-01-05 南京承奕科技有限公司 Flame-retardant and acid-resistant building waterproofing agent and preparation method thereof
CN116640361B (en) * 2023-06-15 2023-12-22 益丰新材料股份有限公司 Release agent composition and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040065454A (en) * 2003-01-14 2004-07-22 주식회사 니드필 Resin composition for producing optical lens having low density and medium refraction index, and optical lens produced with the same
KR20040083942A (en) * 2003-03-25 2004-10-06 장동규 Resin composition with heat stability based on epoxy acrylate for high refractive index optical lens, which is suitable for a lens for glasses and cameras
KR20050029275A (en) * 2002-07-22 2005-03-24 닛폰 유시 가부시키가이샤 Composition for optical material, optical material, process for producing the same, and lens
KR20090034378A (en) * 2001-11-07 2009-04-07 다이소 가부시키가이샤 Curable composition excellent in optical characteristics
KR100897407B1 (en) * 2007-12-11 2009-05-14 주식회사 신대특수재료 Composition for uv rays cutting optical lens preventing yellowing during annealing and optical lens using it
KR20120075434A (en) * 2010-12-28 2012-07-06 주식회사 케이오씨솔루션 New preparation method of allylcarbonate compound and optical resin composition using it

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880171A (en) * 1989-05-01 1999-03-09 2C Optics, Inc. Fast curing polymeric compositions for ophthalmic lenses and apparatus for preparing lenses
JP3362987B2 (en) * 1994-12-22 2003-01-07 三菱レイヨン株式会社 Composition for plastic lens
KR100496911B1 (en) 2000-11-07 2005-06-23 장동규 A Material for Plastic Lense
JP2003238623A (en) * 2002-02-20 2003-08-27 Dainippon Ink & Chem Inc Active-energy-ray curable composition and polymer for optical material
KR100474586B1 (en) * 2002-06-12 2005-03-08 주식회사 두산 Resin compositions, and optical lens prepared by them
JP4228780B2 (en) * 2003-05-23 2009-02-25 Ｄｉｃ株式会社 Active energy ray-curable resin composition for casting polymerization
KR100529369B1 (en) * 2004-03-02 2005-11-21 주식회사 니드필 Resin composition for producing optical lens having low density and medium refraction index, and optical lens produced with the same
KR101142266B1 (en) * 2009-02-17 2012-05-07 주식회사 케이오씨솔루션 High Refractive Index Optical Resin Composition Having Improved Impact Resistance, High Refractive Index Plastic Optical Lens and Manufacturing Method of the Plastic Optical Lens
KR101802480B1 (en) * 2010-12-13 2017-12-28 주식회사 케이오씨솔루션 Epoxy Acryl Optical Resin Composition Comprising Internal Mold Release Agent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090034378A (en) * 2001-11-07 2009-04-07 다이소 가부시키가이샤 Curable composition excellent in optical characteristics
KR20050029275A (en) * 2002-07-22 2005-03-24 닛폰 유시 가부시키가이샤 Composition for optical material, optical material, process for producing the same, and lens
KR20040065454A (en) * 2003-01-14 2004-07-22 주식회사 니드필 Resin composition for producing optical lens having low density and medium refraction index, and optical lens produced with the same
KR20040083942A (en) * 2003-03-25 2004-10-06 장동규 Resin composition with heat stability based on epoxy acrylate for high refractive index optical lens, which is suitable for a lens for glasses and cameras
KR100897407B1 (en) * 2007-12-11 2009-05-14 주식회사 신대특수재료 Composition for uv rays cutting optical lens preventing yellowing during annealing and optical lens using it
KR20120075434A (en) * 2010-12-28 2012-07-06 주식회사 케이오씨솔루션 New preparation method of allylcarbonate compound and optical resin composition using it

Also Published As

Publication number Publication date
CN104583250B (en) 2017-07-07
CN104583250A (en) 2015-04-29
KR102097174B1 (en) 2020-04-06
KR20140027890A (en) 2014-03-07

Similar Documents

Publication Publication Date Title
WO2015020482A1 (en) Polymerizable composition for high-refractive optical material and method for preparing high-refractive optical material
WO2014208994A1 (en) Polymerizable composition for highly refractive optical material, photochromic composition thereof, and method for preparing high-refractive optical material using compositions
WO2014035120A1 (en) Polymerization composition for epoxy acrylic optical material having enhanced storage stability and method for manufacturing epoxy acrylic optical material
KR101802480B1 (en) Epoxy Acryl Optical Resin Composition Comprising Internal Mold Release Agent
KR101816722B1 (en) A method of preparing epoxy acryl based optical material
WO2013187539A1 (en) Method for polymerizing resin casting for use as epoxy acrylic optical lens and resin composition containing internal releasing agent for use in epoxy acrylic optical lens
WO2018216901A1 (en) Resin composition for epoxy acrylic middle-refractive optical lens and preparation method therefor
WO2014027849A1 (en) Polymerizable composition for epoxy acrylic optical material, and method for preparing epoxy acrylic optical material
WO2014077589A1 (en) Polymeric composition for highly refractive epoxy-acrylic optical material, and method for manufacturing highly refractive epoxy-acrylic optical material
WO2012086867A1 (en) Acrylic copolymer resin composition
KR101227436B1 (en) Mold polymerization method for epoxy acryl optical lens and the resin composition containing internal mold release agents
KR20040083942A (en) Resin composition with heat stability based on epoxy acrylate for high refractive index optical lens, which is suitable for a lens for glasses and cameras
WO2016060333A1 (en) Thermoplastic resin composition having excellent transparency and mechanical strength, and molded product comprising same
WO2019050189A1 (en) Resin composition for epoxy acrylic medium-refractive-index optical lens, and preparation method therefor
WO2014035125A1 (en) Polymerization composition for epoxy acrylic optical material and method for manufacturing epoxy acrylic optical material
WO2014035145A1 (en) Method for manufacturing epoxy acrylic optical material
KR101915818B1 (en) Optical Resin Composition using polytiolester composition and the Plastic Ophthalmic Lens using it
WO2014035121A1 (en) Polymerization composition for epoxy acrylic optical material and method for manufacturing epoxy acrylic optical material
WO2018216897A2 (en) Resin composition for epoxy acryl-based medium-refractive optical lens and preparation method therefor
KR20200106729A (en) Internal Mold Release Agent For Optical Lens and Epoxy Acryl Based Optical Lens comprising it
KR20190017007A (en) A method of preparing epoxy acryl based optical material
KR20140030057A (en) A method of preparing epoxy acryl based optical material
KR20200039399A (en) Mold polymerization method for epoxy acryl optical lens and the resin composition containing internal mold release agents
KR20200109779A (en) Composition for improving thermal stability and releasability of optical lenses and composition for Epoxy Acryl Based Optical Lens comprising same
KR20140029275A (en) A method of preparing epoxy acryl based optical material

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13832636

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13832636

Country of ref document: EP

Kind code of ref document: A1