KR100645833B1 - Transparent heat-resistant resin for optical use - Google Patents
Transparent heat-resistant resin for optical use Download PDFInfo
- Publication number
- KR100645833B1 KR100645833B1 KR1020050055481A KR20050055481A KR100645833B1 KR 100645833 B1 KR100645833 B1 KR 100645833B1 KR 1020050055481 A KR1020050055481 A KR 1020050055481A KR 20050055481 A KR20050055481 A KR 20050055481A KR 100645833 B1 KR100645833 B1 KR 100645833B1
- Authority
- KR
- South Korea
- Prior art keywords
- optical
- polymer
- acrylate
- alpha
- weight
- Prior art date
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
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
Abstract
Description
본 발명의 목적은 광학용도로써 압출 및 사출 가공시에 수지를 얇은 시트형태나 렌즈로 제조할 경우 수분 흡수율을 낮추어 변형을 억제하고 또한 기존에 광학용도로 사용되어지는 상용의 PMMA보다 높은 유리전이온도(Tg)가 요구되어지는 경우 사용될 수 있는 공중합 수지에 관한 것이다. It is an object of the present invention to reduce the water absorption rate when the resin is manufactured in the form of a thin sheet or lens during extrusion and injection processing for optical purposes, and to suppress deformation and to have a higher glass transition temperature than commercially available PMMA, which is conventionally used for optical applications. It relates to a copolymer resin which can be used when (T g ) is required.
투명수지는 산업상에 광학용도로써 다양하게 사용되고 있으며 특히, 폴리메틸메타크릴레이트가 대표적이다. 폴리메틸메타크릴레이트는 우수한 투명성과 낮은 복굴절율을 가지고 있으나 얇은 판으로 가공되어졌을 때는 수분흡수로 인하여 변형이 생기는 문제점이 있다. 또한 내열성이 요구되어지는 경우에는 이의 특성에 대한 개선이 요구되어진다.Transparent resins are used in a variety of optical applications in the industry, in particular polymethyl methacrylate. Polymethyl methacrylate has excellent transparency and low birefringence, but when processed into a thin plate, there is a problem in that deformation occurs due to water absorption. In addition, when heat resistance is required, improvement of its characteristics is required.
기존에 내열성을 향상시키기 위해서 일본공개특허 1986-141715에서는 N-치환된 말레이미드를 단량체로 이용하여 공중합체를 제조하였다.In order to improve heat resistance, Japanese Laid-Open Patent No. 1986-141715 prepared a copolymer using N-substituted maleimide as a monomer.
그러나 말레이미드는 수지내 잔류 시에 고온에서 황색을 일으킬 뿐만 아니라 메틸메타크릴레이트와 공중합시 공중합 능력이 떨어지는 단점이 있다. However, maleimide has a disadvantage of not only causing yellow at high temperatures when remaining in the resin but also having poor copolymerization ability when copolymerized with methyl methacrylate.
또한 미국 특허번호 4,868,261호에서는 노보닐메타크릴레이트를 이용한 광학용 수지가 공지되어 있으나, 여전히 충분한 저흡성을 가지지 못할 뿐만 아니라 열분해온도가 낮아 실제 가공시 분해되어 투명성이 저하되는 단점이 있다.In addition, in US Pat. No. 4,868,261, an optical resin using nobornyl methacrylate is known, but it still does not have sufficient low absorption, and has a disadvantage in that the thermal decomposition temperature is low and the transparency is degraded during actual processing.
본 발명의 목적은 광학용도로써 압출 및 사출 가공시에 수지를 얇은 시트 형태나 렌즈로 제조할 경우 수분 흡수율을 낮추어 변형을 억제하고 또한 기존에 광학용도로 사용되어지는 상용의 PMMA보다 가공온도에서 분해온도가 더욱 높고, 기존의 PMMA수지보다 높은 유리전이온도(Tg)가 요구되며 또한 저흡수성 특성을 가지는 광학용 수지를 제공하는 것이다.An object of the present invention is to reduce the water absorption rate when the resin is manufactured in the form of a thin sheet or lens during extrusion and injection processing for optical use, to suppress deformation and to decompose at a processing temperature than commercially available PMMA conventionally used for optical purposes It is to provide an optical resin having a higher temperature, higher glass transition temperature (T g ) than conventional PMMA resins, and having low water absorption.
상기의 목적을 달성하기 위하여 연구한 결과, 본 발명자들은 메틸메타크릴레이트와 하기식 (I)의 5,5,6의 탄소위치에 알킬기가 치환된 이소보닐메타크릴레이트를 단량체로 이용하여 공중합체를 제조함으로써 현탁중합에서도 간편하고 용이하게 열분해온도가 높은 고내열성 수지를 제조할 뿐만 아니라 압출, 사출 가공에 적합한 저흡수율을 가지는 투명한 신규한 수지를 제조할 수 있음을 알게 되어 본 발명을 완성하였다. As a result of the research to achieve the above object, the present inventors have used a copolymer of methyl methacrylate and isobornyl methacrylate substituted with an alkyl group at a carbon position of 5,5,6 of formula (I) as a monomer. The present invention was completed by finding that it is possible to prepare a high temperature resistant resin having high pyrolysis temperature simply and easily even in suspension polymerization, and to prepare a transparent new resin having a low absorption rate suitable for extrusion and injection processing.
(상기 식에서, R1~R3 는 서로 독립적으로 C1~C3에서 선택되는 알킬기이다)Wherein R 1 to R 3 are each independently an alkyl group selected from C 1 to C 3 .
본 발명을 통해 제조된 수지는 메틸메타크릴레이트와 5,5,6-치환된 이소보닐메타크릴레이트 (I) 단량체를 주성분으로 하고, 열분해온도 저하를 막기 위해 일정량의 알파-치환된 비닐 단량체를 공중합한 중합체를 제공하는 것이다. 본 발명에 사용하는 알파-치환된 비닐 단량체의 예로서는, 메틸아크릴레이트, 에틸아크릴레이트, 스티렌, 5,5,6-트리메틸이소보닐아크릴레이트가 있다. 열분해 온도 저하를 막기 위해서는 최소 1중량%~30중량% 이상이 제조 시에 투입되어야 하나 과량이 투입되었을 때는 본 발명의 목적인 유리전이온도(Tg)의 향상을 꾀할 수 없음으로 인해 바람직하게는 투입되는 총 단량체에 2 ~ 5중량%가 바람직하다. 본 발명에서 메틸메타크릴레이트와 상기 일반식(I)의 단량체 및 알파-치환된 비닐단량체를 동시에 사용하지 않을 경우에는 본 발명이 목적으로 하는 고내열성, 광학투명성 및 저흡수성의 특성을 충분히 발휘될 수 없다.Resin prepared through the present invention is a methyl methacrylate and 5,5,6-substituted isobornyl methacrylate (I) monomers as a main component, in order to prevent the thermal decomposition temperature lowering a certain amount of alpha-substituted vinyl monomer It is to provide a copolymer copolymerized. Examples of alpha-substituted vinyl monomers used in the present invention include methyl acrylate, ethyl acrylate, styrene, 5,5,6-trimethylisobonyl acrylate. At least 1% by weight to 30% by weight or more should be added at the time of manufacture in order to prevent the thermal decomposition temperature from being lowered. However, when the excess amount is added, the glass transition temperature (T g ), which is the object of the present invention, cannot be improved. 2 to 5% by weight is preferred for the total monomers. In the present invention, when methyl methacrylate, the monomer of the general formula (I) and the alpha-substituted vinyl monomer are not used at the same time, the characteristics of high heat resistance, optical transparency and low absorption of the object of the present invention may be sufficiently exhibited. Can't.
본 발명에서 메틸메타크릴레이트는 전체 단량체 조성에 대하여 50~85중량%의 범위로 사용하고, 일반식 (I)의 단량체는 10~40중량%, 알파-치환된 비닐단량체는 1~30중량% 사용한다. 상기 조성비 벗어날 경우 본 발명에서 목적으로 하는 충분한 저흡수율과 고내열성 및 고투명성을 모두 만족하기 어렵다. In the present invention, methyl methacrylate is used in the range of 50 to 85% by weight relative to the total monomer composition, the monomer of the general formula (I) is 10 to 40% by weight, the alpha-substituted vinyl monomer is 1 to 30% by weight use. When the composition ratio is out of the range, it is difficult to satisfy both sufficient low water absorption and high heat resistance and high transparency.
본 발명에서 목적으로 하는 내열성 향상된 투명수지는 흡습저항성이 ASTM D570에 근거하여 포화 흡수율로 평가하며 흡습율은 폴리메틸메타크릴레이트 포화 흡습율인 2.2 중량% 보다 낮아야 하며 바람직하게는 1.8%이하이다. The heat-resistant improved transparent resin aimed at the present invention is evaluated for moisture absorption resistance based on saturation absorption based on ASTM D570, and the moisture absorption rate should be lower than 2.2 wt% of polymethyl methacrylate saturation absorption and preferably 1.8% or less.
내열성은 유리전이온도(Tg)와 열분해온도를 기준으로 평가한다. 유리전이온도는 differential scanning calorimeter (DSC)로 측정하며 110 ℃이상이어야 하며 바람직하게는 120 ℃이상이어야 한다. 열분해온도는 thermogravimetric analyzer (TGA)를 이용하여 측정하며 무게 감소에 대한 1차 미분 피크 온도로 평가하는 것으로 315℃ 이상 이어야 가공 중 분해에 의한 투명성의 저하를 방지한다.Heat resistance is evaluated based on the glass transition temperature (T g ) and the pyrolysis temperature. Glass transition temperature is measured by differential scanning calorimeter (DSC) and should be more than 110 ℃ and preferably more than 120 ℃. The pyrolysis temperature is measured using a thermogravimetric analyzer (TGA) and is evaluated as the first derivative peak temperature for weight reduction. The pyrolysis temperature should be at least 315 ℃ to prevent the degradation of transparency due to decomposition during processing.
압출 및 사출 가공의 용이성은 멜트 플로우 인덱스를 측정함으로써 평가하였다. 평가 방법은 폴리메틸메타크릴레이트와 동일하게 230 ℃에서 3.8 kg 하중 하에서 10분 동안 흐른 수지의 무게(g)를 측정한다.Ease of extrusion and injection processing was evaluated by measuring the melt flow index. The evaluation method measures the weight (g) of the resin which flowed for 10 minutes under a 3.8 kg load at 230 ° C. in the same manner as polymethyl methacrylate.
수지의 광학특성인 전광선 투과율은 제조된 수지를 3.2 mm 두께로 사출가공한 후 ASTM D-1003에 의거하여 측정하였다. The total light transmittance, which is an optical property of the resin, was measured according to ASTM D-1003 after injection molding the prepared resin to a thickness of 3.2 mm.
본 발명에 기재한 투명내열성수지는 기존의 자유라디칼 중합법을 이용하여 괴상중합, 용액중합, 현탁중합, 유화중합으로 제조될 수 있으나 이물에 의한 오염을 최소화하기 위해서는 괴상중합이나 현탁중합이 바람직하다. The transparent heat resistant resin described in the present invention may be prepared by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization using conventional free radical polymerization, but bulk polymerization or suspension polymerization is preferable to minimize contamination by foreign substances. .
중합개시제로는 자유라디칼 중합법으로 폴리메틸메타크릴레이트를 제조할 때 사용하는 상용의 과산화물 개시제와 아조계열의 개시제를 사용한다. As the polymerization initiator, a commercially available peroxide initiator and an azo initiator used in the production of polymethyl methacrylate by a free radical polymerization method are used.
고분자의 분자량을 제어하기 위하여 도입되는 사슬이동제(chain transfer agent)는 메르캅탄 계열이 있으나 본 발명의 조건을 만족시키기 위하여서는 노말옥틸메르캅탄을 사용하는 것이 좋다. The chain transfer agent introduced to control the molecular weight of the polymer has a mercaptan series, but in order to satisfy the conditions of the present invention, it is preferable to use normaloctyl mercaptan.
현탁중합은 물 매질에 단량체를 분산시켜 제조하며 이 때 분산안정성을 위해 수용성 고분자분산제 및 이의 분산조제를 사용하며, 이는 이 기술분야에서 통상적으로 사용하는 것이라면 크게 제한하지 않으며, 또한 본 발명에서는 필요할 경우 pH를 조절하기 위한 이 분야에서 일반적으로 사용하는 완충염을 투입하여 사용한다. Suspension polymerization is prepared by dispersing a monomer in a water medium, and at this time, a water-soluble polymer dispersant and a dispersing aid thereof are used for dispersion stability, which is not particularly limited as long as it is commonly used in the art, and in the present invention, if necessary Buffer salt commonly used in this field to adjust pH is used.
본 발명에 따라 제조되는 광학용 중합체는 공지의 가공방법, 예를 들면 압출, 사출, 프레스몰딩, 케스팅 등의 방법으로 시트나 광학용 렌즈 및 광학디스크용 기판을 제조한다. The optical polymer prepared according to the present invention manufactures a sheet, an optical lens, and an optical disk substrate by a known processing method, for example, extrusion, injection, press molding, casting, or the like.
하기는 본 발명의 바람직한 실시예에 대해서 기재하는 바, 본 발명이 하기의 실시 예에 의하여 제한되는 것은 아니다.The following describes a preferred embodiment of the present invention, the present invention is not limited by the following examples.
[실시예 1~4 및 비교예 1~9][Examples 1-4 and Comparative Examples 1-9]
5리터 반응기에 증류수 2000g을 투입하고 분산제로 나트륨이 치환된 메틸메타크릴산-메틸메타크릴레이트 공중합체 0.12g, 완충염으로 NaH2PO4·2H2O 1.2g, Na2HPO4·12H2O 1.8g을 투입하여 용해한다. 하기 표 1에 기재된 단량체 1000 g에 대하여 표 1에 기재된 사슬이동제인 노말옥틸메르캅탄 및 개시제로 1,1,3,3-테트라메틸부틸퍼옥시-2-에틸헥사노에이트 3g 투입하고 단량체 혼합물을 450rpm의 교반하에 서 수상에 분산시켰다. 반응온도 80℃로 중합을 수행하였으며 중합피크가 발생하고 30분 후에 30℃로 냉각하였다. 중합하여 얻어진 비드는 증류수로 3회 세척과 탈수를 반복하였으며 비드는 오븐에서 건조하였다.2000 g of distilled water was added to a 5 liter reactor, 0.12 g of methyl methacrylate-methyl methacrylate copolymer substituted with sodium as a dispersant, 1.2 g of NaH 2 PO 4 · 2H 2 O as a buffer salt, Na 2 HPO 4 · 12H 2 Dissolve by adding 1.8 g of O. 3 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added as an initiator and normal octyl mercaptan as a chain transfer agent shown in Table 1 with respect to 1000 g of the monomer shown in Table 1. The dispersion was dispersed in the water phase under stirring at 450 rpm. The polymerization was carried out at a reaction temperature of 80 ℃ and cooled to 30 ℃ 30 minutes after the polymerization peak occurs. The beads obtained by polymerization were washed and dehydrated three times with distilled water, and the beads were dried in an oven.
얻어진 비드를 이용하여 사출시편을 제조한 후 표 2와 같이 물성을 측정하였다.After the injection specimen was prepared using the obtained beads, the physical properties were measured as shown in Table 2.
<표 1> 중합 처방TABLE 1 Polymerization prescription
*)5,5,6-트리메틸이소보닐메타크릴레이트 대신 노보닐메타크릴레이트를 사용 *) Use of norbornyl methacrylate instead of 5,5,6-trimethylisobonyl methacrylate
<표 2> 제조된 시트의 물성<Table 2> Physical Properties of the Prepared Sheet
*)5,5,6-트리메틸이소보닐메타크릴레이트 대신 노보닐메타크릴레이트를 사용 *) Use of norbornyl methacrylate instead of 5,5,6-trimethylisobonyl methacrylate
상기의 실시예로부터 본 발명의 실시예 1~4는 비교예 1~9에 비하여 광투과율과 포화 흡수율을 전반적으로 우수하게 유지하면서, 비교예에 비하여 열분해 온도가 315℃이상으로 매우 높아 실제 사용 조건에서 열분해를 방지하면서, 가공 안정성과 투과도가 높은 제품을 제조할 수 있어 광학 용도의 재료로 사용가능함을 알 수 있었다.Examples 1 to 4 of the present invention from the above examples, while maintaining the overall excellent light transmittance and saturated absorption rate compared to Comparative Examples 1 to 9, compared to the comparative example very high thermal decomposition temperature of 315 ℃ or more than the actual use conditions It can be seen that it is possible to manufacture a product with high processing stability and transmittance while preventing pyrolysis, and thus it can be used as a material for optical applications.
특히 알파비닐단량체를 사용치 않고 메틸메타크릴레이트와 노보닐메타크릴레 이트만을 사용하였을 때에는 열분해 온도가 낮아 내열 특성이 열세함으로 나타났다. In particular, when only methyl methacrylate and norbornyl methacrylate were used without using an alpha vinyl monomer, the thermal decomposition temperature was low, indicating poor heat resistance.
또한 메틸아크릴레이트의 사용함량이 많아지면 높은 열분해 온도를 갖는 특성을 기대할 수 있지만 유리전이온도(Tg)를 떨어뜨리기 때문에 상기 실시예에서와 같이 적절한 중량%를 조절 사용하여 높은 열분해 온도와 높은 유리전이온도(Tg) 두 가지 특성을 얻고자 하였다. 특히 5,5,6-트리메틸이소보닐아크릴레이트의 호모 폴리머의 유리전이온도(Tg)는 94℃로 메틸아크릴레이트의 호모 폴리머 유리전이온도(Tg)보다 높기 때문에 5,5,6-트리메틸이소보닐아크릴레이트의 사용으로 비슷한 열분해 특성을 가지면서도 유리전이온도(Tg) 떨어짐을 방지할 수 있었다. In addition, if the amount of methyl acrylate is increased, it can be expected to have a characteristic of having a high pyrolysis temperature, but the glass transition temperature (T g ) is lowered, so that a high pyrolysis temperature and a high glass can be controlled by controlling an appropriate weight% as in the above embodiment. Two characteristics of transition temperature (T g ) were obtained. In particular, the glass transition temperature (T g ) of the homopolymer of 5,5,6-trimethylisobonyl acrylate is 94 ° C., which is higher than the homopolymer glass transition temperature (T g ) of methyl acrylate. The use of trimethylisobonyl acrylate prevented the glass transition temperature (T g ) from dropping while having similar thermal decomposition properties.
상기의 실시예와 비교예를 통하여 폴리메틸메타크릴레이트와 비교하여 열분해온도가 저하되지 않으며 유리전이온도(Tg)가 향상되고 수분에 대한 저항성이 향상된 광학용도의 투명내열성 수지를 제공할 수 있다.Compared to the polymethyl methacrylate, the thermal decomposition temperature is not lowered, the glass transition temperature (T g ) is improved, and the resistance to water can be improved. .
본 발명에 따른 구성을 채택하는 경우 높은 유리전이온도(Tg), 저흡습성과 우수한 투명성의 특성을 가지면서, 열분해 온도가 315℃ 이상을 유지하여 높은 온도에서 가공 안정성과 열분해 안정성이 향상된 광학용도의 투명 내열성수지로 사용가능함을 확인할 수 있었다.In the case of adopting the configuration according to the present invention, it has the characteristics of high glass transition temperature (Tg), low hygroscopicity and excellent transparency, and the thermal decomposition temperature is maintained at 315 ° C. or higher to improve processing stability and thermal decomposition stability at high temperatures. It could be confirmed that the transparent heat-resistant resin can be used.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050055481A KR100645833B1 (en) | 2005-06-27 | 2005-06-27 | Transparent heat-resistant resin for optical use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050055481A KR100645833B1 (en) | 2005-06-27 | 2005-06-27 | Transparent heat-resistant resin for optical use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR100645833B1 true KR100645833B1 (en) | 2006-11-14 |
Family
ID=37654579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020050055481A KR100645833B1 (en) | 2005-06-27 | 2005-06-27 | Transparent heat-resistant resin for optical use |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100645833B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200013899A (en) * | 2018-07-31 | 2020-02-10 | 엘지이노텍 주식회사 | Contact lenses module for presbyopia |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04254928A (en) * | 1991-02-07 | 1992-09-10 | Mitsubishi Rayon Co Ltd | Methacrylic resin for optical information recording medium |
| JPH06263827A (en) * | 1993-03-15 | 1994-09-20 | Mitsubishi Rayon Co Ltd | Transparent resin composition |
| KR100281590B1 (en) | 1994-11-09 | 2001-02-15 | 메리 이. 보울러 | Surface-Active Macromonomers |
| JP2003215325A (en) | 2002-01-25 | 2003-07-30 | Kureha Chem Ind Co Ltd | Optical material |
-
2005
- 2005-06-27 KR KR1020050055481A patent/KR100645833B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04254928A (en) * | 1991-02-07 | 1992-09-10 | Mitsubishi Rayon Co Ltd | Methacrylic resin for optical information recording medium |
| JPH06263827A (en) * | 1993-03-15 | 1994-09-20 | Mitsubishi Rayon Co Ltd | Transparent resin composition |
| KR100281590B1 (en) | 1994-11-09 | 2001-02-15 | 메리 이. 보울러 | Surface-Active Macromonomers |
| JP2003215325A (en) | 2002-01-25 | 2003-07-30 | Kureha Chem Ind Co Ltd | Optical material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200013899A (en) * | 2018-07-31 | 2020-02-10 | 엘지이노텍 주식회사 | Contact lenses module for presbyopia |
| KR102564435B1 (en) | 2018-07-31 | 2023-08-08 | 엘지이노텍 주식회사 | Contact lenses module for presbyopia |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100885819B1 (en) | Branched acrylic copolymer with high refractive index and preparation method thereof | |
| JPH059359A (en) | Polymer composition | |
| JPH06313089A (en) | Polymer composition | |
| KR20090076753A (en) | Transparent resin composition | |
| KR100868298B1 (en) | Methacrylic Resin with Excellent Thermal discolor and Transparency and Method of Preparing the Same | |
| KR100645833B1 (en) | Transparent heat-resistant resin for optical use | |
| EP0208291B1 (en) | Heat-resistant methacrylic resin composition | |
| KR101856465B1 (en) | The environmental-friendly Windows Profile compositions with enhanced heat resistance and color | |
| KR101142261B1 (en) | Methacrylic copolymer having good chemical resistance and heat resistance | |
| US8933185B2 (en) | Acrylic resin having excellent transparency, fluidity and scratch-resistance | |
| JPH061903A (en) | Polymer composition | |
| KR100725934B1 (en) | A manufacturing method of acrylic resin with the superior thermal stability and the easy molecular weight control | |
| KR100781125B1 (en) | Methacrylic resin having good discoloration-resistance and thermal property and method for preparing the same | |
| JPH03167245A (en) | Methacrylic resin composition with reduced coloration | |
| JP7467320B2 (en) | Signal lens and lens cover | |
| JPH02175711A (en) | Optical resin and its production | |
| KR20130063455A (en) | Acrylic copolymer with excellent heat resistance and method for preparing the same | |
| JP3891177B2 (en) | Pseudo-crosslinked resin composition, molding material, sheet or film obtained therefrom, and optical component | |
| JPS63234009A (en) | Methacrylic resin composition | |
| WO2021106687A1 (en) | Thermoplastic copolymer and resin molded body | |
| JPS6026014A (en) | Lowly hygroscopic methacrylic resin | |
| JPH04106113A (en) | Heat-resistant methacrylic resin | |
| CN117801151A (en) | Hard vinyl chloride copolymer, method for producing the same, vinyl chloride resin composition, and resin product | |
| KR100748277B1 (en) | Excellent Sheet appearance Methacrylic Resin and Method of Preparing the Same | |
| JPH0386712A (en) | Methacrylic resin with low birefringence and low hygroscopicity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20121031 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20130930 Year of fee payment: 8 |
|
| FPAY | Annual fee payment |
Payment date: 20151002 Year of fee payment: 10 |
|
| FPAY | Annual fee payment |
Payment date: 20161107 Year of fee payment: 11 |
|
| FPAY | Annual fee payment |
Payment date: 20171107 Year of fee payment: 12 |
|
| FPAY | Annual fee payment |
Payment date: 20181107 Year of fee payment: 13 |
|
| FPAY | Annual fee payment |
Payment date: 20191107 Year of fee payment: 14 |