KR100487025B1 - Photo-curable resin composition for optical waveguide and optical waveguide prepared therefrom - Google Patents

Photo-curable resin composition for optical waveguide and optical waveguide prepared therefrom Download PDF

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KR100487025B1
KR100487025B1 KR10-2002-0011002A KR20020011002A KR100487025B1 KR 100487025 B1 KR100487025 B1 KR 100487025B1 KR 20020011002 A KR20020011002 A KR 20020011002A KR 100487025 B1 KR100487025 B1 KR 100487025B1
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acrylate
meth
diisocyanate
optical waveguide
resin composition
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KR20030071343A (en
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김말순
오우정
변현호
김정욱
한관수
오정현
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주식회사 루밴틱스
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/50Polyethers having heteroatoms other than oxygen
    • C08G18/5003Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/671Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Abstract

본 발명은 (A) 하기 화학식 1로 표시되는 불소 치환된 광중합형 우레탄 올리고머, (B) 1개 이상의 (메타)아크릴로일기를 갖는 (메타)아크릴레이트(B 1 ) 또는 1개 이상의 에폭시기를 갖는 광반응성 모노머(B 2 ), 및 (C) 광중합 개시제를 포함하는 광도파로용 광경화성 수지 조성물에 관한 것으로, 상기 조성물은 낮은 복굴절률 및 적은 광손실을 나타내고, 광투과도, 열적 안정성 및 장기 저장성이 우수하며, 또한 상기 수지 조성물을 이용하여 마이크로 트랜스퍼 몰딩 기법에 의해 간편하고 대량생산이 용이하게 광도파로를 제조할 수 있다: The present invention (A) to a fluorine-substituted photopolymerizable urethane oligomer, (B) a (meth) acrylate (B 1) or one or more epoxy groups having a group with one or more (meth) acrylate represented by the general formula (1) photoreactive monomer (B 2), and (C) relates to the optical waveguides a photo-curable resin composition containing a photopolymerization initiator, the composition shows a low birefringence and a low optical loss, the light transmittance, thermal stability and long-term storability is excellent, and it can also be easier and by the micro-transfer molding method using the resin composition producing the optical waveguide to facilitate mass production:
상기 식에서, Wherein
R 1 은 -CH 2 O- 또는 -CH 2 (OCH 2 CH 2 ) m O-이고, R 2 는 탄소수가 6 ∼ 100개로 구성된 방향족 또는 지방족 탄화수소기이고, R 3 은 탄소수가 2 ∼ 10개로 구성된 방향족 또는 지방족 탄화수소기이고, R 4 는 메타(아크릴레이트)기 또는 에폭시기이다. R 1 is -CH 2 O- or -CH 2 (OCH 2 CH 2) m O- and, R 2 is the number of carbon atoms is an aromatic or aliphatic hydrocarbon group consisting of 6-100 pieces, and, R 3 is composed of a carbon number of 2 to 10 pieces an aromatic or aliphatic hydrocarbon group, R 4 is a meth (acrylate) group, or an epoxy group.

Description

광도파로용 광경화성 수지 조성물 및 이로부터 제조된 광도파로{PHOTO-CURABLE RESIN COMPOSITION FOR OPTICAL WAVEGUIDE AND OPTICAL WAVEGUIDE PREPARED THEREFROM} The prepared optical waveguide, and a photo-curable resin composition from which the optical waveguide {PHOTO-CURABLE RESIN COMPOSITION FOR OPTICAL WAVEGUIDE AND OPTICAL WAVEGUIDE PREPARED THEREFROM}

본 발명은 광도파로 소자용 고분자에 관한 것으로서, 보다 구체적으로 저 광진행 손실의 광경화형 (메타)아크릴기 또는 에폭시기를 갖는 불소치환 광경화형 우레탄 올리고머의 제조와 이를 이용한 광도파로용 광경화형 수지 조성물의 제조에 관한 것이며 아울러 상기 조성물을 이용하여 마이크로 몰딩 기법에 의한 고분자 광도파로의 제조방법에 관한 것이다. The present invention is an optical waveguide as elements polymer on for, and more particularly to a low photo-curing of the light proceeding loss (meth) acrylic group or a fluorine-substituted photocurable urethane prepared with the composition for the optical waveguide, photo-curing type resin using the same of the oligomer having an epoxy group It relates to the manufacture as well as to the use of the composition according to the method of manufacturing the polymer optical waveguide by the micro-molding technique.

향후 우리 사회에서 접하게 될 정보화시대에 필요한 고선명·고화질의 동영상, 전자상거래 및 화상통신 등의 무수한 정보량의 이동에 있어서 광(光)통신 산업은 필수 불가결한 전달매체로 자리잡게 되었다. Light (光) in the mobile future countless amount of information, including high-definition, high-definition video, e-commerce and video communications for the information age to be encountered in our society communications industry has Puts itself as an indispensable communication media. 광은 전자에 비해 속도가 훨씬 빨라 일정시간 내에 더 많은 정보를 전달할 수 있으므로 각광을 받고 있다. The light can pass more information within a certain period of time the speed is much faster than the electrons are under the spotlight. 광통신 시스템에는 다중, 역다중화 소자, 광스위치, 광증폭기, 광검출기, 광원 등의 여러 부품이 필요한데, 현재 그 성능을 개선시키기 위한 다양한 설계 및 재료의 개선이 이루어지고 있다. Optical communication system has a multi-demultiplexing device, it requires a number of components such as optical switches, optical amplifiers, optical detectors, a light source, there is now achieved a variety of designs and improvements of materials to improve their performance.

우선 재료적인 측면에서 보면, 상기 광통신 부품 중 광스위치를 비롯한 광도파로의 경우 실리카를 이용하여 제조되고 있는데, 실리카는 광섬유와 동일한 물질이므로 광섬유와의 접속시 접속단면에서의 반사가 적고 물질 자체의 광손실 또한 0.01 dB/cm 정도로 그 값이 매우 작은 특성을 가진다. First, look at the material point of view, there have been manufactured by using the case of silica of the optical waveguide including the optical switch of the optical component, silica is light because it is the same material as the optical fiber less reflections at the connection section during connection of the optical fiber material itself, In addition, the loss value, so 0.01 dB / cm has a very small characteristic. 그러나 실리카를 이용하여 광도파로를 제조할 경우, 매우 높은 고온의 에너지가 가해짐에 따라 제작 후 냉각시에 실리카의 열팽창계수 차이로 인해 열응력을 받고 이러한 응력에 의해 물질 자체의 편광의존도가 심화되며 굴절률 또한 달라지게 된다. However, when producing the optical waveguide using the silica, so that the high-temperature energy is applied under a thermal stress due to thermal expansion coefficient difference between the silica during the post-production cooling according to the load, and the polarization dependence of the substance by such stress deepening In addition, the refractive index become different.

이를 개선하기 위해 유기 고분자소재의 연구가 활발히 진행되었다. To improve this, it was actively studied in the organic polymer material. 유기 고분자 소재는 무기 재료나 반도체에 비해 분자 화학에 의해서 물질의 성능을 쉽게 제어/합성할 수 있고, 저렴한 가격으로 인해 경제성이 좋으며, 응답속도가 빠르고, 광대역폭이 수십 내지 수백 Tbps 정도로 매우 높으며, 이를 이용한 소자 제조시 저온에서 수행될 수 있으며, 공정이 단순하고, 가공성이 좋으며, 집적화가 유리하다는 우수성을 가진다. Organic polymer materials compared to inorganic materials or semiconductors can be easily controlled / synthesized the performance of the material by molecular chemistry, affordable good due to the price affordable, fast, responsive, and very high, so the bandwidth tens to hundreds of Tbps, this can be carried out at a low temperature when using a device manufacturing process is simple, good processability, has the superiority that the integrated glass. 이러한 우수한 특성에도 불구하고, 유기 고분자 물질은 열적 불안정성 및 광통신 파장영역에서의 큰 광전송 손실로 인해 상용화되지 못했었다. In spite of these excellent properties, and the organic polymer material had not been commercialized because of a large optical transmission loss in the thermal instability, and the optical communication wavelength region.

일반적으로 평면 도파로형 광소자 및 광 상호연결(Optical Interconnection)에 사용되는 고분자 재료는 열안정성, 광통신 파장영역에서의 낮은 광 손실, 미세한 굴절률의 제어능력, 낮은 복굴절률, 다양한 기판에 대한 접착성, 다양한 적층성, 치수안정성 및 유연성, 미세 광부품과의 용이한 정렬, 저가 등의 조건이 요구된다. Generally planar waveguide type optical device and an optical interconnection polymer material used in (Optical Interconnection) is bonded to the thermally stable, low optical loss in the optical communication wavelength region, the control ability of the fine refractive index, low birefringence, various substrates Castle, various lamination property, dimensional stability and flexibility, easy alignment of the micro-optical component, conditions for low-cost and so on is required. 이중 광손실 문제를 해결하기 위해 불소치환 고분자에 대한 연구가 활발히 진행되고 있으며, 이는 분자내 CH 결합에서 중수소나 불소로 치환함으로써 광통신 영역인 1.0∼1.8㎛ 파장대에서의 큰 적외흡수 파장을 장파장으로 이동시켜 광통신 영역에서의 광흡수를 최소화할 수 있다. And dual are to address the light loss problem, research on the fluorine-substituted polymer actively, which move a large infrared absorption wavelength in the wavelength band of optical communication area by 1.0~1.8㎛ substituted with deuterium or fluorine in the CH-binding molecules with long wavelength by it is possible to minimize the light absorption in the optical domain.

일본의 NTT사에서는 수동 광소자용 고분자 물질로서 종래의 PMMA를 사용하거나 중수소화된 MMA(deutrated methacrylate)와 중수소화된 퍼플루오로 MMA(deutrated perfluoro methacrylate) 단량체를 여러 조성비로 공중합하여 굴절률이 잘 조절된 물질을 클래딩 및 코아로 이용함으로써 1.3㎛에서 광손실이 0.08 dB/cm로 아주 우수한 저손실 광소자를 구현한 바 있다. The NTT company in Japan with a passive optical device Edition polymer material using the conventional PMMA, or heavy water with a MMA (deutrated methacrylate) and deuterated digestion perfluoro by copolymerizing (deutrated perfluoro methacrylate) MMA monomers in several composition refractive index is well controlled by using a material with a cladding and core can have a light loss implement a very excellent low-loss optical device as 0.08 dB / cm at 1.3㎛ bar. 그러나 PMMA계는 Tg가 100℃ 정도로서 열안정성이 낮은 단점을 가진다[이마무라(S. Imamura) 등, Electronics Letters , 27 , 1342, 1991]. However, PMMA has a Tg of system has the disadvantage that the thermal stability, low degree 100 ℃ [Imamura (S. Imamura), etc., Electronics Letters, 27, 1342, 1991]. 이러한 PMMA의 낮은 열안정성을 극복하기 위해 NTT사에 의해 개발된 퍼플루오르화된 폴리이미드(perfluorinated polyimide)는 큰 복굴절로 인해 편광독립이 어렵고, 비교적 큰 흡습성으로 인한 광손실이 발생하는 문제점이 있다[마쓰우라(T. Matsuura) 등, Electronics Letters , 29 (3), 269, 1993]. To overcome the lower thermal stability of these PMMA perfluorinated polyimide (perfluorinated polyimide) developed by NTT company has a problem that the light loss occurs, it is difficult to polarization independence due to large birefringence, due to the relatively high moisture absorption [ Matsuura (T. Matsuura), etc., Electronics Letters, 29 (3) , 269, 1993].

미국의 얼라이드 시그널(Allied Signal)사에 의해 발표된 UV-경화형 플루오르화된 아크릴레이트(UV-curable fluorinated acrylate)는 아크릴레이트의 광가교(photo-crosslinking) 특성을 이용하여 350℃ 이상의 열안정을 확보하였으며, 1.3㎛ 및 1.55㎛에서의 광손실이 각각 0.03dB/cm 및 0.05dB/cm이고, 1.3에서 1.6까지의 연속적인 굴절률 조절이 가능하며, 복굴절이 0.0008 정도로 편광 독립되었다[엘다다(L. Eldada) 등, J. Lightwave Technology , 14 (7), 1704, 1996]. The UV- curing a fluorinated acrylate (UV-curable fluorinated acrylate) published by the Company Allied Signal (Allied Signal) in the US by using a photo-crosslinking (photo-crosslinking) characteristic of the acrylate product with at least 350 ℃ heat stability was, 1.3㎛ and a light loss, respectively 0.03dB / cm and 0.05dB / cm at 1.55㎛, allows continuous adjustment of the refractive index from 1.3 to 1.6, and polarization was independent so the birefringence 0.0008 [Eldar is (L. Eldada), etc., J. Lightwave Technology, 14 (7 ), 1704, 1996].

한편, 삼성전자에 의해 발표된, 주사슬의 디안하이드라이드(dianhydride)에 불소(CF)가 치환되고 디아민에 염소(C-Cl)가 치환된 폴리이미드 및 불소와 염소가 치환된 폴리머는 복굴절이 큰 단점을 가지며[한(K. Han) 등, Polym. On the other hand, the presented by Samsung, state dianhydride (dianhydride) are fluorine (CF) is substituted for the diamine of the polyimide, and the polymer is substituted with a fluorine and chlorine Chlorine (C-Cl) is substituted in the chain is the birefringence It has a major disadvantage - a (Han K.), etc., Polym. Bull. Bull. 41 , 455, 1998], 한국전자통신연구원에서 발표한, 열경화에 의해 가교된 불소 치환 폴리아릴렌에테르는 열안정성면에서는 우수하지만 열경화 방식이라 생산성이 낮다[이(HJ Lee) 등, J. Polym, Sci., Polym. 41, 455, 1998, Korea, published by the Electronics and Telecommunications Research Institute, the fluorine-substituted cross-linked by a thermosetting polyarylene ether is the productivity low as excellent, but heat curing method, if the thermal stability [the (HJ Lee) et al., J . Polym, Sci., Polym. Chem., 37 , 2355, 1999]. Chem., 37, 2355, 1999 ]. 대한민국 특허출원 제1999-32681호에는 폴리이미드의 주사슬에 불소 치환된 방향족 그룹을 겉사슬에 도입함으로써 등방성 특성을 가지는 불소 치환된 폴리이미드가 개시되어 있으며, 최근에는 광주과학기술원(KJIST)에서 열경화에 의해 가교된 불소 치환 폴리아릴렌에테르설파이드(Cross-linkable Fluorinated Poly(arylene ether sulfide))를 개발하여 발표한 바 있다[강(JW Kang)등, J. Lightwave Tech ., 19 (6), 872, 2001]. Republic of Korea Patent Application No. 1999-32681 discloses a can is a fluorine substituted polyimide has isotropic properties disclosed by introducing a fluorine-substituted aromatic groups in the main chain of the polyimide on the surface chains, in recent years, heat from Gwangju Institute of Science and Technology (KJIST) is one to develop a fluorinated polyarylene ether sulfides (Cross-linkable fluorinated poly (arylene ether sulfide)) crosslinked with the cured release bar [river (JW Kang), etc., J. Lightwave Tech., 19 ( 6), 872, 2001].

한편, 종래에 광도파로를 제작하는 기술로서 포토리소그래피 (Photolithography) 방법이 많이 이용되고 있는데, 이는 포토리지스트 재료를 코어 위에 스핀코팅 한 뒤 원하는 도파로 형태를 가진 마스크를 이용하여 패턴을 형성하고 유도결합플라즈마를 이용하여 코어 재료를 건식 식각하는 단계로 구성된다. On the other hand, there is a photolithographic (Photolithography) method is used much as a technology for manufacturing an optical waveguide in the art, which the photoresist material a spin coating after forming a pattern by using a mask having the desired waveguide shape and inductive coupling over the core using the plasma consists of a core material in the step of dry etching. 그러나, 이 방법은 제작 시간이 많이 소요되며, 또한 코어의 크기가 4∼8 ㎛ 정도인 단일모드 광도파로를 제작할 경우에는 식각이 비교적 용이하나, 다중모드 광도파로 제조시에는 40 ㎛ 이상의 깊이로 식각하여야 하는 문제점을 갖는다. However, this method takes a lot of production time, and when the size of the core creating a single mode optical waveguide of about 4~8 ㎛ is etched is relatively easy one, the multi-mode at the time of manufacturing the optical waveguide by etching more deeply 40 ㎛ It has a problem that must be.

이에 따라, 본 발명의 목적은 광진행 손실이 적고, 광경화에 의한 내화학성 및 열안정성이 향상되며, 낮은 복굴절률을 가지는 저가의 광도파로용 수지 조성물 및 상기 수지 조성물을 코아층 및 클래딩층으로 포함하며 마이크로 트랜스퍼 몰딩(micro-transfer molding) 방법을 이용함으로써 간편하고 대량생산이 용이한 소자의 제조방법을 제공하기 위한 것이다. Accordingly, it is an object of the present invention is less light proceeding lost, the resin composition and the resin composition for use in chemical and thermal stability are improved, and cost of the optical waveguide having a low birefringence due to the photo-curing the core layer and the cladding layer includes and is to provide a simple and a manufacturing method of a device is easy to mass-produced by using a micro-transfer molding (micro-transfer molding) method.

상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 불소 치환된 광중합형 우레탄 올리고머(A)를 제공하며, 또한 상기 (A) 불소 치환된 광중합형 우레탄 올리고머, (B) 광반응성 모노머, (C) 광중합개시제, (D) 중합방지제 및 (E) 산화방지제를 포함하는, 광도파로용 광경화성 수지 조성물을 제공한다: In order to achieve the above object, the present invention provides a fluorine-substituted photopolymerizable urethane oligomer (A) represented by the following general formula (1), and the (A) fluorine-substituted photopolymerizable urethane oligomer, (B) a photoreactive monomer, (C) provides a photopolymerization initiator, (D) a polymerization inhibitor, and (E) optical path comprising an antioxidant, an optical waveguide-curing resin composition:

화학식 1 Formula 1

상기 식에서, Wherein

R 1 은 -CH 2 O- 또는 -CH 2 (OCH 2 CH 2 ) m O-이고, R 2 는 탄소수가 6 ∼ 100개로 구성된 방향족 또는 지방족 탄화수소기이고, R 3 은 탄소수가 2 ∼ 10개로 구성된 방향족 또는 지방족 탄화수소기이고, R 4 는 메타(아크릴레이트)기 또는 에폭시기이다. R 1 is -CH 2 O- or -CH 2 (OCH 2 CH 2) m O- and, R 2 is the number of carbon atoms is an aromatic or aliphatic hydrocarbon group consisting of 6-100 pieces, and, R 3 is composed of a carbon number of 2 to 10 pieces an aromatic or aliphatic hydrocarbon group, R 4 is a meth (acrylate) group, or an epoxy group.

본 발명은 또한 상기 광도파로용 광경화성 수지 조성물을 이용한 고분자 광도파로 및 이의 제조방법을 제공한다. The invention also provides a polymeric optical waveguide and a method using a photo-curable resin composition for the optical waveguide.

이하 본 발명을 상세히 설명한다. Hereinafter the present invention will be described in detail.

(A) 불소 치환된 광중합형 우레탄 올리고머 (A) a fluorine-substituted photopolymerizable urethane oligomer

본 발명에서 사용되는 광중합형 우레탄 올리고머(A)는 (a) 폴리올, (b) 디이소시아네이트(Diisocyanate), (c) 히드록시 (메타)아크릴레이트(Hydroxy (Meth)acrylate) 또는 히드록시 에폭시(Hydroxy Epoxy), (d) 우레탄 반응 촉매 및 (e) 중합개시제를 반응시켜 제조된다. Photopolymerizable urethane oligomer (A) used in the present invention are (a) polyols, (b) diisocyanate (Diisocyanate), (c) hydroxy (meth) acrylate (Hydroxy (Meth) acrylate) or a hydroxyalkyl epoxy (Hydroxy Epoxy), (d) is prepared by reacting a urethane reaction catalyst, and (e) a polymerization initiator.

(a) 폴리올 (A) a polyol

상기 불소 치환된 광중합형 우레탄 올리고머(A)의 제조에 사용되는 폴리올(a)은 분자량이 500 내지 10,000이 바람직하며, 불소 치환된 퍼플루오로 폴리에테르폴리올(Perfluoropolyether polyol) 또는 퍼플루오로 폴리에테르 말단에 비불소폴리에테르기를 갖는 폴리올이 바람직하다. Polyol (a) used for the preparation of the photopolymerizable urethane oligomer (A) with the fluorine substitution and the molecular weight is preferably 500 to 10,000, a fluorine-substituted perfluoroalkyl polyether polyol (Perfluoropolyether polyol) or perfluoro polyether-terminal it is a polyol having a non-fluorinated polyether is preferred. 상기 폴리올(a)은 광중합형 우레탄 올리고머(A) 제조용 조성물의 20 내지 80 중량%의 함량으로 사용되는 것이 바람직하다. The polyol (a) is preferably used in an amount of 20 to 80% by weight of a photopolymerizable urethane oligomer for producing (A) composition.

(b) 디이소시아네이트 (B) a diisocyanate

본 발명의 불소 치환된 광중합형 우레탄 올리고머(A)의 제조에 사용되는 디이소시아네이트(b)는 이소포론 디이소시아네이트(Isophoron diisocyanate, IPDI), 헥산 디이소시아네이트(1,6-Hexane Diisocyanate, HDI), 옥타메틸렌 디이소시아네이트(1,8-Octamethylene Diisocyanate), 테트라메틸크실렌 디이소시아네이트(Tetramethyl xylene diisocyanate, TMXDI), 4,4'-디시클로헥실메탄 디이소시아네이트(4,4'-Dicyclohexylmethane diisocyanate, HMDI), 4,4'-디페닐메탄 디이소시아네이트(4,4'-Diphenylmethane diisocyanate), 3,3'-디메틸 4,4'-비페닐렌 디이소시아네이트(3,3'-Dimethyl-4,4'-biphenylene diisocyanate), 3,3'-디메틸디페닐메탄-4,4'-디이소시아네이트(3,3'-Dimethyldiphenylmethane-4,4'-diisocyanate), 4-브로모-6-메틸-1,3-페닐렌 디이소시아네이트(4-Bromo-6-methyl-1,3-phenylene diisocyanate), 4-클로로-6-메틸-1,3-페닐렌 디이소시아네이트(4-Chloro-6-met D used in the preparation of a photopolymerizable urethane oligomer (A) a fluorine-substituted isocyanate of the present invention (b) is isophorone diisocyanate (Isophoron diisocyanate, IPDI), hexane diisocyanate (1,6-Hexane Diisocyanate, HDI), octamethylene diisocyanate (1,8-Octamethylene diisocyanate), tetramethyl xylene diisocyanate (tetramethyl xylene diisocyanate, TMXDI), 4,4'- dicyclohexylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate, HMDI), 4, 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), 3,3'- dimethyl-4,4'-diisocyanate (3,3'-dimethyl-4,4'-biphenylene diisocyanate) , 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate (3,3'-dimethyldiphenylmethane-4,4'-diisocyanate), 4- bromo-6-methyl-1,3-phenylene-di isocyanate (4-Bromo-6-methyl-1,3-phenylene diisocyanate), 4- chloro-6-methyl-1,3-phenylene diisocyanate (4-chloro-6-met hyl-1,3-phenylene diisocyanate), 폴리(1,4-부탄디올) 톨릴렌 2,4-디이소시아네이트 터미네이티드(Poly(1,4-butanediol) tolylene 2,4-diisocyanate terminated), 폴리(1,4-부탄디올) 이소포론 디이소시아네이트 터미네이티드(Poly(1,4-butanediol) isophorone diisocyanate terminated), 폴리(에틸렌 아디페이트) 톨릴렌 2,4-디이소시아네이트 터미네이티드(Poly(ethylene adipate)tolylene 2,4-diisocyanate terminated), 폴리[1,4-페닐렌 디이소시아네이트-코-폴리(1,4-부탄올)]디이소시아네이트(Poly[1,4-phenylene diisocyanate- co -poly(1,4-butanol)] diisocyanate), 폴리헥사메틸렌 디이소시아네이트(Poly(hexamethylene diisocyanate), 폴리프로필렌글리콜 톨릴렌 2,4-디이소시아네이트 터미네이티드(Poly(propylene glycol)tolylene 2,4-diisocyanate terminated), 폴리(테트라플루오로에틸렌옥시드-코-디플루오로메틸렌옥시드)α,ω-디이소시아네이트(Poly(tetrafluoroeth hyl-1,3-phenylene diisocyanate), poly (1,4-butanediol), tolylene 2,4-diisocyanate terminated lactide (Poly (1,4-butanediol) tolylene 2,4-diisocyanate terminated), poly (1 , 4-butanediol) isophorone diisocyanate terminated lactide (poly (1,4-butanediol) isophorone diisocyanate terminated), poly (ethylene adipate) tolylene 2,4-diisocyanate terminated lactide (poly (ethylene adipate) tolylene 2,4-diisocyanate terminated), poly [1,4 phenylene diisocyanate-co-poly (1,4-butanol) diisocyanate (poly [1,4-phenylene diisocyanate- co -poly (1,4- butanol)] diisocyanate), poly-hexamethylene diisocyanate (poly (hexamethylene diisocyanate), polypropylene glycol-tolylene 2,4-diisocyanate terminated lactide (poly (propylene glycol) tolylene 2,4-diisocyanate terminated), poly (tetramethylene fluoro-ethylene oxide-co-methylene oxide-difluoro) α, ω- diisocyanate (Poly (tetrafluoroeth ylene oxide-co-difluoromethylene oxide)α,ω-diisocyanate), 2,4-톨루엔 디이소시아네이트(2,4-Toluene Diisocyanate), 2,5-톨루엔 디이소시아네이트(2,5-Toluene Diisocyanate), 2,6-톨루엔 디이소시아네이트(2,6-Toluene Diisocyanate), 1,5-나프탈렌 디이소시아네이트(1,5-Naphthalene Diisocyanate) 및 이들의 혼합물로 이루어진 군으로부터 선택된다. ylene oxide-co-difluoromethylene oxide) α, ω-diisocyanate), 2,4- toluene diisocyanate (2,4-Toluene Diisocyanate), 2,5- toluene diisocyanate (2,5-Toluene Diisocyanate), 2,6 is selected from toluene diisocyanate (2,6-toluene diisocyanate), 1,5- naphthalene diisocyanate (1,5-naphthalene diisocyanate) and mixtures thereof. 상기 디이소시아네이트(b)는 광중합형 우레탄 올리고머(A) 제조용 조성물의 10 내지 50 중량%의 함량으로 사용되는 것이 바람직하다. The diisocyanates (b) is preferably used in an amount of 10 to 50% by weight of a photopolymerizable urethane oligomer for producing (A) composition.

(c) 히드록시 (메타)아크릴레이트 또는 히드록시 에폭시 (C) hydroxyalkyl (meth) acrylate, or an epoxy-hydroxy

본 발명의 광중합형 올리고머(A)의 제조에 사용되는 성분 (c)는 하나 이상의 (메타)아크릴로일기 및 히드록시 작용기를 포함하는 화합물(c 1 ), 또는 하나 이상의 에폭시기 및 히드록시 작용기를 포함하는 화합물(c 2 )이다. Ingredients used for the preparation of the photopolymerizable oligomer (A) of the present invention (c) is one or more (meth) with a compound containing the group and a hydroxyl functional acrylate (c 1), or comprising at least one epoxy group and a hydroxyl group a compound (c 2) a.

성분 (c 1 )의 예로는, 2-히드록시에틸(메타)아크릴레이트(2-Hydroxyethyl(meth)acrylate), 2-히드록시프로필(메타)아크릴레이트(2-Hydroxypropyl(meth)acrylate), 2-히드록시부틸(메타)아크릴레이트(2-Hydroxybutyl(meth)acrylate), 1-히드록시부틸(메타)아크릴레이트(1-Hydroxybutyl(meth)acrylate), 2-히드록시-3-페닐옥시프로필(메타)아크릴레이트(2-Hydroxy-3-phenyloxypropyl(meth)acrylate), 네오펜틸글리코모노(메타)아크릴레이트(Neopentylglycolmono(meth)acrylate), 4-히드록시시클로헥실(메타)아크릴레이트(4-Hydroxycyclohexyl(meth)acrylate), 1,6-헥산디올모노(메타)아크릴레이트(1,6-hexanediolmono(meth)acrylate), 펜타에리트리톨펜타(메타)아크릴레이트(Pentaerythritolpenta(meth)acrylate), 디펜타에리트리톨펜타(메타)아크릴레이트(Dipentaerythritolpenta(meth)acrylate), 2-메타크릴록시에틸 2-히드록시 프로필 프탈레이트(2-Methacryloxyethyl 2-Hydr Examples of the component (c 1) are 2-hydroxyethyl (meth) acrylate (2-Hydroxyethyl (meth) acrylate), 2-hydroxypropyl (meth) acrylate (2-Hydroxypropyl (meth) acrylate), 2 -hydroxybutyl (meth) acrylate (2-hydroxybutyl (meth) acrylate), 1- hydroxy-butyl (meth) acrylate (1-hydroxybutyl (meth) acrylate), 2- hydroxy-3-phenyloxy profile ( meth) acrylate (2-hydroxy-3-phenyloxypropyl (meth) acrylate), neopentyl glycolate mono (meth) acrylate (Neopentylglycolmono (meth) acrylate), 4- hydroxycyclohexyl (meth) acrylate, (4-hydroxycyclohexyl (meth) acrylate), 1,6- hexanediol mono (meth) acrylate (1,6-hexanediolmono (meth) acrylate), pentaerythritol penta (meth) acrylate (Pentaerythritolpenta (meth) acrylate), dipentaerythritol erythritol penta (meth) acrylate (Dipentaerythritolpenta (meth) acrylate), 2-hydroxyethyl methacrylate 2-hydroxypropyl phthalate (2-Methacryloxyethyl 2-Hydr oxy Propyl Phthalate), 글리세린 디(메타)아크릴레이트(Glycerin Dimethacrylate), 2-히드록시-3-아크릴로일록시 프로필 (메타)아크릴레이트(2-Hydroxy-3-acryloyloxy Propyl Methacrylate), 폴리카프로락톤 폴리올 모노(메타)아크릴레이트 및 이들의 혼합물로 이루어지는 군으로부터 선택된다. oxy Propyl Phthalate), glycerin di (meth) acrylate (Glycerin Dimethacrylate), 2- hydroxy-3-propyl acrylic ilrok when a (meth) acrylate (2-Hydroxy-3-acryloyloxy Propyl Methacrylate), polycaprolactone polyols mono (meth) acrylate is selected from the group consisting of and mixtures thereof.

성분 (c 2 )의 예로는, 글리시돌(Glycidol), 에폭시화 테트라히드로벤질 알코올(Epoxidized tetrahydrobenzyl alcohol) 등이 있다. Examples of the component (c 2) it has, and the like glycidol (Glycidol), epoxidized tetrahydro-benzyl alcohol (Epoxidized tetrahydrobenzyl alcohol).

상기 성분 (c)는 광중합형 우레탄 올리고머(A) 제조용 조성물의 5 내지 50 중량%의 함량으로 사용되는 것이 바람직하다. The component (c) is preferably used in an amount of 5 to 50% by weight of a photopolymerizable urethane oligomer for producing (A) composition.

(d) 우레탄 반응 촉매 (D) a urethane reaction catalyst,

본 발명의 광중합형 올리고머(A)의 제조에 사용되는 우레탄 반응 촉매(d)는 우레탄 반응 중에 소량 첨가되는 촉매로서, 구리 나프티네이트(copper naphthenate), 코발트 나프티네이트(cobalt naphthenate), 아연 나프테이트(zinc naphthate), n-부틸틴라우레이트(butyltinlaurate), 트리스틸아민(tristhylamine), 2-메틸트리에틸렌디아마이드(methyltriethlenediamide) 및 이들의 혼합물로 이루어지는 군으로부터 선택되며, 상기 광중합형 우레탄 올리고머(A) 제조용 조성물의 0.01 내지 1 중량%의 함량으로 사용되는 것이 바람직하다. Urethane reaction catalyst (d) used for the preparation of the photopolymerizable oligomer (A) of the present invention is a catalyst to be added in a small amount during the urethane reaction, copper naphthyridin carbonate (copper naphthenate), cobalt naphthyridin carbonate (cobalt naphthenate), zinc naphthyl lactate ( zinc naphthate), n- butyl tin dilaurate (butyltinlaurate), tree steel amine (tristhylamine), 2- methyl-amide triethylene di (methyltriethlenediamide) and is selected from the group consisting of and mixtures thereof, (a) the photopolymerizable urethane oligomer to be used as a content of 0.01 to 1% by weight of the composition for preparing preferred.

(e) 중합개시제 (E) a polymerization initiator

본 발명의 광중합형 올리고머(A)의 제조에 사용되는 중합개시제(e)로는 히드로퀴논(Hydroquinone), 히드로퀴논모노메틸에테르(Hydroquinonmonomethylether), 파라-벤조퀴논(Para-benzoquinone), 페노티아진(Phenotiazine) 및 이들의 혼합물로 이루어진 군으로부터 선택되며, 상기 광중합형 우레탄 올리고머(A) 제조용 조성물의 0.01 내지 1 중량%의 함량으로 사용되는 것이 바람직하다. Roneun polymerization initiator (e) used in the preparation of the photopolymerizable oligomer (A) of the present invention, hydroquinone (Hydroquinone), hydroquinone monomethyl ether (Hydroquinonmonomethylether), para-benzoquinone (Para-benzoquinone), phenothiazine (Phenotiazine) and mixtures thereof are preferably used in amount of 0.01 to 1% by weight of the photopolymerizable urethane oligomer (a) for preparing the composition.

상기 불소 치환 광중합형 올리고머(A)의 제조는 통상의 방법에 의해 수행될 수 있으며, 구체예로서, 반응 플라스크에 불소 치환된 퍼플루오로 폴리에테르폴리올 또는 퍼플루오로 폴리에테르 말단에 비불소폴리에테르기를 갖는 폴리올을 넣고, 감압하여 수분을 제거한 후 이소시아네이트 및 사용되는 총 촉매의 1/2를 가하여 200 내지 300 rpm으로 교반하면서 온도를 65 내지 85℃로 유지하고 IR 상에 -OH 피크가 소멸될 때까지 약 2 내지 3시간 동안 반응시킨다. Preparation of the fluorinated photopolymerizable oligomer (A) can be carried out by a conventional method, as a specific example, a fluorine-substituted perfluoroalkyl polyether polyol or perfluoro non-fluorinated poly polyether terminated polyether to the reaction flask into the polyol having a reduced pressure while the water was removed was added to half of the total catalyst that is used and the isocyanate with stirring at 200 to 300 rpm to maintain the temperature from 65 to 85 ℃ and when the extinction peak in the IR -OH to react for about 2 to 3 hours. 이때, 촉매 사용량은 상기 반응에서 전량 사용할 수도 있다. At this time, the catalyst usage amount can be used in this reaction. 반응 종료 후, 중합개시제 및 히드록시(메타)아크릴레이트 또는 히드록시 에폭시를 가하고, 70 내지 90℃로 승온하여 나머지 분량의 촉매를 가하고 IR 상에 -NCO 피크가 소멸할 때까지 반응시킴으로써, 불소 치환 광중합형 올리고머(A)를 제조할 수 있다. By reacting After completion of the reaction, a polymerization initiator and a hydroxy (meth) acrylate or a hydroxyalkyl epoxy was added, the temperature was raised to 70 to 90 ℃ was added to the remaining amount of a catalyst until the -NCO peak disappears in the IR, fluorine-substituted it is possible to manufacture a photo-polymerization type oligomer (a).

상기 불소 치환된 광중합형 우레탄 올리고머(A)는 평균 분자량이 2,000 내지 50,000이고, 종래의 우레탄 올리고머가 갖는 우수한 물성 외에도 굴절율이 1.3 정도로 낮으며, 광도파로 소재가 갖추어야 할 특성인 1.1∼1.8㎛ 파장 영역 대에서 우수한 광투과성을 가지며, 접착성이 우수하다. The fluorine substituted oligomeric photopolymerizable urethane (A) is an average molecular weight of 2,000 to 50,000, and in addition was superior properties with a conventional polyurethane oligomers, a refractive index of as low as 1.3, the characteristic wavelength region 1.1~1.8㎛ an optical waveguide material can be provided has excellent light transmission in the stand, the adhesion is excellent.

상기 불소 치환된 광중합형 우레탄 올리고머(A)는 광도파로용 광경화성 수지 조성물의 20 내지 80 중량%의 함량으로 사용되는 것이 바람직하다. The fluorine substituted oligomeric photopolymerizable urethane (A) is preferably used in an amount of 20 to 80% by weight of the photo-curable resin composition for optical waveguides.

(B) 반응성 모노머 (B) a reactive monomer

본 발명에서 사용되는 반응성 모노머(B)로는, 1개 이상의 (메타)아크릴로일기를 갖는 (메타)아크릴레이트(B 1 ) 또는 1개 이상의 에폭시기를 갖는 광반응성 모노머(B 2 )가 있으며, 상기 (메타)아크릴레이트(B 1 )는 불소 치환된 모노머와 비불소형 모노머를 포함한다. Roneun reactive monomer (B) used in the present invention, and the (meth) acrylate photo-reactive monomer (B 2) having a (B 1) or one or more epoxy groups having a group with one or more (meth) acrylate, the (meth) acrylate (B 1) comprises a fluorine-substituted monomer and bibul small monomer.

상기 반응성 모노머(B)는 (메타)아크릴로일기 또는 에폭시기를 함유하는 수에 따라, 단관능기 모노머, 2관능기 모노머 또는 3관능기 이상을 갖는 모노머로 구분될 수 있다. The reactive monomer (B) is (meth) depending on the number of epoxy group-containing group or an acrylic, a distinction can be made between a monomer having a single functional group monomer, the second monomer or the functional group more than 3 functional groups.

상기 불소 치환된 (메타)아크릴로일기 함유 반응성 모노머로는, 2-퍼플루오로옥틸에틸아크릴레이트(2-Perfluorooctylethyl acrylate), 2-퍼플루오로옥틸에틸메타크릴레이트(2-Perfluorooctylethyl methacrylate), 2,2,3,4,4,4-헥사플루오로부틸메타크릴레이트(2,2,3,4,4,4-Hexafluorobutyl methacrylate), 2,2,3,3-테트라플루오로프로필 메타크릴레이트(2,2,3,3-Terrafluoropropyl methacrylate), 트리플루오로에틸메타크릴레이트(Trifluoroethyl methacrylate), 2-퍼플루오로알킬에틸아크릴레이트(2-Perfluoroalkylethyl acrylate), 2-퍼플루오로알킬에틸메타크릴레이트(2-Perfluoroalkylethyl methacrylate) 등이 있다. In the fluorine-substituted (meth) acryloyl group-containing reactive monomers include 2-perfluorooctyl ethyl acrylate (2-Perfluorooctylethyl acrylate), octyl methacrylate (2-Perfluorooctylethyl methacrylate) 2-perfluoroalkyl, 2 , a 2,3,4,4,4- hexafluoro-butyl methacrylate (2,2,3,4,4,4-Hexafluorobutyl methacrylate), methacrylate 2,2,3,3-tetrafluoroethane (2,2,3,3-Terrafluoropropyl methacrylate), trifluoromethyl methacrylate (Trifluoroethyl methacrylate), 2-perfluoroalkyl ethyl acrylate (2-Perfluoroalkylethyl acrylate), alkyl methacrylate with 2-perfluoroalkyl It includes acrylate (2-Perfluoroalkylethyl methacrylate).

1개의 (메타)아크릴로일기를 함유하는 단관능기 비불소형 반응성 모노머로는, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 1-히드록시부틸(메타)아크릴레이트, 2-히드록시-3-페닐옥시프로필(메타)아크릴레이트, 테트라히드로퍼퓨릴 (메타)아크릴레이트(Tetrahydrofurfuryl (Meth)acrylate), 이소데실 (메타)아크릴레이트(Isodecyl (Meth)acrylate), 2-(2-에톡시에톡시)에틸 (메타)아크릴레이트(2-(2-Ethoxyethoxy) Ethyl(meth)acrylate), 스테아릴 (메타)아크릴레이트(Stearyl (Meth)acrylate), 라우릴 (메타)아크릴레이트(Lauryl (Meth)acrylate), 2-페녹시에틸 (메타)아크릴레이트(2-Phenoxyethyl (Meth)acrylate), 이소보닐 (메타)아크릴레이트(Isobornyl (Meth)acrylate), 트리데실 (메타)아크릴레이트(Tridecyl (Meth)acrylate), 폴리카프로락톤 (메타)아크릴레 One (meth) with only a small functional group bibul reactive monomer containing the acrylic group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxy butyl (meth) acrylate, 2-hydroxy-3-phenyl-oxy-propyl (meth) acrylate, tetrahydro fur furyl (meth) acrylate (Tetrahydrofurfuryl (meth) acrylate), isodecyl ( meth) acrylate (Isodecyl (meth) acrylate), 2- (2-ethoxyethoxy) ethyl (meth) acrylate (2- (2-ethoxyethoxy) ethyl (meth) acrylate), stearyl (meth) acrylate (Stearyl (meth) acrylate), lauryl (meth) acrylate (lauryl (meth) acrylate), 2- phenoxy ethyl (meth) acrylate (2-phenoxyethyl (meth) acrylate), isobornyl (meth) acrylate (Isobornyl (meth) acrylate), tridecyl (meth) acrylate (tridecyl (meth) acrylate), polycaprolactone (meth) acrylate les 트(Polycarprolactone (Meth)acrylate), 페녹시테트라에틸렌글리콜아크릴레이트(Phenoxy Tetraethylene Glycol (Meth)acrylate), 이미드아크릴레이트(Imide acrylate) 등이 포함된다. Bit (Polycarprolactone (Meth) acrylate), and the like are phenoxy tetraethylene glycol acrylate (Phenoxy Tetraethylene Glycol (Meth) acrylate), imide acrylate (Imide acrylate).

2관능기 비불소형 모노머로는 에톡시부과형 노닐페놀 (메타)아크릴레이트(Ethoxylated Nonyl Phenol Acrylate), 에틸렌 글리콜 디(메타)아크릴레이트(Ethylene Glycol Di(meth)acrylate), 디에틸렌 글리콜 디(메타)아크릴레이트(Diethylene Glycol Di(meth)acrylate), 트리에틸렌 글리콜 디(메타)아크릴레이트(Triethylene Glycol Di(meth)acrylate), 테트라에틸렌 글리콜 디(메타)아크릴레이트(Tetraethylene Glycol Di(meth)acrylate), 폴리에틸렌 글리콜 디(메타)아크릴레이트(Polyethylene Glycol Di(meth)acrylate), 1,6-헥산디올 디(메타)아크릴레이트(1,6-Hexanediol Di(meth)acrylate), 1,3-부틸렌 글리콜 디(메타)아크릴레이트(1,3-Butylene Glycol Di(meth)acrylate), 트리프로필렌 글리콜 디(메타)아크릴레이트(Tripropylene Glycol Di(meth)acrylate), 에톡시 부과형 비스페놀 A 디(메타)아크릴레이트(Ethoxylated Bisphenol A Di(meth)acrylate), 시클로헥산 디메 2 functional groups bibul small monomers include nonylphenol ethoxy charge type on a (meth) acrylate (Ethoxylated Nonyl Phenol Acrylate), ethylene glycol di (meth) acrylate (Ethylene Glycol Di (meth) acrylate), diethylene glycol di (meth) acrylate (diethylene glycol di (meth) acrylate), triethylene glycol di (meth) acrylate (triethylene glycol di (meth) acrylate), tetraethylene glycol di (meth) acrylate (tetraethylene glycol di (meth) acrylate), polyethylene glycol di (meth) acrylate (polyethylene glycol di (meth) acrylate), 1,6- hexanediol di (meth) acrylate (1,6-hexanediol di (meth) acrylate), 1,3- butylene glycol di (meth) acrylate (1,3-Butylene glycol di (meth) acrylate), tripropylene glycol di (meth) acrylate (tripropylene glycol di (meth) acrylate), ethoxy charged bisphenol a di (meth) acrylate rate (Ethoxylated Bisphenol A Di (meth) acrylate), cyclohexane-dimethoxy 탄올 디(메타)아크릴레이트(Cyclohexane Dimethanol Di(meth)acrylate), 트리시클로데칸디메탄올 디아크릴레이트(Tricyclo[5.2.1.0 2,6 ]decanedimethanol diacrylate) 등으로 이루어진다. Ethanol comprises a di (meth) acrylate (Cyclohexane Dimethanol Di (meth) acrylate), tricyclodecane dimethanol diacrylate (Tricyclo [5.2.1.0 2,6] decanedimethanol diacrylate ) or the like.

3관능기 이상을 가진 비불소형 모노머는 트리스 아크릴로일록시에틸 이소시아누레이트(Tris[2-(acryloyloxy)ethyl]isocyanurate), 트리메틸올 프로판 트리아크릴레이트, 에틸렌 옥시드 3몰 부가형 트리메틸올 프로판 트리아크릴레이트, 에틸렌 옥시드 6몰 부가형 트리메틸올 프로판 트리아크릴레이트, 펜타에리트리톨 트리아크릴레이트, 트리스(아크릴로옥시에틸)이소시아누레이트, 디펜타에리트리톨 헥사아크릴레이트 및 카프로락톤 변성 디펜타에리트리톨 헥사아크릴레이트로 이루어진 군으로부터 선택된다. 3 bibul small monomer having a functional group is at least one hydroxyethyl isocyanurate (Tris [2- (acryloyloxy) ethyl] isocyanurate), trimethylolpropane triacrylate, ethylene oxide addition type 3 moles of trimethylolpropane triacrylate as acrylic-tris acrylate, ethylene oxide 6 molar addition type trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, and caprolactone-modified dipentaerythritol hexa It is selected from the group consisting of acrylate.

1개 이상의 에폭시기를 갖는 반응성 모노머(B 2 )로는 3,4-에폭시시클로헥실메틸-3,4-에폭시시클로헥산 카복실레이트(3,4-Epoxycyclohexylmethyl-3,4-epoxy cyclohexane carboxylate), 비스-(3,4-에폭시클로헥실)아디페이트(Bis-(3,4-epoxycyclohexyl)adipate), 3-에틸-3-히드록시메틸-옥세탄(3-Ethyl-3-hydroxymethyl-oxetane), 1,2-에폭시헥사데칸(1,2-Epoxyhexadecane), 알킬글리시딜에테르(Alkyl glycidyl ether), 2-에틸헥실디글리콜 글리시딜에테르(2-Ethyl hexyl diglycol glycidyl ether), 에틸렌글리콜 디글리시딜 에테르(Ethyleneglycol diglycidyl ether), 디에틸렌글리콜 디글리시딜 에테르(Diethyleneglycol diglycidyl ether), PEG#200 디글리시딜 에테르(PEG#200 diglycidyl ether), PEG#400 디글리시딜 에테르(PEG#400 diglycidyl ether), 프로필렌글리콜 디글리시딜 에테르(Propyleneglycol diglycidyl ether), 트리프로필렌글리콜 디글리시딜 에테르(Tripropyleneglyc Roneun reactive monomer (B 2) having at least one epoxy group 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (3,4-Epoxycyclohexylmethyl-3,4-epoxy cyclohexane carboxylate), bis- ( 3,4-epoxy claw-hexyl) adipate (Bis- (3,4-epoxycyclohexyl) adipate), 3- ethyl-3-hydroxymethyl-oxetane (3-ethyl-3-hydroxymethyl-oxetane), 1,2 -epoxy hexadecane (1,2-Epoxyhexadecane), alkyl glycidyl ether (alkyl glycidyl ether), 2- ethylhexyl sildi glycol glycidyl ether (2-ethyl hexyl diglycol glycidyl ether), ethylene glycol diglycidyl ether (ethyleneglycol diglycidyl ether), diethylene glycol diglycidyl ether (diethyleneglycol diglycidyl ether), PEG # 200 diglycidyl ether (PEG # 200 diglycidyl ether), PEG # 400 diglycidyl ether (PEG # 400 diglycidyl ether ), propylene glycol diglycidyl ether (propyleneglycol diglycidyl ether), tripropylene glycol diglycidyl ether (Tripropyleneglyc ol diglycidyl ether), PPG#400 디글리시딜 에테르(PPG#400 diglycidyl ether), 네오펜틸글리콜 디글리시딜 에테르(Neopentylglycol diglycidyl ether), 1,6-헥산디올 디글리시딜 에테르(1,6-Hexanediol diglycidyl ether), 수소화 비스페놀 A 디글리시딜 에테르(Hydrogenated bisphenol A diglycidyl ether), 프로필렌옥시드 변형 비스페놀 A형 디글리시딜 에테르(Diglycidyl ether of propyleneoxide modified bisphenol A), 디브로모 네오펜틸글리콜 디글리시딜 에테르(Dibromo neopentylglycol diglycidyl ether) 및 트리메틸올프로판 트리글리시딜 에테르(Trimethylolpropane triglycidyl ether)로 이루어진 군으로부터 선택된다. ol diglycidyl ether), PPG # 400 diglycidyl ether (PPG # 400 diglycidyl ether), neopentyl glycol diglycidyl ether (Neopentylglycol diglycidyl ether), 1,6- hexanediol diglycidyl ether (1,6 -Hexanediol diglycidyl ether), hydrogenated bisphenol A diglycidyl ether (hydrogenated bisphenol A diglycidyl ether), propylene oxide modified bisphenol A diglycidyl ether (diglycidyl ether of bisphenol A propyleneoxide modified), dibromo-neopentyl glycol diglycidyl ether is selected from the group consisting of (Dibromo neopentylglycol diglycidyl ether) and when trimethylolpropane triglycidyl ether (trimethylolpropane triglycidyl ether).

상기 광반응성 모노머(B)는 광도파로용 고분자 수지 조성물의 20 내지 80 중량%의 함량으로 사용되는 것이 바람직하다. The photo-reactive monomer (B) is preferably used in an amount of 20 to 80% by weight of the polymeric resin composition for the optical waveguide.

(C) 광중합개시제 (C) a photopolymerization initiator

본 발명에서 사용되는 광중합개시제(C)로는 Irgacure#184, Irgacure#907, Irgacure#500, Irgacure#651, Darocure#1173, Darocure#116, CGI#1800, CGI#1700, UVI-6990, UVI-6974, Sarcat R CD1010, Sarcat R CD1011, Sarcat R CD1012, Sarcat R K185 및 이들의 혼합물로 이루어진 군으로부터 선택되며, 광도파로용 고분자 수지 조성물의 1 내지 10 중량%의 함량으로 사용되는 것이 바람직하다. Roneun photopolymerization initiator (C) used in the present invention, Irgacure # 184, Irgacure # 907, Irgacure # 500, Irgacure # 651, Darocure # 1173, Darocure # 116, CGI # 1800, CGI # 1700, UVI-6990, UVI-6974 , R Sarcat CD1010, is selected from R Sarcat CD1011, CD1012 Sarcat R, R Sarcat K185, and mixtures thereof, preferably used in an amount of 1 to 10% by weight of the polymeric resin composition for the optical waveguide.

(D) 중합방지제 (D) polymerization inhibitor

본 발명의 조성물에는 중합방지제(D)가 보관 안정성을 향상시키기 위해 사용될 수 있으며, 장기간의 저장 또는 고온 다습한 환경에서 생성될 수 있는 자유 라디칼에 의한 수지의 경화 현상을 방지할 수 있고, 수지 경화 후 고온에서도 황변 현상을 방지할 수 있다. Composition of the present invention may be a polymerization inhibitor (D) is may be used to improve the storage stability, prevent the hardening of the resin by the free radical, which may be generated in the long-term storage or high temperature and humidity environment, the resin curing even at high temperatures, then it is possible to prevent yellowing. 상기 중합방지제로는 히드로퀴논(Hydroquinone), 히드로퀴논모노메틸에테르(Hydroquinonemonomethylether), 파라-벤조퀴논(Para-benzoquinone), 페노티아진(Phenotiazine) 및 이들의 혼합물로 이루어지는 군으로부터 선택되며, 고분자 수지 조성물의 0.01 내지 5 중량%의 함량으로 사용될 수 있다. The polymerization inhibitor is hydroquinone (Hydroquinone), hydroquinone monomethyl ether (Hydroquinonemonomethylether), para-benzoquinone (Para-benzoquinone), is selected from phenothiazine (Phenotiazine) and the group consisting of a mixture thereof, and 0.01 in the polymer resin composition to 5 it may be used in an amount of% by weight.

(E) 산화방지제 (E) an antioxidant

본 발명에서 사용될 수 있는 산화방지제(E)는 Irganox 1010, Irganox 1035, Irganox 1076 (이상 시바가이기(Cibageigy)사 제조) 및 이들의 혼합물로 이루어진 군으로부터 선택되며, 고분자 수지 조성물의 0.01 내지 5 중량%의 함량으로 사용될 수 있다. Antioxidants (E) that can be used in the present invention include Irganox 1010, Irganox 1035, Irganox 1076 (or more Ciba (Cibageigy) Co., Ltd.), and is selected from the group consisting of a mixture thereof, the polymeric resin composition is 0.01 to 5 parts by weight It can be used in an amount of%.

본 발명의 광도파로용 광경화성 수지 조성물은 통상의 방법에 의해 제조될 수 있으며, 구체적으로는, 상기 (A) 내지 (E) 성분들을 반응기에서 혼합하여 15 내지 50 ℃ 및 60 % 이하의 습도 조건에서 500∼1000 rpm의 속도로 교반하여 제조되는 것이 바람직하다. Optical waveguides a photo-curable resin composition of the present invention can be prepared by a conventional method, specifically, the (A) to (E) and mixed with 15 to 50 ℃ and humidity of 60% or less of the reactor components it is produced by stirring with a speed of 500~1000 rpm in are preferred. 반응 온도가 15℃ 미만일 경우에는 올리고머(A)의 점도가 상승하여 공정상의 문제점이 발생하고 50℃를 초과할 경우에는 광중합개시제(C)가 라디칼을 형성하여 경화반응을 일으키므로 좋지 않다. If the reaction temperature is less than 15 ℃ is not good, because if you increase the viscosity of the oligomer (A) is a problem in the process caused by the excess of 50 ℃, the photopolymerization initiator (C) causing a curing reaction to form a radical. 또한 반응시 습도가 60%를 초과할 경우에는, 수지 생성 이후 코팅 공정 중에 수지에서 기포가 발생하며 미반응 물질들이 공기 중의 수분과 반응하여 부반응이 일어나는 문제점을 가진다. In addition, if the humidity exceeds 60%, the reaction, bubbles are generated in the resin during the subsequent coating process and the resin produced has a problem occurs a side reaction by reacting with the moisture present in the unreacted material to the air.

본 발명에 의한, 불소 치환 올리고머 함유 광도파로용 고분자 수지 조성물은 굴절률을 1.38∼1.54 범위로 자유롭게 조절할 수 있으며, 작업성과 밀접한 관계가 있는 점도도 50∼2000 cPs 범위로 용이하게 조절할 수 있고, 장기 저장성도 우수하다. , Fluorinated oligomers containing polymeric resin composition for optical waveguides according to the present invention can freely control a refractive index by 1.38 to 1.54 range, the viscosity of which is closely related to operation and can easily be adjusted to a range of 50~2000 cPs, long-term storability it is also excellent. 또한 열분해온도가 300℃ 이상으로 열적 안정성이 높고, 복굴절율이 1×10 -4 이하로서 낮으며, 간단한 합성 방법을 이용함으로써 제조 비용 또한 절감되어 저가로 제조될 수 있다. In addition, a high thermal stability with thermal decomposition temperature of 300 ℃, birefringence was low as less than 1 × 10 -4, is also reducing the production cost by a simple synthesis method can be manufactured at a low cost. 또한, 광통신 영역인 0.85㎛, 1.3㎛, 1.55㎛ 파장에서 각각 90% 이상의 우수한 광투과도를 가지며, 특히 0.85㎛ 파장에서 0.3 dB/㎝ 정도의 광손실을 갖는다. Further, each having a high light transmittance of 90% or more in the optical region of 0.85㎛, 1.3㎛, 1.55㎛ wavelength, in particular has a light loss of about 0.3 dB / ㎝ in 0.85㎛ wavelength. 종래의 열경화 방식, 즉 오랜 시간과 고온을 필요로 하는 방법이 아닌, 상온에서 간단한 자외선 조사만을 이용하는 광경화 방식에 의해 광도파로를 제조할 수 있으므로 광도파로의 제조 공정, 비용, 시간 등을 감소시킬 수 있다. Reduce the manufacturing process, cost, time and the like of conventional thermal curing method, that is, the optical waveguide can be manufactured an optical waveguide by only photocuring method using a simple UV irradiation at room temperature, rather than a method requiring a long time and high temperature can.

본 발명은 또한 마이크로 트랜스퍼 몰딩(Micro-transfer molding) 방법을 이용한, 고분자 광도파로의 제조방법을 제공한다. The present invention provides a method of manufacturing a polymeric optical waveguide also using the micro-transfer molding (Micro-transfer molding) method. 이는 고가 장비, 까다로운 조작 조건 등을 요하는 종래 방식에 의한 도파로 제조를 단순화시킨 방법으로서, 실록산계 고무를 사용하여 코어의 패턴을 찍어내는 방법이다. This is a way to read the pattern of the core by a method which simplifies the waveguide produced by expensive equipment, the conventional method which requires such demanding operating conditions, using a siloxane-based rubber.

도 1에 도시한 바와 같이, 본 발명에 의한 마이크로 트랜스퍼 몰딩 기법을 이용한 광경화성 고분자 광도파로의 제조공정은 다음과 같다: 1, the production process of the photo-curable polymer optical waveguide by the micro-transfer molding method according to the present invention are as follows:

포토레지스트(photoresist)에 의해 도파로 패턴(core pattern)이 형성된 기판 위에 실록산계 레진, 예를 들면 폴리디메틸실록산(polydimethyl siloxane) 고무를 가하고 상온에서 방치하여 기포를 제거한 후 30 내지 100℃에서 2 내지 10시간 동안 상기 레진을 경화시킨 후 마스터로부터 떼어내어 경화된 실록산계 몰드를 제조한다. Picture waveguide pattern by the resist (photoresist) (core pattern) is, for siloxane-based resin, for example, on a substrate formed of polydimethylsiloxane (polydimethyl siloxane) was added to the rubber allowed to stand at room temperature from 30 to 100 ℃ to remove the air bubbles from 2 to 10 after curing the resin for a time to produce a siloxane-based curing mold it was removed from the master. 상기 실록산계 몰드 위에 본 발명의 광경화형 불소치환 광도파로용 고분자 수지 조성물을 예를 들면, 스핀코팅에 의해 도포하고, 이때 과량의 수지는 제거한다. The siloxane-based photo-curing the fluorine-substituted optical waveguide polymer resin composition of the present invention over the mold, for example, is applied by spin coating, at which time the excess resin is removed.

한편, 실리콘웨이퍼(silicon wafer) 위에 도포하고 경화시킨 하위 클래딩층(under cladding layer) 위에, 상기와 같이 제조된, 본 발명의 고분자 수지가 도포된 실록산계 몰드를, 상기 고분자 수지가 마주보도록 덮고, 자외선으로 경화시킨 후 이로부터 실록산계 몰드를 떼어낸다. On the other hand, a silicon wafer (silicon wafer), covering's a siloxane-based mold the polymer resin is manufactured, the present invention is applied, such as on the lower cladding layer (under cladding layer) was applied and cured over, above, wherein the polymer resin face, after curing with ultraviolet rays and remove the siloxane-based molded therefrom. 상기 경화된 고분자 수지 위에 상위 클래딩층(upper cladding layer)을 코팅하고 자외선으로 경화시킴으로써 수행된다. Coating the upper cladding layer (upper cladding layer) on the cured polymer resin and is carried out by curing with ultraviolet light. 이러한 마이크로 트랜스퍼 몰딩 방법은, 일단 실록산계 몰드가 제조되면 빠른 시간 내에 아주 간단한 공정으로 도파로를 연속적으로 제작할 수 있는 장점이 있고 포토레지스트 재료의 종류에 따라 1mm×1mm 크기의 광도파로 까지도 형성할 수 있다. These micro-transfer molding method, one siloxane can the mold can be produced when formed, even a very simple process and is advantageous for creating a waveguide continuously in the optical waveguide of 1mm × 1mm size according to the type of photoresist material in a short time .

상기 제조공정에서 도파로 패턴의 디자인 형태에 따라 싱글모드(single-mode) 또는 멀티모드(multi-mode) 광도파로가 제조될 수 있다. Depending on the design shape of the waveguide pattern in the manufacturing process, there is a single-mode (single-mode) or a multi-mode (multi-mode) optical waveguides can be produced.

본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다. The invention embodiments of carrying out can be better understood by way of example, below is not intended to limit the scope of protection defined by the appended claims is for the purposes of illustration of the present invention.

실시예 Example

합성예 1: 올리고머의 제조 Synthesis Example 1: Preparation of oligomers

1L 플라스크에 불소치환된 폴리에테르(Fluorolink E10, 제조원: Ausimount사, 이탈리아) 375.27g 및 이소포론디이소시아네이트(IPDI) 89.38g을 혼합하고 40 내지 60℃로 가온한 후 n-부틸틴라우레이트(DBTL) 0.10g을 첨가하였다. Fluorine-substituted polyether in 1L flask (Fluorolink E10, manufactured by: Ausimount Inc., Italy) and 375.27g isophorone diisocyanate (IPDI) were mixed 89.38g and allowed to warm to 40 to 60 ℃ n- butyl tin dilaurate (DBTL ) it was added to 0.10g. 200∼300 rpm으로 교반하면서 발열이 끝난 후 온도를 65 내지 85℃로 유지하면서 -OH 피크가 소멸할 때까지 반응시켰다. With stirring at 200~300 rpm and reacted until the -OH peaks in extinction while maintaining 65 to 85 ℃ the temperature after the heating is finished. IR 상에 -OH 피크가 완전히 소멸되면 히드로퀴논모노메틸에테르(HQMME) 0.13g, 2-히드록시에틸메타크릴레이트(2-HEMA) 34.85g을 첨가하고, 발열이 종료되면 온도를 70 내지 90℃로 유지하여 IR 상의 -NCO 피크가 완전히 소멸될 때까지 반응시킴으로써, 불소치환된 우레탄 올리고머를 제조하였다. If on the IR -OH peak is the complete destruction of hydroquinone monomethyl ether (HQMME) 0.13g, 2- hydroxy ethyl methacrylate (2-HEMA) was added to 34.85g and 70 to 90 ℃ the temperature when heating is ended held in a reaction until the -NCO peak in the IR completely disappeared, to thereby prepare a fluorine-substituted urethane oligomer.

합성예 2 내지 13: 올리고머의 제조 Synthesis Examples 2 to 13 Preparation of the oligomer

하기 표 1에 기재된 성분 및 함량을 이용하여 합성예 1에서와 동일한 방법에 의해 불소치환된 우레탄 올리고머를 제조하였다. To using the ingredients and contents shown in Table 1 was prepared in the fluorine-substituted urethane oligomer by the same method as in Synthesis Example 1.

실시예 1 내지 10 및 비교실시예 1: 광도파로 제조용 고분자 수지의 제조 Examples 1 to 10 and Comparative Example 1: Preparation of the optical waveguide for producing a polymer resin

하기 표 2에 기재된 성분들을 반응기에 넣고 온도 20 내지 30℃, 습도 30 내지 60% 및 300 ∼ 1,000rpm 조건으로 혼합하여 본 발명에 따른 불소치환 고분자 수지 조성물을 제조하였다. To put the components shown in Table 2 to the reactor temperature from 20 to 30 ℃, mixed with 30 to 60% humidity and 300 ~ 1,000rpm conditions to prepare a fluorine-substituted polymer resin composition according to the invention.

실 시 예 BEST MODE Example 비교예1 Comparative Example 1 1 One 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 10 10 (A)올리고머 (A) an oligomer 합성예 1 Synthesis Example 1 40 40 40 40 합성예 3 Synthesis Example 3 40 40 40 40 합성예 4 Synthesis Example 4 40 40 40 40 합성예 6 Synthesis Example 6 40 40 40 40 합성예 11 Synthesis Example 11 40 40 40 40 UVE-150 (주1) UVE-150 (Note 1) 40 40 (B)반응성 모노머 (B) a reactive monomer SR-339 (주2) SR-339 (2) 25 25 35 35 20 20 30 30 20 20 30 30 25 25 35 35 20 20 30 30 20 20 2-퍼플루오로옥틸에틸아크릴레이트 2-perfluorooctyl ethyl acrylate 25 25 15 15 20 20 20 20 20 20 20 20 25 25 15 15 20 20 20 20 10 10 2-히드록시프로필아크릴레이트 2-hydroxypropyl acrylate 10 10 10 10 10 10 20 20 (C)광 개시제 (C) photoinitiator Darocure#1173 (주3) Darocure # 1173 (3) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 (D)중합방지제 (D) polymerization inhibitor Z-6030 (주4) Z-6030 (Note 4) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 (E)산화방지제 (E) an antioxidant BHT (주5) BHT (Note 5) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 합 계 Sum 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

주1 : Croda 제품, 주2 : Sartomer사 제품, 주3 : 시바 가이기사 제품 Note 1: Croda products, State 2: Sartomer Company, Day 3: Ciba-Geigy products

주4 : 다우코닝사 제품, 주5 : 2,6-디-tert-부틸-4-메틸페놀(알드리치-케미컬사 제품) Day 4: Dow Corning Corporation product, * 5: 2,6-di -tert- butyl-4-methylphenol (Aldrich-Chemicals Inc.)

물성 평가 Property Evaluation

상기 실시예 1-10 및 비교실시예 1에서 각각 제조된 고분자 조성물들의 각각의 물성을 하기 방법에 의해 평가하였으며, 그 결과를 표 3에 나타내었다. Example 1-10 and Comparative Examples were evaluated by each to the respective physical properties of the polymeric composition method in Example 1, the results are shown in Table 3.

1) 점도(cPs) : 25℃에서 브룩필드 회전 점도계로 스핀들러 넘버 42번, 2㎖의 용량을 사용하였으며, 점도에 따라 10 ∼ 100rpm으로 측정한다. 1) Viscosity (cPs): at 25 ℃ by a Brookfield rotational viscometer Spindler number 42, was used as the amount of 2㎖, measured at 10 ~ 100rpm according to the viscosity.

2) 굴절률(액상) : 아베 굴절계(Abbe's Refractometer)를 사용하여 23℃에서 589.3μm의 나트륨 D 라인(Sodium D line)에 의해 측정한다. 2) Refractive index (liquid phase) and in 23 ℃ using an Abbe refractometer (Abbe's Refractometer) measured by the sodium D line of 589.3μm (Sodium D line).

3) 굴절률(경화된 필름) : 스핀 코터의 진공 척 위에 실리콘웨이퍼를 놓고 그 위에 실시예에서 제조된 수지 조성물을 골고루 흩뿌린 다음, 수지 조성물의 점도에 따라 1500∼3000rpm의 속도로 20∼30초 동안 코팅한다. 3) Refractive index (cured film): placing the silicon wafer on the vacuum chuck of a spin coater, the scattered evenly disperse the resin compositions prepared in Examples above, and then, depending on the viscosity of the resin composition at a rate of 20-30 seconds 1500~3000rpm It is coated over. 코팅 완료 후 300W의 고압 수은등으로 된 자외선 경화장치인 퓨전 램프(Fusion Lamp)로 100 mJ/㎠ 이상에서 경화시키고, 60∼100℃에서 10분 이상 동안 후(後)경화시킨 후 프리즘-커플러(Prism-Coupler, Sairon Co. Ltd.)로 850nm 파장에서의 굴절률을 측정한다. After completion of the coating was cured at more than 100 mJ / ㎠ a fusion lamp (Fusion Lamp) UV curing device to a high pressure mercury lamp of 300W and, (後) after curing at 60~100 ℃ for 10 minutes or more prism-coupler (Prism a -Coupler, Sairon Co. Ltd.) to measure the refractive index at 850nm wavelength. 프리즘-커플러를 이용하여 굴절률을 측정하는 경우에 필름의 두께는 2∼15㎛가 적당하다. Prism The thickness of the film in order to measure the refractive index using the coupler is suitable 2~15㎛.

고체 상태의 굴절률은 전기장 모드의 굴절률인 nTE와 자기장 모드의 굴절률인 nTM으로 구분되며, 이들의 차인 Δ (nTE-nTM)은 코팅된 물질의 복굴절률을 나타내는 지수이다. The refractive index of the solid state is separated by the refractive index of the refractive index nTE nTM of the mode field of the electric field mode, a difference between these Δ (nTE-nTM) is an index indicating the birefringence index of the coated material.

4) 광투과도(%T) : 실시예에서 수득된 고분자 수지 조성물을 150㎛의 두께로 유리판 위에 코팅한다. 4) the light transmittance (% T): the polymer resin composition obtained in Example is coated on a glass plate to a thickness of 150㎛. 300W의 고압 수은등으로 된 자외선 경화장치인 퓨전 램프로 100 mJ/㎠ 이상에서 경화시킨 후 60∼100℃에서 10분 이상 동안 후 경화를 진행한다. After curing at least 100 mJ / ㎠ with a fusion lamp UV curing unit with a high pressure mercury lamp of 300W it proceeds then cured at 60~100 ℃ for at least 10 minutes. 경화가 완전히 종료된 후 3cm×3cm의 크기로 시편을 분리하여 분광광도계(UV-VIS-NIS Spectrophotometer, Varian, 호주)로 200 내지 1800 nm의 파장에 따른 광투과도(%T)를 측정한다. After the curing has been completed separating the specimen to a size of 3cm × 3cm to measure a spectrophotometer (UV-VIS-NIS Spectrophotometer, Varian, Australia) in light transmittance according to the wavelength of 200 to 1800 nm (% T). 하기 표 2에 기재된 광투과도는 600 내지 1600 nm 파장 영역에서의 광투과도이다. Light transmission described in the following Table 2 is a light transmittance in the 600 to 1600 nm wavelength range.

5) 경도(A 또는 D) : 50mm×20mm×5mm 이상의 크기를 갖는 형태에 실시예에서 수득된 조성물을 조심스럽게 부은 뒤 경화시키고, 이때 경화조건은 상기 광투과도 측정시의 샘플 경화조건과 동일하다. 5) The hardness (A or D): 50mm × 20mm × out for the compositions obtained in the examples in the form having a 5mm or more size carefully cured after swelling, wherein the curing conditions were the same as Sample curing conditions at the time of the light transmittance measurement . 경화가 완료된 후 쇼아경도계(Shore Durometer Hardness)를 이용하여 경도를 측정한다. After curing is complete, it measures the hardness by using a Shore A durometer (Shore Durometer Hardness).

6) 경화수축률(%) : ASTM D-792 조건에 의거 측정한다. 6) Curing shrinkage ratio (%): measured in accordance with ASTM D-792 condition.

7) 유리전이 온도(Tg) : 상술된 광투과도 측정시의 시편 제조방법과 동일하게 150㎛ 두께의 경화된 필름을 제조한 뒤 동역학열분석기(Dynamic Mechanical Thermal Analyzer, DMTA)를 이용하여 유리전이 온도를 측정한다. 7) Glass transition temperature (Tg): in the same manner produced a cured film having a thickness 150㎛ and specimen preparation at the time of the above-mentioned light transmittance measured after using the kinetic thermal analyzer (Dynamic Mechanical Thermal Analyzer, DMTA) The glass transition temperature the measures. 측정조건은 10 ℃/min의 승온 속도로 상온에서 250℃ 온도까지 질소분위기 하에서 진행한다. The measurement conditions proceeds in a nitrogen atmosphere at room temperature at a heating rate of 10 ℃ / min up to 250 ℃ temperature.

8) 열분해 온도(Td) : 열 무게 측정 분석기(Thermogravimeteric Analyzer, TGA)를 이용하여 10 ℃/min의 승온 속도로 상온에서 700℃까지 질소 분위기 하에서 온도 증가에 따른 시료의 무게 변화를 측정한다. 8) Thermal decomposition temperature (Td): and at room temperature at a heating rate of 10 ℃ / min using a thermogravimetric analyzer measurement (Thermogravimeteric Analyzer, TGA) to 700 ℃ measuring the weight change of a sample due to temperature increase in a nitrogen atmosphere.

9) 저장 안정성 : 조성물을 상온에서 6개월 동안 방치한 후 방치 전과 후의 외관 및 코팅 상태의 변화를 관찰한다. 9) Storage stability: The composition was allowed to stand at room temperature for six months to observe changes in appearance and leave the state before and after coating.

10) 광손실(dB/cm) : 광손실 측정을 위한 시편의 제조는 굴절률(고체) 측정시의 시편 제조방법과 동일하다. 10) Optical loss (dB / cm): Preparation of the sample for the optical loss measurement is the same as the manufacturing method of the specimen when measuring the refractive index (solid). 다만, 프리즘-커플러로 굴절률 정합액 방법을 이용하여 박막의 광손실을 측정하려면 이중층 막으로 코팅하여야 한다. However, the prism-method using an index matching fluid in the coupler to measure the optical loss of the thin film to be coated with a double layer film. 즉, 측정하고자 하는 물질보다 굴절률이 낮은 물질을 실리콘웨이퍼 위에 먼저 코팅하고 그 위에 측정하고자 하는 조성물을 코팅하며, 이때 코팅 후엔 반드시 광경화 및 후 경화를 각각 진행한다. That is, a material having a lower refractive index than the material to be measured and the first coating on a silicon wafer and the coating composition to be measured thereon, this time must be conducted, and a photo-curing after each huen coating. 본 실험 방법에서는 총 3cm의 길이에 해당하는 광손실을 취하였으며, 프리즘-커플러는 새론사(Sairon Co., Ltd.)에서 공급하는 프리즘-커플러(Prism-Coupler)를 사용하였다. In this test method was taken out of the light loss for the total length of 3cm, prism-coupler is a prism that is provided by Sharon four (Sairon Co., Ltd.) - were used for coupler (Prism-Coupler).

실시예 11: 광도파로의 제조 Example 11: Production of optical waveguide

실시예 1에서 수득된 수지 조성물을 클래딩 층으로 하여 실리콘웨이퍼 위에 골고루 흩뿌린 뒤 3000rpm으로 30초간 스핀 코팅하였다. Embodiment by the resin composition obtained in the first cladding layer was spin coated at 3000rpm 30 seconds after sprinkling evenly scattered over the silicon wafer. 이어서 300W의 고압 수은등으로 된 자외선 경화장치인 퓨전 램프로 100 mJ/㎠ 이상에서 경화시킨 후 60∼100℃에서 10분 이상 동안 후 경화를 진행시켰다. It was then allowed to proceed after the curing at 60~100 ℃ After curing at least 100 mJ / ㎠ to the high-pressure lamp of Fusion UV curing unit with a mercury lamp of 300W for 10 minutes or more. 한편, 포토레지스트에 의해 도파로 패턴(core pattern)이 형성된 기판 위에 폴리디메틸실록산 고무를 가하고 상온에서 방치하여 기포를 제거한 후 40℃에서 2시간 동안 경화시킨 후 마스터로부터 떼어내어, 경화된 실록산계 몰드(코어 크기: 45 마이크론)를 제조하였다. On the other hand, a waveguide pattern by a photoresist (core pattern) were removed from the master after curing for 2 hours at 40 ℃ then added to the polydimethylsiloxane rubber on a substrate is formed, removing the air bubbles and allowed to stand at room temperature, the cured siloxane-based mold ( It was prepared in a 45 micron) core size.

상기 실록산계 몰드 위에 실시예 2에서 수득된 수지 조성물을 기포가 생기지 않도록 주의하면서 패턴 모양을 따라 골고루 가하였다. The siloxane and the resin composition obtained in Example 2 on the acid-based mold note that air bubbles were not occur evenly along the pattern shape. 상기 수지 조성물이 있는 부분이 아래를 향하도록 하여 상기 클래딩 층이 코팅된 실리콘웨이퍼 위에 얹은 후 퓨전 램프로 100 mJ/㎠ 이상에서 광경화시키고 실록산계 몰드를 떼어낸 후 60∼100℃에서 10분 이상 동안 후 경화시켰다. And such that the portion in which the resin composition face down the cladding layer is then placed on top of the coated silicon wafer after photocuring at least 100 mJ / ㎠ a fusion lamp and, remove the siloxane-based mold at 60~100 ℃ 10 minutes at during cured after. 이렇게 수득된 코아층이 코팅된 웨이퍼의 단면을 전자현미경과 주사전자현미경으로 관찰하여 그 결과를 각각 도 2a 및 2b에 나타내었다. Thus the cross section of the coated wafer obtained core layer was observed by electron microscopy and scanning electron microscopy. The results are shown in Figures 2a and 2b, respectively.

코아 패턴이 올려진 상태에서 다시 상위 클래딩 층을 실시예 1에 수득한 수지 조성물로 1000rpm으로 20초간 스핀코팅 한 후 100 mJ/㎠ 이상에서 광경화시키고, 이어서 60 내지 100℃에서 10분 이상동안 경화시켜 고분자 광도파로를 수득하였다. Core patterns sight the upper cladding layer again in raised position in Example 1 in a 100 mJ after 20 seconds Spin coating to 1000rpm to produce a resin composition / ㎠ than obtained on the screen and then cured at 60 to 100 ℃ for more than 10 minutes to yield a polymer optical waveguide.

실시예 12: 광도파로의 제조 Example 12: Production of optical waveguide

실시예 3 및 실시예 4에서 수득된 수지 조성물을 각각 클래딩 층 및 코어 층으로 사용한 것을 제외하고는, 실시예 11에서와 동일한 방법에 의해 광도파로를 제조하였다. Example 3 and carrying out with the exception of the resin composition obtained in Example 4 was used as each of the cladding layer and the core layer, an optical waveguide was prepared in the same manner as in Example 11.

실시예 13: 광도파로의 물성 측정 Example 13: Measurement of physical properties of the optical waveguide

실시예 11 및 12에서 수득된 고분자 광도파로의 물성을 측정하여 하기 표 4에 나타내었으며, 이중에서 광진행 손실(propagation loss)은 850nm에서 컷-백 방법(cut-back method)을 이용하여 3cm의 도파로에 대해 측정하였다. Example 11 and showed on to measure the physical properties of the polymeric optical waveguide obtained in 12 Table 4, the light proceeding in a double loss (propagation loss) is cut in the 850nm - of using a back method (cut-back method) 3cm It was measured for the waveguide.

구 분 division 실시예 11 Example 11 실시예 12 Example 12 광도파로 형태 An optical waveguide type Buried type Buried type Buried type Buried type 굴절률 차(%) Refractive index difference (%) 1.39% 1.39% 1.40% 1.40% 코어크기 Core Size 45㎛×45㎛ 45㎛ × 45㎛ 45㎛×45㎛ 45㎛ × 45㎛ 광진행손실 (dB/cm) Light proceeding loss (dB / cm) 0.245 .245 0.214 .214

본 발명에 따른 광경화성 불소 치환된 광도파로용 수지 조성물은 1개 이상의 (메타)아크릴로일기를 갖는 합성된 광경화성 불소치환 올리고머와 함께 1개 이상의 (메타)아크릴로일기 및 에폭시기를 갖는 반응성 모노머, 광중합개시제, 중합방지제 및 산화방지제를 혼합하여 제조함으로써, 낮은 복굴절률 및 적은 광손실을 나타내고, 광투과도, 열적 안정성 및 장기 저장성이 우수하며, 또한 상기 수지 조성물을 이용하여 마이크로 몰딩 기법에 의해 통상적인 에칭이나 식각 없이 광 조사만으로 손쉽게 광도파로를 제작할 수 있다. Sight resin composition for chemical conversion fluorine-substituted optical waveguide according to the present invention is a reactive monomer having a group and an epoxy group with one or more (meth) acrylate with a photo-curable fluorinated oligomer synthesized with a group of one or more (meth) acrylate , by producing a mixture of a photopolymerization initiator, a polymerization inhibitor and an antioxidant, it shows a low birefringence and a low optical loss, and has excellent light transmittance, thermal stability and long-term storability, also typically by micro-molding technique using the resin composition without the etching, the etching can be produced easily with only light irradiation optical waveguide.

본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. Simple variations to variations of the present invention can be easily carried out by those of ordinary skill in the art, such variations and modifications can be seen to be all included in the scope of the invention.

도 1은 본 발명의 실시예에 따른 마이크로 트랜스퍼 몰딩 기법을 이용한 광경화성 고분자 광도파로의 제조공정도이고; 1 is a manufacturing process chart of the photo-curable polymer optical waveguide by the micro-transfer molding technique in accordance with an embodiment of the present invention;

도 2a 및 도 2b는 각각 본 발명의 실시예에서 수득한 코아층이 코팅된 웨이퍼의 단면에 대한 전자현미경 및 주사전자현미경(Scanning Electron Microscope) 사진이다. Figures 2a and 2b is an electron microscope and a scanning electron microscope (Scanning Electron Microscope) photograph of the cross section of the core layer with the coated wafer obtained in each embodiment of the present invention.

Claims (12)

  1. 하기 화학식 1로 표시되는, 불소 치환된 광중합형 우레탄 올리고머: To, fluorine-substituted photopolymerizable urethane oligomer represented by the general formula (1):
    화학식 1 Formula 1
    상기 식에서, Wherein
    R 2 는 탄소수가 6 ~ 100개로 구성된 방향족 또는 지방족 탄화수소기이고, R 3 는 탄소수가 2 ~ 10개로 구성된 방향족 또는 지방족 탄화수소기이고, R 4 는 메타(아크릴레이트)기 또는 에폭시기이고, l 및 m은 각각 독립적으로 양의 정수이며, p는 0 또는 양의 정수이다. R 2 is a carbon atoms is 6 to aromatic or aliphatic hydrocarbons composed to 100 groups, R 3 is the number of carbon atoms is an aromatic or aliphatic hydrocarbon group consisting of ten 2 to and, R 4 is meta (acrylate) group, or an epoxy group, l and m is a positive integer, each independently, p is 0 or a positive integer.
  2. (A) 청구항 1에 따른 화학식 1의 불소 치환된 광중합형 우레탄 올리고머 20 내지 79 중량%, (B) 반응성 모노머 20 내지 79 중량% 및 (C) 광중합개시제 1 내지 10 중량%를 포함하는, 광도파로용 광경화성 수지 조성물. (A), the optical waveguide comprising a fluorine-substituted photopolymerizable urethane oligomer 20 to 79% by weight of the formula I as claimed in claim 1, (B) a reactive monomer of 20 to 79% by weight and (C) a photopolymerization initiator, 1 to 10% by weight for the photo-curable resin composition.
  3. 제2항에 있어서, 3. The method of claim 2,
    불소 치환된 광중합형 우레탄 올리고머(A)가 불소 치환체를 가진 폴리올(a)과 디이소시아네이트(b)를 우레탄 반응 촉매(d)의 존재하에 반응시킨 후, 수득된 반응 생성물과 하나 이상의 (메타)아크릴로일기 또는 에폭시기, 및 히드록시기를 가진 화합물(c)을 우레탄 반응 촉매(d) 및 중합개시제(e)의 존재하에 반응시켜 제조된 것임을 특징으로 하는, 광도파로용 광경화성 수지 조성물. Polyol is having a fluorine substituent photopolymerizable urethane oligomer (A) a fluorine-substituted (a) with a diisocyanate (b) the polyurethane was reacted in the presence of a catalyst (d), to give a reaction product with one or more (meth) acrylate a group or an epoxy group, and a hydroxy group with a compound (c) a urethane reaction catalyst (d) and a polymerization initiator (e) that is reacted in the presence of manufacture aspect, the photo-curable resin composition for optical waveguides of.
  4. 제3항에 있어서, 4. The method of claim 3,
    폴리올(a)이 분자량 500 내지 10,000이고, 불소 치환된 퍼플루오로 폴리에테르폴리올(Perfluoropolyether polyol) 또는 퍼플루오로 폴리에테르 말단에 비불소폴리에테르기를 갖는 폴리올임을 특징으로 하는, 광도파로용 광경화성 수지 조성물. Polyol (a) is a molecular weight from 500 to 10,000, a fluorine-substituted perfluoroalkyl polyether polyol (Perfluoropolyether polyol) or perfluoro polyether-terminal non-fluorinated polyether photo-curable resin composition for an optical waveguide, characterized in that the polyol having the composition.
  5. 제3항에 있어서, 4. The method of claim 3,
    디이소시아네이트(b)가 이소포론 디이소시아네이트(IPDI), 헥산 디이소시아네이트(HDI), 옥타메틸렌 디이소시아네이트, 테트라메틸크실렌 디이소시아네이트(TMXDI), 4,4'-디시클로헥실메탄 디이소시아네이트(HMDI), 4,4'-디페닐메탄 디이소시아네이트, 3,3'-디메틸 4,4'-비페닐렌 디이소시아네이트, 3,3'-디메틸디페닐메탄-4,4'-디이소시아네이트, 4-브로모-6-메틸-1,3-페닐렌 디이소시아네이트, 4-클로로-6-메틸-1,3-페닐렌 디이소시아네이트, 폴리(1,4-부탄디올)톨릴렌 2,4-디이소시아네이트 터미네이티드, 폴리(1,4-부탄디올) 이소포론 디이소시아네이트 터미네이티드, 폴리(에틸렌 아디페이트)톨릴렌 2,4-디이소시아네이트 터미네이티드, 폴리[1,4-페닐렌 디이소시아네이트-코-폴리(1,4-부탄올)]디이소시아네이트, 폴리헥사메틸렌 디이소시아네이트, 폴리프로필렌글리콜 톨 Diisocyanate (b) is isophorone diisocyanate (IPDI), hexane diisocyanate (HDI), octamethylene diisocyanate, tetramethyl xylene diisocyanate (TMXDI), 4,4'- dicyclohexylmethane diisocyanate (HMDI), 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, 4-bromo 6-methyl-1,3-phenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, poly (1,4-butanediol), tolylene 2,4-diisocyanate terminated lactide , poly (1,4-butanediol) isophorone diisocyanate terminated lactide, poly (ethylene adipate) tolylene 2,4-diisocyanate terminated lactide, poly [1,4 phenylene diisocyanate-co-poly ( butanol 1,4) diisocyanate, polyhexamethylene diisocyanate, polypropylene glycol toll 릴렌 2,4-디이소시아네이트 터미네이티드, 폴리(테트라플루오로에틸렌옥시드-코-디플루오로메틸렌옥시드)α,ω디이소시아네이트, 2,4-톨루엔 디이소시아네이트, 2,5-톨루엔 디이소시아네이트, 2,6-톨루엔 디이소시아네이트, 1,5-나프탈렌 디이소시아네이트 및 이들의 혼합물로 이루어진 군으로부터 선택됨을 특징으로 하는, 광도파로용 광경화성 수지 조성물. Tolylene 2,4-diisocyanate terminated lactide, poly (tetrafluoroethylene oxide-co-dimethylene oxide fluorophenyl) α, ω-diisocyanate, 2,4-toluene diisocyanate, 2,5-toluene diisocyanate , 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate and mixtures thereof, characterized in that, the waveguide optical path for the optical resin composition.
  6. 제3항에 있어서, 4. The method of claim 3,
    하나 이상의 (메타)아크릴로일기와 히드록시기를 가진 화합물(c 1 )이 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 1-히드록시부틸(메타)아크릴레이트, 2-히드록시-3-페닐옥시프로필(메타)아크릴레이트, 네오펜틸글리코모노(메타)아크릴레이트, 4-히드록시시클로헥실(메타)아크릴레이트, 1,6-헥산디올모노(메타)아크릴레이트, 펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 2-메타크릴록시에틸 2-히드록시 프로필 프탈레이트, 글리세린 디(메타)아크릴레이트, 2-히드록시-3-아크릴로일록시 프로필 (메타)아크릴레이트, 폴리카프로락톤 폴리올 모노(메타)아크릴레이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는, 광도파로용 광 One or more (meth) acryloyl compound having a group with a hydroxy group (c 1) are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 1-hydroxy butyl (meth) acrylate, 2-hydroxy-3-phenyl-oxy-propyl (meth) acrylate, neopentyl glycolate mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-hydroxyethyl methacrylate 2-hydroxypropyl phthalate, glycerol di ( meth) acrylate, 2-hydroxy-3-acryloyl propyl ilrok when (meth) acrylate, polycaprolactone polyol mono (meth), the optical waveguide characterized in that the acrylate, and mixtures thereof for light 화성 수지 조성물. Resin composition.
  7. 제3항에 있어서, 4. The method of claim 3,
    하나 이상의 에폭시기와 히드록시기를 가진 화합물(c 2 )이 글리시돌, 에폭시화 테트라히드로벤질 알코올 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는, 광도파로용 광경화성 수지 조성물. Compounds having at least one epoxy group with a hydroxy group (c 2) is glycidol, epoxidized tetrahydro-benzyl alcohol and characterized in that the mixtures thereof, optical path for the optical waveguide-curing resin composition.
  8. 제2항에 있어서, 3. The method of claim 2,
    1개 이상의 (메타)아크릴로일기를 갖는 (메타)아크릴레이트(B 1 )가 불소 치환되거나 또는 불소 치환되지 않은 모노머이며, 상기 불소 치환된 (메타)아크릴로일기 함유 반응성 모노머가 2-퍼플루오로옥틸에틸아크릴레이트, 2-퍼플루오로옥틸에틸메타크릴레이트, 2,2,3,4,4,4-헥사플루오로부틸메타크릴레이트, 2,2,3,3-테트라플루오로프로필 메타크릴레이트, 트리플루오로에틸메타크릴레이트, 2-퍼플루오로알킬에틸아크릴레이트 및 2-퍼플루오로알킬에틸메타크릴레이트로 이루어진 군으로부터 선택되며; One or more (meth) acryloyl group having a (meth) acrylate (B 1) is fluorine or a fluorine-substituted or an unsubstituted monomers, the fluorine-substituted (meth) acryloyl group-containing reactive monomers 2-perfluoroalkyl as octyl acrylate, 2-perfluoro octyl ethyl methacrylate, a 2,2,3,4,4,4- hexafluoro-butyl methacrylate, propyl meta-2,2,3,3-tetrafluoroethane methacrylate, trifluoroethyl methacrylate, is selected from the group consisting of 2-perfluoroalkyl ethyl acrylate and 2-perfluoroalkyl ethyl methacrylate; 상기 불소 치환되지 않은 (메타)아크릴로일기 함유 반응성 모노머가 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 1-히드록시부틸(메타)아크릴레이트, 2-히드록시-3-페닐옥시프로필(메타)아크릴레이트, 테트라히드로퍼퓨릴 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 2-(2-에톡시에톡시)에틸 (메타)아크릴레이트, 스테아릴 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트, 2-페녹시에틸 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 트리데실 (메타)아크릴레이트, 폴리카프로락톤 (메타)아크릴레이트, 페녹시테트라에틸렌글리콜아크릴레이트, 이미드아크릴레이트, 에톡시부과형 노닐페놀 (메타)아크릴레이트, 에틸렌 글리콜 디(메타)아크릴레이트, 디에틸렌 글리콜 디(메타)아 Unsubstituted, the fluorine (meth) acryloyl group-containing reactive monomers 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1 hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyl-oxy-propyl (meth) acrylate, tetrahydro fur furyl (meth) acrylate, isodecyl (meth) acrylate, 2- (2- ethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) lactone acrylates, polycaprolactone (meth) acrylate, phenoxy tetraethylene glycol acrylate, imide acrylate, ethoxy charged type nonylphenol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ah 릴레이트, 트리에틸렌 글리콜 디(메타)아크릴레이트, 테트라에틸렌 글리콜 디(메타)아크릴레이트, 폴리에틸렌 글리콜 디(메타)아크릴레이트, 1,6-헥산디올 디(메타)아크릴레이트, 1,3-부틸렌 글리콜 디(메타)아크릴레이트, 트리프로필렌 글리콜 디(메타)아크릴레이트, 에톡시 부과형 비스페놀 A 디(메타)아크릴레이트, 시클로헥산 디메탄올 디(메타)아크릴레이트, 트리시클로데칸디메탄올 디아크릴레이트(Tricyclo[5.2.1.0 2,6 ]decanedimethanol diacrylate), 트리스 아크릴로일옥시에틸 이소시아누레이트, 트리메틸올 프로판 트리 아크릴레이트, 에틸렌 옥시드 3몰 부가형 트리메틸올 프로판 트리 아크릴레이트, 에틸렌 옥시드 6몰 부가형 트리메틸올 프로판 트리아크릴레이트, 펜타에리트리톨 트리아크릴레이트, 트리스(아크릴로옥시에틸)이소시아누레이트, 디펜타에 Relate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,3- alkylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxy charged bisphenol a di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricyclodecane dimethanol diacrylate rate (Tricyclo [5.2.1.0 2,6] decanedimethanol diacrylate ), tris-acryloyloxyethyl isocyanurate, trimethylolpropane triacrylate, ethylene oxide addition type 3 moles of trimethylolpropane triacrylate, ethylene oxide 6 the molar addition type trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol 트리톨 헥사 아크릴레이트, 카프로락톤 변성 디펜타에리트리톨 헥사 아크릴레이트로 이루어진 군으로부터 선택됨을 특징으로 하는, 광도파로용 광경화성 수지 조성물. Tall Tree hexaacrylate, caprolactone-modified dipentaerythritol hexa is selected from the group consisting of acrylate, which is characterized, photo-curing resin composition for the optical waveguide.
  9. 제2항에 있어서, 3. The method of claim 2,
    1개 이상의 에폭시기를 갖는 광반응성 모노머(B 2 )가 3,4-에폭시시클로헥실메틸-3,4-에폭시시클로헥산 카복실레이트, 비스-(3,4-에폭시클로헥실)아디페이트, 3-에틸-3-히드록시메틸-옥세탄, 1,2-에폭시헥사데칸, 알킬글리시딜에테르, 2-에틸헥실디글리콜 글리시딜에테르, 에틸렌글리콜 디글리시딜 에테르, 디에틸렌글리콜 디글리시딜 에테르, PEG#200 디글리시딜 에테르, PEG#400 디글리시딜 에테르, 프로필렌글리콜 디글리시딜 에테르, 트리프로필렌글리콜 디글리시딜 에테르, PPG#400 디글리시딜 에테르, 네오펜틸글리콜 디글리시딜 에테르, 1,6-헥산디올 디글리시딜 에테르, 수소화 비스페놀 A 디글리시딜 에테르, 프로필렌옥시드 변형 비스페놀 A형 디글리시딜 에테르, 디브로모 네오펜틸글리콜 디글리시딜 에테르 및 트리메틸올프로판 트리글리시딜 에테르로 이 Photoreactive monomer having at least one epoxy group (B 2) is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis- (3,4-epoxy claw hexyl) adipate, 3-ethyl 3-hydroxymethyl-oxetane, 1,2-epoxy hexadecane, alkyl glycidyl ether, 2-ethylhexyl sildi glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, PEG # 200 di-glycidyl ether, PEG # 400 diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, PPG # 400 diglycidyl ether, neopentyl glycol glycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, propylene oxide modified bisphenol A diglycidyl ether, dibromo neopentyl glycol diglycidyl ether and is a trimethylol propane triglycidyl ether 루어진 군으로부터 선택됨을 특징으로 하는, 광도파로용 광경화성 수지 조성물. Lure for binary optical waveguide as claimed selected from a photo-curable resin composition.
  10. 제2항 내지 제9항중 어느 한 항에 있어서, In the second to claim 9, wherein any one of,
    복굴절률이 1×10 -4 이하이고, 굴절률을 1.38 내지 1.54의 범위로 조절할 수 있고, 점도를 50 내지 2000 cps 범위로 조절할 수 있으며, 열분해온도가 300℃ 이상임을 특징으로 하는, 광도파로용 광경화성 수지 조성물. Birefringence is 1 × 10 -4 or less, the refractive index of 1.38 can be adjusted to a range of 1.54, and to adjust the viscosity to 50 to 2000 cps range, characterized in that the thermal decomposition temperature is above 300 ℃, optical path for the optical waveguide resin composition.
  11. 제2항 내지 제9항중 어느 한 항의 광경화형 수지 조성물을 실록산계 몰드에 적용하고 과량의 광경화형 수지를 제거한 후, 하부 클래딩층이 코팅된 실리콘웨이퍼를 광경화시키고, 상기 광경화형 수지로 도포된 실록산계 몰드를 상기 하부 클래딩 코팅면에 부착시키고 광경화시킨 후 실록산계 몰드를 제거하고, 상기 광경화형 수지에 상부 클래딩층을 코팅 및 광경화시키는 단계를 포함하는, 광도파로의 제조방법. Claim the application on 2 to 9 Compounds of any one of the photocurable resin composition siloxane-based mold and to remove the excess of photocurable resin, the lower cladding layer and Chemistry sight-coated silicon wafer, coated with the photocurable resin attaching a siloxane-based mold on the lower cladding surface coating and photocuring remove the siloxane-based mold after the method of producing an optical waveguide comprising a coating and a photo-solidifying step the upper cladding layer on the photocurable resin.
  12. 제11항의 방법에 따라 제조된 광도파로. The optical waveguide produced according to the method of claim 11.
KR10-2002-0011002A 2002-02-28 2002-02-28 Photo-curable resin composition for optical waveguide and optical waveguide prepared therefrom KR100487025B1 (en)

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