KR101005811B1 - Perfluorinated multi-acrylates with phosphate and the photo-curable components containing them - Google Patents
Perfluorinated multi-acrylates with phosphate and the photo-curable components containing them Download PDFInfo
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- KR101005811B1 KR101005811B1 KR1020080098904A KR20080098904A KR101005811B1 KR 101005811 B1 KR101005811 B1 KR 101005811B1 KR 1020080098904 A KR1020080098904 A KR 1020080098904A KR 20080098904 A KR20080098904 A KR 20080098904A KR 101005811 B1 KR101005811 B1 KR 101005811B1
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- perfluorinated
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- phosphate
- acrylic compound
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- 229910019142 PO4 Inorganic materials 0.000 title abstract description 25
- 239000010452 phosphate Substances 0.000 title abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 21
- -1 acrylic compound Chemical class 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 34
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 13
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical class ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims 2
- 230000003287 optical effect Effects 0.000 abstract description 45
- 239000000463 material Substances 0.000 abstract description 11
- 229920006254 polymer film Polymers 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000004891 communication Methods 0.000 abstract description 6
- 230000001678 irradiating effect Effects 0.000 abstract description 5
- 238000005253 cladding Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000008646 thermal stress Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229920000412 polyarylene Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 2
- BFMDZOWJRVLYPB-UHFFFAOYSA-N 2-[2-[2-(1,1-difluoro-2-hydroxyethoxy)-1,1,2,2-tetrafluoroethoxy]-1,1,2,2-tetrafluoroethoxy]-2,2-difluoroethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)OC(F)(F)CO BFMDZOWJRVLYPB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CCN[C@](*)[C@](C)[C@@](C)*(C)C Chemical compound CCN[C@](*)[C@](C)[C@@](C)*(C)C 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- CWIAFBQLWOMNFY-UHFFFAOYSA-N 2-[2-(1,1-difluoro-2-hydroxyethoxy)-1,1,2,2-tetrafluoroethoxy]-2,2-difluoroethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)OC(F)(F)CO CWIAFBQLWOMNFY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical compound O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical class OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
본 발명은 하기 화학식 1로 표시되는 포스페이트를 갖는 과불소화 다가 아크릴계 화합물 및 이의 제조방법과 이를 함유하는 광중합 조성물에 관한 것이다.The present invention relates to a perfluorinated polyhydric acrylic compound having a phosphate represented by the following formula (1), a method for preparing the same, and a photopolymerization composition containing the same.
[화학식 1][Formula 1]
[상기 화학식 1에서, R1 및 Rf는 명세서에 정의된 바와 같다.][In Formula 1, R 1 and R f are as defined in the specification.]
본 발명에 따른 과불소화 다가 아크릴 화합물 및 광중합 조성물은 자외선 등의 광을 조사함에 의하여 신속히 경화되어 광통신 파장 대에서의 광투명성이 우수하고 복굴절율이 낮으며 열안정성이 우수한 고분자 광경화 필름을 용이하게 제조할 수 있어 광 스위치, 가변 광감쇠기, 광 도파로 등 다양한 광소자의 코어 혹은 클래딩 재료로 사용이 가능한 물질이다. The perfluorinated polyhydric acrylic compound and the photopolymerization composition according to the present invention are rapidly cured by irradiating light such as ultraviolet rays, thereby easily providing a polymer photocurable film having excellent light transparency in the optical communication wavelength range, low birefringence, and excellent thermal stability. It can be manufactured to be used as core or cladding material of various optical devices such as optical switch, variable optical attenuator and optical waveguide.
포스페이트, 과불소화 다가 아크릴, 광투명성, 광중합, 복굴절률, 고분자 필름 Phosphate, perfluorinated polyacrylic, light transparency, photopolymerization, birefringence, polymer film
Description
본 발명은 포스페이트를 중심구조로 지니는 과불소화 다가 아크릴계 화합물, 이의 제조방법 및 이를 함유하는 광중합성 조성물에 관한 것이다. 더욱 상세하게는 포스페이트를 코어구조로 하고 과불소화 알킬기가 가지로 연결되어 있으며 말단에 아크릴기가 도입된 신규 구조의 포스페이트 과불소화 아크릴화합물과 상기 포스페이트 과불소화 아크릴화합물에 다른 불소화아크릴계 화합물, 광개시제 등을 함유시켜 광통신파장영역에서의 광투명성이 우수하고 복굴절율이 낮으며 열안정성이 우수한 광소자용 소재로 적용할 수 있는 광중합성 조성물에 관한 것이다. The present invention relates to a perfluorinated polyhydric acrylic compound having a phosphate as a center structure, a method for preparing the same, and a photopolymerizable composition containing the same. More specifically, a phosphate perfluorinated acrylic compound having a phosphate core structure, a perfluorinated alkyl group connected by a branch, and an acryl group introduced at the terminal, and a fluorinated acrylic compound, a photoinitiator, etc., in the phosphate perfluorinated acrylic compound. The present invention relates to a photopolymerizable composition which can be applied as an optical device material having excellent optical transparency in the optical communication wavelength region, low birefringence, and excellent thermal stability.
광도파로용 고분자 소재는 차세대 종합 정보 통신망의 구현에 절대적으로 필요한 파장분할다중화시스템 관련 광소자뿐 아니라 광 상호 연결소자, 광분할기, 광결합기, 열광학 스위치, 가변 감쇄기 등에 응용될 수 있는 핵심 소재이다. 광도파로 소자용 고분자 재료는 사용 파장대역인 1.3~1.55 파장대에서 광 투명성이 우수해야하고, 복굴절율이 낮아야 하며 높은 열적 및 환경 안정성, 코팅성 등의 특성이 요구된다. 유기고분자 소재는 무기재료 및 반도체재료에 비하여 분자구조 제어에 의하여 용이하게 재료의 특성을 조절하여 합성할 수 있고 가공성이 우수하며 저렴한 가격으로 대량생산이 가능하고 응답속도가 빠르고 열-광학 특성이 우수하다. 그러나 열 안정성이 낮고 광진행손실이 크기 때문에 광도파로 소자로의 응용에 제한을 받고 있으며 특히 광 진행 손실을 크게 낮출 필요가 있다. 유기 소재는 일반적으로 적외선 영역에서 분자 구조 내의 진동에 의한 고유의 흡수 영역을 가지고 있다. 특히, C-H 결합에 의한 근적외선 영역의 진동 흡수 손실은 2차 및 3차의 조화 배진동에 기인하는 것으로써 1.3~1.55 파장대에서의 고분자 소재의 광 손실의 주된 원인이다. 이러한 광손실 문제는 C-H 결합을 불소 (C-F)로 치환하여 환산질량을 증가시킴으로써 조화 배진동을 장파장으로 이동시키고 결과적으로 광통신 파장 영역에서의 광 흡수를 최소화함에 의하여 해결할 수 있다. 또한 이와 같이 플루오로기를 도입하면 광 손실이 낮아질 뿐 아니라 필름의 소수성이 증가하여 수분 침투성이 낮아지며 내화학 안정성이 높아지고 내마모성이 향상되는 장점을 부여할 수 있다.The optical material for optical waveguide is a core material that can be applied to optical interconnection devices, optical splitters, optical couplers, thermo-optic switches, and variable attenuators, as well as optical devices related to wavelength division multiplexing systems, which are absolutely necessary for the implementation of next-generation integrated information and communication networks. . The optical material for optical waveguide device should have excellent optical transparency in the wavelength band of 1.3 ~ 1.55, the low birefringence, high thermal and environmental stability, and coating property. Compared to inorganic materials and semiconductor materials, organic polymer materials can be easily synthesized by controlling the characteristics of materials by controlling the molecular structure, and have excellent processability, mass production at low price, fast response speed, and excellent thermo-optical characteristics. Do. However, due to the low thermal stability and the large optical loss, the application to the optical waveguide device is limited. In particular, the optical propagation loss needs to be greatly reduced. Organic materials generally have an inherent absorption region due to vibrations in the molecular structure in the infrared region. In particular, the vibration absorption loss in the near infrared region due to C-H bonding is caused by the harmonic double oscillation of the 2nd and 3rd order and is the main cause of the light loss of the polymer material in the 1.3 to 1.55 wavelength band. This problem of optical loss can be solved by substituting C-H bonds with fluorine (C-F) to increase the converted mass, thereby shifting harmonic back vibrations to longer wavelengths and consequently minimizing light absorption in the optical communication wavelength range. In addition, the introduction of the fluoro group not only lowers the light loss but also increases the hydrophobicity of the film, thereby lowering the moisture permeability, increasing the chemical resistance and improving the wear resistance.
기존의 광소자용 고분자소재의 연구 방향은 내열성을 부여하기 위하여 높은 유리전이온도를 가지도록 분자구조를 설계하는 것을 기본 지침으로 삼았다. 이를 기반으로 유리전이온도가 매우 높고 열안정성이 우수한, 불소기가 치환된 폴리이미드 소재가 일본 NTT 등에 의하여 개발되었다(T. Matsuura, et.al. Macromoleculaes, 26, 419 (1993).; S. Ando, et.al. Macromoleculaes, 25, 5858 (1992)). Dow Chemical에서는 유리전이온도가 400 ℃이상으로 매우 높아 열안정성이 우수하며 0.25 dB/cm이하의 광손실을 나타내는 폴리아릴렌에테르 화합물을 개발 하였다. 이 고분자는 가열에 의하여 퍼플루오로사이클로부탄(perfluorocyclobutane)을 형성하는 방식인 열경화형 구조를 지니고 있다(K. Petermann, et.al., Electron. Lett., 33, 518 (1997).) 한국전자통신연구원(ETRI)은 고분자 주쇄 양 말단에 아세틸렌이 치환되어 열경화가 가능한 불소기가 치환된 폴리아릴렌에테르를 개발하였다. 이 소재는 광 진행 손실이 0.5 dB/cm이하이며 복굴절율이 0.003정도를 나타내었다(H.J. Lee, et.al., J. Polym. Sci., Poly. Chem., 37, 2355 (1999)). The research direction of the existing polymer materials for optical devices is based on designing the molecular structure to have high glass transition temperature in order to provide heat resistance. Based on this, a fluorine-substituted polyimide material having a very high glass transition temperature and excellent thermal stability was developed by NTT et al. (T. Matsuura, et.al. Macromoleculaes, 26, 419 (1993); S. Ando) , et. al. Macromoleculaes, 25, 5858 (1992). Dow Chemical has developed a polyarylene ether compound that has a high glass transition temperature of more than 400 ℃ and has excellent thermal stability and shows an optical loss of 0.25 dB / cm or less. This polymer has a thermosetting structure that forms perfluorocyclobutane by heating (K. Petermann, et.al., Electron. Lett., 33, 518 (1997).) ETRI developed a polyarylene ether substituted with a fluorine group capable of thermosetting by replacing acetylene at both ends of the polymer main chain. This material has a light propagation loss of 0.5 dB / cm or less and a birefringence of about 0.003 (HJ Lee, et . Al. , J. Polym. Sci., Poly. Chem., 37, 2355 (1999)).
그러나 Gemfire사의 연구결과(H.S. Lackritz, et.al., US 6 236 774)에 의하면 상기와 같이 높은 유리전이온도를 가지는 고분자 소재를 열광학스위치 등의 광소자에 사용하면, 장기 사용 견뢰도에 문제가 발생하는 것으로 보고되었다. 즉 100 ℃ 정도 범위의 온도 구간에서 수 밀리초 동안 가열과 냉각을 수 없이 반복하면 (즉 소자를 구동하면) 고분자 필름에 열 응력이 쌓이게 되며, 장기적으로 이러한 열 응력이 축적됨에 의하여 열 이력 (thermal hysteresis) 거동을 보이고 초기 성능보다 저하된 소자 성능을 나타내게 된다는 것이다. 따라서 축적된 열 응력을 해소해 주기 위해 고분자 필름의 유리전이온도가 소자 구동온도보다 낮도록 분자 설계를 하고, 수치안정성을 위해서 그물망 구조를 지니도록 가교형 구조 설계를 하는 것이 바람직한 방향으로 제안되고 있다. 즉, 광가교 등으로 네트워크 구조를 형성하여 형태안정성을 유지하고 상온보다 낮은 유리전이온도를 가져 상온에서 분자구조들의 국소적인 자유운동이 가능하도록 분자 설계를 하는 것이다. 과불소화폴리알킬에테르 구조는 폴리알킬에테르구조에서 불소가 치환된 형태이다. Corning 사 는 트리아진화합물 등에 과불소화폴리알킬에테르 구조가 연결된 다가 아크릴화합물을 개발하였으며, 상기 화합물들의 광경화 필름의 유리전이온도는 상온보다 훨씬 낮은 수치를 나타내었다. (L.W. Shacklette, et.al., Adv. Func. Mater., 13, 453 (2003))However, according to Gemfire's research results (HS Lackritz, et.al., US 6 236 774), if a polymer material having a high glass transition temperature is used in an optical device such as a thermo-optic switch, there is a problem in the fastness of long-term use. It has been reported to occur. In other words, repeated heating and cooling for several milliseconds in the temperature range of about 100 ° C (ie driving the device) will cause thermal stress to accumulate in the polymer film, and in the long term, the thermal stress will be accumulated. hysteresis) behavior and lower device performance than initial performance. Therefore, in order to solve the accumulated thermal stress, it is suggested that the molecular design is performed so that the glass transition temperature of the polymer film is lower than the device driving temperature, and the crosslinked structure design has a mesh structure for the numerical stability. . In other words, the molecular structure is designed to maintain the morphological stability by forming a network structure, such as optical cross-linking, and to have a glass transition temperature lower than room temperature to enable local free movement of molecular structures at room temperature. The perfluorinated polyalkyl ether structure is a fluorine-substituted form in the polyalkyl ether structure. Corning has developed a polyhydric acrylic compound in which a perfluorinated polyalkyl ether structure is connected to a triazine compound and the like, and the glass transition temperature of the photocurable films of these compounds is much lower than room temperature. (LW Shacklette, et.al., Adv. Func. Mater., 13, 453 (2003))
한편 포스페이트계 아크릴 화합물에 의한 광경화 고분자는 열안정성이 높고 코팅성 및 필름형성능이 우수하며 광투명성이 뛰어난 특성을 나타내어 광학용 투명 소재로 많이 응용되어 개발되었다(JP2007-245622; JP2007-314765). On the other hand, the photocurable polymer by the phosphate-based acrylic compound has been developed by applying a lot of applications as a transparent material for optics because of high thermal stability, excellent coating properties, film forming ability and excellent light transparency (JP2007-245622; JP2007-314765).
광소자로의 응용을 위해서는 복굴절율을 10-4 이하로 낮추는 것이 필요하다. 높은 유리전이온도를 가지도록 설계하기 위해서 채용된 폴리이미드, 폴리아릴렌에테르 등의 대부분의 방향족 고분자의 경우 편광의존성이 높아 복굴절율이 10-3이상의 값을 나타내는 것이 일반적이다. 그러므로 낮은 복굴절율을 지니도록 가능한 한 방향족 구조 대신 지방족 과불소화 구조를 지니도록 분자 설계를 하는 것이 바람직하다 하겠다.It is necessary to lower the birefringence below 10 -4 for the application to the optical device. In the case of most aromatic polymers such as polyimide and polyarylene ether, which are employed for designing to have a high glass transition temperature, it is common that the birefringence is higher than 10 -3 due to the high polarization dependency. Therefore, it is desirable to design the molecule to have aliphatic perfluorinated structure instead of aromatic structure as much as possible to have low birefringence.
따라서, 본 발명자들은 광투명성 향상을 위하여 수소가 불소로 치환된 구조를 지니고 있으며, 편광의존성을 낮추기 위하여 방향족 대신 지방족 사슬 구조를 채택하였으며, 낮은 유리전이온도를 가지도록 포스페이트 화합물에 과불소화폴리알킬에테르 구조가 연결된 구조를 지니고 있으며, 수치안정성 및 내열, 내화학성의 확보를 위하여 광조사에 의하여 그물망 구조를 형성할 수 있도록 말단에 아크릴기가 도입된 다가 아크릴계 구조를 도입함으로써 광소자로의 응용에 적합한 재료를 개발하였다. Therefore, the present inventors have a structure in which hydrogen is substituted with fluorine to improve light transparency, and an aliphatic chain structure is used instead of aromatics to reduce polarization dependence, and a perfluorinated polyalkyl ether is used in the phosphate compound to have a low glass transition temperature. It has a structure in which the structure is connected, and a material suitable for application to an optical device is introduced by introducing a polyvalent acrylic structure in which an acryl group is introduced at the end to form a network structure by light irradiation in order to secure numerical stability, heat resistance, and chemical resistance. Developed.
본 발명은 광통신파장대에서 광투명성이 우수하고 편광의존성이 낮으며 소자의 신뢰성을 향상시키기 위하여 포스페이트 구조에 과불소화 지방족 사슬이 연결되어 있고 말단에 광경화에 의하여 가교구조의 형성이 가능하도록 아크릴기가 결합된 신규 화합물 및 이를 함유하는 광중합 조성물을 제공하는데 그 목적이 있다. 본 발명에 따른 과불소화 화합물 및 광중합 조성물은 광 진행 손실이 낮고 편광의존성이 낮으며 자외선 등의 광을 조사함에 의하여 신속히 경화하므로 광 스위치, 가변 광감쇠기, 광 도파로 등 다양한 광소자의 코어 혹은 클래딩 재료로의 적용이 가능하다. The present invention has excellent optical transparency in the optical communication wavelength band, low polarization dependence, perfluoro fluorinated aliphatic chain is connected to the phosphate structure in order to improve the reliability of the device, and acrylic groups are bonded to form a crosslinked structure by photocuring at the end. It is an object to provide a new compound and a photopolymerization composition containing the same. The perfluorinated compound and the photopolymerization composition according to the present invention have low light propagation loss, low polarization dependence, and rapidly cure by irradiating light such as ultraviolet light, so that they can be used as cores or cladding materials of various optical devices such as optical switches, variable optical attenuators, and optical waveguides. It is possible to apply.
상기의 과제를 달성하기 위하여 본 출원인은 많은 연구와 검토를 한 결과, 포스페이트 구조를 갖는 과불소화 다가 아크릴계 화합물을 개발함으로써 본 발명을 완성하게 되었다.In order to achieve the above object, the present inventors have conducted a lot of studies and studies, and have completed the present invention by developing a perfluorinated polyhydric acrylic compound having a phosphate structure.
본 발명은 포스페이트 구조를 갖는 과불소화 다가 아크릴계 화합물, 이의 제조방법 및 이를 함유하는 광중합성 조성물에 관한 것이다.The present invention relates to a perfluorinated polyhydric acrylic compound having a phosphate structure, a preparation method thereof, and a photopolymerizable composition containing the same.
좀 더 자세히 설명하면, 본 발명은 하기 화학식 1로 표시되는 포스페이트 구조를 갖는 과불소화 다가 아크릴계 화합물을 제공한다.In more detail, the present invention provides a perfluorinated polyvalent acryl-based compound having a phosphate structure represented by the following formula (1).
[화학식 1][Formula 1]
[상기 화학식 1에서, R1은 수소원자 또는 메틸기이고; Rf는 -CH2-(CF2)p-CH2-, -CH2-(CF2OCF2)q-CH2-, 또는 -CH2CF2O-(CF2CF2O)r-(CF2O)v-CF2CH2-이고; p 및 q는 서로 독립적으로 1 내지 12의 정수이고; r 및 v는 서로 독립적으로 1 내지 30의 정수이다.][In Formula 1, R 1 is a hydrogen atom or a methyl group; R f is —CH 2 — (CF 2 ) p —CH 2 —, —CH 2 — (CF 2 OCF 2 ) q —CH 2 —, or —CH 2 CF 2 O— (CF 2 CF 2 O) r − (CF 2 O) v -CF 2 CH 2- ; p and q are independently of each other an integer from 1 to 12; r and v are each independently an integer from 1 to 30.]
상기 Rf는 상업적으로 얻을 수 있는 과불소화 알킬 디올로부터 얻어지는 것으로써, 예를 들면 옥타플루오로헥산디올, 도데카플루오로옥탄디올 등의 불소화 디올(HO-CH2-(CF2)p-CH2-OH(p=1~12)), 플루오로화 트리에틸렌글리콜, 플루오로화 테트라에틸렌글리콜, 테트라플루오로에틸렌옥시드-디플루오로메틸렌옥시드 공중합체의 디올화합물 (HO-CH2-(CF2OCF2)q-CH2-OH(q=1~12)), 또는 솔베이솔렉시스에서 제공하는 FLUOROLINK계 화합물(HO-CH2CF2O-(CF2CF2O)r-(CF2O)v-CF2CH2-OH(r 및 v = 서로 독립적으로 1 ~ 30))등이 있으나, 이에 한정되는 것은 아니다.The R f is obtained from a commercially available perfluorinated alkyl diol, for example, fluorinated diols such as octafluorohexanediol and dodecafluorooctanediol (HO-CH 2- (CF 2 ) p -CH 2- OH (p = 1-12)), fluorinated triethylene glycol, fluorinated tetraethylene glycol, diol compound of tetrafluoroethylene oxide-difluoromethylene oxide copolymer (HO-CH 2- (CF 2 OCF 2 ) q -CH 2 -OH (q = 1-12), or FLUOROLINK compound (HO-CH 2 CF 2 O- (CF 2 CF 2 O) r -provided by Solvay Solexis (CF 2 O) v -CF 2 CH 2 -OH (r and v = 1 to 30 independently from each other)), but is not limited thereto.
상기 화학식 1로 표시되는 포스페이트 함유 과불소화 다가 아크릴 화합물은 광중합 가능한 단량체로서 광에 의해 신속하게 중합되어 광투명성이 우수한 고분자 박막을 얻을 수 있어 자외선을 이용한 광소자용 박막 제조 등에 매우 유리하다. 특히, 상기 화학식 1로 표시되는 화합물은 C-H 흡수 등에 의한 광손실을 최소화할 수 있도록 불소기로 치환되어 광진행손실을 최소화할 수 있다. 또한 화학식 1로 표시되는 화합물은 방향족 화합물 대신 지방족 화합물만 함유함에 의하여 편광의존성이 낮으며 포스페이트 화합물과 불소치환 알킬옥시드 구조를 함유하여 열안정성이 우수하며 낮은 유리전이온도를 지녀 소자 구동시에 발생하는 잔존 열응력의 제거에 용이하여 소자의 장기신뢰성을 향상시킬 수 있다. The phosphate-containing perfluorinated polyhydric acrylic compound represented by Chemical Formula 1 may be polymerized by light as a monomer capable of photopolymerization to obtain a polymer thin film having excellent light transparency, which is very advantageous for manufacturing a thin film for an optical device using ultraviolet light. In particular, the compound represented by Chemical Formula 1 may be substituted with a fluorine group to minimize light loss due to C-H absorption, thereby minimizing light loss. In addition, the compound represented by Formula 1 has a low polarization dependence by containing only an aliphatic compound instead of an aromatic compound, and has excellent thermal stability due to a phosphate compound and a fluorine-substituted alkyl oxide structure, and has a low glass transition temperature. It is easy to remove the residual thermal stress and improve the long-term reliability of the device.
본 발명에 따른 상기 화학식 1로 표시되는 포스페이트 함유 과불소화 다가 아크릴계 화합물은 다음과 같은 합성과정을 수행하여 제조한다.The phosphate-containing perfluorinated polyhydric acrylic compound represented by Chemical Formula 1 according to the present invention is prepared by performing the following synthesis process.
반응식 1에 나타낸 바와 같이 불소화 디올 화합물과 아크릴로일클로리드 등을 트리에틸아민 등과 같은 염기 하에서 반응시켜 한 쪽 히드록시기를 아크릴기로 치환한다.As shown in Scheme 1, the fluorinated diol compound, acryloyl chloride, and the like are reacted under a base such as triethylamine to replace one hydroxy group with an acryl group.
[반응식 1]Scheme 1
(상기 반응식 1에서, R1 및 Rf는 화학식 1에서의 정의와 동일하다.)(In Reaction Scheme 1, R 1 and R f are the same as defined in Formula 1.)
상기 반응식 1에서 얻은 아크릴 치환 알코올을 하기 반응식 2에 나타낸 바와 같이 포스포러스옥시클로리드와 염기하에서 반응시켜 포스페이트 중심구조에 3개의 과불소화 알킬 아크릴이 치환된 과불소화 다가 아크릴 화합물을 얻는다. The acryl-substituted alcohol obtained in Scheme 1 is reacted with phosphorus oxcyclolide under a base as shown in Scheme 2 to obtain a perfluorinated polyhydric acryl compound in which three perfluorinated alkyl acryl are substituted in the phosphate core structure.
[반응식 2]Scheme 2
(상기 반응식 2에서, R1 및 Rf는 화학식 1에서의 정의와 동일하다.)(In Reaction Scheme 2, R 1 and R f are the same as defined in Formula 1.)
본 발명은 하기 화합물(1) 내지 (4)로부터 선택되는 포스페이트 구조를 갖는 과불소화 다가 아크릴계 화합물을 포함한다.The present invention includes a perfluorinated polyhydric acrylic compound having a phosphate structure selected from the following compounds (1) to (4).
본 발명의 광중합성 조성물은 상기 화학식 1로 표시되는 포스페이트 구조를 갖는 과불소화 다가 아크릴계 화합물 1종 이상 및 광개시제를 포함하여 구성된다. 또한, 점도 조절 및 광중합 속도 조절과 경화 필름의 기계적, 굴절율 및 광학 특성 제어를 위하여 1종 이상의 과불소화 1가 혹은 2가 아크릴 화합물을 더 포함할 수 있다.The photopolymerizable composition of the present invention comprises at least one perfluorinated polyhydric acrylic compound having a phosphate structure represented by Chemical Formula 1 and a photoinitiator. In addition, one or more perfluorinated monohydric or divalent acrylic compounds may be further included for viscosity control, photopolymerization rate control, and mechanical, refractive index, and optical property control of the cured film.
과불소화 1가 혹은 2가 아크릴 화합물은 시판되는 화합물 혹은 공지의 사실로 알려져 있는 화합물들 중에서 선택될 수 있으며, 대표적인 예를 들면 하기 화학식 5 내지 8에 나타낸 바와 같다.The perfluorinated monovalent or divalent acrylic compound may be selected from among commercially available compounds or compounds known to be known, and are representative as shown in the following Chemical Formulas 5 to 8, for example.
[화학식 5][Chemical Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
(상기 식에서, m은 2 내지 10의 정수이고; X 및 y는 서로 독립적으로 1 내지 30의 정수이다.)(Wherein m is an integer from 2 to 10; X and y are each independently an integer from 1 to 30).
과불소화 1가 혹은 2가 아크릴 화합물은 구체적으로 하기 화합물로 예시되나, 이에 한정되지는 않는다.The perfluorinated monovalent or divalent acrylic compound is specifically exemplified by the following compounds, but is not limited thereto.
본 발명에서 포스페이트 함유 과불소화 다가 아크릴계 화합물을 함유하는 광중합성 조성물은 그 필요에 따라서 조성비를 적절히 조절가능하며, 상기 화학식 1의 포스페이트 함유 과불소화 다가 아크릴계 화합물은 광중합성 조성물 전체에 대하여 5 내지 99 중량%가 포함될 수 있으며, 좋게는 10 내지 40 중량%로 포함될 수 있다.In the present invention, the photopolymerizable composition containing the phosphate-containing perfluorinated polyhydric acrylic compound can be appropriately adjusted in proportion as necessary, and the phosphate-containing perfluorinated polyhydric acrylic compound of Formula 1 may be used in an amount of 5 to 99 weight based on the total photopolymerizable composition. % May be included, preferably 10 to 40% by weight.
또한, 더 첨가되는 성분인 과불소화 1가 혹은 2가 아크릴 화합물은 전체 조성물에 대하여 0~95 중량%로 투입되며, 좋게는 60~90 중량%로 투입될 수 있다.In addition, the perfluorinated monohydric or divalent acrylic compound to be added is added in an amount of 0 to 95% by weight, preferably 60 to 90% by weight based on the total composition.
본 발명의 광중합성 조성물의 또 다른 성분으로 광개시제는 Irgacure369 등의 시바가이기사의 자외선 광개시제, 2,2-디메톡시-2-페닐아세토페논, 2,2-디에톡시아세토페논 등의 벤조일 라디칼 생성 개시제 등의 광개시제를 불소화 아크릴계 화합물, 즉, 화학식 1의 포스페이트 함유 과불소화 다가 아크릴계 화합물과 추가로 투입하는 불소화 1가 또는 2가 아크릴계 화합물의 합 중량의 0.01~5 %로 투입하며, 바람직하게는 0.1~3 %로 투입하는 것이 본 발명의 목적을 달성하는데 좋다. As another component of the photopolymerizable composition of the present invention, the photoinitiator is an ultraviolet photoinitiator of Shivagaigi Corporation such as Irgacure369, a benzoyl radical generation initiator such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, etc. A photoinitiator, such as a fluorinated acrylic compound, that is, a phosphate-containing perfluorinated polyhydric acrylic compound of formula (1) and a fluorinated monovalent or divalent acrylic compound to be added at 0.01 to 5% of the total weight, preferably 0.1 to 3% is good for achieving the object of the present invention.
본 발명의 화학식 1의 포스페이트 함유 과불소화 다가 아크릴계 화합물 및/또는 불소화 1가 혹은 2가 아크릴계 화합물 및 광개시제를 함유하는 조성물은 그 자체로서 스핀코팅의 방법 등으로 제조한 박막을 자외선 조사하여 광 투명성이 우수한 필름을 제조할 수 있으며, 혹은 프로필렌글리콜모노메틸에테르아세테이트, 사이클로헥사논, 또는 사이클로펜타논 등의 용매에 1~40 중량%로 녹여 제조한 용액을 스핀코팅하고 자외선 조사하여 광 투명성이 우수한 필름을 제조할 수 있다. The composition containing the phosphate-containing perfluorinated polyhydric acrylic compound and / or the fluorinated monovalent or divalent acrylic compound and the photoinitiator of the formula (I) of the present invention is light transparency by ultraviolet irradiation of a thin film prepared by spin coating or the like. Excellent film can be prepared, or a solution prepared by dissolving 1-40% by weight in a solvent such as propylene glycol monomethyl ether acetate, cyclohexanone, or cyclopentanone by spin coating and UV irradiation to excellent light transparency Can be prepared.
본 발명에 따른 포스페이트 함유 과불소화 다가 아크릴 화합물은 포스페이트를 중심구조로 하고 과불소화 알킬기가 가지로 연결되어 있으며 말단에 아크릴기가 도입된 신규 구조의 화합물로, 이를 포함하는 광중합성 조성물은 자외선 등의 광을 조사함에 의하여 신속히 경화되어 광통신 파장 대에서의 광투명성이 우수하고 복굴절율이 낮으며 열안정성이 우수한 고분자 광경화 필름을 용이하게 제조할 수 있어 광 스위치, 가변 광감쇠기, 광 도파로 등 다양한 광소자의 코어 혹은 클래딩 재료로의 적용이 가능하다.The phosphate-containing perfluorinated polyhydric acrylic compound according to the present invention is a compound of a novel structure having a phosphate as a center structure, a perfluorinated alkyl group connected by a branch, and an acryl group introduced at the terminal. It can be rapidly cured by irradiating light, and it is easy to manufacture polymer photocurable film with excellent optical transparency, low birefringence and excellent thermal stability in optical communication wavelength band, so that it can be used for various optical devices such as optical switch, variable optical attenuator, optical waveguide, etc. Application to the core or cladding material is possible.
이하는 본 발명에 따른 상기 화합물들을 합성하는 반응들에 대하여 다음의 구체적인 실시예를 통하여 더욱 상세히 설명하며, 본 발명이 하기의 실시예에만 한정하는 것은 아니다.Hereinafter, reactions for synthesizing the compounds according to the present invention will be described in more detail with reference to the following specific examples, and the present invention is not limited to the following examples.
[실시예 1] 포스페이트 함유 과불소화 다가 아크릴계 화합물(1)의 합성Example 1 Synthesis of Phosphate-containing Perfluorinated Polyvalent Acrylic Compound (1)
[1-1] 화합물 (A)의 합성[1-1] Synthesis of Compound (A)
3구 플라스크에 플루오리네이티드 테트라에틸렌 글리콜(fluorinated tetraethylene glycol) (20 g, 48.77 mmol)을 무수 테트라하이드로퓨란 (150 ㎖)에 용해시킨 후 0 ℃로 냉각시켰다. 트리에틸아민 (5.1 ㎖)을 천천히 투입하고 30분 교반 후 아크릴로일 클로리드 (3 ㎖)를 천천히 투입하였다. 이 용액을 상온에서 3시간 교반 반응하였다. 침전물을 여과한 후 다이클로로메탄으로 추출한 후 컬럼 크로마토그래피(다이클로로메탄/헥산=2:1)로 분리하여 무색의 액체를 수득율 44 %로 얻었다. In a three-necked flask, fluorinated tetraethylene glycol (20 g, 48.77 mmol) was dissolved in anhydrous tetrahydrofuran (150 mL) and cooled to 0 ° C. Triethylamine (5.1 mL) was added slowly, and after stirring for 30 minutes, acryloyl chloride (3 mL) was added slowly. The solution was stirred for 3 hours at room temperature. The precipitate was filtered off, extracted with dichloromethane and separated by column chromatography (dichloromethane / hexane = 2: 1) to give a colorless liquid at 44% yield.
1H-NMR (300 MHz, CDCl3) : δ 6.56-6.50 (d, J=18 Hz, 1H), 6.22-6.13 (q, 1H), 6.01-5.98 (d, J=10.5 Hz, 1H), 4.60-4.54 (t, 2H), 3.99-3.91 (q, 2H), 2.73-2.68 (t, 1H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.56-6.50 (d, J = 18 Hz, 1H), 6.22-6.13 (q, 1H), 6.01-5.98 (d, J = 10.5 Hz, 1H), 4.60-4.54 (t, 2H), 3.99-3.91 (q, 2H), 2.73-2.68 (t, 1H).
[1-2] 화합물 (1)의 합성[1-2] Synthesis of Compound (1)
3구 플라스크에 상기의 화합물 (A) (4.54 g, 9.78 mmol)를 다이클로로 메탄에 녹인 후 트리에틸아민 (1.36 ㎖)을 천천히 적하한 후 1시간 동안 교반하였다. 나트륨으로 정제된 포스포러스 옥시클로리드 (0.5 g, 3.26 mmol)를 천천히 적하한 후 질소 분위기 하에서 50 ℃로 12 시간동안 환류시킨 후 냉각시켰다. 침전물을 여과한 후 에틸아세테이트로 추출한 후 유기층은 MgSO4로 건조시킨 후 컬럼 크로마토그래피 (다이클로로메탄/헥산=2:1)로 분리하여 무색 액체로 화합물 (1)을 수득율 32% 로 얻었다. The compound (A) (4.54 g, 9.78 mmol) was dissolved in dichloromethane in a three neck flask, and triethylamine (1.36 mL) was slowly added dropwise, followed by stirring for 1 hour. Phosphorus oxcyclolide (0.5 g, 3.26 mmol) purified with sodium was slowly added dropwise and then refluxed at 50 ° C. for 12 hours under a nitrogen atmosphere, followed by cooling. The precipitate was filtered and extracted with ethyl acetate, and then the organic layer was dried over MgSO 4 and separated by column chromatography (dichloromethane / hexane = 2: 1) to give a compound (1) as a colorless liquid with a yield of 32%.
1H-NMR (300 MHz, CDCl3) : δ 6.54-6.48 (d, J=17.4 Hz, 3H), 6.21-6.12 (q, 3H), 5.98-5.95 (d, J=10.5 Hz, 3H), 4.59-4.52 (t, 6H), 4.46-4.37 (q, 6H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.54-6.48 (d, J = 17.4 Hz, 3H), 6.21-6.12 (q, 3H), 5.98-5.95 (d, J = 10.5 Hz, 3H), 4.59-4.52 (t, 6H), 4.46-4.37 (q, 6H).
[실시예 2] 포스페이트 함유 과불소화 다가 아크릴계 화합물(2)의 합성Example 2 Synthesis of Phosphate-containing Perfluorinated Polyvalent Acrylic Compound (2)
[2-1] 화합물 (B)의 합성[2-1] Synthesis of Compound (B)
2구 플라스크에 질소 분위기 하에 플루오리네이티드 트리에틸렌글리콜(fluorinated triethylene glycol) (15g, 0.05 mol) 및 트리에틸아민 (7.74g, 0.08 mol)을 무수 테트라히드로퓨란 (50 ㎖)에 용해한 후 0 ℃ 얼음물 내에서 교반하면서 20 ㎖의 무수 테트라히드로퓨란에 용해된 아크릴로일 클로리드 (6.93 g, 0.08 mol)을 적하하였다. 4 시간 교반 반응 후 침전물을 여과하고 용매를 감압하여 제거하였다. 남아있는 침전물은 에틸아세테이트로 2회 반복하여 녹인 후 여과하고 감압하였다. 노란색의 점성을 띄는 액체 생성물을 메틸렌클로리드에 녹여 물로 여러 번 추출하고 유기층을 무수마그네슘설페이트로 건조시킨 후 컬럼크로마토그래피 (메틸렌클로리드/헥산=1/1 후 메틸렌클로리드 단독) 분리 하여 7.5g의 화합물 (B)을 얻었다 (수율 : 42 %). In a two-neck flask, fluorinated triethylene glycol (15 g, 0.05 mol) and triethylamine (7.74 g, 0.08 mol) were dissolved in anhydrous tetrahydrofuran (50 mL) under a nitrogen atmosphere, and then cooled to 0 ° C. While stirring inside, acryloyl chloride (6.93 g, 0.08 mol) dissolved in 20 ml of anhydrous tetrahydrofuran was added dropwise. After stirring for 4 hours, the precipitate was filtered and the solvent was removed under reduced pressure. The remaining precipitate was dissolved twice with ethyl acetate, filtered and depressurized. The yellow viscous liquid product was dissolved in methylene chloride, extracted several times with water, and the organic layer was dried over anhydrous magnesium sulfate, and then separated by column chromatography (methylene chloride / hexane = 1/1, followed by methylene chloride alone). Compound (B) was obtained (yield: 42%).
1H-NMR (300 MHz, CDCl3) : δ 6.56-6.50 (d, 1H), 6.23-6.14 (m, 1H), 6.01-5.97 (d, 1H), 4.60-4.54 (m, 2H), 3.96-3.88 (t, 2H), 2.70-2.65 (t, 1H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.56-6.50 (d, 1H), 6.23-6.14 (m, 1H), 6.01-5.97 (d, 1H), 4.60-4.54 (m, 2H), 3.96 -3.88 (t, 2 H), 2.70-2.65 (t, 1 H).
[2-2] 화합물 (2)의 합성[2-2] Synthesis of Compound (2)
2구 플라스크에 질소 분위기 하에 화합물 (B) (4.65 g, 0.013 mol) 를 메틸렌클로리드 (40 ㎖)에 용해한 후 교반하면서 트리에틸아민 (1.50 g, 0.015 mol)을 적하한 후 교반하면서 나트륨으로 정제된 포스포러스 옥시클로리드 (0.69g, 0.005 mol)을 적하하였다. 12 시간 반응 후 침전물을 여과하고 메틸렌클로리드를 감압하여 제거하였다. 남아있는 침전물은 에틸아세테이트로 2회 반복하여 녹인 후 여과하고 감압하였다. 노란색의 점성을 띄는 액체 생성물을 메틸렌클로리드에 녹여 물로 여러 번 추출하고 유기층을 무수 마그네슘설페이트로 건조시킨 후 컬럼크로마토그래피 (메틸렌클로리드/헥산=1/1 후 메틸렌클로리드 단독) 분리하여 2 g의 액상 화합물 (2)를 얻었다 (수율 : 40 %).In a two-necked flask, Compound (B) (4.65 g, 0.013 mol) was dissolved in methylene chloride (40 mL) under nitrogen atmosphere, and triethylamine (1.50 g, 0.015 mol) was added dropwise with stirring, followed by purification with sodium. Phosphorus oxcyclolide (0.69 g, 0.005 mol) was added dropwise. After the reaction for 12 hours, the precipitate was filtered off and methylene chloride was removed under reduced pressure. The remaining precipitate was dissolved twice with ethyl acetate, filtered and depressurized. The yellow viscous liquid product was dissolved in methylene chloride and extracted several times with water. The organic layer was dried over anhydrous magnesium sulfate, and then separated by column chromatography (methylene chloride / hexane = 1/1, methylene chloride alone), and separated. 2 g The liquid compound (2) was obtained (yield: 40%).
1H-NMR (300 MHz, CDCl3) : δ 6.55-6.48 (d, 3H), 6.22-6.13 (m, 3H), 5.99-5.95 (d, 3H), 4.60-4.52 (t, 6H), 4.45-4.36 (m, 6H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.55-6.48 (d, 3H), 6.22-6.13 (m, 3H), 5.99-5.95 (d, 3H), 4.60-4.52 (t, 6H), 4.45 -4.36 (m, 6 H).
[실시예 3] 포스페이트 함유 과불소화 다가 아크릴계 화합물(3)의 합성Example 3 Synthesis of Phosphate-containing Perfluorinated Polyvalent Acrylic Compound (3)
(r 및 v는 서로 독립적으로 1 내지 30의 정수이다.)
(r and v are each independently an integer from 1 to 30.)
[3-1] 화합물 (C)의 합성[3-1] Synthesis of Compound (C)
3구 플라스크에 플루오로린크 D10 (fluorolink D10, 평균분자량 1000) (25 g, 25.0 mmol)을 테트라하이드로퓨란 (20 ㎖)과 에톡시노나플루오로부탄 (ethoxynonafluorobutane) (5 ㎖)에 용해한 후 0 ℃로 냉각시켰다. 트리에틸아민 (3 ㎖)을 천천히 투입하고 30분 교반 후 아크릴로일 클로리드 (1.5 ㎖)를 천천히 투입하였다. 이 용액을 상온에서 10시간 교반 반응하였다. 반응이 끝나면 침전물을 여과하여 제거한 후 용매를 감압 하에서 제거하였다. 잔존물을 다이클로로메탄 으로 추출한 후 컬럼 크로마토그래피(다이클로로메탄/헥산=1:1)로 분리하여 무색의 액체를 수득율 40 %로 얻었다.In a three-necked flask, fluorolink D10 (molecular weight 1000) (25 g, 25.0 mmol) was dissolved in tetrahydrofuran (20 mL) and ethoxynonafluorobutane (5 mL), followed by 0 ° C. Cooled to. Triethylamine (3 mL) was added slowly, and after stirring for 30 minutes, acryloyl chloride (1.5 mL) was added slowly. The solution was stirred for 10 hours at room temperature. After the reaction was completed, the precipitate was filtered off and the solvent was removed under reduced pressure. The residue was extracted with dichloromethane and separated by column chromatography (dichloromethane / hexane = 1: 1) to give a colorless liquid with a yield of 40%.
1H-NMR (300 MHz, CDCl3) : δ 6.54-6.48 (d, 1H), 6.21-6.13 (q, 1H), 6.03-5.98 (d, 1H), 4.60-4.52 (m, 2H), 3.94-3.88 (m, 2H), 2.74-2.67 (m, 1H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.54-6.48 (d, 1H), 6.21-6.13 (q, 1H), 6.03-5.98 (d, 1H), 4.60-4.52 (m, 2H), 3.94 -3.88 (m, 2 H), 2.74-2.67 (m, 1 H).
[3-2] 화합물 (3)의 합성[3-2] Synthesis of Compound (3)
3구 플라스크에 상기의 화합물 (5) (10 mmol)를 테트라하이드로퓨란과 에톡시노나플루오로부탄에 녹인 후 트리에틸아민 (1.5 ㎖)을 천천히 적하한 후 2시간 동안 교반하였다. 나트륨으로 정제된 포스포러스 옥시클로리드(3.1 mmol)를 천천히 적하한 후 질소 분위기하에 50 ℃로 12 시간동안 반응시킨 후 냉각시켰다. 침전물을 여과한 후 에틸아세테이트로 추출한 후 유기층은 무수마그네슘으로 건조시킨 후 컬럼 크로마토그래피 (에틸아세테이트/헥산=1:5)로 분리하여 무색 액체를 수득율 30% 로 얻었다.The compound (5) (10 mmol) was dissolved in tetrahydrofuran and ethoxynonafluorobutane in a three neck flask, and triethylamine (1.5 mL) was slowly added dropwise thereto, followed by stirring for 2 hours. Phosphorus oxcyclolide (3.1 mmol) purified with sodium was slowly added dropwise, and then reacted at 50 ° C. for 12 hours under a nitrogen atmosphere, followed by cooling. The precipitate was filtered, extracted with ethyl acetate, and then the organic layer was dried over anhydrous magnesium and separated by column chromatography (ethyl acetate / hexane = 1: 5) to give a colorless liquid at a yield of 30%.
1H-NMR (300 MHz, CDCl3) : δ 6.54-6.48 (d, 3H), 6.21-6.12 (q, 3H), 5.98-5.95 (d, 3H), 4.64-4.52 (m, 6H), 4.48-4.37 (m, 6H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.54-6.48 (d, 3H), 6.21-6.12 (q, 3H), 5.98-5.95 (d, 3H), 4.64-4.52 (m, 6H), 4.48 -4.37 (m, 6 H).
[실시예 4] 포스페이트 함유 과불소화 다가 아크릴계 화합물(4)의 합성Example 4 Synthesis of Phosphate-containing Perfluorinated Polyvalent Acrylic Compound (4)
[4-1] 화합물 (D)의 합성[4-1] Synthesis of Compound (D)
3구 플라스크에 도데카플루오로옥탄다이올(dodecafluorooctanediol) (10 g, 27.6 mmol)을 테트라하이드로퓨란 (15 ㎖)에 용해한 후 0 ℃로 냉각시켰다. 트리에틸아민 (3 ㎖)을 천천히 투입하고 30분 교반 후 아크릴로일 클로리드 (1.5 ㎖)를 천천히 투입하였다. 이 용액을 상온에서 8시간 교반 반응하였다. 반응이 끝나면 침전물을 여과하여 제거한 후 용매를 감압 하에서 제거하였다. 잔존물을 에틸아세테이트로 추출한 후 컬럼 크로마토그래피(다이클로로메탄/헥산=1:2)로 분리하여 화합물 (D)를 수득율 43 %로 얻었다. Dodecafluorooctanediol (10 g, 27.6 mmol) was dissolved in tetrahydrofuran (15 mL) in a three neck flask and cooled to 0 ° C. Triethylamine (3 mL) was added slowly, and after stirring for 30 minutes, acryloyl chloride (1.5 mL) was added slowly. The solution was stirred for 8 hours at room temperature. After the reaction was completed, the precipitate was filtered off and the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate and separated by column chromatography (dichloromethane / hexane = 1: 2) to give compound (D) in a yield of 43%.
1H-NMR (300 MHz, CDCl3) : δ 6.52-6.47 (d, 1H), 6.22-6.13 (q, 1H), 6.05-5.98 (d, 1H), 4.61-4.52 (m, 2H), 3.93-3.86 (m, 2H), 2.73-2.66 (m, 1H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.52-6.47 (d, 1H), 6.22-6.13 (q, 1H), 6.05-5.98 (d, 1H), 4.61-4.52 (m, 2H), 3.93 -3.86 (m, 2 H), 2.73-2.66 (m, 1 H).
[4-2] 화합물 (4)의 합성[4-2] Synthesis of Compound (4)
3구 플라스크에 상기의 화합물 (D) (10 mmol)를 테트라하이드로퓨란에 녹인 후 트리에틸아민 (1.5 ㎖)을 천천히 적하한 후 2시간 동안 교반하였다. 나트륨으로 정제된 포스포러스 옥시클로리드(3.1 mmol)를 천천히 적하한 후 질소 분위기하에 40 ℃로 12 시간동안 반응시킨 후 냉각시켰다. 침전물을 여과한 후 에틸아세테이트로 추출한 후 유기층은 무수마그네슘으로 건조시킨 후 컬럼 크로마토그래피 (에틸아세테이트/헥산=1:4)로 분리하여 무색의 액체를 수득율 34% 로 얻었다.The compound (D) (10 mmol) was dissolved in tetrahydrofuran in a three neck flask, and triethylamine (1.5 mL) was slowly added dropwise thereto, followed by stirring for 2 hours. Phosphorus oxcyclolide (3.1 mmol) purified with sodium was slowly added dropwise, and then reacted at 40 ° C. for 12 hours under a nitrogen atmosphere, followed by cooling. The precipitate was filtered, extracted with ethyl acetate, and then the organic layer was dried over anhydrous magnesium and separated by column chromatography (ethyl acetate / hexane = 1: 4) to obtain a colorless liquid at a yield of 34%.
1H-NMR (300 MHz, CDCl3) : δ 6.56-6.49 (d, 3H), 6.22-6.12 (q, 3H), 5.97-5.93 (d, 3H), 4.62-4.50 (m, 6H), 4.50-4.39 (m, 6H). 1 H-NMR (300 MHz, CDCl 3 ): δ 6.56-6.49 (d, 3H), 6.22-6.12 (q, 3H), 5.97-5.93 (d, 3H), 4.62-4.50 (m, 6H), 4.50 -4.39 (m, 6 H).
[실시예 5] Example 5
실시예 1에서 합성한 포스페이트 함유 과불소화 다가 아크릴계 화합물 (1) (1.0 g)와 광개시제인 Irgacure369 (0.02 g)를 용매인 PGMEA (propylene glycol monomethyl ether acetate) (1 ml)에 녹인 후 0.2 μm 실린지 필터로 여과하여 샘플을 준비하였다. 이 용액을 UV-오존 처리한 실리콘 웨이퍼에 스핀코팅법으로 코팅한 후 90 ℃ 핫플레이트에서 5 분간 건조 후 90 ℃ 진공오븐에서 10 분간 건조하여 용매를 제거하였다. 질소 분위기하에서 Medium-pressure mercury lamp (출력: 80 W)로 20 분간 자외선을 조사하여 광 경화 시킨 후 130 ℃ 진공오븐에서 30 분간 후 처리하여 광경화 고분자 필름을 얻었다. 제조된 필름의 열분해 안정성을 평가하기 위하여 열중량분석기 (Thermogravimetric Analysis)로 고분자 필름의 열중량감소 측정 실험을 질소기류하에서 수행하였으며, 그 결과를 도 3에 나타내었다. 광경화 고분자 필름은 포스페이트 구조 및 불소원자를 지니고 있어 250 ℃까지는 거의 열분해에 의한 중량감소가 일어나지 않았으며, 초기 5 중량% 열분해 감소가 380 ℃에서 관측되는 특성을 보이는 등 높은 열분해안정성을 나타내었다. 굴절율, 광손실, 복굴절율 및 열광학특성계수(Thermo-Optic Coefficient)를 프리즘 커플러로 1550 nm 레이저 광원을 사용하여 측정하였다. 그 결과, 굴절률 1.357, 광진행손실 0.10 dB/cm, 복굴절율 7.0×10-4, 열광학특성계수 -6.13×10-5 을 얻었다.A phosphate-containing perfluorinated polyhydric acrylic compound (1) (1.0 g) synthesized in Example 1 and Irgacure369 (0.02 g), a photoinitiator, were dissolved in PGMEA (propylene glycol monomethyl ether acetate) (1 ml), followed by a 0.2 μm syringe. Samples were prepared by filtration with a filter. The solution was coated on a UV-ozone treated silicon wafer by spin coating, followed by drying for 5 minutes on a 90 ° C. hotplate and then drying for 10 minutes at a 90 ° C. vacuum oven to remove the solvent. Under a nitrogen atmosphere, a light was cured by irradiation with ultraviolet light for 20 minutes with a medium-pressure mercury lamp (output: 80 W), followed by 30 minutes in a vacuum oven at 130 ° C. to obtain a photocurable polymer film. In order to evaluate the thermal decomposition stability of the prepared film, a thermogravimetric analysis of the thermogravimetric measurement of the polymer film was carried out under a nitrogen stream, and the results are shown in FIG. 3. Since the photocurable polymer film has a phosphate structure and a fluorine atom, the weight loss due to pyrolysis hardly occurred until 250 ° C., and the initial 5 wt% reduction in pyrolysis showed high thermal decomposition stability. Refractive index, light loss, birefringence and thermo-optic coefficient were measured using a 1550 nm laser light source with a prism coupler. As a result, a refractive index of 1.357, optical progression loss of 0.10 dB / cm, birefringence of 7.0 × 10 -4 and a thermo-optical characteristic coefficient of -6.13 × 10 -5 were obtained.
[실시예 6]Example 6
실시예 2에서 합성한 포스페이트 함유 과불소화 다가 아크릴계 화합물 (2) (0.5 g)와 
[실시예 7]Example 7
실시예 3에서 합성한 포스페이트 함유 과불소화 다가 아크릴계 화합물 (3) (0.3 g)와 
[실시예 8]Example 8
실시예 4에서 합성한 포스페이트 함유 과불소화 다가 아크릴계 화합물 (4) (0.3 g)과 
도 1 -실시예 1에서 제조된 포스페이트 구조를 갖는 과불소화 다가 아크릴계 화합물(2)의 핵자기공명분광분석 그래프1-Nuclear magnetic resonance spectroscopy graph of the perfluorinated polyhydric acrylic compound (2) having a phosphate structure prepared in Example 1
도 2 -실시예 2에서 제조된 포스페이트 구조를 갖는 과불소화 다가 아크릴계 화합물(4)의 핵자기공명분광분석 그래프Figure 2-Nuclear magnetic resonance spectroscopy graph of the perfluorinated polyhydric acrylic compound (4) having a phosphate structure prepared in Example 2
도 3 -실시예 5에서 제조된 광경화 고분자 필름의 열중량분석 그래프3-thermogravimetric analysis graph of the photocurable polymer film prepared in Example 5
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| KR20000016321A (en) * | 1996-06-04 | 2000-03-25 | 토마스 에프.멀베니 | Polymeric perfluoro polyether phosphate lubricant topcoat |
| JP2007245622A (en) | 2006-03-17 | 2007-09-27 | Toppan Printing Co Ltd | Composition for hard coat layer, and laminated body |
-
2008
- 2008-10-09 KR KR1020080098904A patent/KR101005811B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124456A (en) | 1976-05-21 | 1978-11-07 | Yagupolsky Lev M | Method of tris(perfluoroalkyl)phosphine oxides |
| JPH0797586A (en) * | 1993-09-28 | 1995-04-11 | Nisshin Fine Chem Kk | Lubricant containing perfluoroalkyl group-containing phosphoric ester |
| KR20000016321A (en) * | 1996-06-04 | 2000-03-25 | 토마스 에프.멀베니 | Polymeric perfluoro polyether phosphate lubricant topcoat |
| JP2007245622A (en) | 2006-03-17 | 2007-09-27 | Toppan Printing Co Ltd | Composition for hard coat layer, and laminated body |
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| KR20100039922A (en) | 2010-04-19 |
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