KR100740994B1 - Cross-linkable perfluorinated di (meth) acrylic compound, photopolymerizable composition containing the same, and photopolymerizable membrane using the same - Google Patents
Cross-linkable perfluorinated di (meth) acrylic compound, photopolymerizable composition containing the same, and photopolymerizable membrane using the same Download PDFInfo
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- KR100740994B1 KR100740994B1 KR1020060028687A KR20060028687A KR100740994B1 KR 100740994 B1 KR100740994 B1 KR 100740994B1 KR 1020060028687 A KR1020060028687 A KR 1020060028687A KR 20060028687 A KR20060028687 A KR 20060028687A KR 100740994 B1 KR100740994 B1 KR 100740994B1
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- South Korea
- Prior art keywords
- compound
- photopolymerizable
- group
- perfluorinated
- photopolymerizable composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- -1 acrylic compound Chemical class 0.000 title claims abstract description 33
- 239000012528 membrane Substances 0.000 title abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000002952 polymeric resin Substances 0.000 claims abstract description 8
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 8
- 238000000016 photochemical curing Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- 229920002492 poly(sulfone) Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims description 2
- JJPHCFJECRBXFG-UHFFFAOYSA-N 2-(2-carboxyoxyethoxy)ethyl hydrogen carbonate Chemical compound OC(=O)OCCOCCOC(O)=O JJPHCFJECRBXFG-UHFFFAOYSA-N 0.000 claims description 2
- HZMXJTJBSWOCQB-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl prop-2-enoate Chemical compound COCCOCCOC(=O)C=C HZMXJTJBSWOCQB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 2
- 239000012968 metallocene catalyst Substances 0.000 claims description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims 2
- 125000005529 alkyleneoxy group Chemical group 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 42
- 230000003287 optical effect Effects 0.000 abstract description 14
- 239000010409 thin film Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003999 initiator Substances 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000013500 data storage Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 48
- 238000003786 synthesis reaction Methods 0.000 description 48
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 10
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 5
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
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- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 4
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- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 3
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 description 3
- LDIOUQIXNSSOGU-UHFFFAOYSA-N 8-(3-pentylamino)-2-methyl-3-(2-chloro-4-methoxyphenyl)-6,7-dihydro-5h-cyclopenta[d]pyrazolo[1,5-a]pyrimidine Chemical compound CC1=NN2C(NC(CC)CC)=C3CCCC3=NC2=C1C1=CC=C(OC)C=C1Cl LDIOUQIXNSSOGU-UHFFFAOYSA-N 0.000 description 3
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- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
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Images
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
- C08F20/24—Esters containing halogen containing perhaloalkyl radicals
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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Abstract
본 발명은 가교 가능한 과불소화 디（메타）아크릴계 화합물과 이를 함유한 광중합성 조성물 및 이를 이용한 광중합성 막에 관한 것으로서, 더욱 상세하게는 개시제 또는 열에 의하여 쉽게 중합될 수 있는 신규의 과불소화 디(메타)아크릴계 화합물과, 상기 과불소화 디(메타)아크릴계 화합물, 실록산 전구체로부터 제조된 졸-겔 용액 또는 투명 고분자 수지의 바인더 및 광개시제를 일정량 함유하여 광경화 시 수축율이 낮으면서도 굴절율 차이가 커 광기록 효과가 우수한 광중합성 조성물, 그리고 상기 광중합성 조성물을 광경화하여 홀로그래피 데이터 저장 장치용 포토폴리머로서 매우 유용할 뿐 아니라, 우수한 내열성, 내화학성, 기계적 강성 및 박막특성을 나타내어 기타 컬러필터, 확산판 코팅용 기판재료 등 디스플레이 부품소자에 응용 가능한 광중합성 막에 관한 것이다.The present invention relates to a crosslinkable perfluorinated di (meth) acrylic compound, a photopolymerizable composition containing the same, and a photopolymerizable membrane using the same, and more particularly, a novel perfluorinated di (meth) which can be easily polymerized by an initiator or heat. The optical recording effect of the acrylic compound, a sol-gel solution prepared from the perfluorinated di (meth) acrylic compound, a siloxane precursor, a binder of a transparent polymer resin, and a certain amount of a binder and a photoinitiator, so that the refractive index difference is large while the photocuring is low. Photopolymerizable composition, and the photopolymerizable composition is not only very useful as a photopolymer for holographic data storage devices, but also exhibits excellent heat resistance, chemical resistance, mechanical rigidity and thin film properties for coating other color filters and diffusion plates. Applicable to display parts such as substrate materials It relates to a polymeric film.
Description
도 1은 본 발명에 따라 합성예 1의 1H NMR 스펙트럼을 나타낸 것이다.1 shows the 1 H NMR spectrum of Synthesis Example 1 according to the present invention.
도 2는 본 발명에 따른 합성예 3의 1H NMR 스펙트럼을 나타낸 것이다.2 shows the 1 H NMR spectrum of Synthesis Example 3 according to the present invention.
도 3은 본 발명에 따른 합성예 1과 합성예 3의 열중량분석(TGA) 결과를 나타낸 것이다.Figure 3 shows the results of thermogravimetric analysis (TGA) of Synthesis Example 1 and Synthesis Example 3 according to the present invention.
도 4는 본 발명에 따른 실시예 1 및 비교예의 회절효율 측정결과를 나타낸 것이다.Figure 4 shows the diffraction efficiency measurement results of Example 1 and Comparative Example according to the present invention.
본 발명은 가교 가능한 과불소화 디（메타）아크릴계 화합물과 이를 함유한 광중합성 조성물 및 이를 이용한 광중합성 막에 관한 것으로서, 더욱 상세하게는 개시제 또는 열에 의하여 쉽게 중합될 수 있는 신규의 과불소화 디(메타)아크릴계 화합물과, 상기 과불소화 디(메타)아크릴계 화합물, 실록산 전구체로부터 제조된 졸-겔 용액 또는 투명 고분자 수지의 바인더 및 광개시제를 일정량 함유하여 광경화 시 수축율이 낮으면서도 굴절율 차이가 커 광기록 효과가 우수한 광중합성 조성물, 그리고 상기 광중합성 조성물을 광경화하여 홀로그래피 데이터 저장 장치용 포토폴리머로서 매우 유용할 뿐 아니라, 우수한 내열성, 내화학성, 기계적 강성 및 박막특성을 나타내어 기타 컬러필터, 확산판 코팅용 기판재료 등 디스플레이 부품소자에 응용 가능한 광중합성 막에 관한 것이다. The present invention relates to a crosslinkable perfluorinated di (meth) acrylic compound, a photopolymerizable composition containing the same, and a photopolymerizable membrane using the same, and more particularly, a novel perfluorinated di (meth) which can be easily polymerized by an initiator or heat. The optical recording effect of the acrylic compound, a sol-gel solution prepared from the perfluorinated di (meth) acrylic compound, a siloxane precursor, a binder of a transparent polymer resin, and a certain amount of a binder and a photoinitiator, so that the refractive index difference is large while the photocuring is low. Photopolymerizable composition, and the photopolymerizable composition is not only very useful as a photopolymer for holographic data storage devices, but also exhibits excellent heat resistance, chemical resistance, mechanical rigidity and thin film properties for coating other color filters and diffusion plates. Applicable to display parts such as substrate materials It relates to a polymeric film.
홀로그램 구현을 위한 포토폴리머인 경우, 모노머에 포함되어 있는 광중합 가능한 작용기에 의하여 광 간섭 패턴을 홀로그램으로 저장할 수 있는 장점으로 말미암아 광메모리 시스템의 매질과 광확산판, 광파장 분할기 등 많은 용도가 제안되고 있다. In the case of the photopolymer for the hologram, many applications such as the medium of the optical memory system, the light diffuser, and the optical wavelength divider have been proposed due to the advantage of storing the optical interference pattern as a hologram by the photopolymerizable functional groups included in the monomer. .
널리 사용되어지고 있는 광반응성 포토폴리머 화합물의 조성은 광증감제, 단량체, 개시제, 바인더로 구성되어져 있는데, 두 빔의 간섭광의 조사에 의하여 광증감제의 특정파장의 광흡수로부터 개시제가 활성화되어 모노머들의 중합이 시작된다. 이때, 두 입사빔의 간섭현상에 의한 보강간섭이 일어난 부분에서 활발한 광중합 반응이 진행되어 모노머가 고분자로 전이되고 상쇄간섭이 일어난 영역에서는 광흡수에 의한 단량체의 개시가 일어나지 않아 미반응된 단량체가 높은 농도로 존재하게 된다. 이러한 단량체의 농도구배를 줄여 농도의 평형상태를 이루기 위 해 단량체는 상쇄간섭 영역에서 보강간섭영역으로의 확산현상이 일어나게 된다. 즉, 간섭패턴에 따라 모노머와 고분자의 농도 구배가 발생하게 되어 이러한 원리로 인해 두 영역의 굴절율 변조가 가능하게 된다.The photoreactive photopolymer compound, which is widely used, is composed of a photosensitizer, a monomer, an initiator, and a binder. The monomer is activated by light absorption of a specific wavelength of the photosensitizer by irradiation of interference light of two beams. Polymerization of these compounds begins. At this time, the active photopolymerization reaction proceeds in the area where constructive interference occurs due to the interference of two incident beams so that the monomer is transferred to the polymer, and in the region where the offset interference occurs, the initiation of the monomer by light absorption does not occur and thus the unreacted monomer is high. Will be present in concentration. In order to achieve a concentration equilibrium by reducing the concentration gradient of these monomers, the diffusion of monomers from the destructive interference region to the constructive interference region occurs. That is, the concentration gradient of the monomer and the polymer is generated according to the interference pattern, and thus the refractive index modulation of the two regions is possible due to this principle.
정보화시대에 들어와 광화학적 중합이 도료, 인쇄용 기판, 인쇄회로, 집적회로, 정보기록 및 전자 기기 분야 등 여러 분야에서 다양하게 사용되고 있다. 광화학적 중합은 중합성 화합물에 빛을 조사하여 중합시키는 기술로 중합성 화합물에 직접 광 조사하여 활성화시킴으로써 중합을 개시하는 광중합과, 중합성 화합물에 광증감제를 혼합한 상태에서 광 조사하여 광증감제의 성장활성종을 생성시켜 중합하는 광증감 중합으로 구분된다. 이러한 광화학적 중합은 중합개시 및 정지가 여기광의 점멸에 의해 제어될 수 있으며, 여기광의 강도나 파장을 적절히 선택함으로써 중합속도나 중합도를 용이하게 제어할 수 있다. 또한, 광화학적 중합은 속도가 빠르며 일반적으로 중합개시 에너지가 낮기 때문에 저온에서도 중합이 가능하다.In the information age, photochemical polymerization has been used in various fields such as paints, printed boards, printed circuits, integrated circuits, information recording, and electronic devices. Photochemical polymerization is a technique of irradiating light to a polymerizable compound to polymerize it. It is divided into photosensitization polymerization which produces and polymerizes the growth active species. In the photochemical polymerization, the start and stop of the polymerization can be controlled by the blinking of the excitation light, and the polymerization rate and the degree of polymerization can be easily controlled by appropriately selecting the intensity or wavelength of the excitation light. In addition, the photochemical polymerization is fast and can be polymerized even at low temperatures because of low energy initiation.
이에 따라, 다양한 광중합성 조성물이 개발되고 있는데, 일례로 한국특허공개 제1992-4550호는 a) 중합체성 결합제, b) 유리라디칼에 의해 중합가능하며 적어도 하나의 말단 에틸렌성 이중결합을 갖는 화합물, 및 c) 광개시제로서의 N-헤테로고리화 화합물, 티오크산톤 유도체 및 디알킬아미노 화합물을 함유하는 광중합성 조성물이 개시되어 있다. 또한, 한국특허공개 제1991-17382호, 제1991-1467호, 제1990-3685호, 제1989-10615 호 및 제1988-11262호, 미국 특허 출원 제08/698,142호에는 다가 알콜의 아크릴레이트 또는 알카크릴레이트를 주성분으로 하며 자유라 디칼에 의해 중합 가능한 아크릴레이트 에스테르와 같은 액상 단량체를 포함하는 광중합성 조성물이 개시되어 있다. 그러나, 이러한 조성물은 단량체들이 중합되면서 광 기록시 수축이 일어나 저장된 정보의 해독이 어려운 단점을 갖는다.Accordingly, various photopolymerizable compositions have been developed. For example, Korean Patent Publication No. 1992-4550 discloses a compound polymerizable by a) a polymeric binder, b) free radicals, and having at least one terminal ethylenic double bond, And c) N-heterocyclic compounds, thioxanthone derivatives and dialkylamino compounds as photoinitiators are disclosed. Also, Korean Patent Publication Nos. 1991-17382, 1991-1467, 1990-3685, 1989-10615 and 1988-11262, and US Patent Application Nos. 08 / 698,142 disclose acrylates of polyhydric alcohols or A photopolymerizable composition is disclosed that comprises a liquid monomer, such as an acrylate ester, which is based on alkacrylate and is polymerizable by free radicals. However, such a composition has a disadvantage in that, as the monomers are polymerized, shrinkage occurs during optical recording, making it difficult to decode the stored information.
이러한 문제를 해결하기 위하여, 양이온 중합반응을 이용하는 에폭시 중합이 제안되어 수축이 1/2 정도로 감소하였으며[Waldman et al, "Cationic Ring-opening photopolymerization methods for volume hologram recording", SPIE vol. 2689, 1996, 127], 팽창제라고 불리우는 스피로-오르토에스테르(spiro-orthoester) 및 스피로-오르토카보네이트(spiro-orthocarbonate)가 에폭시계 중합성 조성물에 첨가되어 수축이 감소되고 경우에 따라서는 부피가 팽창하는 결과도 발표되었다[Expanding Monomers: Synthesis. Characterization, and Applications (R. K. Sadhir and R. M. Luck, eds., 1992) 1-25, 237-260; T. Takata and T. Endo, "Recent Advances in the Development of Expanding Monomers: Synthesis, Polymerization and Volume Change", Prog. Polym. Sci., Vol. 18, 1993, 839-870]. 또한, 미국특허 제6,221,536호는 중합 시 수축보상을 가져오기 위해 특정 스피로 화합물 팽창제를 중합성 조성물에 첨가하는 것을 제시한 바 있다.To solve this problem, epoxy polymerization using cationic polymerization has been proposed, reducing shrinkage by about 1/2 [Waldman et al, "Cationic Ring-opening photopolymerization methods for volume hologram recording", SPIE vol. 2689, 1996, 127], spiro-orthoester and spiro-orthocarbonate, called swelling agents, are added to epoxy-based polymerizable compositions to reduce shrinkage and in some cases volume Results were also published [Expanding Monomers: Synthesis. Characterization, and Applications (R. K. Sadhir and R. M. Luck, eds., 1992) 1-25, 237-260; T. Takata and T. Endo, "Recent Advances in the Development of Expanding Monomers: Synthesis, Polymerization and Volume Change", Prog. Polym. Sci., Vol. 18, 1993, 839-870. In addition, U. S. Patent No. 6,221, 536 has suggested adding a specific spiro compound swelling agent to the polymerizable composition to bring shrinkage compensation upon polymerization.
그러나, 스피로 화합물의 수축보상은 부분적인 상변화에 의한 것으로 그 효과가 그다지 크지 않고, 특히 개환반응과 그에 따른 분해반응 속도를 제어하기 어렵다는 문제를 갖는다[C. Bolln et al., "Synthesis and Photoinitiated Cationic Polymerization of 2-methylene-7-phenyl-1,4,6,9-tetraoxaspiro-[4,4]nonane," Macromolecules, Vol. 29, 1996, 3111-3116].However, the shrinkage compensation of the spiro compound is caused by partial phase change, and the effect thereof is not so large, and in particular, it is difficult to control the ring-opening reaction and the decomposition reaction rate thereof [C. Bolln et al., "Synthesis and Photoinitiated Cationic Polymerization of 2-methylene-7-phenyl-1,4,6,9-tetraoxaspiro- [4,4] nonane," Macromolecules, Vol. 29, 1996, 3111-3116.
미국특허 제4,842,968호는 다공성 유리재료 내에 광이미지 재료를 포함하는 매체를 개시하고 있다. 이 경우 광조사 기록 후 빛에 노출되지 않은 부분을 용매로 제거해야 하는데, 이때 용매 확산, 화학반응, 미반응된 단량체 제거의 어려움 등의 문제가 있다.U. S. Patent No. 4,842, 968 discloses a medium comprising an optical image material in a porous glass material. In this case, the part not exposed to light after the light irradiation recording should be removed with a solvent, and there are problems such as solvent diffusion, chemical reaction, and difficulty in removing unreacted monomers.
미국특허 제6,268,089호에는 규소, 티타늄, 게르마늄, 지르코늄, 바나듐 또는 알루미늄계의 유·무기 혼성 전구체를 이용한 홀로그래피용 광기록 매질이 제기되어 있으며, 유·무기 혼성 전구체가 중합되는 화학반응과 홀로그래피 기록에 이용되는 단량체의 광화학 반응을 서로 다른 경로로 일어나게 함으로써 미반응된 단량체의 제거공정을 생략하고, 올리고머를 산화물과 결합시켜 열안정성, 화학적 안정성 및 기계적 강도 등이 향상된 기록막을 제공하는 방법을 개시하고 있다. 그러나, 상기 방법은 유·무기 혼성 전구체의 중합반응(열 공정) 도중에 광경화성 단량체들이 중합되어 광기록 효율이 떨어지는 문제를 갖는다U.S. Patent No. 6,268,089 discloses an optical recording medium for holography using an organic-inorganic hybrid precursor of silicon, titanium, germanium, zirconium, vanadium, or aluminum. Disclosed is a method of providing a recording film having improved thermal stability, chemical stability and mechanical strength by omitting an oligomer with an oxide by omitting a process of removing unreacted monomers by causing photochemical reactions of monomers to be used in different paths. . However, the above method has a problem in that the photocurable monomers are polymerized during the polymerization reaction of the organic / inorganic hybrid precursor (thermal process), thereby decreasing the optical recording efficiency.
이에, 본 발명자들은 상기 문제점을 해결하기 위하여 연구 노력한 결과, 종래 통상적으로 사용되는 개시제 또는 열에 의하여 용이하게 중합이 수행될 수 있는 과불소화 디(메타)아크릴계 화합물을 합성하였으며, 상기 과불소화 디(메타)아크릴계 화합물과, 바인더 및 광개시제를 일정량 함유한 광중합성 조성물은 광경화 시 수축율이 낮으면서도 굴절율 차이가 커서 기록효과가 우수한 광중합성 막의 제조가 가능하다는 것을 알게되어 본 발명을 완성하게 되었다.Accordingly, the present inventors have made a research effort to solve the above problems, synthesized a perfluorinated di (meth) acrylic compound that can be easily polymerized by a conventionally used initiator or heat, the perfluorinated di (meta The photopolymerizable composition containing a certain amount of the acryl-based compound, a binder and a photoinitiator was found to be capable of producing a photopolymerizable film having excellent recording effect due to a large difference in refractive index while having a low shrinkage rate during photocuring.
따라서, 본 발명은 개시제 또는 열에 의한 가교반응으로 중합이 가능한 신규 과불소화 디(메타)아크릴계 화합물을 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide a novel perfluorinated di (meth) acrylic compound capable of polymerization by crosslinking reaction by an initiator or heat.
또한, 본 발명은 광경화 시 수축율이 낮으면서도 굴절율 차이가 커서 기록효과가 우수한 후막 제공이 가능한 광중합성 조성물을 제공하는데 다른 목적이 있다.In addition, another object of the present invention is to provide a photopolymerizable composition capable of providing a thick film having excellent recording effect due to a large difference in refractive index while having a low shrinkage rate during photocuring.
또한, 본 발명은 광중합성 조성물을 광경화하여 제조된 광중합성 막을 제공하는데 또 다른 목적이 있다.It is another object of the present invention to provide a photopolymerizable film prepared by photocuring a photopolymerizable composition.
다음 화학식 1로 표시되는 것을 특징으로 하는 과불소화 디(메타)아크릴계 화합물 :The perfluorinated di (meth) acrylic compound, characterized in that represented by the following formula (1):
[화학식 1][Formula 1]
상기 화학식 1에서, In Chemical Formula 1,
A는 산소이며; A is oxygen;
B는 에스테르기 또는 카보닐기이며; B is an ester group or a carbonyl group;
D는 C2 ∼ C6의 알킬렌 또는 알킬렌옥시기로서, 구체적으로는 
X는 알킬기 또는 할로알킬기로 치환 또는 비치환된 C6 ∼ C18의 알킬렌기 또는 아릴렌기로서, 구체적으로는
Y는 수소원자 또는 C1 ∼ C6의 알킬기이며; Y is a hydrogen atom or an alkyl group of C 1 to C 6 ;
m은 0 또는 1이며; m is 0 or 1;
n은 1 내지 5의 정수이다.n is an integer of 1-5.
상기 화학식 1로 표시되는 과불소화 디(메타)아크릴계 화합물은 광중합 가능한 단량체로서 광에 의해 중합되면서 이미지를 기록하는 역할 수행이 가능하며, 방 향족으로 치환되어 있어서 굴절율 변화가 큰 반면 부피 변화는 최소화할 수 있다는 장점을 갖는다. 특히, 상기 화학식 1로 표시되는 화합물은 C-F 결합으로 인해 C-H 결합을 갖는 유도체와 가교하여 높은 열적, 화학적 안정성을 갖게 되어 박막제조 및 홀로그램 저장매체의 보존성 등에서 유용하다.The perfluorinated di (meth) acrylic compound represented by Chemical Formula 1 may perform a role of recording an image while polymerizing by light as a monomer capable of photopolymerization, and is substituted with an aromatic group to minimize refractive index change while minimizing volume change. Has the advantage that it can. In particular, the compound represented by Formula 1 has high thermal and chemical stability by crosslinking with a derivative having a C-H bond due to the C-F bond, which is useful in thin film manufacturing and preservation of hologram storage media.
본 발명에 따른 상기 화학식 1로 표시되는 과불소화 화합물의 제조방법에 대해 설명하면 다음과 같다.Hereinafter, a method for preparing a perfluorinated compound represented by Chemical Formula 1 according to the present invention will be described.
다음 반응식 1은 본 발명에 따른 상기 화학식 1로 표시되는 과불소화 디(메타)아크릴계 화합물 중에서도 방향족 작용기와 에틸렌 작용기가 각각 에테르 결합과 카보네이트 결합으로 연결되어 있는 화합물의 합성방법을 일례로 예시한 것으로, 본 발명의 화합물 및 이를 제조하는 방법에 이에 한정되는 것은 아니다. 이때, 다음 반응식 1에서, A, X 및 Y은 각각 상기에서 정의한 바와 같다.The following
상기 반응식 1에 따른 제조방법에 의하면, 먼저 방향족 디올/디티올 유도체에 염기하에서 2-클로로에톡시에탄올을 한 쪽만 반응시키고, 여기에 데카플루오로바이페닐을 염기하에서 반응시킨다. 이렇게 얻어진 화합물에 아크릴로일 클로라이드나 메타크릴로일 클로라이드를 반응시킴으로써 과불소화 디(메타)아크릴계 화합물을 합성한다.According to the preparation method according to
상기 반응식 1에 따른 제조방법에 의해 얻어진 양쪽 말단에 (메타)아크릴기를 포함하는 과불소화 화합물은 주쇄에 에테르기를 도입함으로써 고분자의 유연성을 증대시켜 복굴절율을 줄일 수 있으며, 과불소화 작용기를 도입함으로써 열적 특성을 개선한 장점을 가지고 있다.The perfluorinated compound including a (meth) acryl group at both ends obtained by the preparation method according to
한편, 본 발명은 상기 화학식 1로 표시되는 과불소화 디(메타)아크릴계 화합물, 특정의 바인더 및 광개시제를 함유시킨 광중합성 조성물을 또 다른 특징으로 한다.On the other hand, the present invention is another feature of the photopolymerizable composition containing a perfluorinated di (meth) acrylic compound represented by the formula (1), a specific binder and a photoinitiator.
본 발명에 따른 광중합성 조성물은 1) 과불소화 디(메타)아크릴계 화합물은 0.5 ∼ 80 중량%, 2) 바인더 10 ∼ 95 중량%, 및 3) 광개시제 0.01 ∼ 10 중량%을 포함하여 이루어진다.The photopolymerizable composition according to the present invention comprises 1) 0.5 to 80% by weight of perfluorinated di (meth) acrylic compound, 2) 10 to 95% by weight of binder, and 3) 0.01 to 10% by weight of photoinitiator.
본 발명에 따른 광중합성 조성물 중에는 광중합성 단량체 화합물로서 상기 화학식 1로 표시되는 과불소화 디(메타)아크릴계 화합물은 0.5 ∼ 80 중량%, 바람직하기로는 30 ∼ 60 중량% 함유될 수 있는 바, 과불소화 디아크릴계/디메타크릴계 화합물의 함량이 0.5 중량% 미만일 경우에는 박막형성에 문제가 있으며, 80 중량%를 초과할 경우에는 고점도로 인해 표면거칠기를 조절하기 어려운 문제가 있다.In the photopolymerizable composition according to the present invention, as the photopolymerizable monomer compound, the perfluorinated di (meth) acrylic compound represented by
본 발명에 따른 광중합성 조성물에는 통상의 바인더 성분이 전체 조성물 중에 10 ∼ 95 중량%, 바람직하기로는 40 ∼ 70 중량 % 포함될 수 있으며, 바인더 성분의 함량이 10 중량% 미만일 경우에는 일정한 강성을 갖는 홀로그램 저장용 박막의 생성이 어렵고, 95 중량%를 초과할 경우에는 홀로그램 기록 시 사용되는 단량체의 농도가 낮아져 굴절율 구배가 제대로 생성되지 않는 문제점이 있다. In the photopolymerizable composition according to the present invention, a conventional binder component may be included in an amount of 10 to 95% by weight, preferably 40 to 70% by weight, and a hologram having a constant rigidity when the content of the binder component is less than 10% by weight. If the storage thin film is difficult to produce, and if it exceeds 95% by weight, there is a problem in that the concentration of the monomer used for hologram recording is low, so that a refractive index gradient is not properly generated.
본 발명에 따른 광중합성 조성물 중에 포함되는 바인더 성분으로서 특히 바람직하기로는 실록산계 졸-겔 용액 또는 투명성 고분자 수지를 선택 사용하는 것이다. 본 발명에 따른 광중합성 조성물 중에 바인더 성분으로서 사용될 수 있는 실록산계 졸-겔 용액은 실록산 전구체로부터 제조된 졸-겔 용액으로 공지된 방법에 의해 제조될 수 있다[한국등록특허 제212534호]. Particularly preferred as the binder component included in the photopolymerizable composition according to the present invention is a siloxane sol-gel solution or a transparent polymer resin. The siloxane-based sol-gel solution which can be used as a binder component in the photopolymerizable composition according to the present invention can be prepared by a method known as a sol-gel solution prepared from a siloxane precursor (Korean Patent No. 212534).
구체적으로는 다음 화학식 2로 표시되는 실록산 전구체 2 ∼ 80 중량%, 테트라알콕시실란 2 ∼ 80 중량% 및 유기용매 0.1 ∼ 80 중량% 포함하는 혼합물을 상온에서 1 ∼ 10 시간동안 격렬하게 교반하고 30 ∼ 70 ℃에서 다시 1 ∼ 10일 동안 교반한 후, 감압 하에서 10 내지 60% 범위의 무게로 농축시킴으로써 고점도의 졸-겔 조성물을 제조할 수 있다. Specifically, a mixture containing 2 to 80% by weight of siloxane precursor, 2 to 80% by weight of tetraalkoxysilane and 0.1 to 80% by weight of an organic solvent represented by the following
상기 화학식 2에서, R 및 R'는 서로 같거나 다른 것으로 C1 ∼ C10 저급알킬기 또는 페닐기이고; R"는 R과 동일하거나, 또는 -(CH2-CH2-O)p-Z이며; Z는 R'과 동일하거나, 또는 -CF3, -SO2CH3 또는 
이때, 상기 졸-겔 반응물 중에는 트리에톡시페닐실란, 3-글리시시실란, 유기실록산 올리고머 플레이크(flake) 또는 이들의 혼합물을 추가로 첨가할 수 있으며, 또한, 상기 졸-겔 반응물 중에는 졸-겔 반응을 촉진시키기 위하여, 아세트산, 트리플루오로아세트산, 기타 유기산, 피리딘, 4-(N,N-디메틸아미노피리딘), 이염화코발트 등의 염기성 촉매를 추가로 첨가할 수 있다.At this time, in the sol-gel reactant, triethoxyphenylsilane, 3-glycisysilane, organosiloxane oligomer flake or a mixture thereof may be further added, and in the sol-gel reactant, In order to accelerate the reaction, basic catalysts such as acetic acid, trifluoroacetic acid, other organic acids, pyridine, 4- (N, N-dimethylaminopyridine), cobalt dichloride and the like can be further added.
본 발명에 따른 광중합성 조성물 중에 바인더 성분으로서 사용될 수 있는 투명성 고분자 수지로서는 폴리올레핀, 폴리스티렌, 폴리카보네이트, 폴리우레탄, 폴리술폰 및 폴리아크릴레이트 중에서 선택된 1종 이상의 수지를 사용할 수 있다. 상기 투명성 고분자 수지의 용해성을 향상시키기 위하여, 클로로포름, 디클로로메탄, 테트라히드로푸란, N-메틸피롤리돈, 메틸설폭사이드, N,N-디메틸아미노피리딘), 디옥산, 에탄올, 메탄올, 프로판올, 벤젠, 에틸렌글리콜 디메틸에테르, 아세토니트릴 및 물로부터 선택된 1종 이상의 용매를 첨가 사용할 수도 있다. 상기 용매는 전체 광중합성 조성물에 대하여 50 ∼ 80 중량% 첨가 사용할 수 있으며, 더욱 바람직하기로는 65 ∼ 75 중량% 사용할 수 있다.As the transparent polymer resin that can be used as the binder component in the photopolymerizable composition according to the present invention, at least one resin selected from polyolefin, polystyrene, polycarbonate, polyurethane, polysulfone and polyacrylate can be used. In order to improve the solubility of the transparent polymer resin, chloroform, dichloromethane, tetrahydrofuran, N-methylpyrrolidone, methylsulfoxide, N, N-dimethylaminopyridine), dioxane, ethanol, methanol, propanol, benzene One or more solvents selected from ethylene glycol dimethyl ether, acetonitrile and water may be used. The solvent may be used in an amount of 50 to 80 wt% based on the total photopolymerizable composition, and more preferably 65 to 75 wt%.
본 발명에 따른 광중합성 조성물 중에 포함되는 광개시제는 광에 의해 자유 라디칼 또는 양이온을 발생시키는 통상의 개시제로서, 이가큐어(Irgacure) 184, 이가큐어 784, 메탈로센촉매, 다로큐어(Darocure), 아크리딘, 페나진 및 퀴녹살린으로부터 선택된 1종 이상의 화합물을 사용할 수 있다. 본 발명에서 상기 광개시제는 전체 광중합성 조성물에 대하여 0.01 ∼ 10 중량%의 함량으로 사용하는 것이 바람직하며, 더욱 바람직하기로는 0.1 ∼ 5 중량%를 사용한다. 만일 광개시제의 함량이 0.01 중량% 미만일 경우에는 산소 등의 불순물로 인해 분해되어 라디칼의 생성이 어려운 문제가 있고, 10 중량%를 초과하면 급격한 반응을 유도하여 기포발생등의 원인이 될 수 있다.Photoinitiators included in the photopolymerizable composition according to the present invention are conventional initiators that generate free radicals or cations by light, such as Irgacure 184, Igacure 784, metallocene catalysts, Darocure, One or more compounds selected from chridine, phenazine and quinoxaline can be used. In the present invention, the photoinitiator is preferably used in an amount of 0.01 to 10% by weight based on the total photopolymerizable composition, and more preferably 0.1 to 5% by weight. If the content of the photoinitiator is less than 0.01% by weight, it is difficult to generate radicals due to decomposition due to impurities such as oxygen, and when it exceeds 10% by weight, a rapid reaction may be induced to cause bubbles.
상기 화학식 1의 과불소화 디(메타)아크릴계 화합물 0.5 ∼ 80 중량%, 화학식 2의 실록산 전구체로부터 제조된 졸-겔 용액 또는 투명 고분자 수지 10 ∼ 95 중량%, 및 광개시제 0.01 ∼ 10 중량%를 상온에서 교반한 후 여과함으로써 본 발명의 투명한 광중합성 조성물을 제조할 수 있다.0.5 to 80% by weight of the perfluorinated di (meth) acrylic compound of
또한, 본 발명에 따른 광중합성 조성물 중에는 추가로 2-나프틸-1-옥시에틸아크릴레이트, 2(N-카바졸릴-1-옥시에틸)아크릴레이트, N-비닐카바졸, 이소보닐아크릴레이트, 페녹시에틸아크릴레이트, 디에틸렌글리콜 모노메틸에테르아크릴레이트, 디에틸렌글리콜 비스카보네이트, 알릴계 단량체, α-메틸스티렌, 스티렌, 디비닐벤젠, 폴리에틸렌옥시메타크릴레이트, 폴리에틸렌옥시아크릴레이트, 폴리에틸렌옥시디아크릴레이트, 알킬렌트리아크릴레이트 및 기타 공지의 불포화기를 갖는 단량체 중에서 선택된 1 종 이상의 화합물을 공단량체로서 포함할 수 있다. 상기 공단량체는 전체 광중합성 조성에 대하여 1 ∼ 30 중량% 첨가할 수 있으며, 더욱 바람직하기로는 5 ∼ 15 중량%이다. In addition, in the photopolymerizable composition according to the present invention, 2-naphthyl-1-oxyethyl acrylate, 2 (N-carbazolyl-1-oxyethyl) acrylate, N-vinylcarbazole, isobornyl acrylate, Phenoxyethyl acrylate, diethylene glycol monomethyl ether acrylate, diethylene glycol biscarbonate, allyl monomer, α-methyl styrene, styrene, divinylbenzene, polyethyleneoxy methacrylate, polyethyleneoxy acrylate, polyethyleneoxydi One or more compounds selected from acrylates, alkylenetriacrylates, and other known unsaturated group monomers may be included as comonomers. The comonomer may be added in an amount of 1 to 30% by weight based on the total photopolymerizable composition, and more preferably 5 to 15% by weight.
또한, 본 발명에 따른 광중합성 조성물 중에는 추가로 광증감제를 전체 조성에 대하여 0.01 ∼ 20 중량% 추가 사용할 수 있다. 광증감제로는 안트라센, 페릴렌, 메틸레드, 메틸오렌지, 메틸렌블루, 피란유도체, 아크리딘화합물, 모노-, 디- 또는 트리-할로메틸치환된 트리아진 및 퀴나졸리논으로부터 선택된 1 종 이상의 화합물을 사용할 수 있다[한국특허공개 제2001-24993호 및 제1989-7118호].In addition, in the photopolymerizable composition according to the present invention, a photosensitizer may be further used in an amount of 0.01 to 20% by weight based on the total composition. As a photosensitizer, at least one compound selected from anthracene, perylene, methyl red, methyl orange, methylene blue, pyran derivatives, acridine compounds, mono-, di- or tri-halomethyl-substituted triazines and quinazolinones Can be used (Korean Patent Publication Nos. 2001-24993 and 1989-7118).
본 발명에 따른 광중합성 조성물 중에는 필요에 따라, 팽창제, 층상실리케이트, 나노분말, 액정 및 기타 염료 등을 0.01 ∼ 20 중량%의 양으로 첨가할 수 있으며, 내열특성, 기계적 특성 및 가공특성 등을 개선하기 위해 통상의 산화방지제, 염료, 안료, 윤활제, 증점제 등과 같은 각종 첨가제 및/또는 충전제를 첨가할 수 있다. 또한, 본 발명의 조성물에는 중합반응을 촉진시키기 위한 중합촉매, 내후성 개량을 위한 자외선흡수제 및 착색방지제 등을 첨가할 수 있다.In the photopolymerizable composition according to the present invention, an expanding agent, layered silicate, nanopowder, liquid crystal, and other dyes may be added in an amount of 0.01 to 20% by weight, and the heat resistance, mechanical properties, and processing properties may be improved. To this end various additives and / or fillers such as conventional antioxidants, dyes, pigments, lubricants, thickeners and the like can be added. In addition, to the composition of the present invention, a polymerization catalyst for promoting the polymerization reaction, a UV absorber for improving weather resistance, a color inhibitor, and the like can be added.
이상에서 설명한 바와 같은 조성성분으로 구성되는 본 발명에 따른 광중합성 조성물은 통상의 방법으로 광경화하여 광중합성 막을 제조할 수 있다. 즉, 광중합성 조성물을 유리판, ITO막, 실리콘웨이퍼, 기타 고체 지지체 등의 기재 위에 스핀코팅, 바코팅 등의 방법으로 코팅을 수행한 후 상온 내지 130 ℃에서 30분 내지 14일 동안 건조시킴으로써, 광중합성 막을 제조할 수 있다. The photopolymerizable composition according to the present invention composed of the composition components as described above can be photocured by a conventional method to produce a photopolymerizable film. That is, the photopolymerizable composition is coated on a substrate such as a glass plate, an ITO film, a silicon wafer, or another solid support by spin coating, bar coating, or the like, and then dried at room temperature to 130 ° C. for 30 minutes to 14 days. Synthetic membranes can be prepared.
구체적으로는, 200 ㎛의 스페이서를 유리판 위에 놓고 광중합성 조성물을 코팅한 후, 상온에서 1 일 방치시킨 다음 진공오븐에 넣고 온도를 서서히 높이면서 100 ℃에서 8시간동안 감압 건조시킴으로써, 기계적 특성이 우수하고 투명한 광중 합성 막을 제조할 수 있다. 본 발명에 따른 광중합성 막은 0.0001 ∼ 30 mm의 두께를 가질 수 있다.Specifically, the spacer having a 200 μm was placed on a glass plate, coated with a photopolymerizable composition, and then left at room temperature for 1 day, and then placed in a vacuum oven and dried under reduced pressure at 100 ° C. for 8 hours while gradually increasing the temperature, thereby providing excellent mechanical properties. And a transparent optical film can be prepared. The photopolymerizable film according to the present invention may have a thickness of 0.0001 to 30 mm.
광중합성 막에 UV 또는 가시광선 등의 광을 조사하면 광에 의해 모노머가 중합되어 굴절율이 상승함으로써 회절효율이 증가하며, 간섭광을 조사하면 홀로그래피 기록이 막 위에 형성되는데, 본 발명에 따른 광중합성 막은 굴절율 변화가 커서 신호기록이 효율적이며 광중합에 의한 수축율이 낮아 기록신호 해독에 신뢰성이 높다. 특히, 상기 졸-겔 용액을 포함하는 광중합성 막은 유기적으로 성형된 실록산 중합체 매트릭스를 제공하므로 광중합 시 기계적 특성이 보다 향상된다.When the photopolymerizable film is irradiated with light such as UV or visible light, the monomer is polymerized by the light and the refractive index is increased to increase the diffraction efficiency. When the interfering light is irradiated, a holographic recording is formed on the film. Since the film has a large refractive index change, the signal recording is efficient, and the shrinkage rate due to photopolymerization is low, so that the film is highly reliable in decoding the recording signal. In particular, the photopolymerizable membrane comprising the sol-gel solution provides an organically formed siloxane polymer matrix which further improves mechanical properties during photopolymerization.
본 발명의 광중합성 조성물 및 광중합성 막은 홀로그래피 시스템, 디스플레이용 동영상 제조 시스템, 볼륨 홀로그램을 이용한 광분리기, 광헤드장치, 액정표시장치, 다단계 그레이팅(grating) 인쇄조판 또는 감광성 내식막, 정보기록막, 광필터 등에 융용 가능하다. 그 예로서, 본 발명의 광중합성 조성물로부터 제조된 광중합성막에 홀로그래피 시스템을 이용하여 그레이팅을 형성할 수 있다.The photopolymerizable composition and the photopolymerizable film of the present invention are a holographic system, a video production system for display, an optical separator using a volume hologram, an optical head device, a liquid crystal display, a multi-step grating printing typesetting or a photoresist, an information recording film, It can be fused to an optical filter. As an example, gratings can be formed using a holographic system on a photopolymerizable film prepared from the photopolymerizable composition of the present invention.
또한, 본 발명의 광중합성 조성물에 액정이 혼합된 조성물을 주입하여 밀봉하고 반도체 기판에 유전체 막을 형성한 후, 특정부위가 노출되도록 상기 유전체 막에 창을 형성한 다음, 홀로그래피 시스템을 이용하여 노출된 기판부위에 특정주기를 갖는 그레이팅을 형성할 수 있다.In addition, after injecting and sealing a composition mixed with liquid crystal in the photopolymerizable composition of the present invention and forming a dielectric film on the semiconductor substrate, a window is formed on the dielectric film to expose a specific portion, and then exposed using a holography system. A grating having a specific period can be formed on the substrate portion.
이하, 본 발명은 다음 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.
합성예 : 과불소화 디(메타)아크릴계 화합물의 합성Synthesis Example: Synthesis of Perfluorinated Di (meth) acrylic Compound
합성예 1 : 화합물 1 Synthesis Example 1
(1) 질소 분위기 하에서 250 mL 2-넥 둥근 플라스크에 환류 콘덴서를 설치 후 4,4'-(헥사플루오로 아이소프로필-아이덴)다이페놀(10 g, 0.03 mol)넣고 DMF(100 mL)에 완전히 용해시킨 후 NaOH(1.19 g, 0.033 mol)와 KI(0.12 g, 0.0008 mol)를 넣고 교반하였다. 여기에 2-(2-클로로에톡시)에탄올(5.1 mL, 0.03 mol)를 천천히 적하한 후에 반응기내 온도를 90 ℃로 올려 48시간 반응시킨 후 상온으로 냉각시켜 유리여과기(glass fiter)를 이용해서 잔유물을 걸러내고 250 mL 물을 넣고, 300 mL의 에틸 아세테이트를 넣어 유기층을 분리하였다. 이후에 마그네슘 설페이트를 넣어 드라이 후 에틸아세테이트를 제거하였다. 이렇게 얻은 조 생성물(crude product)을 에틸아세테이트를 전개용매로 컬럼 크로마토그래피 분리하고 진공 건조하여 튜명한 시럽상태의 2-클로로에톡시엔탄올이 치환된 화합물(1a, 5.3g)을 얻었다.(1) Install a reflux condenser in a 250 mL 2-neck round flask under nitrogen atmosphere, add 4,4 '-(hexafluoro isopropyl-idene) diphenol (10 g, 0.03 mol) and place completely in DMF (100 mL). After dissolution, NaOH (1.19 g, 0.033 mol) and KI (0.12 g, 0.0008 mol) were added thereto and stirred. Then, 2- (2-chloroethoxy) ethanol (5.1 mL, 0.03 mol) was slowly added dropwise, and the temperature was increased to 90 ° C. in the reactor for 48 hours, followed by cooling to room temperature using a glass filter. The residue was filtered off, 250 mL of water was added, and 300 mL of ethyl acetate was added to separate the organic layer. Thereafter, magnesium sulfate was added thereto, followed by drying to remove ethyl acetate. The crude product thus obtained was purified by column chromatography with ethyl acetate as a developing solvent, and dried in vacuo to obtain a compound ( 1a , 5.3 g) substituted with 2-chloroethoxy ethanol in a clear syrup state.
[화합물 1a][Compound 1a ]
1H-NMR (CDCl3, 300MHz) δ 2.5(s, 1H, OH), 3.67-3.70(q, 2H), 3.77-3.80(t, 2H), 3.86-3.89(q, 2H), 4.16-4.14(t, 2H), 6.3(s, 1H, OH), 6.79-6.88(dd, 4H, ArH), 7.20-7.31(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 2.5 (s, 1H, OH), 3.67-3.70 (q, 2H), 3.77-3.80 (t, 2H), 3.86-3.89 (q, 2H), 4.16-4.14 (t, 2H), 6.3 (s, 1H, OH), 6.79-6.88 (dd, 4H, ArH), 7.20-7.31 (dd, 4H, ArH)
(2) 질소 분위기 하에서 250 mL 둥근바닥 2-구 플라스크에 환류냉각기를 설치한 후 화합물 1a(2.5 g, 6 mmol)을 DMAc(40 mL)에 완전히 용해시킨 후, 데카플루오로바이페닐(0.82 g, 2.4 mmol)과 탄산칼륨(0.81 g, 6 mmol)를 넣고 교반한 다음 반응기내 온도를 60 ℃로 올려 9시간 반응시킨 후 상온으로 냉각시켜 유리여과기(glass fiter)를 이용해서 잔유물을 걸러내고 200 mL의 물을 넣고 200 mL의 에틸 아세테이트를 넣어 유기층을 분리하였다. 이후에 황산마그네슘을 넣어 수분을 제거한 후 용매를 제거하였다. 이렇게 얻은 반응 혼합물을 에틸아세테이트를 전개용매로 컬럼크로마토그래피 분리하고 진공 건조하여 투명한 시럽상태로 하기 구조의 화합물(1b, 2.4g)을 86%의 수득율로 얻었다. (2) A reflux condenser was installed in a 250 mL round bottom two-necked flask under nitrogen atmosphere, and then Compound 1a (2.5 g, 6 mmol) was completely dissolved in DMAc (40 mL), followed by decafluorobiphenyl (0.82 g). , 2.4 mmol) and potassium carbonate (0.81 g, 6 mmol) were added to the mixture, followed by stirring. The reaction mixture was heated to 60 ° C. for 9 hours, cooled to room temperature, and filtered through a glass filter to filter out the residue. Put mL of water and put 200 mL of ethyl acetate to separate the organic layer. Thereafter, magnesium sulfate was added to remove moisture, and then the solvent was removed. Thus obtained reaction mixture was separated by column chromatography with ethyl acetate as a developing solvent and dried in vacuo to give the compound ( 1b , 2.4g) having the following structure in a clear syrup state at a yield of 86%.
[화합물 1b] [Compound 1b ]
1H-NMR (CDCl3, 300MHz) δ 3.66-3.69(q, 2H), 3.75-3.78(q, 2H), 3.86-3.89(t, 2H), 4.15-4.18(t, 2H), 6.90-7.05(dd, 4H, ArH), 7.29-7.43(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.66-3.69 (q, 2H), 3.75-3.78 (q, 2H), 3.86-3.89 (t, 2H), 4.15-4.18 (t, 2H), 6.90-7.05 (dd, 4H, ArH), 7.29-7.43 (dd, 4H, ArH)
(3) 상온에서 250 mL 둥근 플라스크에 화합물 1b(5.00 g, 4.38 mmol)를 이염화메탄(130 mL)에 넣고 녹인 후, 트리에틸아민(triethylamine, 1.42 mL, 17.52 mmol)을 넣고 교반하였다. 이후에 0 ℃에서 아크릴로일클로라이드(acryloyl chloride, 1.83 mL, 13.14 mmol)를 천천히 적하한 후, 반응온도를 실온으로 올려 9시간 동안 반응시켰다. 반응종료 후 300 mL의 물을 넣고 클로로포름으로 유기층 분리하였다(500 mL × 3). 이후에 황산마그네슘으로 수분을 제거하고 진공하에서 유기용매를 제거하여 시럽상태의 화합물 1(5.00 g)을 92%의 수득율로 얻었다.(3) Compound 1b (5.00 g, 4.38 mmol) was dissolved in methane dichloride (130 mL) in a 250 mL round flask at room temperature, and triethylamine (1.42 mL, 17.52 mmol) was added thereto and stirred. After slowly dropping acryloyl chloride (acryloyl chloride, 1.83 mL, 13.14 mmol) at 0 ℃, the reaction temperature was raised to room temperature and reacted for 9 hours. After completion of the reaction, 300 mL of water was added and the organic layer was separated with chloroform (500 mL × 3). Thereafter, water was removed with magnesium sulfate and the organic solvent was removed under vacuum to obtain a compound 1 (5.00 g) in a syrup state at a yield of 92%.
1H-NMR (CDCl3, 300MHz) δ 3.81-3.84(t, 2H), 3.86-3.90(t, 2H), 4.15-4.18(q, 2H), 4.34-4.37(t, 2H), 5.81-5.82(d, 1H), 6.10-6.19(q, 1H), 6.40-6.46(d, 1H), 6.90-7.06(dd, 4H, ArH), 7.28-7.43(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.81-3.84 (t, 2H), 3.86-3.90 (t, 2H), 4.15-4.18 (q, 2H), 4.34-4.37 (t, 2H), 5.81-5.82 (d, 1H), 6.10-6.19 (q, 1H), 6.40-6.46 (d, 1H), 6.90-7.06 (dd, 4H, ArH), 7.28-7.43 (dd, 4H, ArH)
합성예 2 : 화합물 2 Synthesis Example 2
상기 합성예 1에서 아크릴로일 클로라이드 (acryloyl chloride) 대신에 메타크릴로일 클로라이드 (methacryloyl chloride)를 반응시킨 것을 제외하고는 합성예 1과 같은 방법으로 실시하여 상기 구조의 화합물 2를 합성하였다.
1H-NMR (CDCl3, 300MHz) δ 3.81-3.84(t, 2H), 3.86-3.90(t, 2H), 4.15-4.18(q, 2H), 4.34-4.37(t, 2H), 5.81-5.82(d, 1H), 6.10-6.19(q, 1H), 6.40-6.46(d, 1H), 6.90-7.06(dd, 4H, ArH), 7.28-7.43(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.81-3.84 (t, 2H), 3.86-3.90 (t, 2H), 4.15-4.18 (q, 2H), 4.34-4.37 (t, 2H), 5.81-5.82 (d, 1H), 6.10-6.19 (q, 1H), 6.40-6.46 (d, 1H), 6.90-7.06 (dd, 4H, ArH), 7.28-7.43 (dd, 4H, ArH)
합성예 3 : 화합물 3 Synthesis Example 3 Compound 3
(1) 상기 합성예 1에서 4,4'-(헥사플루오로아이소프로필리덴)다이페놀이 아닌 비스페놀 A(10.00 g, 0.44 mol)을 이용한 것을 제외하고는 합성예 1과 같은 방법으로 실시하여 하기 구조의 화합물 3a의 화합물을 합성하였다.(1) The same procedure as in Synthesis Example 1 was performed except that Bisphenol A (10.00 g, 0.44 mol) was used instead of 4,4 '-(hexafluoroisopropylidene) diphenol in Synthesis Example 1. The compound of the compound 3a of the structure was synthesize | combined.
[화합물 3a][Compound 3a ]
1H-NMR (CDCl3, 300MHz) δ 1.61(s, 6H, CH3), 3.65-3.68(q, 2H), 3.75-3.77(q, 2H), 3.83-3.88(q, 2H), 4.10-4.13(q, 2H), 5.62(s, 1H, OH), 6.70-6.82(dd, 4H, ArH), 7.04-7.13(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 1.61 (s, 6H, CH 3), 3.65-3.68 (q, 2H), 3.75-3.77 (q, 2H), 3.83-3.88 (q, 2H), 4.10-4.13 (q, 2H), 5.62 (s, 1H, OH), 6.70-6.82 (dd, 4H, ArH), 7.04-7.13 (dd, 4H, ArH)
(2) 상기 합성예 1에서, 화합물 1a 대신에 화합물 3a을 반응시킨 것을 제외 하고는 합성예 1에서와 같은 방법으로 실시하여 화합물 3b를 80%의 수득율로 합성하였다.(2) In Synthesis Example 1, except that Compound 3a was reacted instead of Compound 1a , Compound 3b was synthesized in a yield of 80% by the same method as in Synthesis Example 1.
[화합물 3b] [Compound 3b]
1H-NMR (CDCl3, 300MHz) δ 1.65(s, 6H, CH3), 3.65-3.69(q, 2H), 3.74-3.76(t, 2H), 3.85-3.88(q, 2H), 4.11-4.14(t, 2H), 6.82-6.95(dd, 4H, ArH), 7.12-7.22(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 1.65 (s, 6H, CH 3), 3.65-3.69 (q, 2H), 3.74-3.76 (t, 2H), 3.85-3.88 (q, 2H), 4.11-4.14 (t, 2H), 6.82-6.95 (dd, 4H, ArH), 7.12-7.22 (dd, 4H, ArH)
(3) 상기 합성예 1에서, 화합물 1b 대신에 화합물 3b를 반응시킨 것을 제외하고는 합성예 1과 같은 방법으로 실시하여 화합물 3을 81%의 수득율로 합성하였다.(3) In Synthesis Example 1, except that Compound 3b was reacted instead of Compound 1b , Compound 3 was synthesized in a yield of 81% by the same method as Synthesis Example 1.
1H-NMR (CDCl3, 300MHz) δ 1.65(s, 6H, CH3), 3.80-3.83(t, 2H), 3.84-3.87(t, 2H), 4.10-4.13(q, 2H), 4.32-4.36(t, 2H), 5.81-5.85(d, 1H), 6.10-6.19(q, 1H), 6.40-6.46(d, 1H), 6.82-6.95(dd, 4H, ArH), 7.19-7.22(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 1.65 (s, 6H, CH 3), 3.80-3.83 (t, 2H), 3.84-3.87 (t, 2H), 4.10-4.13 (q, 2H), 4.32-4.36 (t, 2H), 5.81-5.85 (d, 1H), 6.10-6.19 (q, 1H), 6.40-6.46 (d, 1H), 6.82-6.95 (dd, 4H, ArH), 7.19-7.22 (dd, 4H, ArH)
합성예 4 : 화합물 4 Synthesis Example 4
상기 합성예 3에서 아크릴로일 클로라이드(acryloyl chloride) 대신에 메타크릴로일 클로라이드 (methacryloyl chloride)를 반응시킨 것을 제외하고는 합성예 3과 같은 방법으로 실시하여 상기 구조의 화합물 4를 합성하였다.
1H-NMR (CDCl3, 300MHz) δ 1.65(s, 12H, CH3), 1.96(s, 6H) 3.80-3.83(t, 4H), 3.84-3.87(t, 4H), 4.10-4.13(q, 4H), 4.32-4.36(t, 4H), 5.83-5.87(d, 2H), 6.42-6.48(d, 2H), 6.82-6.95(dd, 8H, ArH), 7.19-7.22(dd, 8H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 1.65 (s, 12H, CH 3), 1.96 (s, 6H) 3.80-3.83 (t, 4H), 3.84-3.87 (t, 4H), 4.10-4.13 (q, 4H), 4.32-4.36 (t, 4H), 5.83-5.87 (d, 2H), 6.42-6.48 (d, 2H), 6.82-6.95 (dd, 8H, ArH), 7.19-7.22 (dd, 8H, ArH )
합성예 5 : 화합물 5 Synthesis Example 5
(1) 상기 합성예 1에서 4,4'-(헥사플루오로아이소프로필리덴)다이페놀이 아닌 4,4'-술포닐다이페놀(8.25 g, 33 mmol)을 이용한 것을 제외하고는 합성예 1과 같은 방법으로 실시하여 하기 구조의 화합물 5a의 화합물을 합성하였다.(1) Synthesis Example 1 except that 4,4'-sulfonyldiphenol (8.25 g, 33 mmol) was used instead of 4,4 '-(hexafluoroisopropylidene) diphenol in Synthesis Example 1. In the same manner, a compound of Compound 5a having the following structure was synthesized.
[화합물 5a][Compound 5a ]
1H-NMR (CDCl3, 300MHz) δ 2.04(s, 1H, OH), 3.48-3.51(t, 2H), 3.65-3.74(t, 2H), 3.86-3.88(t, 2H), 4.14-4.17(t, 2H), 5.41(s, 1H, OH), 6.95-6.99(dd, 4H, ArH), 7.82-7.85(dd, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 2.04 (s, 1H, OH), 3.48-3.51 (t, 2H), 3.65-3.74 (t, 2H), 3.86-3.88 (t, 2H), 4.14-4.17 (t, 2H), 5.41 (s, 1H, OH), 6.95-6.99 (dd, 4H, ArH), 7.82-7.85 (dd, 4H, ArH)
(2) 상기 합성예 1에서, 화합물 1a이 아닌 화합물 5a을 반응시킨 것을 제외하고는 합성예 1에서와 같은 방법으로 실시하여 화합물 5b를 83%의 수득율로 합성하였다.(2) In Synthesis Example 1, except that Compound 5a was reacted instead of Compound 1a , Compound 5b was synthesized in a yield of 83% by the same method as in Synthesis Example 1.
[화합물 5b][Compound 5b ]
1H-NMR (CDCl3, 300MHz) δ 3.49-3.51(t, 4H), 3.66-3.74(t, 4H), 3.88-3.90(t, 4H), 4.14-4.18(t, 4H), 5.41(s, 2H, OH), 6.96-7.02(dd, 8H, ArH), 7.82-7.86(dd, 8H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.49-3.51 (t, 4H), 3.66-3.74 (t, 4H), 3.88-3.90 (t, 4H), 4.14-4.18 (t, 4H), 5.41 (s , 2H, OH), 6.96-7.02 (dd, 8H, ArH), 7.82-7.86 (dd, 8H, ArH)
(3) 상기 합성예 1에서, 화합물 1b대신에 화합물 5b를 반응시킨 것을 제외하고는 합성예 1과 같은 방법으로 실시하여 화합물 5를 88%의 수득율로 합성하였다.(3) In Synthesis Example 1, except that Compound 5b was reacted instead of Compound 1b ,
1H-NMR (CDCl3, 300MHz) δ 3.74-3.76(t, 4H), 3.86-3.91(t, 4H), 4.07-4.11(q, 4H), 4.36-4.39(t, 4H), 5.81-5.84(d, 2H), 6.08-6.17(q, 2H), 6.38-6.44(d, 1H), 6.95-6.98(dd, 8H, ArH), 7.82-7.85(dd, 8H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.74-3.76 (t, 4H), 3.86-3.91 (t, 4H), 4.07-4.11 (q, 4H), 4.36-4.39 (t, 4H), 5.81-5.84 (d, 2H), 6.08-6.17 (q, 2H), 6.38-6.44 (d, 1H), 6.95-6.98 (dd, 8H, ArH), 7.82-7.85 (dd, 8H, ArH)
합성예 6 : 화합물 6 Synthesis Example 6
[화합물 6]
상기 합성예 5에서 아크릴로일 클로라이드 (acryloyl chloride) 대신에 메타크릴로일 클로라이드(methacryloyl chloride)를 반응시킨 것을 제외하고는 합성예 3과 같은 방법으로 실시하여 상기 구조의 화합물 6을 합성하였다.
1H-NMR (CDCl3, 300MHz) δ 1.96(s, 6H), 3.74-3.76(t, 4H), 3.86-3.91(t, 4H), 4.07-4.11(q, 4H), 4.36-4.39(t, 4H), 5.82-5.84(d, 2H), 6.38-6.43(d, 1H), 6.95-6.98(dd, 8H, ArH), 7.82-7.85(dd, 8H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 1.96 (s, 6H), 3.74-3.76 (t, 4H), 3.86-3.91 (t, 4H), 4.07-4.11 (q, 4H), 4.36-4.39 (t , 4H), 5.82-5.84 (d, 2H), 6.38-6.43 (d, 1H), 6.95-6.98 (dd, 8H, ArH), 7.82-7.85 (dd, 8H, ArH)
합성예 7 : 화합물 7 Synthesis Example 7 Compound 7
[화합물 7][Compound 7 ]
(1) 상기 합성예 1에서 4,4'-(헥사플루오로아이소프로필리덴)다이페놀이 아닌 4-((4-히드록시페닐)(페닐)포스포릴)페놀 (12.4g, 40 mmol)을 이용한 것을 제외하고는 합성예 1과 같은 방법으로 실시하여 하기 구조의 화합물 7a의 화합물을 합성하였다.(1) In Synthesis Example 1, 4-((4-hydroxyphenyl) (phenyl) phosphoryl) phenol (12.4 g, 40 mmol) other than 4,4 '-(hexafluoroisopropylidene) diphenol was substituted. A compound of Compound 7a having the following structure was synthesized in the same manner as in Synthesis Example 1, except that it was used.
[화합물 7a][Compound 7 a ]
1H-NMR (CDCl3, 300MHz) δ 3.73(s, 1H, OH), 3.65-3.67(t, 2H), 3.73-3.75(t, 2H), 3.84-3.86(t, 2H), 4.14-4.15(t, 2H), 6.94-6.80(q 4H, ArH), 7.50-7.65(m, 9H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.73 (s, 1H, OH), 3.65-3.67 (t, 2H), 3.73-3.75 (t, 2H), 3.84-3.86 (t, 2H), 4.14-4.15 (t, 2H), 6.94-6.80 (q 4H, ArH), 7.50-7.65 (m, 9H, ArH)
(2) 상기 합성예 1에서, 화합물 1a이 아닌 화합물 7a을 반응시킨 것을 제외하고는 합성예 1에서와 같은 방법으로 실시하여 화합물 7b를 73%의 수득율로 합성하였다.(2) In Synthesis Example 1, except that Compound 7a was reacted instead of Compound 1a , Compound 7b was synthesized in a yield of 73% by the same method as in Synthesis Example 1.
[화합물 7b][Compound 7b ]
1H-NMR (CDCl3, 300MHz) δ 3.64-3.67(t, 4H), 3.73-3.75(t, 4H), 3.86-3.88(t, 4H), 4.15-4.17(t, 4H), 6.94-6.81(q 8H, ArH), 7.51-7.67(m, 18H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.64-3.67 (t, 4H), 3.73-3.75 (t, 4H), 3.86-3.88 (t, 4H), 4.15-4.17 (t, 4H), 6.94-6.81 (q 8H, ArH), 7.51-7.67 (m, 18H, ArH)
(3) 상기 합성예 1에서, 화합물 1b대신에 화합물 7b를 반응시킨 것을 제외하고는 합성예 1과 같은 방법으로 실시하여 화합물 7을 92%의 수득율로 합성하였다.(3) In Synthesis Example 1, except that Compound 7b was reacted instead of Compound 1b , Compound 7 was synthesized in a yield of 92% by the same method as in Synthesis Example 1.
1H-NMR (CDCl3, 300MHz) δ 3.80-3.82(t, 4H), 3.86-3.89(t, 4H), 4.15-4.19(t, 4H), 4.33-4.36(t, 4H), 5.81-5.84(d, 2H), 6.14-6.18(q, 2H), 6.38-6.39(d, 2H), 6.96-6.99(q, 4H, ArH), 7.52-7.60(m, 4H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 3.80-3.82 (t, 4H), 3.86-3.89 (t, 4H), 4.15-4.19 (t, 4H), 4.33-4.36 (t, 4H), 5.81-5.84 (d, 2H), 6.14-6.18 (q, 2H), 6.38-6.39 (d, 2H), 6.96-6.99 (q, 4H, ArH), 7.52-7.60 (m, 4H, ArH)
합성예 8 : 화합물 8 Synthesis Example 8
[화합물 8]
상기 합성예 7에서 아크릴로일 클로라이드 (acryloyl chloride) 대신에 메타크릴로일 클로라이드 (methacryloyl chloride)를 반응시킨 것을 제외하고는 합성예 3과 같은 방법으로 실시하여 상기 구조의 화합물 8를 합성하였다.
1H-NMR (CDCl3, 300MHz) δ 1.96(s, 6H), 3.80-3.82(t, 4H), 3.86-3.89(t, 4H), 4.15-4.19(t, 4H), 4.33-4.36(t, 4H), 5.81-5.84(d, 2H), 6.38-6.39(d, 2H), 6.96-6.99(q, 8H, ArH), 7.52-7.59(m, 18H, ArH) 1 H-NMR (CDCl 3 , 300 MHz) δ 1.96 (s, 6H), 3.80-3.82 (t, 4H), 3.86-3.89 (t, 4H), 4.15-4.19 (t, 4H), 4.33-4.36 (t , 4H), 5.81-5.84 (d, 2H), 6.38-6.39 (d, 2H), 6.96-6.99 (q, 8H, ArH), 7.52-7.59 (m, 18H, ArH)
제조예 : 졸-겔(Sol-Gel) 조성물의 제조Preparation Example: Preparation of Sol-Gel Composition
(1) 실란계 전구체의 합성 (1) Synthesis of Silane Precursor
질소 분위기 하에서 THF 300 mL에 폴리(에틸렌글리콜)메틸 에테르(140 g, 0.4 mol)를 넣고 용해시킨 후, 3-(이소시아네이토)프로필 에톡시실란(99.34 g, 0.4 mol)을 서서히 적하하였다. 여기에 디-n-부틸틴 디라우레이트 8 방울을 넣고 70 ℃에서 8시간 동안 반응시킨 후 냉각시켜 n-헥산:THF (90:10) 20 mL로 3번 씻어주었다. 감압 증발하여 남은 용매를 제거한 후 투명한 액체상태의 생성물 167.7 g(수율 70.2%)를 얻었다.Poly (ethyleneglycol) methyl ether (140 g, 0.4 mol) was dissolved in 300 mL of THF under nitrogen atmosphere, and then 3- (isocyanato) propyl ethoxysilane (99.34 g, 0.4 mol) was slowly added dropwise. . 8 drops of di-n-butyltin dilaurate was added thereto, reacted at 70 ° C. for 8 hours, cooled, and washed three times with 20 mL of n-hexane: THF (90:10). After evaporation under reduced pressure to remove the remaining solvent, 167.7 g (yield 70.2%) of a clear liquid product was obtained.
(2) 유-무기 하이브리드형 졸-겔 조성물의 제조(2) Preparation of Organic-Inorganic Hybrid Sol-Gel Composition
질소 분위기 하에서 3-(글리독시트리메톡시실란) (14.99 g, 0.1227 mol)에 2-메톡시에탄올 20 mL와 이소프로필 알콜 20 mL를 넣고 용해시킨 후 테트라오르토실리케이트(12.79 g, 0.0614 mol), 메틸트리메톡시실란(8.36 g, 0.061 mol), 다음화학식으로 표시되는 PEGTAS를 각각 0, 0.5, 1.0, 1.5, 2.0 당량을 순서대로 넣은 다음 마지막으로 0.05N HCl 5 mL를 넣고 교반하였다. 온도를 70 ℃로 올려 24시간 동안 반응시킨 후 실온으로 냉각시키고 감압 증발하여 남은 용매를 제거하였다. 여기에 테트라에틸암모늄 퍼클로레이트와 열경화제(BYKㄾ-301, BYK Chemie)을 각각의 조성물에 대해 0.5 중량%, 0.05 중량% 넣고 교반하여 녹인 다음 0.45 ㎛ 시린지 필터링(syringe filtering)하여 투명한 액체상태의 생성물을 얻었다.20 mL of 2-methoxyethanol and 20 mL of isopropyl alcohol were dissolved in 3- (glydocitrimethoxysilane) (14.99 g, 0.1227 mol) in a nitrogen atmosphere, followed by dissolution of tetraorthosilicate (12.79 g, 0.0614 mol), Methyltrimethoxysilane (8.36 g, 0.061 mol) and PEGTAS represented by the following chemical formulas were added in order of 0, 0.5, 1.0, 1.5 and 2.0 equivalents, respectively, and finally 5 mL of 0.05N HCl was added thereto and stirred. The reaction mixture was heated to 70 ° C. for 24 hours, cooled to room temperature, and evaporated under reduced pressure to remove the remaining solvent. Tetraethylammonium perchlorate and thermosetting agent (BYK ㄾ -301, BYK Chemie) were added to 0.5 wt% and 0.05 wt% of each composition, stirred and dissolved, and then 0.45 μm syringe filtering to give a clear liquid product. Got.
[화학식 : 폴리에틸렌글리콜-치환된 트리알콕시실란(PEGTAS)][Formula: polyethylene glycol-substituted trialkoxysilane (PEGTAS)]
상기 n은 1 ∼ 50 의 정수를 나타낸다.N represents the integer of 1-50.
실시예 : 광경화 필름(포토폴리머 필름)의 제조Example: Preparation of Photocured Film (Photopolymer Film)
실시예 1 : 졸-겔 용액을 이용한 광경화 필름의 제조Example 1 Preparation of Photocurable Film Using Sol-Gel Solution
상기 제조예에서 제조된 졸-겔 용액(PEGTAS 0.5 당량) 2.0 g에 상기 합성예 1에서 제조된 과불소화 디(메타)아크릴계 화합물 1(1.0 g)과 0.33 g의 POEA(2-페녹시에틸 아크릴레이트)을 용해시킨 후, 광개시제로서 이가큐어 784 (0.026 g) 및 광개시제의 분해방지제인 3차 부틸하이드로퍼옥사이드 0.0052 g(광개시제 중량의 20%)를 첨가하여 교반하였다. 진한 노란색의 혼합액을 0.45 ㎛ 필터를 통해 여과하여 투명한 광중합성 조성물을 제조하였다. 이렇게 준비된 포토폴리머 용액을 이미드필름을 스페이서로 한 유리판에 코팅하여 200 ㎛ 박막 제조한 후 70 ℃에서 2일 내지 15일간 열 경화/건조시켜 최종 졸-겔 광경화 필름을 제조하였다.To 2.0 g of the sol-gel solution (PEGTAS 0.5 equivalent) prepared in Preparation Example 1, perfluorinated di (meth)
실시예 2 ∼ 8 : 졸-겔 용액을 이용한 광경화 필름의 제조Examples 2-8: Preparation of Photocured Film Using Sol-Gel Solution
상기 실시예 1과 동일하게 실시하되, 다음 표 1에 나타낸 바와 같이 단량체 화합물(1 ∼ 8)의 종류를 달리하여 광경화 필름을 제조하였다.The same procedure as in Example 1, except that the photocurable film was prepared by varying the type of monomer compound ( 1 to 8 ) as shown in Table 1.
실시예 9 ∼ 16 : 폴리술폰 수지를 이용한 포토폴리머 필름의 제조Examples 9-16: Preparation of Photopolymer Film Using Polysulfone Resin
다음 표 1에 나타낸 바와 같은 함량비로 폴리술폰 포토폴리머 필름을 제조하였다. 즉, 갈색 바이알에 폴리술폰(Aldrich, Mn=16,000)을 넣고 클로로포름 (Aldrich, anhydrous, 99+%)과 1,1,2,2-테트라클로로에탄(Aldrich, 98%)을 넣어 상온에서 2 ∼ 3시간 동안 완전히 녹였다. 이 용액에 2-페녹시에틸 아크릴레이트(POEA)와 상기 합성예에서 제조된 과불소화 디아크릴레이트 화합물(1 ∼ 8)를 각각 첨가한 후 광개시제인 Irgacure 784를 첨가, 교반하였다. 이렇게 준비된 포토폴리머 용액을 이미드필름을 스페이서로 한 유리판에 코팅하여 200 ㎛ 박막 제조한 후 60 ℃에서 24시간 열 경화/건조시켜 최종 폴리술폰 광경화 필름을 제조하였다.Next, a polysulfone photopolymer film was prepared at a content ratio as shown in Table 1. In other words, polysulfone (Aldrich, Mn = 16,000) is added to the brown vial, and chloroform (Aldrich, anhydrous, 99 +%) and 1,1,2,2-tetrachloroethane (Aldrich, 98%) are added at room temperature. Dissolved completely for 3 hours. The solution was 2-phenoxy ethyl acrylate (POEA) and stirring the above Synthesis Example A perfluorinated diacrylate compound prepared in (1-8) was added to the Irgacure 784 photoinitiator, and then respectively added to, the. The photopolymer solution thus prepared was coated on a glass plate having an imide film as a spacer to prepare a 200 μm thin film, followed by thermal curing / drying at 60 ° C. for 24 hours to prepare a final polysulfone photocured film.
시험예 : 포토폴리머 필름의 물성 측정Test Example: Measurement of Physical Properties of Photopolymer Film
상기 실시예 1 ∼ 16에 따른 포토폴리머 필름 및 비교예로 현재 시판되고 있는 듀폰(DuPont) 필름에 대하여, 다음과 같은 방법으로 수축율, 회절효율 및 간섭무늬 등의 물성을 측정하였고, 그 결과를 다음 표 1에 정리하여 나타내었다. For the photopolymer film according to Examples 1 to 16 and the DuPont film currently marketed as a comparative example, physical properties such as shrinkage, diffraction efficiency and interference fringe were measured by the following method, and the results were as follows. Table 1 summarized.
[물성측정][Property Measurement]
(1) 수축율: (1) Shrinkage:
광중합성 막 일부분에 가시광선(532 nm)을 5분간 노출시켜 비노출영역과의 두께차를 알파스텝으로 측정하여 막 전체 두께에 대한 수축율을 측정하였다.Part of the photopolymerizable film was exposed to visible light (532 nm) for 5 minutes, and the difference in thickness from the non-exposed area was measured by alpha step to measure the shrinkage of the entire film thickness.
(2) 회절효율:(2) diffraction efficiency:
광중합성 막의 홀로그래피 특성을 다음과 같이 측정하였다. 다이오드 레이저(532 nm)를 기록원으로 사용하였으며, 편광판으로 편광을 조절하고 공간필터를 이용하여 평면파를 사용하였다. 참조광 대 물체광의 강도비는 1:1이고, 박막의 표면 법선에 대해 20 °의 입사각도로 시료에 조사시킴으로써 홀로그램을 기록하였 다. 이어, 홀로그램을 참조광에 단독 노광시킴으로써 기록이미지를 판독하였다. 회절효율은 하기 수학식 1에 의해 산출하였다.The holographic properties of the photopolymerizable film were measured as follows. A diode laser (532 nm) was used as a recording source, and polarization was controlled by a polarizer and plane waves were used by using a spatial filter. The intensity ratio of the reference light to the object light was 1: 1, and the hologram was recorded by irradiating the sample with an incident angle of 20 ° with respect to the surface normal of the thin film. Then, the recorded image was read by exposing the hologram to the reference light alone. The diffraction efficiency was calculated by the following equation.
상기 표 1에서 나타낸 바와 같이, 실시예 1 ∼ 16의 광경화 필름(포토폴리머 필름)은 비교예에 비해 수축율이 현저히 감소하였으며, 특히, 졸-겔을 이용한 실시예 1 ∼ 8는 0.5% 내외의 우수한 특성을 보여주었으며, 회절효율(%)도 대조군에 비해 우수하였다. As shown in Table 1, the shrinkage rate of the photocurable film (photopolymer film) of Examples 1 to 16 was significantly reduced compared to the comparative example, and in particular, Examples 1 to 8 using the sol-gel were about 0.5%. It showed excellent characteristics and diffraction efficiency (%) was also superior to the control.
또한, 도 3은 합성예 1과 합성예 3에서 제조된 화합물의 열중량분석(TGA)를 나타낸 것으로, 열에 대한 안정성이 좋아 상기 화합물을 이용하여 제조된 박은 내열성이 우수하다는 것을 미루어 짐작할 수 있다. In addition, Figure 3 shows the thermogravimetric analysis (TGA) of the compounds prepared in Synthesis Example 1 and Synthesis Example 3, it can be guessed that the foil prepared using the compound is excellent in thermal stability.
도 4는 시간에 따른 회절효율 증가를 나타낸 것으로 본 발명이 수 십초 이내에 최고의 효율을 보여주고 있음을 확인할 수 있었다.4 shows an increase in diffraction efficiency with time, and it was confirmed that the present invention showed the highest efficiency within several tens of seconds.
이상에서 상술한 바와 같이, 본 발명에 따른 가교 가능한 과불소화 디(메타)아크릴계 화합물을 이용한 광중합성 조성물은 광경화 시 수축율이 낮으면서도 굴절율 차이가 커서 기록효과가 우수한 광중합성 막을 제공할 수 있으며, 상기 제조된 광중합성 막은 홀로그래피 시스템, 디스플레이용 동영상 제조 시스템, 볼륨 홀로그램을 이용한 광분리기, 광헤드장치, 액정표시장치, 다단계 그레이팅, 인쇄조판 또는 감광성 내식막, 정보기록막 등에 유용하게 적용될 수 있다.As described above, the photopolymerizable composition using the crosslinkable perfluorinated di (meth) acrylic compound according to the present invention can provide a photopolymerizable film having excellent recording effect due to a low refractive index difference and a low shrinkage rate during photocuring. The prepared photopolymerizable film may be usefully applied to a holography system, a video production system for display, an optical separator using a volume hologram, an optical head device, a liquid crystal display device, a multi-step grating, a printing type or a photoresist, an information recording film, and the like.
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| KR19990039435A (en) * | 1997-11-12 | 1999-06-05 | 이계철 | Fluorine-substituted polyaryl ether for optical device, method for manufacturing same, and optical waveguide type optical device using same |
| KR20040090403A (en) * | 2003-04-16 | 2004-10-22 | 김환규 | Monomers, Copolyacrylates & Their Synthetic Methods for Photonic Devices |
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| JPS625936A (en) * | 1985-06-24 | 1987-01-12 | S D S Baiotetsuku:Kk | Fluorine-containing aromatic compounds and antibacterial and antifungal agents |
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| KR19990039435A (en) * | 1997-11-12 | 1999-06-05 | 이계철 | Fluorine-substituted polyaryl ether for optical device, method for manufacturing same, and optical waveguide type optical device using same |
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| KR20190141895A (en) | 2018-06-15 | 2019-12-26 | 인하대학교 산학협력단 | Resist materials comprising highly fluorinated polymers having a solubility in highly fluorinated solvents |
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