KR101567837B1 - Photoinitiators with fluorene structure and reactive liquid crystal compositions, and photoresist compositions comprising the same - Google Patents
Photoinitiators with fluorene structure and reactive liquid crystal compositions, and photoresist compositions comprising the same Download PDFInfo
- Publication number
- KR101567837B1 KR101567837B1 KR1020130066691A KR20130066691A KR101567837B1 KR 101567837 B1 KR101567837 B1 KR 101567837B1 KR 1020130066691 A KR1020130066691 A KR 1020130066691A KR 20130066691 A KR20130066691 A KR 20130066691A KR 101567837 B1 KR101567837 B1 KR 101567837B1
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- KR
- South Korea
- Prior art keywords
- liquid crystal
- formula
- fluorene structure
- group
- general formula
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 38
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 32
- 229920002120 photoresistant polymer Polymers 0.000 title description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 6
- 229940123457 Free radical scavenger Drugs 0.000 claims description 6
- 239000002318 adhesion promoter Substances 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 239000003349 gelling agent Substances 0.000 claims description 6
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 6
- 239000002952 polymeric resin Substances 0.000 claims description 6
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 239000006254 rheological additive Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 230000009257 reactivity Effects 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- -1 oxime ester Chemical class 0.000 description 24
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 230000036211 photosensitivity Effects 0.000 description 6
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 6
- VVSGSQMLYOTNIE-UHFFFAOYSA-N (ethylideneamino) acetate Chemical compound CC=NOC(C)=O VVSGSQMLYOTNIE-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- DPPFREDTHDJUOI-UHFFFAOYSA-N 9,9-dibutylfluorene Chemical compound C1=CC=C2C(CCCC)(CCCC)C3=CC=CC=C3C2=C1 DPPFREDTHDJUOI-UHFFFAOYSA-N 0.000 description 5
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 5
- 238000001757 thermogravimetry curve Methods 0.000 description 5
- QLSFVCNMOPGKSP-UHFFFAOYSA-N 1-(9,9-dibutylfluoren-2-yl)ethanone Chemical compound C1=C(C(C)=O)C=C2C(CCCC)(CCCC)C3=CC=CC=C3C2=C1 QLSFVCNMOPGKSP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 4
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- 238000000605 extraction Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FZENGILVLUJGJX-UHFFFAOYSA-N acetaldehyde oxime Chemical compound CC=NO FZENGILVLUJGJX-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- AVCNDQUBVOMMSL-UHFFFAOYSA-N 2-bromo-9,9-dibutylfluorene Chemical compound C1=C(Br)C=C2C(CCCC)(CCCC)C3=CC=CC=C3C2=C1 AVCNDQUBVOMMSL-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QGAIFCANMMRLAI-UHFFFAOYSA-N C(CCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)C(=O)Cl)CCCC Chemical compound C(CCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)C(=O)Cl)CCCC QGAIFCANMMRLAI-UHFFFAOYSA-N 0.000 description 2
- SYOTYHMHMPSZDQ-UHFFFAOYSA-N C(CCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)C(C(C)(C)N(C)C)=O)CCCC Chemical compound C(CCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)C(C(C)(C)N(C)C)=O)CCCC SYOTYHMHMPSZDQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 206010034960 Photophobia Diseases 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940035423 ethyl ether Drugs 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 208000013469 light sensitivity Diseases 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- OBQRODBYVNIZJU-UHFFFAOYSA-N (4-acetylphenyl)boronic acid Chemical compound CC(=O)C1=CC=C(B(O)O)C=C1 OBQRODBYVNIZJU-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 1
- NNYSRQDAPSNOKV-UHFFFAOYSA-N 2-bromo-9,9-dihexylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCC)(CCCCCC)C3=CC=CC=C3C2=C1 NNYSRQDAPSNOKV-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- KRSDHUVUYGPFTD-NJZRLIGZSA-N C(CCC)C1(C2=CC(=CC=C2C=2C=CC(=CC12)C(=O)C1=CC=CC=C1)/C(/C)=N/O)CCCC Chemical compound C(CCC)C1(C2=CC(=CC=C2C=2C=CC(=CC12)C(=O)C1=CC=CC=C1)/C(/C)=N/O)CCCC KRSDHUVUYGPFTD-NJZRLIGZSA-N 0.000 description 1
- KOPSMUVMXJOGRP-JJIBRWJFSA-N C(CCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)/C(/C)=N/O)CCCC Chemical compound C(CCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)/C(/C)=N/O)CCCC KOPSMUVMXJOGRP-JJIBRWJFSA-N 0.000 description 1
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- VHMAVATUIJESHO-UHFFFAOYSA-N C(CCCCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)C1=CC=C(C=C1)C(C)=O)CCCCCC Chemical compound C(CCCCC)C1(C2=CC=CC=C2C=2C=CC(=CC12)C1=CC=C(C=C1)C(C)=O)CCCCCC VHMAVATUIJESHO-UHFFFAOYSA-N 0.000 description 1
- NMVKCQFRJMRPRD-UHFFFAOYSA-N CCCCC1(C2=C(C=CC(=C2)C(=O)C)C3=C1C=C(C=C3)C(=O)C4=CC=CC=C4)CCCC Chemical compound CCCCC1(C2=C(C=CC(=C2)C(=O)C)C3=C1C=C(C=C3)C(=O)C4=CC=CC=C4)CCCC NMVKCQFRJMRPRD-UHFFFAOYSA-N 0.000 description 1
- XJYGZFIBICFTJE-UHFFFAOYSA-N CCCCC1(CCCC)C(CC(CC2)C3OC3P(C3CCCCC3)(C3CCCCC3)=O)C2C2C1CCCC2 Chemical compound CCCCC1(CCCC)C(CC(CC2)C3OC3P(C3CCCCC3)(C3CCCCC3)=O)C2C2C1CCCC2 XJYGZFIBICFTJE-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
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- 150000001721 carbon Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 239000000852 hydrogen donor Substances 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- OAADXJFIBNEPLY-UHFFFAOYSA-N methoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(OC)C1=CC=CC=C1 OAADXJFIBNEPLY-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
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- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C207/00—Compounds containing nitroso groups bound to a carbon skeleton
-
- 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
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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
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- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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Abstract
본 발명은 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물에 관한 것으로, UV 광원에 대한 장파장 흡수율이 높아 내부 경화에 우수한 반응성을 보이며, 광감도 특성이 우수하여 반응 전환율이 높아 반응성 액정 조성물 및 감광성 조성물에서 상용성이 우수한 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물에 관한 것이다.
본 발명의 플루오렌구조를 갖는 신규한 광개시제 하기 [일반식]으로 표시되는 것을 특징으로 한다.
[일반식]
상기 [일반식]에서 R1, R2는 서로 독립적으로 수소(이때, R1 및 R2가 모두 수소는 아니다.), 하기 [화학식 1] 내지 [화학식 9]으로 표시되는 광개시 그룹중에서 어느 하나 선택되며, R3, R4 는 서로 독립적으로 수소, 불소, 탄소수가 1-6인 직쇄형 또는 분지형의 알킬이다.The present invention relates to a novel photoinitiator having a fluorene structure, a reactive liquid crystal composition comprising the same, and a photosensitive composition, which exhibits excellent reactivity to internal hardening due to high absorption of a long wavelength to a UV light source, The present invention relates to a novel photoinitiator having a fluorene structure excellent in compatibility with a reactive liquid crystal composition and a photosensitive composition, and a reactive liquid crystal composition and a photosensitive composition containing the same.
A novel photoinitiator having a fluorene structure of the present invention is characterized by being represented by the following general formula.
[General formula]
In the above general formula, R 1 and R 2 independently of one another are hydrogen (wherein R 1 and R 2 are And R 3 and R 4 are independently selected from the group consisting of hydrogen, fluorine, and straight-chained groups having 1 to 6 carbon atoms. Or branched alkyl.
Description
본 발명은 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물에 관한 것으로, UV 광원에 대한 장파장 흡수율이 높아 내부 경화에 우수한 반응성을 보이며, 광감도 특성이 우수하여 반응 전환율이 높아 반응성 액정 조성물 및 감광성 조성물에서 상용성이 우수한 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물에 관한 것이다.
The present invention relates to a novel photoinitiator having a fluorene structure, a reactive liquid crystal composition comprising the same, and a photosensitive composition, which exhibits excellent reactivity to internal hardening due to high absorption of a long wavelength to a UV light source, The present invention relates to a novel photoinitiator having a fluorene structure excellent in compatibility with a reactive liquid crystal composition and a photosensitive composition, and a reactive liquid crystal composition and a photosensitive composition containing the same.
광 개시제(photo initiator)는 자외선 경화형 도료(자외선을 이용한 모든 coating, ink, adhesive 등을 총칭함)에 첨가되어, 빛을 흡수하고 분해되어 화학적으로 활성을 지닌 원자 또는 분자를 생성하는 물질로서, 자외선 광원으로부터 에너지를 흡수하여 photo polymerization 반응을 개시시키는 물질을 말하며, 반응형 액정 조성물 및 감광성 조성물 등에 널리 사용되는데, 화학적으로 활성을 지닌 물질의 예로는 산이나 염기 그리고 라디칼 등이 있으며, 특히, 라디칼이 생성되는 광개시제는 생성된 라디칼과 함께 중합 반응을 일으키는 아크릴기와 함께 사용되어 코팅막을 형성하는 목적으로 사용된다.
Photo initiators are substances that are added to ultraviolet curable paints (all coatings, inks, and adhesives using ultraviolet rays) to absorb atoms and decompose to produce chemically active atoms or molecules. Ultraviolet Refers to a substance that absorbs energy from a light source to initiate a photo polymerization reaction and is widely used in a reactive liquid crystal composition and a photosensitive composition. Examples of the chemically active substance include an acid, a base, and a radical. Particularly, The resulting photoinitiator is used together with the resulting radical to form a coating film with the acrylic group causing the polymerization reaction.
이러한 광개시제는 광경화반응 메카니즘에 따라 크게 free radical polymerization과 cationic polymerization으로 분류되는데, 이 중 free radical polymerization이 약 90% 이상 생산 현장에서 적용되고 있으며, 이러한 free radical 메카니즘은 광개시제 자체가 분리되면서 라디칼을 형성하게 되고, cationic 메카니즘은 수소를 주는 물질과 반응하여 라디칼을 형성하게 되며, 생성된 라디칼은 단량체와의 반응으로 인해 라디칼 중합과정을 거쳐 고분자를 생성하게 된다.
These photoinitiators are classified into free radical polymerization and cationic polymerization according to the photo-curing reaction mechanism. Among them, about 90% of free radical polymerization is applied at the production site. The free radical mechanism separates the photoinitiator itself and forms radicals The cationic mechanism reacts with the hydrogen donor to form radicals, and the resulting radicals undergo radical polymerization through the reaction with monomers to produce polymers.
광개시제로서 요구되는 특성으로는 반응을 개시시키는 활성종(radical, acid)을 생성하는 능력(양자수율, 몰흡광계수)이 높아야 하며 생성된 활성종의 반응성이 크고 광개시제의 자외선 스펙트럼과 광원이 가지는 스펙트럼이 서로 겹쳐야한다. 또한 올리고머, 모노머와의 상용성과 저장안정성이 좋아야 하며 독성이나 황변성이 없어야 하며 이러한 조건이외에도 경제성을 고려하여야 한다.
The characteristics required for the photoinitiator include high activity (quantum yield, molar extinction coefficient) to generate reactive radicals (acid and acid) to initiate the reaction, high reactivity of the generated active species, and a spectrum of the photoinitiator Must overlap each other. It should also have good compatibility with oligomers and monomers, good storage stability, no toxicity or sulfur degradation, and economic considerations in addition to these conditions.
광개시제의 대표적인 반응으로는 다음 그림과 같이 benzoyl 그룹을 포함하는 구조로서, Benzoyl 그룹과 이웃하는 탄소 원자에 연결된 산소 원자와 벤젠 고리는 전자 친화도가 높기 때문에 UV에 노출되면 이중결합에 인접한 탄소에서 라디칼을 형성한다.Typical reactions for photoinitiators are benzoyl groups as shown in the following figure. The benzoyl group and the oxygen atom connected to the adjacent carbon atom and the benzene ring have high electron affinity. Therefore, when exposed to UV, .
상기와 같은 광개시제와 모노머 또는 올리고머와의 반응은 첫번째 단계로 UV를 조사하게 되면 광개시제가 UV광원에 노출되면서 라디칼로 분해된다. 두번째 단계로 라디칼은 모노머 또는 올리고머의 말단에 존재하는 아크릴 그룹의 C=C 이중결합에서 하나의 탄소와 결합하면서 안정화되고 남은 탄소는 안정화되기 위해 전자가 하나 부족한 상태의 새로운 라디칼이 되며, 새로이 형성된 라디칼은 다른 모노머 또는 올리고머의 이중결합과 반응하게 되며 모노머 또는 올리고머가 모두 소모될 때까지 반복적으로 반응이 진행된다. 세번째 단계로 라디칼 모노머 또는 올리고머들이 서로 반응하거나 활성을 잃은 광개시제가 라디칼로 재분해되지 못할 때 반응은 끝나게 된다.
When the photoinitiator is reacted with the monomer or oligomer in the first step, the photoinitiator is decomposed into radicals by exposure to the UV light source. In the second step, the radical is stabilized while bonding with one carbon at the C = C double bond of the acrylic group existing at the end of the monomer or oligomer, and the remaining carbon becomes a new radical in which one electron is insufficient for stabilization, Reacts with the double bond of the other monomer or oligomer and the reaction proceeds repeatedly until the monomer or oligomer is consumed. In the third step, the reaction is terminated when the radical monomer or oligomers react with each other or the photoinitiator, which has lost its activity, can not be decomposed into radicals.
종래의 광개시제의 일반적인 예로는 아세토페논 유도체, 벤조페논 유도체, 비이미다졸 유도체, 아실포스핀 옥사이드 유도체, 트리아진 유도체, 옥심 에스테르 유도체 등 여러 종류가 알려져 있는데, 이중 옥심 에스테르 유도체의 경우 자외선을 흡수하여 색을 거의 띄지않고 라디칼 발생 효율이 높을 뿐 아니라, 조성물 내에서의 안정성이 뛰어난 장점이 있어 많이 사용되고 있는데, 옥심 에스테르 구조의 광개시제로는, α-옥소옥심 유도체, 티오옥산톤과 옥심에스테르 화합물을 같이 사용한 것, 시너지스트로 p-디알킬아미노벤젠을 사용한 옥심 에스테르, β-아미노옥심을 사용한 광개시제, 에틸렌성 불포화기가 분자 구조내에 포함된 옥심 에테르 광개시제 등이 개발되었다.
As typical examples of conventional photoinitiators, various kinds of acetophenone derivatives, benzophenone derivatives, nonimidazole derivatives, acylphosphine oxide derivatives, triazine derivatives and oxime ester derivatives are known. Among them, oxime ester derivatives absorb ultraviolet rays A photoacid generator having an oxime ester structure, an oxime oxime derivative, a thioxanthone derivative, and an oxime ester compound are used in combination as a photoinitiator. Oxime ester using p-dialkylaminobenzene, photoinitiator using? -Aminooxime, and oxime ether photoinitiator wherein an ethylenic unsaturated group is contained in the molecular structure have been developed.
종래 광개시제들로는 한국공개특허 특2001-0062219호에 황변이 최소화되는, 에틸렌계 불포화 중합체성 화합물을 경화시키는 다음 화학구조를 갖는 포스핀 옥사이드 광개시제가 공지되어 있다.Conventional photoinitiators are disclosed in Korean Patent Laid-Open No. 2001-0062219, which discloses a phosphine oxide photoinitiator having the following chemical structure for curing an ethylenically unsaturated polymeric compound in which yellowing is minimized.
또한, 한국등록특허 10-0685153호에는 경화된 기판이 단지 낮은 황변도를 갖도록 하는 반응성 광경화제인 다음 화학구조를 갖는 광개시제가 공지되어 있다.In addition, Korean Patent No. 10-0685153 discloses a photoinitiator having the following chemical structure, which is a reactive photo-curing agent that causes the cured substrate to have only a low yellowing degree.
또한, 한국공개특허 특2001-0022593에는 다음의 화학구조를 갖는 α-아미노 에놀 에테르 화합물의 형태의 광개시제가 공지되어 있다.Korean Patent Laid-Open Publication No. 2001-0022593 discloses a photoinitiator in the form of an? -Aminoenol ether compound having the following chemical structure.
또한, 한국공개특허 10-2010-0017755에 대표적으로 다음의 화학구조식과 같은 헤테로사이클을 비롯한 다방향족계 상의 치환기로서 2개 이상의 옥심 에스테르 기를 포함하는 광개시제가 공지된 바 있다.Also, Korean Patent Laid-Open No. 10-2010-0017755 discloses a photoinitiator comprising two or more oxime ester groups as a substituent on a polyaromatic phase including a heterocycle such as the following chemical formula.
또한, 한국공개특허 10-2008-0080208에 대표적으로 다음의 화학구조식을 가지는 헤테로사이클을 포함하는 다중 방향족(polyaromatic) 시스템상에서 치환체로서 2개 이상의 옥심에스테르 그룹을 갖는 옥심에스테르 광개시제가 공지되어 있다.Also, Korean Patent Laid-Open No. 10-2008-0080208 discloses oxime ester photoinitiators having two or more oxime ester groups as substituents on a polyaromatic system including a heterocycle having the following chemical structure.
또한, 한국등록특허 10-0781690에는 다음의 화학구조식을 가지는 옥심에스테르 광개시제가 공지되어 있다.Korean Patent No. 10-0781690 discloses oxime ester photoinitiators having the following chemical structural formulas.
또한, 한국공개특허 10-2009-0046108에는 다음의 화학구조식을 가지는 옥심에스테르 광개시제가 공지되어 있다.In Korean Patent Laid-open No. 10-2009-0046108, oxime ester photoinitiators having the following chemical structural formulas are known.
또한, 한국공개특허 10-2009-0051858에는 다음의 화학구조식을 가지는 옥심에스테르 광개시제가 공지되어 있다.Korean Patent Laid-Open No. 10-2009-0051858 discloses oxime ester photoinitiators having the following chemical structural formulas.
또한, 한국공개특허 10-2009-0107977에는 다음의 화학구조식을 가지는 옥심에스테르 광개시제가 공지되어 있다.In Korean Patent Laid-open No. 10-2009-0107977, oxime ester photoinitiators having the following chemical structural formulas are known.
한편, 반응성 액정(Reactive liquid crystals) 조성물은 두 개 이상의 중합성기를 포함하고 있는 저분자량의 액정 물질로 광개시제에 의해 중합되어 편광판이나 위상차판 등의 광학 소자로 응용되고 있다. 즉, 반응성 액정 단량체를 액정상태에서 적절한 배향 제어를 행한 뒤 그 배향 상태를 수평 배향(homogeneous alignment), 하이브리드 배향(hybrid alignment), 수직 배향(homeotropic alignment) 또는 트위스트 배향 (twist alignment) 등의 상태로 유지하면서 광개시제에 의해 중합하고 그 상태를 고정하는 것에 의해 광학 이방성을 가지는 배향막 필름을 얻을 수 있으며, 이후 액정상 온도 범위를 벗어나더라도 액정이 가지는 특성을 유지하게 함으로써 광학 이방성 광학소자에 매우 유용하게 사용된다.
On the other hand, a reactive liquid crystals composition is a low molecular weight liquid crystal material containing two or more polymerizable groups and is polymerized by a photoinitiator and applied as an optical element such as a polarizing plate or a retarder. That is, after the reactive liquid crystal monomer is properly controlled in the liquid crystal state, the alignment state is changed into a state such as homogeneous alignment, hybrid alignment, homeotropic alignment, or twist alignment An orientation film having an optically anisotropic property can be obtained by polymerizing it with a photoinitiator while keeping its state, and then keeping the properties of the liquid crystal even when the temperature is out of the liquid crystal temperature range, do.
또한, 감광성 수지 조성물은 기판상에 도포되어 도막을 형성하고, 이 도막의 특정 부분에 포토마스크 등을 이용하여 광 조사에 의한 노광을 실시한 후, 비노광부를 현상 처리하여 제거함으로써 패턴을 형성하는데 사용할 수 있으며, 이러한 감광성 수지 조성물은 광을 조사하고 중합하고 경화시키는 것이 가능하므로 광경화성 잉크, 감광성 인쇄판, 각종 포토레지스트, LCD용 컬러 필터 포토레지스트, 수지 블랙 매트릭스용 포토레지스트, 또는 투명 감광재 등에 이용되고 있다.
Further, the photosensitive resin composition is applied on a substrate to form a coated film, and after exposing to a specific portion of the coated film using a photomask or the like by light irradiation, the non-exposed portion is removed by development to be used for forming a pattern Such a photosensitive resin composition can be irradiated with light and can be polymerized and cured. Therefore, it can be used for a photo-curable ink, a photosensitive printing plate, various photoresists, a color filter photoresist for LCD, a photoresist for resin black matrix, .
상기한 반응성 액정 조성물 및 감광성 수지 조성물의 중합 및 경화는 사용되는 광개시제가 빛에 빠르게 반응하는 특성, 즉 광개시제의 광감도가 매우 중요하며, 광감도가 우수한 광개시제는 적은 양으로도 충분한 감도를 구현할 수 있어 배향막 필름 및 패턴의 기계적 물성이 우수하게 되는 등의 여러가지 장점이 있다.
Polymerization and curing of the reactive liquid crystal composition and the photosensitive resin composition described above are very important in that the photoinitiator used reacts rapidly with light, that is, the photosensitizer has a high photosensitivity. The photoinitiator having excellent photosensitivity can realize sufficient sensitivity even in a small amount, The mechanical properties of the film and the pattern are excellent, and the like.
그러나, 반응성 액정 조성물 및 감광성 수지 조성물에 사용되는 종래 광개시제들은 광개시 효율이 낮고, 안료의 농도가 높을 경우 UV 광원 흡수에 효율적이지 못한 문제가 있었으며, 이에 따른 공정 시간을 단축하는데 한계가 있었고, 코팅막이 후막인 경우 내부경화가 불충분하여 경화도 및 기계적 강도를 충분히 만족하지 못할 뿐만 아니라, 상당히 고가여서 경제적인 측면에서 충분한 광감도를 낼 정도로 사용할 수 없는 문제점이 있었으므로 UV 광원에 대한 장파장 흡수율이 높아 내부 경화에 우수한 반응성을 보이며, 광감도 특성이 우수하여 반응 전환율이 높은 광개시제의 개발과 이를 포함하는 반응성 액정조성물 및 감광성 조성물 개발이 절실히 요구되고 있다.
However, the conventional photoinitiators used in the reactive liquid crystal compositions and photosensitive resin compositions have low photoinitiator efficiency, and when the concentration of the pigment is high, there is a problem that the photoinitiator is not efficient in absorbing the UV light source, In the case of this thick film, the internal hardening is insufficient, so that the curing degree and the mechanical strength are not sufficiently satisfied, and since it is quite expensive, it can not be used enough to give sufficient photosensitivity in terms of economy. Therefore, Development of a photoinitiator having excellent reactivity to curing, excellent photosensitivity and high reaction conversion rate, and development of a reactive liquid crystal composition and a photosensitive composition containing the same are urgently required.
본 발명은 상기 문제점을 햐결하기 위하여 UV 광원에 대한 장파장 흡수율이 높아 내부 경화에 우수한 반응성을 보이며, 광감도 특성이 우수하여 반응 전환율이 높아 반응성 액정 조성물 및 감광성 조성물에서 상용성이 우수한 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물을 제공하는 것을 해결하고자 하는 과제로 한다.
In order to overcome the above problems, the present invention provides a reactive liquid crystal composition and a fluorene structure excellent in compatibility with the photosensitive composition, because the UV light source has a long wavelength absorption rate and exhibits excellent reactivity to internal hardening, And to provide a novel photoinitiator, a reactive liquid crystal composition containing the same, and a photosensitive composition.
상기 과제를 해결하기 위하여 본 발명은, 하기 [일반식]으로 표시되는 것을 특징으로 하는 플루오렌구조를 갖는 신규한 광개시제를 과제의 해결수단으로 한다.In order to solve the above problems, the present invention provides a novel photoinitiator having a fluorene structure, which is represented by the following general formula.
[일반식][General formula]
상기 [일반식]에서 R1는 수소이고, R2는 하기 [화학식 1], [화학식 3], [화학식 6] 또는 [화학식 7]로 표시되는 광개시 그룹중에서 어느 하나 선택되며, R3, R4 는 서로 독립적으로 수소, 불소, 탄소수가 1-6인 직쇄형 또는 분지형의 알킬이다.
[화학식 1]
Wherein R 1 in the [formula] is hydrogen, R 2 is to Formula 1, Formula 3, are selected one of a photoinitiating group represented by Formula 6 or Formula 7], R 3, R 4 is, independently of each other, hydrogen, fluorine, straight-chain or branched alkyl having 1 to 6 carbon atoms.
[Chemical Formula 1]
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상기 [화학식 1]에서 R5, R6는 서로 독립적으로 수소, C1-C12 직쇄 또는 분지쇄의 알킬기, 알케닐기 또는 알키닐기, C3-C6 시클로알킬기, C6-C30 아릴기에서 선택되며, 상기 C1-C12 직쇄 또는 분지쇄의 알킬기, 알케닐기 또는 알키닐기, C3-C6 시클로알킬기, C6-C30 아릴기는 각각 C1-C6 알킬기, 페닐기, 할로겐, 니트로기, -CN, -OR, -SR, -NRR, -NHR, -C(=O)OR, -C(=O)NHR, -C(=O)ArOR 및 -C(=O)ArNHR로 치환되거나 비치환될 수 있고, 상기 R은 C1-C12 직쇄 또는 분지쇄의 알케닐기, Ar는 C6-C30 아릴기이다.Wherein R 5 and R 6 independently represent hydrogen, a C 1 -C 12 linear or branched alkyl group, an alkenyl group or an alkynyl group, a C 3 -C 6 cycloalkyl group, a C 6 -C 30 aryl group C 1 -C 6 straight or branched chain alkyl, alkenyl or alkynyl group, C 3 -C 6 cycloalkyl group or C 6 -C 30 aryl group is selected from C 1 -C 6 alkyl group, phenyl group, halogen, -C (= O) NHR, -C (= O) ArOR, and -C (= O) ArNHR by a nitro group, -CN, -OR, -SR, -NRR, -NHR, R is a C 1 -C 12 linear or branched alkenyl group, and Ar is a C 6 -C 30 aryl group.
[화학식 3](3)
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상기 [화학식 3]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같다.Wherein R 5 and R 6 are the same as defined in the above formula (1).
[화학식 6][Chemical Formula 6]
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상기 [화학식 6]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같으며, R7은 R5 또는 R6과 같다.Wherein R 5 and R 6 are the same as defined in Formula 1, and R 7 is the same as R 5 or R 6 .
[화학식 7](7)
상기 [화학식 7]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같다.In the above formula (7), R 5 and R 6 are as defined in the above formula (1).
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 12]으로 표시되는 것을 과제의 해결수단으로 한다.The novel photoinitiator having a fluorene structure represented by the above general formula is a solution to the problem expressed by the following general formula (12).
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[화학식 12][Chemical Formula 12]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 13]으로 표시되는 것을 과제의 해결수단으로 한다.The novel photoinitiator having a fluorene structure represented by the above general formula is a solution to the problem represented by the following general formula (13).
[화학식 13][Chemical Formula 13]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 14]으로 표시되는 것을 과제의 해결수단으로 한다.The novel photoinitiator having a fluorene structure represented by the above general formula is represented by the following formula (14) as a solution to the problem.
[화학식 14][Chemical Formula 14]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 15]으로 표시되는 것을 과제의 해결수단으로 한다.A novel photoinitiator having a fluorene structure represented by the above general formula is a solution to the problem expressed by the following formula (15).
[화학식 15][Chemical Formula 15]
상기 플루오렌 구조를 갖는 신규한 광개시제와 반응성 액정 단량체 및 용매를 포함하여 조성되는 것을 특징으로 하는 반응성 액정 조성물을 과제의 해결수단으로 한다.
A novel photoinitiator having a fluorene structure, a reactive liquid crystal monomer, and a solvent.
상기 반응성 액정 조성물은 액정, 염료, 배열촉진제, 열개시제, 계면활성제, 중합억제제, 광안정제, 열안정제, 이형제, 레올로지 조절제, 겔화제, 레벨링제, 자유라디칼 소거제, 커플링제, 틸트(tilt)조절 첨가제, 고분자 수지 화합물, 중합성 화합물, 접착촉진제로 이루어진 군으로부터 선택되는 1종 이상의 첨가제를 포함하여 조성되는 것을 특징으로 하는 반응성 액정 조성물을 과제의 해결수단으로 한다.
The reactive liquid crystal composition may be in the form of a liquid crystal, a dye, an alignment promoter, a thermal initiator, a surfactant, a polymerization inhibitor, a light stabilizer, a heat stabilizer, a releasing agent, a rheology modifier, a gelling agent, a leveling agent, a free radical scavenger, ) Regulating additive, a polymer resin compound, a polymerizable compound, and an adhesion promoter. The present invention also provides a reactive liquid crystal composition comprising the reactive liquid crystal composition.
상기 플루오렌 구조를 갖는 신규한 광개시제와 고분자 수지 화합물, 중합성 화합물 및 용매를 포함하여 조성되는 것을 특징으로 하는 감광성 조성물을 과제의 해결수단으로 한다.
A novel photoinitiator having a fluorene structure, and a polymer resin compound, a polymerizable compound and a solvent.
상기 감광성 조성물은 액정, 염료, 배열촉진제, 열개시제, 계면활성제, 중합억제제, 광안정제, 열안정제, 이형제, 레올로지 조절제, 겔화제, 레벨링제, 자유라디칼 소거제, 커플링제, 틸트(tilt)조절 첨가제, 접착촉진제로 이루어진 군으로부터 선택되는 1종 이상의 첨가제를 포함하여 조성되는 것을 특징으로 하는 감광성 조성물을 과제의 해결수단으로 한다.
The photosensitive composition may be in the form of a liquid, a dye, an alignment promoter, a thermal initiator, a surfactant, a polymerization inhibitor, a light stabilizer, a heat stabilizer, a releasing agent, a rheology modifier, a gelling agent, a leveling agent, a free radical scavenger, Wherein the photosensitive composition is composed of at least one additive selected from the group consisting of an additive, an adjusting additive, and an adhesion promoter.
본 발명에 따른 플루오렌 구조를 갖는 신규한 광개시제는 UV 광원에 대한 장파장 흡수율이 높아 내부 경화에 우수한 반응성을 보이며, 광감도 특성이 우수하여 반응 전환율이 높아 반응성 액정 조성물 및 감광성 조성물에서 상용성이 우수한 장점이 있다.
The novel photoinitiator having a fluorene structure according to the present invention has a high absorption rate of a long wavelength to a UV light source and exhibits excellent reactivity to internal hardening and has excellent photosensitivity and high reaction conversion rate, thus being excellent in compatibility with a reactive liquid crystal composition and a photosensitive composition .
도 7은 본 발명의 [화학식 12]화합물의 1H-NMR spectrum 및 FT-IR spectrum 그래프
도 8은 본 발명의 [화학식 12]화합물의 GC-MS Spectrometer 및 UV-vis spectrum 그래프
도 9는 본 발명의 [화학식 12]화합물의 TGA curves 및 DSC Thermogram
도 10은 본 발명의 [화학식 13]화합물의 1H-NMR spectrum 및 FT-IR spectrum 그래프
도 11은 본 발명의 [화학식 13]화합물의 GC-MS Spectrometer 및 UV-vis spectrum 그래프
도 12는 본 발명의 [화학식 13]화합물의 TGA curves 및 DSC Thermogram7 is a graph showing the < 1 > H-NMR spectrum and the FT-IR spectrum
8 is a graph showing the GC-MS spectrometer and UV-vis spectrum graph of the compound of the formula [12]
9 shows the TGA curves and the DSC Thermogram
10 is a graph showing the < 1 > H-NMR spectrum and the FT-IR spectrum
11 is a graph showing the GC-MS spectrometer and the UV-vis spectrum of the compound of the formula [13]
12 shows the TGA curves and DSC Thermograms of the compound of Formula 13 of the present invention
본 발명은, 하기 [일반식]으로 표시되는 것을 특징으로 하는 플루오렌구조를 갖는 신규한 광개시제를 기술구성의 특징으로 한다.The present invention is a technical feature of a novel photoinitiator having a fluorene structure, which is represented by the following general formula.
[일반식][General formula]
상기 [일반식]에서 R1는 수소이고, R2는 하기 [화학식 1], [화학식 3], [화학식 6] 또는 [화학식 7]로 표시되는 광개시 그룹중에서 어느 하나 선택되며, R3, R4 는 서로 독립적으로 수소, 불소, 탄소수가 1-6인 직쇄형 또는 분지형의 알킬이다.
[화학식 1]
Wherein R 1 in the [formula] is hydrogen, R 2 is to Formula 1, Formula 3, are selected one of a photoinitiating group represented by Formula 6 or Formula 7], R 3, R 4 is, independently of each other, hydrogen, fluorine, straight-chain or branched alkyl having 1 to 6 carbon atoms.
[Chemical Formula 1]
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상기 [화학식 1]에서 R5, R6는 서로 독립적으로 수소, C1-C12 직쇄 또는 분지쇄의 알킬기, 알케닐기 또는 알키닐기, C3-C6 시클로알킬기, C6-C30 아릴기에서 선택되며, 상기 C1-C12 직쇄 또는 분지쇄의 알킬기, 알케닐기 또는 알키닐기, C3-C6 시클로알킬기, C6-C30 아릴기는 각각 C1-C6 알킬기, 페닐기, 할로겐, 니트로기, -CN, -OR, -SR, -NRR, -NHR, -C(=O)OR, -C(=O)NHR, -C(=O)ArOR 및 -C(=O)ArNHR로 치환되거나 비치환될 수 있고, 상기 R은 C1-C12 직쇄 또는 분지쇄의 알케닐기, Ar는 C6-C30 아릴기이다.Wherein R 5 and R 6 independently represent hydrogen, a C 1 -C 12 linear or branched alkyl group, an alkenyl group or an alkynyl group, a C 3 -C 6 cycloalkyl group, a C 6 -C 30 aryl group C 1 -C 6 straight or branched chain alkyl, alkenyl or alkynyl group, C 3 -C 6 cycloalkyl group or C 6 -C 30 aryl group is selected from C 1 -C 6 alkyl group, phenyl group, halogen, -C (= O) NHR, -C (= O) ArOR, and -C (= O) ArNHR by a nitro group, -CN, -OR, -SR, -NRR, -NHR, R is a C 1 -C 12 linear or branched alkenyl group, and Ar is a C 6 -C 30 aryl group.
[화학식 3](3)
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상기 [화학식 3]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같다.Wherein R 5 and R 6 are the same as defined in the above formula (1).
[화학식 6][Chemical Formula 6]
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상기 [화학식 6]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같으며, R7은 R5 또는 R6과 같다.Wherein R 5 and R 6 are the same as defined in Formula 1, and R 7 is the same as R 5 or R 6 .
[화학식 7](7)
상기 [화학식 7]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같다.In the above formula (7), R 5 and R 6 are as defined in the above formula (1).
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 12]으로 표시되는 것을 기술구성의 특징으로 한다.The novel photoinitiator having a fluorene structure represented by the above general formula is characterized by the following structural formula (12).
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[화학식 12][Chemical Formula 12]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 13]으로 표시되는 것을 기술구성의 특징으로 한다.The novel photoinitiator having a fluorene structure represented by the above general formula is characterized by the technical structure represented by the following formula (13).
[화학식 13][Chemical Formula 13]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 14]으로 표시되는 것을 기술구성의 특징으로 한다.The novel photoinitiator having a fluorene structure represented by the above general formula is characterized by the following structural formula (14).
[화학식 14][Chemical Formula 14]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 15]으로 표시되는 것을 기술구성의 특징으로 한다.The novel photoinitiator having a fluorene structure represented by the above general formula is characterized by the technical structure represented by the following formula (15).
[화학식 15][Chemical Formula 15]
상기 플루오렌 구조를 갖는 신규한 광개시제와 반응성 액정 단량체 및 용매를 포함하여 조성되는 것을 특징으로 하는 반응성 액정 조성물을 기술구성의 특징으로 한다.
A novel photoinitiator having a fluorene structure, a reactive liquid crystal monomer, and a solvent.
상기 반응성 액정 조성물은 액정, 염료, 배열촉진제, 열개시제, 계면활성제, 중합억제제, 광안정제, 열안정제, 이형제, 레올로지 조절제, 겔화제, 레벨링제, 자유라디칼 소거제, 커플링제, 틸트(tilt)조절 첨가제, 고분자 수지 화합물, 중합성 화합물, 접착촉진제로 이루어진 군으로부터 선택되는 1종 이상의 첨가제를 포함하여 조성되는 것을 특징으로 하는 반응성 액정 조성물을 기술구성의 특징으로 한다.
The reactive liquid crystal composition may be in the form of a liquid crystal, a dye, an alignment promoter, a thermal initiator, a surfactant, a polymerization inhibitor, a light stabilizer, a heat stabilizer, a releasing agent, a rheology modifier, a gelling agent, a leveling agent, a free radical scavenger, ) Adjusting additive, a polymer resin compound, a polymerizable compound, and an adhesion promoter. The present invention also provides a reactive liquid crystal composition comprising the reactive liquid crystal composition.
상기 플루오렌 구조를 갖는 신규한 광개시제와 고분자 수지 화합물, 중합성 화합물 및 용매를 포함하여 조성되는 것을 특징으로 하는 감광성 조성물을 기술구성의 특징으로 한다.
A novel photoinitiator having a fluorene structure, and a polymer resin compound, a polymerizable compound and a solvent.
상기 감광성 조성물은 액정, 염료, 배열촉진제, 열개시제, 계면활성제, 중합억제제, 광안정제, 열안정제, 이형제, 레올로지 조절제, 겔화제, 레벨링제, 자유라디칼 소거제, 커플링제, 틸트(tilt)조절 첨가제, 접착촉진제로 이루어진 군으로부터 선택되는 1종 이상의 첨가제를 포함하여 조성되는 것을 특징으로 하는 감광성 조성물을 기술구성의 특징으로 한다.
The photosensitive composition may be in the form of a liquid, a dye, an alignment promoter, a thermal initiator, a surfactant, a polymerization inhibitor, a light stabilizer, a heat stabilizer, a releasing agent, a rheology modifier, a gelling agent, a leveling agent, a free radical scavenger, And at least one additive selected from the group consisting of an antioxidant, an antioxidant, an antioxidant, a control additive, and an adhesion promoter.
이하에서는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 바람직한 실시예 및 도면을 통하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 여기에서 설명하는 실시예 및 도면들에 한정되지 않는다.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
일반적으로 흡수파장이 250nm 이하의 단파장의 자외선 흡수 스펙트럼을 가지고 있는 광개시제는 단파장으로 인한 표면경화에 우수한 반응성을 보이고 300nm 이상의 장파장의 광개시제는 장파장으로 인한 내부 경화에 우수한 반응성을 보이는 것으로 알려져 있다.
In general, a photoinitiator having an ultraviolet absorption spectrum with a short wavelength of 250 nm or less exhibits excellent reactivity to surface hardening due to a short wavelength, and a photoinitiator having a long wavelength of 300 nm or more has excellent reactivity to internal hardening due to a long wavelength.
현재 대표적인 광개시제인 Irgacure 184는 단파장인 205, 248nm에서 흡수파장을 나타내고, Irgacure 907도 역시 204, 238, 305nm에서 흡수파장을 나타내며, Darocur MBF의 흡수파장도 204, 256nm의 단파장이므로 단일 광개시제 사용으로는 광개시제의 효율과 반응성이 낮아 최종전환율이 낮은 결과를 초래하며, 특히 표면경화는 양호하나 내부경화 반응성이 낮아 경화도 및 기계적 강도가 취약한 치명적인 단점이 있으므로 장파장의 광개시제와 혼용사용하여 하는데, 현재 흡수파장 300nm 이상을 초과하는 장파장 광개시제는 광개시 효율이 낮고, 합성이 복잡하며, 상당히 고가여서 경제적인 문제점이 있다.
At present, Irgacure 184, which is a representative photoinitiator, exhibits absorption wavelengths at short wavelengths of 205 and 248 nm, Irgacure 907 also exhibits absorption wavelengths at 204, 238 and 305 nm, and Darocur MBF has a short absorption wavelength of 204 and 256 nm. The photoinitiator has a low efficiency and reactivity, resulting in a low final conversion. Particularly, it has good surface hardening but low internal hardening reactivity, so it has a fatal disadvantage that its hardness and mechanical strength are weak. Therefore, it is mixed with long- A long-wavelength photoinitiator having a wavelength longer than 300 nm has a low photoinitiation efficiency, is complicated in synthesis, and is extremely expensive, which is economically disadvantageous.
그러나, 상기 [일반식]으로 표시되는 본 발명의 플루오렌구조를 갖는 신규한 광개시제는 식중 R1, R2위치에 [화학식 1] 내지 [화학식 9]에 따른 광개시그룹을 도입하여 합성한 바, 290~330nm의 장파장에서의 UV흡수능이 탁월하여 내부경화 반응성이 매우 우수한 것으로 확인되었다.
However, the novel photoinitiator having a fluorene structure of the present invention represented by the above general formula is synthesized by introducing photo-initiating groups represented by Formulas 1 to 9 into the positions of R 1 and R 2 in the formula , The UV absorbing ability in a long wavelength of 290 to 330 nm was excellent, and it was confirmed that the internal hardening reactivity was excellent.
다음 [반응식 10]에 따른 [화학식 10]의 화합물인 (E)-1-(9,9-(E) -1- (9,9-dihydropyridazinone) which is a compound of the formula [10] dibutyldibutyl -9H-fluoren-2-yl)ethanone O--9H-fluoren-2-yl) ethanone O- acetylacetyl oximeoxime 의 합성Synthesis of
(1) 9,9-(1) 9,9- dibutyldibutyl -9H--9H- fluorene불소 의 합성Synthesis of
Fluorene 10g(60.16mmol)에 1-iodobutane 16.43ml, KOH 33.02g(589.6mmol)을 넣고 DMSO 120ml에 녹인 후, 40 ℃에서 overnight 해준다. 반응 종결 후 DMSO를 날린 후 D.W와 methylene chloride로 추출하고, 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 96% 수득율을 얻었다.Add 16.43 ml of 1-iodobutane and 33.02 g (589.6 mmol) of KOH to 10 g (60.16 mmol) of Fluorene, dissolve in 120 ml of DMSO, and let stand overnight at 40 ° C. After completion of the reaction, DMSO was blown off, extracted with DW and methylene chloride, and CH 2 Cl 2 -hexane (1: 3) was separated into a column to obtain a 96% yield.
(2) 1-(9,9-(2) 1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone 의 합성Synthesis of
Acetyl chloride 2.163ml를 MC에 녹이고, AlCl3 3.89g(29.16mmol)을 MC에 녹인 후 ice bath에서 stir하였다. 다음, MC에 녹인 Acethyl chloride를 MC에 녹인 AlCl3에 넣어주었다. 9,9-dibutyl-9H-fluorene 7g(25.14mmol)을 MC에 녹인 후 dropping해주고, 상온에서 교반 후 반응 후 HCl첨가한 후 stir하였다. D.W와 methylene chloride로 추출하고, 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 95% 수득율을 얻었다.2.163 ml of acetyl chloride was dissolved in MC, and 3.89 g (29.16 mmol) of AlCl 3 was dissolved in MC, followed by stirring in an ice bath. Next, acetyl chloride dissolved in MC was added to AlCl 3 dissolved in MC. 9,9-dibutyl-9H-fluorene (7 g, 25.14 mmol) was dissolved in MC and dropped. After stirring at room temperature, HCl was added after the reaction. Extraction with DW and methylene chloride and separation of CH 2 Cl 2 -hexane (1: 3) into a column yielded a 95% yield.
(3) (E)-1-(9,9-(3) (E) -1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone oximeoxime 의 합성Synthesis of
암실에서 에탄올 50ml에 1-(9,9-dibutyl-9H-fluoren-2-yl)ethanone 7g(21.8mmol)을 넣고 hydroxyamine hydrochloride 4.55g(65.5mmol)를 넣어준다. 그 다음 NaOH 수용액 5.24g (131.06mmol)을 넣어준다. D.W 넣으면 하얀 파우더 생성하고, 필터하여 97% 수득율을 얻었다.Add 7 g (21.8 mmol) of 1- (9,9-dibutyl-9H-fluoren-2-yl) ethanone to 50 ml of ethanol in the dark room and add 4.55 g (65.5 mmol) of hydroxyamine hydrochloride. Then add 5.24 g (131.06 mmol) of aqueous NaOH solution. D.W to produce white powder, which was filtered to yield a 97% yield.
(4) (E)-1-(9,9-(4) (E) -1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone O- O- acetylacetyl oximeoxime 의 합성Synthesis of
(E)-1-(9,9-dibutyl-9H-fluoren-2-yl)ethanone oxime 3g(8.94mmol)와 triethylamine 1.62ml을 30ml의 dichloromethane에 녹인 후 acetic anhydride 1.01ml를 첨가하여 상온에서 6시간 stir하였다. D.W와 methylene chloride로 추출하고, 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 94% 수득율을 얻었다.(E) -1- (9,9-dibutyl-9H-fluoren-2-yl) ethanone oxime and 1.62 ml of triethylamine were dissolved in 30 ml of dichloromethane and then 1.01 ml of acetic anhydride was added thereto. . Extraction with DW and methylene chloride and separation of CH 2 Cl 2 -hexane (1: 3) into a column yielded a 94% yield.
1One H H NMRNMR (600 (600 MHzMHz , , CDClCDCl 33 ) δ 7.70 (4H, m), 7.31 (3H, m), 2.42 (3H, s), 2.26 (3H, s ), 1.95 (4H, m), 1.03 (8H, m), 0.63 (6H, t). )? 7.70 (4H, m), 7.31 (3H, m), 2.42 (3H, s), 2.26 .
1313 C C NMRNMR (600 (600 MHzMHz , , CDClCDCl 33 ) δ 14.03, 15.04, 20.16, 23.21, 26.11, 40.31, 55.45, 119.88, 120.43, 121.33, 123.18, 126.47, 127.11, 128.05, 133.63, 140.35, 143.93, 151.20, 151.51, 163.37, 169.37.) [delta] 14.03, 15.04, 20.16, 23.21, 26.11, 40.31, 55.45, 119.88, 120.43, 121.33, 123.18, 126.47, 127.11, 128.05, 133.63, 140.35, 143.93, 151.20, 151.51, 163.37, 169.37.
[반응식 10][Reaction Scheme 10]
[도 1]은 [화학식 10]화합물의 1H-NMR spectrum 및 FT-IR spectrum 그래프, [도 2]는 GC-MS Spectrometer 그래프 및 UV-vis spectrum 그래프, [도 3]은 TGA curves 및 DSC Thermogram이다.[Figure 1] is a graph of a 1 H-NMR spectrum and an FT-IR spectrum of a compound of the formula [10], a GC-MS spectrometer graph and a UV-vis spectrum graph, [Figure 3] is a TGA curves and a DSC thermogram .
[도 1]에 나타난 바와 같이, [화학식 10]의 구조중 1,750cm-1에서 -C=O 피크가 나타났으며, [도 2]에 나타난 바와 같이 자외선 흡수파장 290~320nm의 장파장 범위의 흡수를 확인할 수 있다.
As shown in FIG. 1, a -C═O peak was observed at 1,750 cm -1 in the structure of
다음 [반응식 11]에 따른 [화학식 11]의 화합물인 (E)-1-(9,9-(E) -1- (9,9-dihydropyrimidin-2-yl) dibutyldibutyl -9H-fluoren-2-yl)ethanone O--9H-fluoren-2-yl) ethanone O- acetylacetyl oximeoxime 의 합성Synthesis of
(1) 9,9-(1) 9,9- dibutyldibutyl -9H--9H- fluorene불소 의 합성Synthesis of
Fluorene 10g(60.16mmol)에 1-iodobutane 16.43ml, KOH 33.02g(589.6mmol)을 넣고 DMSO 120ml에 녹인 후 40 ℃에서 overnight 해준다. 반응 종결 후 DMSO를 날린 후 D.W와 methylene chloride로 추출하고 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 95% 수득율을 얻었다.Add 16.43 ml of 1-iodobutane and 33.02 g (589.6 mmol) of KOH to 10 g (60.16 mmol) of Fluorene, dissolve in 120 ml of DMSO, and overnight at 40 ° C. After completion of the reaction, DMSO was blown off, extracted with DW and methylene chloride, and separated into CH 2 Cl 2 -hexane (1: 3) to obtain a 95% yield.
(2) 1-(9,9-(2) 1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone 의 합성Synthesis of
Acetyl chloride 2.273ml 를 MC에 녹인다. AlCl3 4.26g(31.96mmol)을 MC에 녹인 후 ice bath에서 stir하였다. MC에 녹인 Acethyl chloride를 MC에 녹인 AlCl3에 넣어주었다. 9,9-dibutyl-9H-fluorene 8.9g(31.96mmol)을 MC에 녹인 후 dropping해준다. TLC로 1-(9,9-dibutyl-9H-fluoren-2-yl)ethanone의 생성을 확인하였다.2.273 ml of acetyl chloride are dissolved in MC. AlCl 3 4.26g (31.96mmol) was dissolved in MC and stirred in an ice bath. Acethyl chloride dissolved in MC was added to AlCl 3 dissolved in MC. Dissolve 8.9 g (31.96 mmol) of 9,9-dibutyl-9H-fluorene in MC and drop the solution. The formation of 1- (9,9-dibutyl-9H-fluoren-2-yl) ethanone was confirmed by TLC.
(3) 1-(7-(3) 1- (7- benzoylbenzoyl -9,9--9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone 의 합성Synthesis of
Benzoyl chloride 4.31ml를 MC에 녹인다. AlCl3 5.16g(38.68mmol)을 MC에 녹인 후 ice bath에서 stir하였다. MC에 녹인 Benzoyl chloride를 MC에 녹인 AlCl3에 넣어주었다. 상기 (2)에서 제조한 1-(9,9-dibutyl-9H-fluoren-2-yl)ethanone을 dropping해준 다음, MC와 D.W로 추출하고 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 97% 수득율을 얻었다.4.31 ml of Benzoyl chloride are dissolved in MC. 5.16 g (38.68 mmol) of AlCl 3 was dissolved in MC and stained in an ice bath. Benzoyl chloride dissolved in MC was added to AlCl 3 dissolved in MC. The 1- (9,9-dibutyl-9H-fluoren-2-yl) ethanone prepared in (2) was dropped and extracted with MC and DW, and CH 2 Cl 2 -hexane (1: 3) Yielding 97% yield.
(4) (E)-1-(9,9-(4) (E) -1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone oximeoxime 의 합성Synthesis of
암실에서 에탄올 50ml에 1-(7-benzoyl-9,9-dibutyl-9H-fluoren-2-yl)ethanone 1.6g(3.77mmol)을 넣고 hydroxyamine hydrochloride 0.786g(11.31mmol)를 넣어준다. 그 다음 NaOH 수용액 0.904g (22.61mmol)을 넣어준다. D.W 넣으면 하얀 파우더가 생성되고 이를 필터하여 99% 수득율을 얻었다.Add 1.6 g (3.77 mmol) of 1- (7-benzoyl-9,9-dibutyl-9H-fluoren-2- yl) ethanone in 50 ml of ethanol in the dark room and add 0.786 g (11.31 mmol) of hydroxyamine hydrochloride. Then add 0.904 g (22.61 mmol) of aqueous NaOH solution. When D.W was added, a white powder was formed and filtered to obtain a 99% yield.
(5) (E)-1-(9,9-(5) (E) -1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone O- O- acetylacetyl oximeoxime 의 합성Synthesis of
(E)-(9,9-dibutyl-7-(1-(hydroxyimino)ethyl)-9H-fluoren-2-yl)(phenyl)methanone 0.35g(0.796mmol)와 triethylamine 0.0144ml을 30ml dichloromethane에 녹인 후 acetic anhydride 0.0901ml를 첨가하여 상온에서 6시간 stir하였다. D.W와 methylene chloride로 추출하고, 컬럼으로 CH2Cl2-hexane (1:1) 분리하여 95% 수득율을 얻었다.(0.796 mmol) of (E) - (9,9-dibutyl-7- (1- (hydroxyimino) ethyl) -9H-fluoren-2-yl) (phenyl) methanone and 0.0144 ml of triethylamine were dissolved in 30 ml of dichloromethane 0.0901 ml of acetic anhydride was added and the mixture was stirred at room temperature for 6 hours. Extraction with DW and methylene chloride and separation of CH 2 Cl 2 -hexane (1: 1) into a column yielded a 95% yield.
1H 1H NMRNMR (600 (600 MHzMHz , , CDCl3CDCl3 ) δ 7.78 (2H, m), 7.58 (3H, m), 7.47 (5H, m), 7.23 (1H, s), 2.44 (3H, s), 2.27 (3H, s), 2.01 (4H, m).s), 2.27 (3H, s), 2.01 (4H, m), 7.27 (2H, m) .
13C 13C NMRNMR (600 (600 MHzMHz , , CDCl3CDCl3 ) δ 14.04, 15.07, 20.12, 23.14, 26.19, 40.07, 55.76, 77.01-77.44, 120.09, 120.94, 121.54, 124.96, 126.73, 128.47, 130.21, 130.29, 132.55, 134.98, 136.84, 138.34, 142.53, 144.63, 151.48, 152.42, 163.12, 169.20, 197.07.)? 14.04, 15.07, 20.12, 23.14, 26.19, 40.07, 55.76, 77.01-77.44, 120.09, 120.94, 121.54, 124.96, 126.73, 128.47, 130.21, 130.29, 132.55, 134.98, 136.84, 138.34, 142.53, 144.63, 151.48, 152.42, 163.12, 169.20, 197.07.
[반응식 11][Reaction Scheme 11]
[도 4]는 [화학식 11]화합물의 1H-NMR spectrum 및 FT-IR spectrum 그래프, [도 5]는 GC-MS Spectrometer 그래프 및 UV-vis spectrum 그래프, [도 6]은 TGA curves 및 DSC Thermogram이다.[Figure 4] is a graph of a 1H-NMR spectrum and an FT-IR spectrum of a compound of Formula 11, [Figure 5] is a GC-MS Spectrometer graph and a UV-vis spectrum graph, and [Figure 6] is a TGA curves and a DSC thermogram .
[도 4]에 나타난 바와 같이, [화학식 11]의 구조중 1.750cm-1에서-C=O 피크가 나타났으며, [도 5]에 나타난 바와 같이 자외선 흡수파장 328nm의 장파장 범위의 흡수를 확인할 수 있다.
As shown in Fig. 4, a -C = O peak was observed at 1.750 cm < -1 > in the structure of the formula [11], and absorption of a long wavelength range of 328 nm in ultraviolet absorption wavelength .
다음 [반응식 12]에 따른 [화학식 12]의 화합물인 (E)-1-(4-(9,9-(E) -1- (4- (9,9-dihydropyridazin-1- dihexyl이열 -9H-fluoren-2-yl)phenyl)ethanone O--9H-fluoren-2-yl) phenyl) ethanone O- acetylacetyl oximeoxime 의 합성Synthesis of
(1) 1-(4-(9,9-(1) 1- (4- (9,9- dihexyl이열 -9H--9H- fluorenfluoren -2--2- ylyl )) phenylphenyl )) ethanoneethanone 의 합성Synthesis of
2-bromo-9,9-dihexyl-9H-fluorene 4g (9.675mmol), (4-acetylphenyl)boronic acid 2.38g(14.513mmol), THF 120ml, Pd(PPh3) 0.335g (0.290mmol)를 넣고 상온에서 20분간 질소 퍼지하에 버블링시켜준다. 버블링 후 후드안에서 K2CO3를 50℃에서 12h 교반한 후, D.W와 methylene chloride로 추출하고, 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 95% 수득율을 얻었다.(9.675 mmol) of 2-bromo-9,9-dihexyl-9H-fluorene, 2.38 g (14.513 mmol) of 4-acetylphenyl boronic acid, 120 ml of THF and 0.335 g (0.290 mmol) of Pd (PPh3) Bubbling under nitrogen purge for 20 minutes. After bubbling, K 2 CO 3 was stirred in the hood at 50 ° C for 12 hours, extracted with DW and methylene chloride, and separated into CH 2 Cl 2 -hexane (1: 3) to obtain a 95% yield.
(2) (E)-1-(4-(9,9-(2) (E) -1- (4- (9,9- dihexyl이열 -9H--9H- fluorenfluoren -2--2- ylyl )) phenylphenyl )) ethanoneethanone oximeoxime 의 합성Synthesis of
암실에서 에탄올 50ml에 1-(4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl)ethanone 3.27g(7.22mmol)을 넣고 hydroxyamine hydrochloride 1.51g(21.7mmol)를 넣어준다. 그 다음 NaOH 수용액 1.73g (43.3mmol)을 넣어준다. D.W 넣으면 하얀 파우더가 생성되고, 이를 필터링하여 96% 수득율을 얻었다.Add 3.27 g (7.22 mmol) of 1- (4- (9,9-dihexyl-9H-fluoren-2-yl) phenyl) ethanone to 50 ml of ethanol in the dark room and add 1.51 g (21.7 mmol) of hydroxyamine hydrochloride. Then add 1.73 g (43.3 mmol) of aqueous NaOH solution. When D.W was added, a white powder was formed, which was filtered to give a 96% yield.
(3) (E)-1-(4-(9,9-(3) (E) -1- (4- (9,9- dihexyl이열 -9H--9H- fluorenfluoren -2--2- ylyl )) phenylphenyl )) ethanoneethanone O- O- acetylacetyl oxime의 합성 Synthesis of oxime
(E)-1-(4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl)ethanone oxime 3.27g(7.22mmol)와 triethylamine 1.06ml을 30ml dichloromethane에 녹인 후 acetic anhydride 0.6602ml를 첨가하여 상온에서 6시간 stir하였다. D.W와 methylene chloride로 추출하고, 컬럼으로 CH2Cl2-hexane (1:2) 분리하여 96% 수득율을 얻었다.3.27 g (7.22 mmol) of (E) -1- (4- (9,9-dihexyl-9H-fluoren-2-yl) phenyl) ethanone oxime and 1.06 ml of triethylamine were dissolved in 30 ml of dichloromethane and 0.6602 ml of acetic anhydride was added And stained for 6 hours at room temperature. Extraction with DW and methylene chloride and separation of CH 2 Cl 2 -hexane (1: 2) into a column yielded a 96% yield.
1H 1H NMRNMR (600 (600 MHzMHz , , CDCl3CDCl3 ) δ 7.72 (6H, m), 7.55 (2H, t), 7.31 (2H, m), 2.41 (3H, s), 2.27 (3H, s), 1.97 (4H, m), 1.02 (16H, m), 0.72 (3H, t).), 7.72 (6H, m), 7.55 (2H, t), 7.31 (2H, m), 2.41 (3H, s), 2.27 , 0.72 (3H, t).
13C 13C NMRNMR (600 (600 MHzMHz , , CDCl3CDCl3 ) δ 14.22, 14.57, 20.15, 22.77, 23.94, 29.89, 31.67, 40.57, 55.39, 120.06, 120.23, 121.57, 123.12, 126.20, 127.03, 127.44, 127.66, 128.28, 133.57, 139.03, 140.74, 141.26, 144.10, 151.23, 151.74, 162.30, 169.32.) δ 14.22, 14.57, 20.15, 22.77, 23.94, 29.89, 31.67, 40.57, 55.39, 120.06, 120.23, 121.57, 123.12, 126.20, 127.03, 127.44, 127.66, 128.28, 133.57, 139.03, 140.74, 141.26, 144.10, 151.23, 151.74, 162.30, 169.32.
[반응식 12][Reaction Scheme 12]
[도 7]은 [화학식 12]화합물의 1H-NMR spectrum 및 FT-IR spectrum 그래프, [도 8]은 GC-MS Spectrometer 그래프 및 UV-vis spectrum 그래프, [도 9]는 TGA curves 및 DSC Thermogram이다.[Figure 7] is a graph of a 1H-NMR spectrum and an FT-IR spectrum of a compound of Formula 12, a GC-MS Spectrometer graph and a UV-vis spectrum graph, and a TGA curves and a DSC thermogram .
[도 7]에 나타난 바와 같이, [화학식 12]의 구조중 1.750cm-1에서 -C=O 피크가 나타났으며, [도 8]에 나타난 바와 같이 자외선 흡수파장 321nm의 장파장 범위의 흡수를 확인할 수 있다.
As shown in Fig. 7, a -C = O peak was observed at 1.750 cm < -1 > in the structure of Formula 12, and absorption of a long wavelength range of 321 nm in ultraviolet absorption wavelength was confirmed .
다음 [반응식 13]에 따른 [화학식 13]의 화합물인 1-(9,9-The compound of formula (13) according to the following Reaction Scheme 13, 1- (9,9- dibutyldibutyl -9H-fluoren-2-yl)-2-hydroxy-2-methylpropan-1-one의 합성-9H-fluoren-2-yl) -2-hydroxy-2-methylpropan-1-
(1) 9,9-(1) 9,9- dibutyldibutyl -9H--9H- fluorene불소 의 합성Synthesis of
Fluorene 1.5g(9.02mmol)에 1-iodobutane 3.98ml, KOH 4.95g(88.4mmol)을 넣고 DMSO 40ml에 녹인 후 40 ℃에서 overnight 해준다. 반응 종결 후 DMSO를 날린 후 D.W와 methylene chloride로 추출하고, 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 91% 수득율을 얻었다.Add 3.98 ml of 1-iodobutane and 4.95 g (88.4 mmol) of KOH to 1.5 g (9.02 mmol) of Fluorene, dissolve in 40 ml of DMSO, and overnight at 40 ° C. After completion of the reaction, DMSO was blown off, extracted with DW and methylene chloride, and CH 2 Cl 2 -hexane (1: 3) was separated from the column to obtain 91% yield.
(2) 1-(9,9-(2) 1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )) ethanoneethanone 의 합성Synthesis of
α-bromoisobutyryl bromide2.28g(21.7mmol)를 차갑게 한 후 20ml MC에 0도에서 교반(Ar충진하에)하였다. AlCl3 1.27g(20.8mmol)을 MC에 녹인 후 넣어준다. 9,9-dibutyl-9H-fluorene 2.28g (18mmol)을 MC에 녹인 후 dropping 해준다. 상온에서 12시간 교반 후 반응 완결 후 HCl을 넣고 stir한 다음 D.W로 추출하고, 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 92% 수득율을 얻었다.2.8 g (21.7 mmol) of α-bromoisobutyryl bromide was cooled and stirred in 20 ml of MC at 0 ° C. (under Ar filling). Dissolve 1.27 g (20.8 mmol) of AlCl 3 in MC and add to it. Dissolve 2.28 g (18 mmol) of 9,9-dibutyl-9H-fluorene in MC and drop the solution. After stirring for 12 hours at room temperature, HCl was added to the reaction mixture, and the reaction mixture was stirred and then extracted with DW. The column was washed with CH 2 Cl 2 -hexane (1: 3) to obtain a yield of 92%.
(3) 1-(9,9-(3) 1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )-2-)-2- hydroxyhydroxy -2--2- methylpropanmethylpropan -1--One- oneone 합성 synthesis
1-(9,9-dibutyl-9H-fluoren-2-yl)ethanone 3.03g(7.08mmol)에 50wt% NaOH수용액 1.76ml를 넣어준다. Benzyltriethylammonium chloride 0.209g(0.92mmol)을 넣은 후 80 ℃에서 12시간 반응하고, 반응 완결 D.W와 methylene chloride 로 추출하고, 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 90% 수득율을 얻었다.1.76 ml of a 50 wt% NaOH aqueous solution was added to 3.03 g (7.08 mmol) of 1- (9,9-dibutyl-9H-fluoren-2-yl) ethanone. After adding 0.209 g (0.92 mmol) of benzyltriethylammonium chloride, the mixture was reacted at 80 ° C. for 12 hours. The reaction mixture was extracted with DW and methylene chloride, and CH 2 Cl 2 -hexane (1: 3) was separated from the column.
1H 1H NMRNMR (600 (600 MHzMHz , , CDCl3CDCl3 ) δ 8.01 (1H, m), 7.73 (3H, m), 7.34 (3H, m), 4.30 (1H, s), 2.0 (4H, t), 1.7 (6H, s), 1.04 (8H, m), 0.64 (6H, t).), 8.01 (1H, m), 7.73 (3H, m), 7.34 (3H, m), 4.30 , 0.64 (6 H, t).
13C 13C NMRNMR (600 (600 MHzMHz , , CDCl3CDCl3 ) δ 13.99, 23.16, 26.14, 29.01, 40.11, 55.48, 76.31, 77.30-77.44, 119.49, 121.02, 123.33, 124.54, 127.31, 128.85, 129.56, 131.78, 139.75, 146.33, 151.05, 152.22, 204.52.) [delta] 13.99, 23.16, 26.14, 29.01, 40.11, 55.48, 76.31, 77.30-77.44, 119.49, 121.02, 123.33, 124.54, 127.31, 128.85, 129.56, 131.78, 139.75, 146.33, 151.05, 152.22, 204.52.
[반응식 13][Reaction Scheme 13]
[도 10]은 [화학식 13]화합물의 1H-NMR spectrum 및 FT-IR spectrum 그래프, [도 11]은 GC-MS Spectrometer 그래프 및 UV-vis spectrum 그래프, [도 12]는 TGA curves 및 DSC Thermogram이다.[Figure 10] is a graph of a 1H-NMR spectrum and an FT-IR spectrum of a compound of the formula [13], a GC-MS spectrometer graph and a UV-vis spectrum graph, .
[도 10]에 나타난 바와 같이, [화학식 13]의 구조중 1.750cm-1에서 -C=O 피크, 3,400nm에서 -OH 피크가 나타났으며, [도 11]에 나타난 바와 같이 자외선 흡수파장 316nm의 장파장 범위의 흡수를 확인할 수 있다.
As shown in FIG. 10, a -C = O peak at 1.750 cm -1 and an -OH peak at 3,400 nm were found in the structure of Formula 13, and as shown in FIG. 11, the ultraviolet absorption wavelength 316 nm The absorption of the long wavelength range of the absorption spectrum can be confirmed.
다음 [반응식 14]에 따른 [화학식 14]의 화합물인 1-(9,9-The compound of formula (14) according to the following scheme (14), 1- (9,9- dibutyldibutyl -9H-fluoren-2-yl)-2-(dimethylamino)-2-methylpropan-1-one의 합성-9H-fluoren-2-yl) -2- (dimethylamino) -2-methylpropan-1-
(1) 9,9-(1) 9,9- dibutyldibutyl -9H--9H- fluorene불소 의 합성Synthesis of
Fluorene 10g(60.16mmol)에 1-iodobutane 16.43ml, KOH 33.02g(589.58mmol)을 넣고 DMSO 120ml에 녹인 후, 40℃에서 overnight해주었다. 반응종결 후 DMSO를 날린 후 D.W와 methylene chloride로 추출하였다. 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 91% 수득율을 얻었다.16.43 ml of 1-iodobutane and 33.02 g (589.58 mmol) of KOH were added to 10 g (60.16 mmol) of Fluorene and dissolved in 120 ml of DMSO, followed by overnight incubation at 40 ° C. After completion of the reaction, DMSO was blown off and extracted with DW and methylene chloride. The column was washed with CH 2 Cl 2 -hexane (1: 3) to give 91% yield.
(2) 2-(2) 2- bromobromo -9,9--9,9- dibutyldibutyl -9H--9H- fluorene불소 의 합성Synthesis of
9,9-dibutyl-9H-fluorene 3g(10.77mmol을 벤젠에 녹인 후, Bromine 1,89g(11.75mmol)과 Iron(Ⅲ) oxide 1.91g(12.93mmol)을 넣은 후 40℃에서 2시간 반응시켰다. 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 78% 수득율을 얻었다.After dissolving 10.77 mmol of 9,9-dibutyl-9H-fluorene in benzene, 1,89 g (11.75 mmol) of Bromine and 1.91 g (12.93 mmol) of Iron (III) oxide were added and reacted at 40 ° C. for 2 hours. The column was separated into CH 2 Cl 2 -hexane (1: 3) to give a 78% yield.
(3) 9,9-(3) 9,9- dibutyldibutyl -9H--9H- fluorene불소 -2--2- carboxyliccarboxylic acidacid 의 합성Synthesis of
2-bromo-9,9-dibutyl-9H-fluorene 2g(6.20mmol)을 THF에 녹인 후, magnesium 0.15g(6.20mmol)을 넣고 66℃에서 10분간 stir.해주었다. 10분 후에 66℃에서 -78℃로 온도를 내려준뒤 carbon dioxide 0.27g(6.20mmol)을 넣고 2시간 반응시켰다. 반응종결 후 솔벤트를 날린 후 D.W와 ethylether로 추출하여 유기층을 날렸다. 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 87% 수득율을 얻었다.After dissolving 2 g (6.20 mmol) of 2-bromo-9,9-dibutyl-9H-fluorene in THF, 0.15 g (6.20 mmol) of magnesium was added and the mixture was stirred at 66 ° C for 10 minutes. After 10 minutes, the temperature was lowered from 66 ° C to -78 ° C, and 0.27g (6.20mmol) of carbon dioxide was added and reacted for 2 hours. After completion of the reaction, the solvent was blown off and extracted with DW and ethylether to blow off the organic layer. The column was washed with CH 2 Cl 2 -hexane (1: 3) to obtain a 87% yield.
(4) 1-(9,9-(4) 1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )-2-)-2- methylpropanmethylpropan -1--One- oneeonee 의 합성Synthesis of
Isopropyllithium(2.62mmol, 1.2eq), CuCN을 ET2O ETCH2Et에 녹인 후, 0℃에서 5분간 반응시켰다. 반응물 (2.184mmol, 1eq)을 ET2O에 0℃에서 1시간 돌린 후 상온에서 14시간 반응시켰다. NH4Cl(2.62mmol, 1.2eq)와 물을 넣고 상온에서 반응시켰다. 반응종결 후 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 75% 수득율을 얻었다.Isopropyllithium (2.62 mmol, 1.2 eq) and CuCN were dissolved in ET 2 O ETCH 2 Et and reacted at 0 ° C for 5 minutes. The reaction product (2.184 mmol, 1 eq) was reacted in ET 2 O at 0 ° C for 1 hour and then reacted at room temperature for 14 hours. NH 4 Cl (2.62 mmol, 1.2 eq) and water were added and reacted at room temperature. After completion of the reaction, CH 2 Cl 2 -hexane (1: 3) was separated from the column to obtain a 75% yield.
(5) 2-(5) 2- aminoamino -1-(9,9--1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )-2-)-2- methylpropanmethylpropan -1--One- oneone 의 합성Synthesis of
반응물에 1,1-dimethylhydrazine(1.205mmol, 1.2eq)과 Me-I(1.205mmol, 1.2eq)를 넣고 메탄올과 HCl을 넣었다. 반응종결 후 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 69% 수득율을 얻었다.To the reaction mixture, 1,1-dimethylhydrazine (1.205 mmol, 1.2 eq) and Me-I (1.205 mmol, 1.2 eq) were added and methanol and HCl were added. After completion of the reaction, CH 2 Cl 2 -hexane (1: 3) was separated from the column to obtain a 69% yield.
(6) 1-(9,9-(6) 1- (9,9- dibutyldibutyl -9H--9H- fluorenfluoren -2--2- ylyl )-2-()-2-( dimethylaminodimethylamino )-2-)-2- methylpropanmethylpropan -1-one의 합성-1-one
반응물과 K2CO3를 MeCN에 넣어 1시간 동안 교반하였다. 그 후 methylbromide를넣고 20시간동안 리플럭스시켰다. 반응종결 후 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 82% 수득율을 얻었다.The reaction and K 2 CO 3 were added to MeCN and stirred for 1 h. Methylbromide was then added and refluxed for 20 h. After completion of the reaction, CH 2 Cl 2 -hexane (1: 3) was separated from the column to obtain an 82% yield.
1One H H NMRNMR (600(600 MHzMHz , , CDClCDCl 33 )) δδ 8.05 (2H, s), 8.00 (4H, m), 7.64 (2H, m), 7.36 (2H, m), 7.29 (4H, m), 2.51 (6H, s), 2.01 (4H, m), 1.47 (6H, m), 1.36 (8H, m), 1.10 (6H, m).(2H, m), 8.04 (2H, s), 8.00 (4H, m), 7.64 (6H, m), 1.36 (8H, m), 1.10 (6H, m).
1313 C C NMRNMR (600 (600 MHzMHz , , CDClCDCl ₃)₃) δδ 14.1, 22.1, 26.6, 38.2, 43.6, 52.9, 85.1, 121.6, 123.2, 126.8, 128.3, 129.6, 136.1, 141.0, 145.4, 147.7, 200.7.14.1, 22.1, 26.6, 38.2, 43.6, 52.9, 85.1, 121.6, 123.2, 126.8, 128.3, 129.6, 136.1, 141.0, 145.4, 147.7, 200.7.
[반응식 14][Reaction Scheme 14]
다음 [반응식 15]에 따른 [화학식 15]의 화합물인 1-(9,9-The compound of formula 15 according to scheme 15 is then reacted with 1- (9,9- dibutyldibutyl -9H-fluoren-2-yl)-2-(dimethylamino)-2-methylpropan-1-one의 합성-9H-fluoren-2-yl) -2- (dimethylamino) -2-methylpropan-1-
(1) 9,9-(1) 9,9- dibutyldibutyl -9H--9H- fluorene불소 의 합성Synthesis of
Fluorene 10g(60.16mmol)에 1-iodobutane 16.43ml, KOH 33.02g(589.58mmol)을 넣고 DMSO 120ml에 녹인 후, 40℃에서 overnight해주었다. 반응종결 후 DMSO를 날린 후 D.W와 methylene chloride로 추출하였다. 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 91% 수득율을 얻었다.16.43 ml of 1-iodobutane and 33.02 g (589.58 mmol) of KOH were added to 10 g (60.16 mmol) of Fluorene and dissolved in 120 ml of DMSO, followed by overnight incubation at 40 ° C. After completion of the reaction, DMSO was blown off and extracted with DW and methylene chloride. The column was washed with CH 2 Cl 2 -hexane (1: 3) to give 91% yield.
(2) 2-(2) 2- bromobromo -9,9--9,9- dibutyldibutyl -9H--9H- fluorene불소 의 합성Synthesis of
9,9-dibutyl-9H-fluorene 3g(10.77mmol을 벤젠에 녹인 후, Bromine 1,89g(11.75mmol)과 Iron(Ⅲ) oxide 1.91g(12.93mmol)을 넣은 후 40℃에서 2시간 반응시켰다. 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 78% 수득율을 얻었다.After dissolving 10.77 mmol of 9,9-dibutyl-9H-fluorene in benzene, 1,89 g (11.75 mmol) of Bromine and 1.91 g (12.93 mmol) of Iron (III) oxide were added and reacted at 40 ° C. for 2 hours. The column was separated into CH 2 Cl 2 -hexane (1: 3) to give a 78% yield.
(3) 9,9-(3) 9,9- dibutyldibutyl -9H--9H- fluorene불소 -2--2- carboxyliccarboxylic acidacid 의 합성Synthesis of
2-bromo-9,9-dibutyl-9H-fluorene 2g(6.20mmol)을 THF에 녹인 후, magnesium 0.15g(6.20mmol)을 넣고 66℃에서 10분간 stir.해주었다. 10분 후에 66℃에서 -78℃로 온도를 내려준뒤 carbon dioxide 0.27g(6.20mmol)을 넣고 2시간 반응시켰다. 반응종결 후 솔벤트를 날린 후 D.W와 ethylether로 추출하여 유기층을 날렸다. 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 87% 수득율을 얻었다.After dissolving 2 g (6.20 mmol) of 2-bromo-9,9-dibutyl-9H-fluorene in THF, 0.15 g (6.20 mmol) of magnesium was added and the mixture was stirred at 66 ° C for 10 minutes. After 10 minutes, the temperature was lowered from 66 ° C to -78 ° C, and 0.27g (6.20mmol) of carbon dioxide was added and reacted for 2 hours. After completion of the reaction, the solvent was blown off and extracted with DW and ethylether to blow off the organic layer. The column was washed with CH 2 Cl 2 -hexane (1: 3) to obtain a 87% yield.
(4) 1-(9,9- dibutyl -9H- fluoren -2- yl )-2-( dimethylamino )-2- methylpropan -1-one의 합성 (4) 1- (9,9- dibutyl -9H- fluoren -2- yl) -2- (dimethylamino) -2- methylpropan -1-one Synthesis of
반응물 5g(15.5mmol)을 thionyl chloride 10ml에 녹여 60℃로 끓였다. 3시간 후 용매를 감압 제거하여 9,9-dibutyl-9H-fluorene-2-carbonyl chloride 5.28g(15.5mmol)을 얻었다. 얻은 9,9-dibutyl-9H-fluorene-2-carbonyl chloride 5.28g(15.5mmol)와 methoxydiphenylphosphine 3.4g(15.7mmol)을 정제된 THF에 넣고 65℃로 2시간 동안 반응시켰다. 반응종결 후 컬럼으로 CH2Cl2-hexane (1:3) 분리하여 91% 수득율을 얻었다.5 g (15.5 mmol) of the reaction product was dissolved in 10 ml of thionyl chloride and boiled at 60 ° C. After 3 hours, the solvent was removed under reduced pressure to obtain 5.28 g (15.5 mmol) of 9,9-dibutyl-9H-fluorene-2-carbonyl chloride. 5.28 g (15.5 mmol) of 9,9-dibutyl-9H-fluorene-2-carbonyl chloride and 3.4 g (15.7 mmol) of methoxydiphenylphosphine were added to purified THF and reacted at 65 ° C for 2 hours. After completion of the reaction, CH 2 Cl 2 -hexane (1: 3) was separated into a column to obtain a yield of 91%.
1One H H NMRNMR (600 (600 MHzMHz , , CDClCDCl 33 ) δ 7.87 (2H, m), 7.57 (6H, m), 7.43 (7H, m), 7.30 (2H, m), 2.05 (4H, t), 1.85 (8H, m), 1.12 (6H, t)), 7.87 (2H, m), 7.57 (6H, m), 7.43 (7H, m), 7.30
1313 C C NMRNMR (600 (600 MHzMHz , , CDClCDCl 33 ) δ 14.04, 15.07, 20.13, 23.15, 23.3, 26.6, 43.6, 52.9, 121.6, 123.1, 126.8, 128.8, 129.8, 131.0, 133.1, 134.2, 136.1, 141.0, 146.8, 146.7, 149.4, 216.5)? 14.04, 15.07, 20.13, 23.15, 23.3, 26.6, 43.6, 52.9, 121.6, 123.1, 126.8, 128.8, 129.8, 131.0, 133.1, 134.2, 136.1, 141.0, 146.8, 146.7,
[반응식 15][Reaction Scheme 15]
광개시제Photoinitiator 특성[ characteristic[ 광감도Light sensitivity (반응전환율), 배향도, 투과도]평가(Reaction Conversion), Orientation, Transmittance] Evaluation
(1) 유기기판의 제조(1) Production of organic substrate
유리기판에 수평 배향막인 Polyimide(PI)를 스핀코터로 코팅한 후, 80 ℃와 235 ℃에서 각각 30분, 1시간 열처리를 해주어 이미드화 반응을 유도하였다. 이 유리기판에 러빙기로 러빙 처리하였다.Polyimide (PI), a horizontal alignment film, was coated on a glass substrate by a spin coater and heat treatment was carried out at 80 ° C and 235 ° C for 30 minutes and 1 hour, respectively, to induce imidization reaction. This glass substrate was rubbed with a rubbing machine.
(2) (2) 광감도Light sensitivity 측정을 위한 반응성 액정 조성물의 제조 및 코팅 Preparation and coating of reactive liquid crystal compositions for measurement
다음 [표 1]에 실시한 바와 같이, 반응형 액정 혼합물 14.5 wt%, 광개시제 5 wt%, Toluene 80 wt%, 첨가제 0.5 wt%를 쉐이커를 이용하여 1시간 동안 혼합시켰다. 이 용액을 5마이크로 필터로 여과하여 얻은 감광성 조성물을 준비하였다. 준비한 유리기판에 러빙기로 러빙 후, 감광성 조성물을 도포하여 UV 경화를 실시하였다. 경화조건은 365nm, 60", 20mW/㎠으로 하였다.14.5 wt% of a reactive liquid crystal mixture, 5 wt% of a photoinitiator, 80 wt% of Toluene, and 0.5 wt% of an additive were mixed for 1 hour using a shaker, as described in the following [Table 1]. This solution was filtered with a 5-microfilter to prepare a photosensitive composition. After rubbing the prepared glass substrate with a rubbing machine, a photosensitive composition was applied and UV curing was performed. Curing conditions were 365 nm, 60 ", 20 mW / cm < 2 >.
비교예 1) BASF 社 의 Irgacure-907Comparative Example 1 Irgacure-907 manufactured by BASF
비교예 2) BASF 社 의 OXE-02Comparative Example 2) OXE-02 manufactured by BASF
(3)광감도 평가(반응 전환율)(3) Photosensitivity evaluation (reaction conversion rate)
UV 경화된 유리기판을 FT-IR을 측정하여 -C=C 의 잔량을 확인하였다. 즉, -C=C 의 1638Cm-1의 피크들이 감소하는 것을 확인하여 반응 전환율을 계산한 바, 기존 BASF사의 광개시제에 비하여 본 발명의 광개시제들의 반응전환율이 우수한 것을 확인할 수 있었다. The residual amount of -C = C was confirmed by measuring FT-IR on the UV cured glass substrate. That is, it was confirmed that the peaks of 1638Cm-1 of -C = C were reduced, and the reaction conversion ratio was calculated. As a result, it was confirmed that the photoinitiators of the present invention had a higher reaction conversion rate than the conventional photoinitiators of BASF.
(4) 배향도 평가(4) Evaluation of orientation degree
UV 경화된 유리기판을 편광현미경으로 관찰하여 표면에 빛샘현상을 관찰하였다. 액정분자의 배향이 잘 된 유리기판은 검은색으로 어두운 표면이 관찰되었다. 이때 미배향된 부분은 흰색 점으로 확인이 되며, 이 흰색점들의 상대면적으로 배향도를 계산한 결과 기존 BASF사의 광개시제와 본 발명의 광개시제들의 배향도가 균등한 것을 확인할 수 있었다. The UV cured glass substrate was observed with a polarizing microscope to observe the light leakage phenomenon on the surface. In the glass substrate in which the liquid crystal molecules were well aligned, a black and dark surface was observed. In this case, the unoriented portion was identified as a white dot, and the degree of orientation was calculated by the relative area of the white dots. As a result, it was confirmed that the degree of orientation of the conventional photoinitiator of BASF and the photoinitiator of the present invention were uniform.
(5) 투과도 평가(5) Evaluation of permeability
UV 경화된 유리기판을 UV-Vis Spectroscopy를 측정하여 파장영역 400~800nm의 구간의 투과도를 평균하여 측정한 결과 기존 BASF사의 광개시제와 본 발명의 광개시제들의 투과도가 균등한 것을 확인할 수 있었다.
UV-Vis spectroscopy was performed on the UV-cured glass substrate, and the transmittance of the photo-initiator of the present invention and the photoinitiators of the present invention were measured by averaging the transmittance of the region of 400 to 800 nm in the wavelength region.
이상의 설명은 본 발명의 기술사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예 및 도면들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예 및 도면들에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The foregoing description is merely illustrative of the technical idea of the present invention and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments and the drawings disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the present invention is not limited by these embodiments and drawings. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.
Claims (11)
[일반식]
상기 [일반식]에서 R1는 수소이고, R2는 하기 [화학식 1], [화학식 3] 또는 [화학식 7]로 표시되는 광개시 그룹중에서 어느 하나 선택되며, R3, R4 는 서로 독립적으로 수소, 불소, 탄소수가 1-6인 직쇄형 또는 분지형의 알킬이다.
[화학식 1]
상기 [화학식 1]에서 R5, R6는 서로 독립적으로 수소, C1-C12 직쇄 또는 분지쇄의 알킬기, 알케닐기 또는 알키닐기, C3-C6 시클로알킬기, C6-C30 아릴기에서 선택되며, 상기 C1-C12 직쇄 또는 분지쇄의 알킬기, 알케닐기 또는 알키닐기, C3-C6 시클로알킬기, C6-C30 아릴기는 각각 C1-C6 알킬기, 페닐기, 할로겐, 니트로기, -CN, -OR, -SR, -NRR, -NHR, -C(=O)OR, -C(=O)NHR, -C(=O)ArOR 및 -C(=O)ArNHR로 치환되거나 비치환될 수 있고, 상기 R은 C1-C12 직쇄 또는 분지쇄의 알케닐기, Ar는 C6-C30 아릴기이다.
[화학식 3]
상기 [화학식 3]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같다.
[화학식 7]
상기 [화학식 4]에서 R5, R6는 상기 [화학식 1]에서 정의한 바와 같다.
A novel photoinitiator having a fluorene structure represented by the following general formula
[General formula]
In the above general formula, R 1 is hydrogen, and R 2 is selected from any one of the photo-initiating groups represented by the following Chemical Formulas 1, 3, or 7, and R 3 and R 4 are independently Is hydrogen, fluorine, straight-chain or branched alkyl having 1 to 6 carbon atoms.
[Chemical Formula 1]
Wherein R 5 and R 6 independently represent hydrogen, a C 1 -C 12 linear or branched alkyl group, an alkenyl group or an alkynyl group, a C 3 -C 6 cycloalkyl group, a C 6 -C 30 aryl group C 1 -C 6 straight or branched chain alkyl, alkenyl or alkynyl group, C 3 -C 6 cycloalkyl group or C 6 -C 30 aryl group is selected from C 1 -C 6 alkyl group, phenyl group, halogen, -C (= O) NHR, -C (= O) ArOR, and -C (= O) ArNHR by a nitro group, -CN, -OR, -SR, -NRR, -NHR, R is a C 1 -C 12 linear or branched alkenyl group, and Ar is a C 6 -C 30 aryl group.
(3)
Wherein R 5 and R 6 are the same as defined in the above formula (1).
(7)
Wherein R 5 and R 6 are the same as defined in the above formula (1).
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 12]으로 표시되는 것을 특징으로 하는 플루오렌 구조를 갖는 신규한 광개시제
[화학식 12]
The method according to claim 1,
The novel photoinitiator having a fluorene structure represented by the above general formula is a novel photoinitiator having a fluorene structure represented by the following general formula
[Chemical Formula 12]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 13]으로 표시되는 것을 특징으로 하는 플루오렌 구조를 갖는 신규한 광개시제
[화학식 13]
The method according to claim 1,
A novel photoinitiator having a fluorene structure represented by the above general formula is a novel photoinitiator having a fluorene structure represented by the following formula
[Chemical Formula 13]
상기 [일반식]으로 표시되는 플루오렌 구조를 갖는 신규한 광개시제는 하기 [화학식 15]으로 표시되는 것을 특징으로 하는 플루오렌 구조를 갖는 신규한 광개시제
[화학식 15]
The method according to claim 1,
A novel photoinitiator having a fluorene structure represented by the above general formula is a novel photoinitiator having a fluorene structure represented by the following formula
[Chemical Formula 15]
A reactive liquid crystal composition comprising a novel photoinitiator having a fluorene structure according to any one of claims 4 to 5 and a reactive liquid crystal monomer and a solvent
상기 반응성 액정 조성물은 액정, 염료, 배열촉진제, 열개시제, 계면활성제, 중합억제제, 광안정제, 열안정제, 이형제, 레올로지 조절제, 겔화제, 레벨링제, 자유라디칼 소거제, 커플링제, 틸트(tilt)조절 첨가제, 고분자 수지 화합물, 중합성 화합물, 접착촉진제로 이루어진 군으로부터 선택되는 1종 이상의 첨가제를 포함하여 조성되는 것을 특징으로 하는 반응성 액정 조성물
9. The method of claim 8,
The reactive liquid crystal composition may be in the form of a liquid crystal, a dye, an alignment promoter, a thermal initiator, a surfactant, a polymerization inhibitor, a light stabilizer, a heat stabilizer, a releasing agent, a rheology modifier, a gelling agent, a leveling agent, a free radical scavenger, ) Regulating additive, a polymer resin compound, a polymerizable compound, and an adhesion promoter. The reactive liquid crystal composition according to claim 1,
A photosensitive composition comprising a novel photoinitiator having a fluorene structure according to any one of claims 4 to 5 and a polymeric resin compound, a polymerizable compound and a solvent
상기 감광성 조성물은 액정, 염료, 배열촉진제, 열개시제, 계면활성제, 중합억제제, 광안정제, 열안정제, 이형제, 레올로지 조절제, 겔화제, 레벨링제, 자유라디칼 소거제, 커플링제, 틸트(tilt)조절 첨가제, 접착촉진제로 이루어진 군으로부터 선택되는 1종 이상의 첨가제를 포함하여 조성되는 것을 특징으로 하는 감광성 조성물
11. The method of claim 10,
The photosensitive composition may be in the form of a liquid, a dye, an alignment promoter, a thermal initiator, a surfactant, a polymerization inhibitor, a light stabilizer, a heat stabilizer, a releasing agent, a rheology modifier, a gelling agent, a leveling agent, a free radical scavenger, Wherein the photosensitive composition is composed of at least one additive selected from the group consisting of an additive, an adjusting additive, and an adhesion promoter.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11054743B2 (en) | 2015-12-15 | 2021-07-06 | Changzhou Tronly Advanced Electronic Materials Co., Ltd. | Fluorene polyfunctional photoinitiator and preparation and use thereof, and photosensitive resin composition containing fluorene photoinitiator and use thereof |
| WO2018049976A1 (en) * | 2016-09-13 | 2018-03-22 | 常州强力先端电子材料有限公司 | Fluorene photoinitiator, preparation method therefor, photocurable composition having same, and use of same in photocuring field |
| EP3514135A4 (en) * | 2016-09-13 | 2020-04-29 | Changzhou Tronly Advanced Electronic Materials Co., Ltd. | Fluorene photoinitiator, preparation method therefor, photocurable composition having same, and use of same in photocuring field |
| US10976660B2 (en) | 2016-09-13 | 2021-04-13 | Changzhou Tronly Advanced Electronic Materials Co , Ltd. | Fluorene photoinitiator, preparation method therefor, photocurable composition having same, and use of same in photocuring field |
| US11118065B2 (en) | 2017-02-17 | 2021-09-14 | Changzhou Tronly Advanced Electronic Materials Co., Ltd. | Fluorenylaminoketone photoinitiator, preparation method thereof, and UV photocurable composition containing same |
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| KR20140144809A (en) | 2014-12-22 |
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