KR20150145414A - Oxime ester compound and a photopolymerizable composition comprising the same - Google Patents
Oxime ester compound and a photopolymerizable composition comprising the same Download PDFInfo
- Publication number
- KR20150145414A KR20150145414A KR1020140074750A KR20140074750A KR20150145414A KR 20150145414 A KR20150145414 A KR 20150145414A KR 1020140074750 A KR1020140074750 A KR 1020140074750A KR 20140074750 A KR20140074750 A KR 20140074750A KR 20150145414 A KR20150145414 A KR 20150145414A
- Authority
- KR
- South Korea
- Prior art keywords
- oxime ester
- ester compound
- photopolymerizable composition
- formula
- photopolymerizable
- Prior art date
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- -1 Oxime ester compound Chemical class 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 150000002923 oximes Chemical class 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000002956 ash Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005157 alkyl carboxy group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- QTHQYNCAWSGBCE-UHFFFAOYSA-N docosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCC(Cl)=O QTHQYNCAWSGBCE-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- APNSGVMLAYLYCT-UHFFFAOYSA-N isobutyl nitrite Chemical compound CC(C)CON=O APNSGVMLAYLYCT-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 2
- UOMUPDCRXJLVGR-UHFFFAOYSA-N propane-1,2,2-triol Chemical compound CC(O)(O)CO UOMUPDCRXJLVGR-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- 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 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- BOGFHOWTVGAYFK-UHFFFAOYSA-N 1-[2-(2-propoxyethoxy)ethoxy]propane Chemical compound CCCOCCOCCOCCC BOGFHOWTVGAYFK-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- JPQXNTOALKRJMH-UHFFFAOYSA-N 5-methoxypentyl acetate Chemical compound COCCCCCOC(C)=O JPQXNTOALKRJMH-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- SEEVRZDUPHZSOX-UHFFFAOYSA-N [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-UHFFFAOYSA-N 0.000 description 1
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VFXVAXFIFHSGNR-UHFFFAOYSA-N octyl carbonochloridate Chemical compound CCCCCCCCOC(Cl)=O VFXVAXFIFHSGNR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQKDTTWZXHEGAQ-UHFFFAOYSA-N propyl carbonochloridate Chemical compound CCCOC(Cl)=O QQKDTTWZXHEGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/30—Sulfides having the sulfur atom of at least one thio group bound to two carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/63—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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Abstract
Description
The present invention relates to oxime ester compounds and photopolymerizable compositions containing them, and more particularly to a photopolymerizable composition comprising a photopolymerizable compound and a photopolymerization initiator, wherein the photopolymerization initiator comprises an oxime ester compound.
The photoactive compound is a substance that generates chemically active atoms or molecules by decomposing and absorbing light, and is widely used as a photopolymerization initiator for various compositions such as photo-curable ink, photosensitive printing plate, photoresist and the like.
As typical examples of the photopolymerization initiator, various kinds of acetophenone based compounds, benzophenone based compounds, triazine based compounds, nonimidazole based compounds, acylphosphine oxide based compounds and oxime ester based compounds are known, Absorbs ultraviolet light to hardly show color, has a high radical generation efficiency, and is excellent in compatibility and stability with photoresist composition materials.
In the case of a photopolymerization initiator having an oxime ester compound, it is easy to synthesize various photopolymerization initiators capable of regulating the absorption region of the photopolymerization initiator by introducing an appropriate substituent into the compound.
Oxime ester compound can polymerize and cure a polymerizable compound having an unsaturated bond by irradiating light of 365 to 435 nm to a photopolymerizable composition and is used for a black matrix, a color filter, a column spacer, a flexible insulating film, a photoresist composition for an overcoat .
Therefore, the photopolymerization initiator has a high sensitivity to a long wavelength light source such as 365 to 435 nm, has good photopolymerization reactivity, is easy to produce, has high thermal stability and storage stability and is easy to handle, and has excellent properties for a solvent such as propylene glycol monomethyl ether acetate There is a continuing need for new photopolymerization initiators suitable for a variety of applications that meet the needs of industrial sites, such as satisfactory solubility.
Exemplary oxime ester compounds include oxime ester compounds using p-dialkylaminobenzene in U.S. Patent No. 4,255,513, acrylamino-substituted oxime ester compounds in U.S. Patent No. 4,202,697, U.S. Patent No. 4,590,145 Include benzophenone oxime ester compounds and the like.
However, when a conventionally known oxime ester compound is used as a photopolymerization initiator, decomposition products generated by light at the time of exposure adhere to the mask, resulting in pattern defects in the printing process, resulting in a decrease in the yield. Further, there is a problem that the decomposition temperature is 240 ° C or lower, and the photopolymerization initiator decomposes in the heat curing step after the development treatment, thereby deteriorating the adhesion and alkali resistance of the photopolymerizable composition.
Therefore, there is a high demand for oxime ester compounds having a novel structure that can fundamentally solve such problems, and photopolymerizable compositions containing them.
An object of the present invention is to provide an oxime ester compound having a novel structure.
In addition, the present invention provides a photopolymerizable composition comprising a photopolymerizable compound and a photopolymerization initiator, wherein the photolymerizable composition contains the novel oxime ester compound of the present invention as the photopolymerization initiator and has excellent linearity of pattern, Which is capable of improving the compatibility with the photopolymerizable composition of the present invention.
In order to achieve the above object,
The present invention provides an oxime ester compound represented by the following general formula (1).
[Chemical Formula 1]
R is an alkyl group having 1 to 20 carbon atoms,
And n is an integer of 12 to 20.
The present invention also provides a photopolymerizable composition comprising a photopolymerizable compound and a photopolymerization initiator, wherein the photopolymerization initiator comprises an oxime ester compound represented by the following general formula (1).
[Chemical Formula 1]
R is an alkyl group having 1 to 20 carbon atoms,
And n is an integer of 12 to 20.
When the light is irradiated to the novel oxime ester compound of the present invention, long-chain alkyl radicals are generated. Since the radicals are long, the radicals are less mobile and the curing proceeds only in the region irradiated with light. The ester compound has characteristics of excellent linearity of the pattern.
In addition, the novel oxime ester compound of the present invention has high solubility and is excellent in compatibility with other components, and has little color when absorbing ultraviolet rays, which is advantageous for application of an optical composition.
Therefore, the photopolymerizable composition comprising the photopolymerizable compound and the photopolymerization initiator of the present invention contains the novel oxime ester compound of the present invention as a photopolymerization initiator, and thus has an excellent linearity of the pattern upon irradiation with light, .
1 is a 1 H-NMR spectrum of an oxime ester derivative of formula (2) prepared in Preparation Example 1.
2 is a 1 H-NMR spectrum of the oxime ester compound of Chemical Formula 4 prepared in Preparation Example 3. FIG.
Hereinafter, the present invention will be described in more detail.
The present invention relates to an oxime ester compound represented by the following general formula (1).
[Chemical Formula 1]
R is an alkyl group having 1 to 20 carbon atoms,
And n is an integer of 12 to 20.
In the oxime ester compound of Formula 1, R is preferably an alkyl group having 1 or 6 carbon atoms, and n is preferably an integer of 12 or 20.
The oxime ester compound of formula (1) may be at least one selected from the group consisting of the following formulas (2) to (5), but is not limited thereto.
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
The oxime ester compound of
[Reaction Scheme 1]
The oxime ester compound of Formula 1, which is a novel compound of the present invention, includes a diphenylsulfide group. Therefore, when the oxime ester compound of Formula 1 is irradiated with light, the photoreactivity of the oxime ester compound of Chemical Formula 1 is improved due to the energy transfer of the diphenylsulfide group, and the light efficiency can be maximized. Further, it can be used for an optical composition without coloring even after irradiation with light.
Accordingly, the present invention provides a photopolymerizable composition using the oxime ester compound of Formula 1 as a photopolymerization initiator, taking advantage of the oxime ester compound of Formula 1.
More specifically, the present invention provides a photopolymerizable composition comprising a photopolymerizable compound and a photopolymerization initiator, wherein the photopolymerization initiator comprises an oxime ester compound of the following general formula (1).
[Chemical Formula 1]
R is an alkyl group having 1 to 20 carbon atoms,
And n is an integer of 12 to 20.
The photopolymerizable compound is a component for supplementing light efficiency and color change, and the kind thereof is not particularly limited, but an acrylic oligomer having an ethylenic unsaturated bond is preferable.
The acrylic oligomer having an ethylenically unsaturated bond is a photocurable acrylic oligomer configured to be capable of ultraviolet curing reaction by a chemical reaction of an acrylic oligomer precursor and a monomer for introducing an ethylenic unsaturated bond.
The acrylic oligomer precursor may be a copolymer of a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms and a polymerizable monomer. The method of producing the acrylic oligomer precursor is not particularly limited, and can be produced by methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and bulk polymerization is preferable. A polymerization initiator such as azo type, peroxide type, acetal type, hemiacetal type, and redox type can be used as a solvent usually used in polymerization.
The alkyl group of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms includes an aliphatic alkyl group and an aromatic alkyl group. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, ethylhexyl (meth) acrylate, ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl , Isobornyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl (meth) acrylate. These monomers may be used alone or in combination of two or more.
Specific examples of the polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 2-hydroxypropyleneglycol (meth) acrylate, 2-hydroxypropyleneglycol (meth) acrylate and 4-hydroxybutylvinylether A monomer having a hydroxy group; And monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid and fumaric acid. These polymerizable monomers may be used alone or in combination of two or more.
The kind of the monomer for introducing the ethylenically unsaturated bond is not particularly limited. Preferably, however, an isocyanate monomer having an isocyanate group and a double bond at the same time in one molecule is used, and for example, 2-isocyanatoethyl (meth) acrylate can be given.
The method of producing the photocurable acrylic oligomer preferably used as the photopolymerizable compound is not particularly limited. Specifically, for example, 0.5 to 20 parts by weight of an isocyanate monomer and 0.001 to 0.5 parts by weight of a catalyst are added to 100 parts by weight of the acrylic oligomer precursor prepared from the acrylic oligomer precursor, and reacted. The catalyst is not particularly limited as long as it can accelerate the reaction of a hydroxyl group or an isocyanate group with a carboxyl group or an isocyanate group contained in an acrylic oligomer precursor. For example, an organic tin compound, an organic silver compound or a mixture thereof can be used.
The photopolymerizable compound may have a weight average molecular weight (polystyrene conversion, Mw) of from 200,000 to 100 as measured by Gel Permeation Chromatography (GPC).
The photopolymerization initiator is characterized by containing an oxime ester compound represented by the following formula (1).
[Chemical Formula 1]
R is an alkyl group having 1 to 20 carbon atoms,
And n is an integer of 12 to 20.
In the oxime ester compound of
The oxime ester compound of formula (1) may be at least one selected from the group consisting of the following formulas (2) to (5), but is not limited thereto.
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
The oxime ester compound of
The photopolymerization initiator is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the solid content of the photopolymerizable compound. If the content is less than 0.01 part by weight, the overall curability of the photopolymerizable composition is lowered. If the content is more than 10 parts by weight, the transmittance of ultraviolet light is lowered and the degree of curing at the core part is lowered.
In addition, the photopolymerizable composition of the present invention may further comprise a solvent, and if the solvent is effective for dissolving other components contained in the photopolymerizable composition, the solvent used in a conventional photopolymerizable composition is not particularly limited and may be used Ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are particularly preferred.
Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; And alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate.
Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.
Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.
Examples of the esters include esters such as ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as? -Butyrolactone.
Of these solvents, organic solvents having a boiling point of 100 ° C to 200 ° C are more preferably used in terms of coatability and dryness. Examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butylacetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.
These solvents may be used alone or in combination of two or more.
In addition, the photopolymerizable composition of the present invention may further include known additives such as a colorant, an alkali-soluble resin and a surfactant.
The photopolymerizable composition of the present invention is applicable for various purposes. For example, it can be applied to a printing ink, a finishing material, a covering material, a point / adhesive, and the like, and absorbs ultraviolet rays to hardly color, so that it can be applied as an optical composition for various image display devices requiring transparency.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
<
Manufacturing example 1. A compound of formula Oxime Ester compound production
1-1. Ashes Produce
20 g (107.5 mmol) of diphenyl sulfide was added to a solution of 100 g of dichloroethane and 21.7 g (163 mmol) of aluminum chloride, and 17.4 g (107.5 mmol) of octyl carboxy chloride was added dropwise at a temperature of 6 캜 or lower. After stirring for 1 hour, the reaction mixture was poured into ice water, ethyl acetate was added, and the mixture was subjected to oil-water separation. Thereafter, the separated organic layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was removed to obtain 26.3 g of ashes.
The obtained ashes were analyzed by 1 H-NMR and their structure was confirmed. As a result, it was confirmed that they had the structure of the following formula (6), and the spectrum was as follows.
[Chemical Formula 6]
1 H-NMR (CDCl 3, ppm): 2.01 (t, 3H), 2.55 (m, 10H), 3.65 (s, 2H), 7.00 (t, 1H), 7.07 (t, 2H), 7.20 (d, 2H), 7.32 (d, 2H), 7.66 (d, 2H).
1-2. Oxime Produce
5.4 g (52 mmol) of isobutyl nitrite was added to a mixture of 13 g (47.4 mmol) of the acyl group of the
The obtained oxime was analyzed by 1 H-NMR and its structure was confirmed. As a result, it was confirmed that it had the structure of
(7)
1 H-NMR (CDCl 3, ppm): 2.01 (t, 3H), 2.65 (m, 8H), 3.25 (t, 2H), 7.02 (t, 1H), 7.09 (t, 2H), 7.18 (d, 2H), 7.31 (d, 2H), 7.62 (d, 2H), 12.8 (s, 1H).
1-3. 2 Oxime Ester compound production
A solution obtained by mixing 4 g (13.2 mmol) of the oxime of formula (7) obtained in 1-2 above, 2.1 g (27 mmol) of pyridine and 12 g of dimethylformamide was maintained at -10 ° C or lower, 3.7 g (15 mmol) of the acid chloride was added dropwise. After that, the mixture was stirred at 5 캜 for 2 hours. Ethyl acetate and water were added to the reaction mixture, and the mixture was subjected to oil-water separation. The separated organic layer was washed with water. Thereafter, the washed organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain 3.5 g of oxime ester compound.
The oxime ester compound thus obtained was analyzed by 1 H-NMR and an elemental analyzer to confirm its structure. As a result, it was confirmed that the compound had a structure of the following formula (2). The spectrum is shown in FIG. 1 and the result of elemental analysis is as follows.
(2)
Elemental analysis: C, 74.21; H, 9.02; N, 2.38; S, 5.45.
Manufacturing example 2. The compound of formula Oxime Ester compound production
A solution obtained by mixing 4 g (13.2 mmol) of the oxime obtained in 1-2 above, 2.1 g (27 mmol) of pyridine and 12 g of dimethylformamide was maintained at -10 ° C or lower, and to this mixture was added 5.4 g of behenic acid chloride (15 mmol) was added dropwise. After that, the mixture was stirred at 5 캜 for 2 hours. Ethyl acetate and water were added to the reaction mixture, and the mixture was subjected to oil-water separation. The separated organic layer was washed with water. Thereafter, the washed organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain 3.5 g of an oxime ester compound of the following formula (3).
The obtained oxime ester compound was analyzed with an elemental analyzer to confirm its structure. As a result, it was confirmed that the compound had the structure of the following formula (3), and the result of elemental analysis was as follows.
(3)
Elemental analysis: C, 76.27; H, 9.97; N, 2.04; S, 4.71.
Manufacturing example 3. The compound of formula Oxime Ester compound production
3-1. Ashes Produce
20 g (107.5 mmol) of diphenyl sulfide was added to a solution of 100 g (1 mol) of dichloroethane and 21.7 g (163 mmol) of aluminum chloride, and 9.94 g (107.5 mmol) of propylcarboxy chloride was added dropwise at a temperature of 6 ° C or lower. After stirring for 1 hour, the reaction mixture was poured into ice water, ethyl acetate was added, and the mixture was subjected to oil-water separation. Thereafter, the separated organic layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was removed to obtain 248 g of ashes.
The structure of the obtained acid group was as shown in the following formula (8).
[Chemical Formula 8]
3-2. Oxime Produce
5.4 g (52 mmol) of isobutyl nitrite was added to a solution of 13 g (47.4 mmol) of the acyl group of the
The structure of the obtained oxime was as shown in the following formula (9).
[Chemical Formula 9]
3-3. 4 Oxime Ester compound production
A solution obtained by mixing 3.6 g (13.2 mmol) of the oxime of the
The obtained oxime ester compound was analyzed by 1 H-NMR and an elemental analyzer to confirm its structure. As a result, it was confirmed that the compound had a structure of the following formula (4), the spectrum thereof is shown in FIG. 2, and the result of element analysis is as follows.
[Chemical Formula 4]
Elemental analysis: C, 72.32; H, 8.15; N, 2.93; S, 6.69.
Manufacturing example 4. The compound of formula Oxime Ester compound production
A mixture of 3.6 g (13.2 mmol) of the oxime obtained in the above step 3-2, 2.1 g (27 mmol) of pyridine and 12 g of dimethylformamide was maintained at -10 ° C or lower, and behenic acid chloride 5.4 g (15 mmol) of triethylamine were added dropwise. After that, the mixture was stirred at 5 캜 for 2 hours. Ethyl acetate and water were added to the reaction mixture, and the mixture was subjected to oil-water separation. The separated organic layer was washed with water. Thereafter, the washed organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain 3.5 g of oxime ester compound.
The oxime ester compound thus obtained was analyzed by an elemental analyzer and its structure was confirmed. As a result, it was confirmed that the compound had the structure of
[Chemical Formula 5]
Elemental analysis: C, 74.84; H, 9.31; N, 2.38; S, 5.41.
< Photopolymerization Composition Preparation>
Example One.
As the photopolymerizable compound, 50 g of bisphenol A glycerolate (1 glycerol / phenol) diacrylate of the following formula (10) and 10 g of dipentaerythritol hexaacrylate, 40 g of carbon black as a coloring agent as an additive, 2 was added to 100 g of a propylene glycol monomethyl ether acetate solvent, and the mixture was stirred for 30 minutes to prepare a photopolymerizable composition.
[Chemical formula 10]
Example 2.
A photopolymerizable composition was prepared in the same manner as in Example 1 except that the oxime ester compound of
Example 3.
A photopolymerizable composition was prepared in the same manner as in Example 1 except that the oxime ester compound of
Example 4.
A photopolymerizable composition was prepared in the same manner as in Example 1 except that the oxime ester compound of
Comparative Example One.
A photopolymerizable composition was prepared in the same manner as in Example 1 except that 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO, BASF Corp.) was used as a photopolymerization initiator.
Comparative Example 2.
The procedure of Example 1 was repeated except that OXE-01 (1,2-octanedione-1- [4- (phenylthio) phenyl] -2-O-benzoyloxime, Ciba) was used as a photopolymerization initiator To prepare a photopolymerizable composition.
Comparative Example 3.
Except that OXE-02 (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1-O-acetyloxime, Ciba) was used as a photopolymerization initiator Was prepared in the same manner as in Example 1 to prepare a photopolymerizable composition.
Experimental Example One. Photopolymerization Evaluation of pattern accuracy and straightness of composition
The photopolymerizable compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were coated on a glass substrate having a clean surface with a thickness of 1 mm by using a spin coater so that the film thickness after drying was 1.0 占 퐉, Minute to form a photopolymerizable composition film. The photopolymerizable composition film was irradiated with ultraviolet rays selectively through a negative mask having a line width of 20 mu m and spray-developed at 25 DEG C for 60 seconds in a 0.5 wt% sodium carbonate aqueous solution to form a black matrix.
The formed black matrix was observed with a microscope to measure the precision of the pattern, and the linearity of the line was evaluated. The evaluation criteria are as follows.
<Accuracy Evaluation Standard>
The line width of the cured pattern film through a negative mask having a line width of 20 mu m was subtracted by 20 mu m, and the smaller the numerical value (less than 5 mu m), the higher the accuracy.
<Straightness Evaluation Standard>
During microscopic observation,
No fine bend or drop off observed on the side of pattern straight line: ○
Fine bending or dropout was observed but only in a small part: △
Fine bend or drop was observed at the front of the pattern: x
The precision and straightness results of the pattern are shown in Table 1 below.
From the results of Table 1, it can be seen that the pattern of the black matrix prepared from the photopolymerizable composition of Examples 1 to 4, in which the oxime ester compound of the present invention was used as a photopolymerization initiator, showed a slight increase in line width, No dropouts were observed, showing excellent results in accuracy and straightness.
However, the pattern of the black matrix prepared from the photopolymerizable composition of Comparative Examples 1 to 3, in which a compound not corresponding to the oxime ester compound of the present invention was used as a photopolymerization initiator, greatly increased the line width, and the curvature and the dropout Respectively.
Therefore, it can be confirmed that the photopolymerizable composition using the oxime ester compound of the present invention as a photopolymerization initiator is excellent in the linearity of the pattern, and is capable of producing a pattern more precisely.
Claims (10)
[Chemical Formula 1]
R is an alkyl group having 1 to 20 carbon atoms,
And n is an integer of 12 to 20.
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 1]
R is an alkyl group having 1 to 20 carbon atoms,
And n is an integer of 12 to 20.
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140074750A KR20150145414A (en) | 2014-06-19 | 2014-06-19 | Oxime ester compound and a photopolymerizable composition comprising the same |
| TW104118541A TWI680960B (en) | 2014-06-19 | 2015-06-08 | Oxime ester compound and a photopolymerizable composition comprising the same |
| CN201510338665.8A CN105198779B (en) | 2014-06-19 | 2015-06-17 | Oxime ester compound and the optical polymerism composition including the oxime ester compound |
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| KR1020140074750A KR20150145414A (en) | 2014-06-19 | 2014-06-19 | Oxime ester compound and a photopolymerizable composition comprising the same |
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| KR20150145414A true KR20150145414A (en) | 2015-12-30 |
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| KR1020140074750A KR20150145414A (en) | 2014-06-19 | 2014-06-19 | Oxime ester compound and a photopolymerizable composition comprising the same |
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| CN (1) | CN105198779B (en) |
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| WO2018135249A1 (en) * | 2017-01-23 | 2018-07-26 | 富士フイルム株式会社 | Curable composition, cured film, color filter, light-blocking film, solid-state imaging element, image display device, and method for manufacturing cured film |
| KR101910734B1 (en) * | 2017-03-28 | 2018-10-22 | 동우 화인켐 주식회사 | Colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter |
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| JP4570999B2 (en) * | 2004-03-30 | 2010-10-27 | 新日鐵化学株式会社 | Photosensitive resin composition and color filter using the same |
| JP2009203299A (en) * | 2008-02-27 | 2009-09-10 | Toyo Ink Mfg Co Ltd | Non-yellowing polymerizable composition and method for producing polymerized material |
| JP5583353B2 (en) * | 2009-03-06 | 2014-09-03 | 富士フイルム株式会社 | Colored curable composition for solid-state imaging device, color filter, and production method thereof |
| JP5511415B2 (en) * | 2010-02-02 | 2014-06-04 | 富士フイルム株式会社 | Curable composition for imprint, pattern forming method and pattern |
| JP2014149432A (en) * | 2013-02-01 | 2014-08-21 | Adeka Corp | Alkali developable photosensitive composition |
| CN103293855B (en) * | 2013-05-20 | 2015-12-23 | 常州强力先端电子材料有限公司 | A kind of esters of acrylic acid Photocurable composition |
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Non-Patent Citations (3)
| Title |
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| 미국특허공보 제4,202,697호 |
| 미국특허공보 제4,255,513호 |
| 미국특허공보 제4,590,145호 |
Also Published As
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|---|---|
| CN105198779B (en) | 2017-06-20 |
| CN105198779A (en) | 2015-12-30 |
| TWI680960B (en) | 2020-01-01 |
| TW201600500A (en) | 2016-01-01 |
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