KR20150145415A - 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
- KR20150145415A KR20150145415A KR1020140074751A KR20140074751A KR20150145415A KR 20150145415 A KR20150145415 A KR 20150145415A KR 1020140074751 A KR1020140074751 A KR 1020140074751A KR 20140074751 A KR20140074751 A KR 20140074751A KR 20150145415 A KR20150145415 A KR 20150145415A
- Authority
- KR
- South Korea
- Prior art keywords
- oxime ester
- photopolymerizable composition
- formula
- ester compound
- photopolymerizable
- Prior art date
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- -1 Oxime ester compound Chemical class 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 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
- 239000002904 solvent Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000002923 oximes Chemical class 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 6
- 239000002956 ash Substances 0.000 description 6
- 238000004519 manufacturing process Methods 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
- 238000000926 separation method Methods 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
- 238000002360 preparation method Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 238000000921 elemental analysis Methods 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
- 239000011541 reaction mixture Substances 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
- 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
- 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
- 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
- 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
- 238000005452 bending Methods 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
- 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- STFZDGMULLWAKJ-UHFFFAOYSA-N 2-heptylbenzoyl chloride Chemical compound CCCCCCCC1=CC=CC=C1C(Cl)=O STFZDGMULLWAKJ-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
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- WHTFLTOKFXTJGV-UHFFFAOYSA-N 4-heptylbenzoyl chloride Chemical compound CCCCCCCC1=CC=C(C(Cl)=O)C=C1 WHTFLTOKFXTJGV-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
- 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
- 239000002253 acid Substances 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
- 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
- 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
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- 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
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- 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
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- 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
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- 230000035945 sensitivity Effects 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
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- 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
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
Description
본 발명은 옥심 에스테르계 화합물 및 이를 포함하는 광중합성 조성물에 관한 것으로, 보다 자세하게는 광중합성 화합물 및 광중합 개시제를 포함하며, 상기 광중합 개시제는 옥심 에스테르계 화합물을 포함하는 광중합성 조성물에 관한 것이다.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.
광활성 화합물은 빛을 흡수하여 분해됨으로써 화학적으로 활성을 지닌 원자 또는 분자를 생성하는 물질로, 광경화성 잉크, 감광성 인쇄판, 포토레지스트 등과 같은 각종 조성물의 광중합 개시제로 널리 사용된다.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.
광중합 개시제의 일반적인 예는 아세토페논계 화합물, 벤조페논계 화합물, 트리아진계 화합물, 비이미다졸계 화합물, 아실포스핀 옥사이드계 화합물 및 옥심 에스테르계 화합물 등 여러 종류가 알려져 있으며, 이중 옥심 에스테르계 화합물은 자외선을 흡수하여 색을 거의 나타내지 않고, 라디칼 발생 효율이 높으며, 포토레지스트 조성물 재료들과의 상용성 및 안정성이 우수한 장점을 갖고 있다.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.
옥심 에스테르계 화합물을 갖는 광중합 개시제의 경우 상기 화합물에 적절한 치환기를 도입하여 광중합 개시제의 흡수영역이 조절 가능한 다양한 광중합 개시제의 합성이 용이하다.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.
옥심 에스테르계 화합물은 광중합성 조성물에 365 내지 435nm의 빛을 조사함으로써 불포화 결합을 갖는 중합성 화합물을 중합 및 경화시킬 수 있어 블랙매트릭스, 컬러필터, 컬럼스페이서, 유연절연막, 오버코트용 포토레지스트 조성물 등에 이용되고 있다.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 .
따라서, 광중합 개시제는 365 내지 435nm 등 장파장 광원에 높은 감도를 가지며, 광중합 반응성이 좋고, 제조가 용이하며, 열안정성 및 저장안정성이 높아 취급이 용이하며, 프로필렌 글리콜 모노메틸 에테르 아세테이트와 같은 용제에 대한 만족할 만한 용해도 등 산업 현장의 요구를 충족시킬 수 있는 다양한 용도에 적합한 새로운 광중합 개시제가 지속적으로 요구되고 있다.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.
기존에 공지된 옥심 에스테르계 화합물로는 미국특허공보 제4,255,513호에 p-디알킬아미노벤젠을 사용한 옥심 에스테르 화합물, 미국특허공보 제4,202,697호에는 아크릴아미노-치환된 옥심 에스테르 화합물, 미국특허공보 제4,590,145호에는 벤조페논 옥심 에스테르 화합물 등이 개시되어 있다.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.
그러나, 기존에 알려진 옥심 에스테르계 화합물을 광중합 개시제로서 이용했을 경우, 노광시의 광에 의해 발생하는 분해물이 마스크에 부착해 프린팅 공정에서 패턴형상 불량을 야기하고, 수율의 저하를 초래한다. 또한, 분해온도가 240℃ 이하이며, 현상처리 후의 열경화 공정에 있어서 광중합 개시제가 분해함으로써 광중합성 조성물의 밀착성 및 내알칼리성을 저하시키는 문제점이 있다. 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.
따라서, 이러한 문제점을 근본적으로 해결할 수 있는 새로운 구조의 옥심 에스테르계 화합물 및 이를 포함하는 광중합성 조성물 등에 대한 요구가 높은 실정이다.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.
본 발명은 신규한 구조의 옥심 에스테르계 화합물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an oxime ester compound having a novel structure.
또한, 본 발명은 광중합성 화합물 및 광중합 개시제를 포함하는 광중합성 조성물을 제공하며, 상기 광중합 개시제로 본 발명의 신규한 옥심 에스테르계 화합물을 포함함으로써 패턴의 직진성이 우수하며, 우수한 용해성으로 다른 성분들과의 상용성을 향상시킬 수 있는 광중합성 조성물을 제공하는 것을 목적으로 한다.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.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 하기 화학식 1로 표시되는 옥심 에스테르계 화합물을 제공한다.The present invention provides an oxime ester compound represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
상기 R은 탄소수 1 내지 20의 알킬기이고,R is an alkyl group having 1 to 20 carbon atoms,
상기 n은 6 내지 21의 정수이다.And n is an integer of 6 to 21.
또한, 본 발명은 광중합성 화합물 및 광중합 개시제를 포함하는 광중합성 조성물로, 상기 광중합 개시제는 하기 화학식 1의 옥심 에스테르계 화합물을 포함하는 것을 특징으로 하는 광중합성 조성물을 제공한다.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).
[화학식 1][Chemical Formula 1]
상기 R은 탄소수 1 내지 20의 알킬기이고,R is an alkyl group having 1 to 20 carbon atoms,
상기 n은 6 내지 21의 정수이다.And n is an integer of 6 to 21.
본 발명의 신규한 옥심 에스테르계 화합물에 광을 조사하면 장쇄 알킬 라디칼이 생성되며, 상기 라디칼은 길이가 길기 때문에 라디칼의 이동성이 작아 광이 조사된 영역에서만 경화가 진행되므로, 본 발명의 신규한 옥심 에스테르계 화합물은 패턴의 직진성이 우수한 특성을 지니고 있다.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.
또한, 본 발명의 신규한 옥심 에스테르계 화합물은 용해도가 높아 다른 성분들과의 상용성이 우수하며, 자외선을 흡수하였을 때 색을 거의 띠지 않아 광학용 조성물의 적용에 유리하다.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.
따라서, 본 발명의 광중합성 화합물 및 광중합 개시제를 포함하는 광중합성 조성물은 광중합 개시제로 본 발명의 신규한 옥심 에스테르계 화합물을 포함함으로써 광 조사시 패턴의 직진성이 우수하며, 색을 거의 띠지 않는 효과를 나타낸다.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, .
도 1은 제조예 1에서 제조한 화학식 2의 옥심 에스테르게 화합물의 1H-NMR 스펙트럼이다.
도 2는 제조예 2에서 제조한 화학식 3의 옥심 에스테르게 화합물의 1H-NMR 스펙트럼이다.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 3 prepared in Preparation Example 2. FIG.
이하, 본 발명을 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명은 하기 화학식 1로 표시되는 옥심 에스테르계 화합물에 관한 것이다.The present invention relates to an oxime ester compound represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
상기 R은 탄소수 1 내지 20의 알킬기이고,R is an alkyl group having 1 to 20 carbon atoms,
상기 n은 6 내지 21의 정수이다.
And n is an integer of 6 to 21.
상기 화학식 1의 옥심 에스테르계 화합물은 R이 탄소수 1 또는 6의 알킬기인 것이 바람직하다.In the oxime ester compound of Formula 1, R is preferably an alkyl group having 1 or 6 carbon atoms.
또한, 상기 화학식 1의 옥심 에스테르계 화합물은 하기 화학식 2 내지 3으로 이루어진 군으로부터 선택되는 1종 이상일 수 있으나, 이에 한정되는 것은 아니다.The oxime ester compound of formula (1) may be at least one selected from the group consisting of the following formulas (2) to (3), but is not limited thereto.
[화학식 2](2)
[화학식 3](3)
본 발명의 신규한 화합물인 상기 화학식 1의 옥심 에스테르계 화합물의제조는 (1)디페닐설파이드 및 알킬카르복시클로라이드를 반응시켜 아실체를 제조하는 단계; (2)상기 아실체와 아질산을 반응시켜 옥심체를 제조하는 단계; 및 (3)상기 옥심체와 알킬카르복시클로라이드를 반응시켜 상기 화학식 1의 옥심 에스테르계 화합물을 제조하는 단계를 거쳐 제조될 수 있으며, 하기 반응식 1에 메커니즘을 나타내었다. 또한, 상기 화학식 1의 옥심 에스테르계 화합물의 R 및 n은 (1) 및 (3)단계의 알킬카르복시클로라이드의 알킬기에 따라 결정된다.The oxime ester compound of
[반응식 1][Reaction Scheme 1]
본 발명의 신규한 화합물인 상기 화학식 1의 옥심 에스테르계 화합물은 디페닐설파이드기를 포함한다. 따라서, 상기 화학식 1의 옥심 에스테르계 화합물에 광을 조사할 경우, 디페닐설파이드기의 에너지 전이로 인해 상기 화학식 1의 옥심 에스테르계 화합물의 광 반응성이 향상되며, 광 효율이 극대화될 수 있다. 또한, 광을 조사한 후에도 색을 띠지 않아 광학용 조성물에 유용하게 사용될 수 있다.
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.
따라서, 상기 화학식 1의 옥심 에스테르계 화합물의 장점을 이용하여, 본 발명에서는 상기 화학식 1의 옥심 에스테르계 화합물을 광중합 개시제로 사용하는 광중합성 조성물을 제공한다.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.
보다 자세하게는, 본 발명은 광중합성 화합물 및 광중합 개시제를 포함하는 광중합성 조성물로, 상기 광중합 개시제는 하기 화학식 1의 옥심 에스테르계 화합물을 포함하는 것을 특징으로 하는 광중합성 조성물을 제공한다.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).
[화학식 1][Chemical Formula 1]
상기 R은 탄소수 1 내지 20의 알킬기이고,R is an alkyl group having 1 to 20 carbon atoms,
상기 n은 6 내지 21의 정수이다.
And n is an integer of 6 to 21.
상기 광중합성 화합물은 광효율과 색상 변화를 보완하기 위한 성분으로서, 그 종류가 특별히 한정되지 않으나, 에틸렌성 불포화 결합을 갖는 아크릴계 올리고머인 것이 바람직하다. 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.
상기 에틸렌성 불포화 결합을 갖는 아크릴계 올리고머는 아크릴계 올리고머 전구체와 에틸렌성 불포화 결합을 도입하기 위한 단량체의 화학 반응에 의해 자외선 경화 반응이 가능하도록 구성된 광경화형 아크릴계 올리고머이다.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.
상기 아크릴계 올리고머 전구체는 탄소수 1 내지 14의 알킬기를 갖는 (메타)아크릴계 단량체와 중합성 단량체가 공중합된 것일 수 있다. 아크릴계 올리고머 전구체의 제조방법은 특별히 한정되지 않으며, 당 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 괴상중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매를 사용하며, 아조계, 퍼옥사이드계, 아세탈계, 헤미아세탈계 및 레독스계 등의 중합 개시제를 사용할 수 있다.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.
상기 탄소수 1 내지 14의 알킬기를 갖는 (메타)아크릴계 단량체의 알킬기는 지방족 알킬기와 방향족 알킬기를 포함하며, 이러한 단량체로는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 에틸헥실(메타)아크릴레이트, 에틸부틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 이소노닐(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 이소데실(메타)아크릴레이트 및 라우릴(메타)아크릴레이트 등을 들 수 있다. 상기 단량체들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.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.
상기 중합성 단량체로는 구체적으로 예를 들어, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 2-히드록시에틸렌글리콜(메타)아크릴레이트, 2-히드록시프로필렌글리콜(메타)아크릴레이트 및 4-히드록시부틸비닐에테르 등의 히드록시기를 갖는 단량체; (메타)아크릴산, 크로톤산, 말레인산, 이타콘산 및 푸마르산 등의 카르복시기를 갖는 단량체 등을 들 수 있다. 상기 중합성 단량체들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.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.
상기 에틸렌성 불포화 결합을 도입하기 위한 단량체의 종류는 특별히 한정되지 않는다. 그러나 바람직하게는 1분자 내에 이소시아네이트기와 이중결합을 동시에 갖는 이소시아네이트계 단량체를 사용하며, 예를 들어 2-이소시아네이토에틸(메타)아크릴레이트를 들 수 있다.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.
상기 광중합성 화합물로 바람직하게 사용되는 광경화형 아크릴계 올리고머의 제조방법은 특별히 한정되지 않는다. 구체적으로 예를 들어, 아크릴계 올리고머 전구체를 제조한 후 제조된 아크릴계 올리고머 전구체 100 중량부에 대하여 이소시아네이트계 단량체 0.5 내지 20 중량부 및 촉매 0.001 내지 0.5 중량부를 첨가하고 반응시키는 방법으로 제조할 수 있다. 촉매는 아크릴계 올리고머 전구체에 함유된 히드록시기 또는 카르복시기와 이소시아네이트기의 반응을 촉진시킬 수 있는 것이라면 그 종류가 특별히 한정되지 않으며, 예컨대 유기 주석계 화합물, 유기 은계 화합물 또는 이들의 혼합물을 사용할 수 있다.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.
상기 광중합성 화합물은 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산, Mw)이 20만 내지 100만일 수 있다.
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).
또한, 상기 광중합 개시제는 하기 화학식 1의 옥심 에스테르계 화합물을 포함하는 것이 특징이다.The photopolymerization initiator is characterized by containing an oxime ester compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 R은 탄소수 1 내지 20의 알킬기이고,R is an alkyl group having 1 to 20 carbon atoms,
상기 n은 6 내지 21의 정수이다.And n is an integer of 6 to 21.
상기 화학식 1의 옥심 에스테르계 화합물은 R이 탄소수 1 또는 6의 알킬기인 것이 바람직하다.In the oxime ester compound of
또한, 상기 화학식 1의 옥심 에스테르계 화합물은 하기 화학식 2 내지 3으로 이루어진 군으로부터 선택되는 1종 이상일 수 있으나, 이에 한정되는 것은 아니다.The oxime ester compound of formula (1) may be at least one selected from the group consisting of the following formulas (2) to (3), but is not limited thereto.
[화학식 2](2)
[화학식 3](3)
본 발명의 광중합성 조성물의 광중합 개시제로 사용되는 상기 화학식 1의 옥심 에스테르계 화합물은 n이 6 내지 21의 정수이므로 긴 알킬 체인을 가진다. 그러므로, 상기 화학식 1의 옥심 에스테르계 화합물에 광을 조사하였을 때 장쇄 알킬 라디칼이 생성되며, 길이가 길기 때문에 라디칼의 이동성이 작아 광이 조사된 영역에서만 경화가 진행된다. 따라서, 광중합 개시제로 상기 화학식 1의 옥심 에스테르계 화합물을 포함하는 광중합성 조성물을 사용하여 패턴을 형성하면 직진성이 우수한 패턴을 확보할 수 있다.The oxime ester compound of
상기 광중합 개시제는 광중합성 화합물의 고형분 100 중량부에 대하여 0.01 내지 10 중량부로 포함된다. 상기 함량이 0.01 중량부 미만이면, 광중합성 조성물의 전체적인 경화도가 저하되며, 10 중량부를 초과하면, 자외선의 투과율이 저하되어 심부에서의 경화도가 저하된다는 문제점이 있다.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.
또한, 본 발명의 광중합성 조성물은 추가로 용제를 포함할 수 있으며, 상기 용제는 광중합성 조성물에 포함되는 다른 성분들을 용해시키는데 효과적인 것이면, 통상의 광중합성 조성물에서 사용되는 용제를 특별히 제한하지 않고 사용할 수 있으며, 특히 에테르류, 방향족 탄화수소류, 케톤류, 알콜류, 에스테르류 또는 아미드류 등이 바람직하다.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.
상기 에테르류로는 예를 들어, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노부틸에테르등의 에틸렌글리콜모노알킬에테르류; 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디프로필에테르, 디에틸렌글리콜디부틸에테르 등의 디에틸렌글리콜디알킬에테르류; 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트 등의 에틸렌글리콜알킬에테르아세테이트류; 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노프로필에테르아세테이트, 메톡시부틸아세테이트, 메톡시펜틸아세테이트 등의 알킬렌글리콜알킬에테르아세테이트류 등이 있다.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.
상기 방향족 탄화수소류로는 예를 들어, 벤젠, 톨루엔, 크실렌, 메시틸렌 등이 있다.Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.
상기 케톤류로는 예를 들어, 메틸에틸케톤, 아세톤, 메틸아밀케톤, 메틸이소부틸케톤, 시클로헥사논 등이 있다.Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.
상기 알코올류로는 에탄올, 프로판올, 부탄올, 헥산올, 시클로헥산올, 에틸렌글리콜, 글리세린 등이 있다.Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.
상기 에스테르류로는 에틸락테이트, 부틸락테이트, 3-에톡시프로피온산에틸, 3-메톡시프로피온산메틸 등의 에스테르류; 및 γ-부티롤락톤 등의 환상 에스테르류 등을 들 수 있다.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.
상기 용제 중에서도 도포성 및 건조성면에서 비점이 100℃ 내지 200℃인 유기 용제를 사용하는 것이 더욱 바람직하며 그 예로는 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 시클로헥사논, 에틸락테이트, 부탈락테이트, 3-에톡시프로피온산에틸 및 3-메톡시프로피온산메틸 등이 있다.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.
상기 용제는 각각 단독 또는 2종 이상을 혼합하여 사용할 수 있다.These solvents may be used alone or in combination of two or more.
또한, 본 발명의 광중합성 조성물은 착색제, 알칼리 가용성 수지 및 계면 활성제 등의 공지된 첨가제를 추가로 포함할 수 있다.
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.
본 발명의 광중합성 조성물은 다양한 용도로 적용 가능하다. 예컨대, 인쇄용 잉크, 마감재, 피복재, 점/접착제 등에 적용될 수 있으며, 자외선을 흡수하여 색을 거의 띠지 않게 하므로 투명성이 요구되는 각종 화상표시장치의 광학용 조성물로서 적용될 수 있다.
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.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
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.
<화학식 1의 <
제조예Manufacturing example 1. 화학식 2의 1. A compound of formula 옥심Oxime 에스테르계 화합물 제조 Ester compound production
1-1. 1-1. 아실체Ashes 제조 Produce
디클로로에탄 100g과 염화알루미늄 21.7g(163mmol)을 혼합한 용액에 디페닐설파이드 20g(107.5mmol)을 첨가한 후 6℃ 이하의 온도에서 옥틸카르복시클로라이드 17.4g(107.5mmol)을 적하하였다. 그 후, 1시간 동안 교반한 후 반응액을 얼음물에 넣고 아세트산에틸을 첨가하여 유수 분리하였다. 그 후, 분리된 유기층을 물로 세정하고, 무수 황산마그네슘을 첨가하여 건조시킨 후 용매를 제거하여 아실체 26.3g을 수득하였다.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.
수득된 아실체를 1H-NMR로 분석하여 구조를 확인한 결과, 하기 화학식 4의 구조를 갖는 것을 확인하였으며, 스펙트럼은 하기와 같다.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 (4), and the spectrum was as follows.
[화학식 4][Chemical Formula 4]
1H-NMR(CDCl3, 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 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. 1-2. 옥심체Oxime 제조 Produce
상기 1-1에서 수득한 화학식 6의 아실체 13g(47.4mmol), 농염산 3.6g(35mmol) 및 디메틸포름아미드 50g을 혼합한 용액에 아질산이소부틸 5.4g(52mmol)을 첨가한 후 실온에서 3.5시간 동안 교반하였다. 그 후, 반응액에 아세트산에틸과 물을 첨가하여 유수 분리하고, 분리된 유기층을 물로 세정하였다. 그 후, 고체가 석출된 유기층에 헥산을 첨가하고 여과한 후 얻어진 고체를 감압 건조하여 옥심체 10.6g을 수득하였다.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
수득된 옥심체를 1H-NMR로 분석하여 구조를 확인한 결과, 하기 화학식 5의 구조를 갖는 것을 확인하였으며, 스펙트럼은 하기와 같다.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
[화학식 5] [Chemical Formula 5]
1H-NMR(CDCl3, 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 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. 화학식 2의 1-3. 2 옥심Oxime 에스테르계 화합물 제조 Ester compound production
상기 1-2에서 수득한 화학식 5의 옥심체 4g(13.2mmol), 피리딘 2.1g(27mmol) 및 디메틸포름아미드 12g을 혼합한 용액을 -10℃ 이하의 상태로 유지하고, 상기 혼합 용액에 4-헵틸벤조산클로라이드 3.6g(15mmol)을 적하하였다. 그 후, 5℃에서 2시간 동안 교반한 후 반응액에 아세트산에틸과 물을 첨가하여 유수 분리하고, 분리된 유기층을 물로 세정하였다. 그 후, 세정된 유기층에 무수 황산마그네슘을 첨가하여 건조시킨 후 용매를 제거하여 옥심 에스테르계 화합물 3.5g을 수득하였다.A solution obtained by mixing 4 g (13.2 mmol) of the oxime of the
수득된 옥심 에스테르계 화합물을 1H-NMR 및 원소 분석기로 분석하여 구조를 확인한 결과, 하기 화학식 2의 구조를 갖는 것을 확인하였으며, 스펙트럼은 도 1에 나타내었으며, 원소 분석 결과는 하기와 같다.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.
[화학식 2](2)
원소 분석 : C, 75.12; H, 7.58; N, 2.57; S, 5.91
Elemental analysis: C, 75.12; H, 7.58; N, 2.57; S, 5.91
제조예Manufacturing example 2. 화학식 3의 2. The compound of formula 옥심Oxime 에스테르계 화합물 제조 Ester compound production
2-1. 2-1. 아실체Ashes 제조 Produce
디클로로에탄 100g(1mol)과 염화알루미늄 21.7g(163mmol)을 혼합한 용액에 디페닐설파이드 20g(107.5mmol)을 첨가한 후 6℃ 이하의 온도에서 프로필카르복시클로라이드 9.94g(107.5mmol)을 적하하였다. 그 후, 1시간 동안 교반한 후 반응액을 얼음물에 넣고 아세트산에틸을 첨가하여 유수 분리하였다. 그 후, 분리된 유기층을 물로 세정하고, 무수 황산마그네슘을 첨가하여 건조시킨 후 용매를 제거하여 아실체 20.7g을 수득하였다.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 20.7 g of ashes.
상기 수득된 아실체의 구조는 하기 화학식 6과 같았다.The structure of the obtained aseptic body was as shown in the following formula (6).
[화학식 6][Chemical Formula 6]
2-2. 2-2. 옥심체Oxime 제조 Produce
상기 2-1에서 수득한 화학식 6의 아실체 13g(47.4mmol), 농염산 3.6g(35mmol) 및 디메틸포름아미드 50g을 혼합한 용액에 아질산이소부틸 5.4g(52mmol)을 첨가한 후 실온에서 3.5시간 동안 교반하였다. 그 후, 반응액에 아세트산에틸과 물을 첨가하여 유수 분리하고, 분리된 유기층을 물로 세정하였다. 그 후, 고체가 석출된 유기층에 헥산을 첨가하고 여과한 후 얻어진 고체를 감압 건조하여 옥심체 19.8g을 수득하였다.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
상기 수득된 옥심체의 구조는 하기 화학식 7과 같았다.The structure of the obtained oxime was as shown in the following formula (7).
[화학식 7](7)
2-3. 화학식 3의 2-3. (3) 옥심Oxime 에스테르계 화합물 제조 Ester compound production
상기 2-2에서 수득한 화학식 7의 옥심체 3.6g(13.2mmol), 피리딘 2.1g(27mmol) 및 디메틸포름아미드 12g(164.2mmol)을 혼합한 용액을 -10℃ 이하의 상태로 유지하고, 상기 혼합 용액에 4-헵틸벤조산클로라이드 3.6g(15mmol)을 적하하였다. 그 후, 5℃에서 2시간 동안 교반한 후 반응액에 아세트산에틸과 물을 첨가하여 유수 분리하고, 분리된 유기층을 물로 세정하였다. 그 후, 세정된 유기층에 무수 황산마그네슘을 첨가하여 건조시킨 후 용매를 제거하여 옥심 에스테르계 화합물 3.5g을 수득하였다.A mixture of 3.6 g (13.2 mmol) of the oxime of the
수득된 옥심 에스테르계 화합물을 1H-NMR 및 원소 분석기로 분석하여 구조를 확인한 결과, 하기 화학식 3의 구조를 갖는 것을 확인하였으며, 스펙트럼은 도 2에 나타내었으며, 원소 분석 결과는 하기와 같다.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 (3). The spectrum is shown in FIG. 2, and the result of elemental analysis is as follows.
[화학식 3](3)
원소 분석 : C, 73.51; H, 6.61; N, 2.94; S, 6.74
Elemental analysis: C, 73.51; H, 6.61; N, 2.94; S, 6.74
<< 광중합성Photopolymerization 조성물 제조> Composition Preparation>
실시예Example 1. One.
광중합성 화합물로 하기 화학식 8의 비스페놀 A 글리세롤레이트(1글리세롤/페놀) 디아크릴레이트 50g 및 디펜타에리트리톨헥사아크릴레이트 10g, 첨가제로 착색제인 카본블랙 40g, 광중합 개시제로 제조예 1에서 제조한 화학식 2의 옥심 에스테르계 화합물 3g을 프로필렌글리콜모노메틸에테르아세테이트 용제 100g에 첨가하여 30분 동안 교반하여 광중합성 조성물을 제조하였다.As a photopolymerizable compound, 50 g of bisphenol A glycerolate (1 glycerol / phenol) diacrylate having the following general formula (8) 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.
[화학식 8][Chemical Formula 8]
실시예Example 2. 2.
광중합 개시제로 제조예 2에서 제조한 화학식 3의 옥심 에스테르계 화합물을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 광중합성 조성물을 제조하였다.
A photopolymerizable composition was prepared in the same manner as in Example 1 except that the oxime ester compound of
비교예Comparative Example 1. One.
광중합 개시제로 2,4,6-트리메틸벤조일디페닐포스핀옥사이드(TPO, 바스프사)를 사용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 광중합성 조성물을 제조하였다.
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.
비교예Comparative Example 2. 2.
광중합 개시제로 OXE-01(1,2-옥탄디온-1-[4-(페닐티오)페닐]-2-O-벤조일옥심, 시바사)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 광중합성 조성물을 제조하였다.
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.
비교예Comparative Example 3. 3.
광중합 개시제로 OXE-02(1-[9-에틸-6-(2-메틸벤조일)-9H-카바졸-3-일]에탄온-1-O-아세틸옥심, 시바사)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 광중합성 조성물을 제조하였다.
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.
실험예Experimental Example 1. One. 광중합성Photopolymerization 조성물의 패턴 정밀도 및 직진성 평가 Evaluation of pattern accuracy and straightness of composition
상기 실시예 1 내지 2 및 비교예 1 내지 3의 광중합성 조성물을 각각 두께 1㎜의 청정한 표면을 가지는 유리 기판 상에 스핀 코터를 이용해 건조 후의 막 두께가 1.0㎛가 되도록 도포하고, 100℃에서 5분간 건조하여 광중합성 조성막을 형성하였다. 상기 광중합성 조성막에 선폭 20㎛의 네가티브 마스크를 통하여 자외선을 선택적으로 조사한 뒤, 0.5 중량% 탄산나트륨 수용액에서 25℃, 60초간 스프레이 현상함으로써, 블랙 매트릭스를 형성하였다. The photopolymerizable compositions of Examples 1 to 2 and Comparative Examples 1 to 3 were coated on a glass substrate having a clean surface of 1 mm in thickness 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.
형성된 블랙 매트릭스는 현미경으로 관찰하여, 패턴의 정밀도을 측정하고, 선의 직진성을 평가하였으며, 평가 기준은 하기와 같다.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.
<정밀도 평가기준><Accuracy Evaluation Standard>
선폭 20㎛의 네가티브 마스크를 통하여 경화된 패턴막의 선 폭에서 20㎛을 뺀 값으로, 수치가 작을수록(5㎛ 이하) 정밀도가 높은 것으로 평가한다.The line width of the patterned film cured through a negative mask having a line width of 20 mu m was subtracted by 20 mu m, and the smaller the numerical value (5 mu m or less), the higher the accuracy.
<직진성 평가기준><Straightness Evaluation Standard>
현미경 관찰시, During microscopic observation,
직선의 옆면에서 미세한 굴곡이나, 탈락이 관찰되지 않음 : ○ No fine bending or dropping was observed on the side of the straight line: ○
미세한 굴곡이나, 탈락이 관찰되나, 일부분에서만 관찰됨 : △Fine bending or dropout was observed but only in a small part: △
미세한 굴곡이나, 탈락이 패턴의 전면에서 관찰됨 : ×
Fine bend or drop was observed at the front of the pattern: x
패턴의 정밀도 및 직진성 결과는 하기 표 1과 같다.The precision and straightness results of the pattern are shown in Table 1 below.
상기 표 1의 결과에서, 본 발명의 옥심 에스테르계 화합물을 광중합 개시제로 사용한 실시예 1 내지 2의 광중합성 조성물로 제조한 블랙 매트릭스의 패턴은 선폭이 미세하게 증가하였고, 패턴 직선의 옆면에서 굴곡과 탈락이 관찰되지 않아 정밀도 및 직진성에서 우수한 결과를 보였다.From the results of the above Table 1, it can be seen that the pattern of the black matrix prepared from the photopolymerizable composition of Examples 1 and 2, 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.
그러나, 본 발명의 옥심 에스테르계 화합물에 해당하지 않는 화합물을 광중합 개시제로 사용한 비교예 1 내지 3의 광중합성 조성물로 제조한 블랙 매트릭스의 패턴은 선폭이 크게 증가하였으며, 직선의 옆면에서 굴곡과 탈락이 관찰되었다.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.
따라서, 본 발명의 옥심 에스테르계 화합물을 광중합 개시제로 사용한 광중합성 조성물은 패턴의 직진성이 우수하여, 보다 정밀하게 패턴을 제조할 수 있는 효과가 있는 것을 확인할 수 있다.
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)
[화학식 1]
상기 R은 탄소수 1 내지 20의 알킬기이고,
상기 n은 6 내지 21의 정수이다.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 6 to 21.
[화학식 2]
[화학식 3]
The oxime ester-based compound according to claim 1, wherein the formula (1) is at least one selected from the group consisting of the following formulas (2) to (3).
(2)
(3)
[화학식 1]
상기 R은 탄소수 1 내지 20의 알킬기이고,
상기 n은 6 내지 21의 정수이다.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 6 to 21.
[화학식 2]
[화학식 3]
[4] The photopolymerizable composition according to claim 4, wherein the formula (1) is at least one selected from the group consisting of the following formulas (2) to (3).
(2)
(3)
Priority Applications (3)
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KR1020140074751A KR20150145415A (en) | 2014-06-19 | 2014-06-19 | Oxime ester compound and a photopolymerizable composition comprising the same |
TW104118542A TW201600501A (en) | 2014-06-19 | 2015-06-08 | Oxime ester compound and a photopolymerizable composition comprising the same |
CN201510338292.4A CN105198780B (en) | 2014-06-19 | 2015-06-17 | Oxime ester compound and the optical polymerism composition including the oxime ester compound |
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미국특허공보 제4,202,697호 |
미국특허공보 제4,255,513호 |
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