KR20160129385A - Colored Dye for color filter and Preparation method thereof - Google Patents
Colored Dye for color filter and Preparation method thereof Download PDFInfo
- Publication number
- KR20160129385A KR20160129385A KR1020150061454A KR20150061454A KR20160129385A KR 20160129385 A KR20160129385 A KR 20160129385A KR 1020150061454 A KR1020150061454 A KR 1020150061454A KR 20150061454 A KR20150061454 A KR 20150061454A KR 20160129385 A KR20160129385 A KR 20160129385A
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- color filter
- dye
- substituent
- compound
- Prior art date
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- 238000002360 preparation method Methods 0.000 title description 2
- 125000001424 substituent group Chemical group 0.000 claims abstract description 40
- 239000011342 resin composition Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000004040 coloring Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 14
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 abstract description 8
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 description 54
- 239000000203 mixture Substances 0.000 description 48
- 239000000975 dye Substances 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 239000000049 pigment Substances 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000003818 flash chromatography Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 12
- 235000019439 ethyl acetate Nutrition 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- -1 acetate compound Chemical class 0.000 description 7
- 125000005907 alkyl ester group Chemical group 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229940022663 acetate Drugs 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 4
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 4
- RRCAJFYQXKPXOJ-UHFFFAOYSA-N 4-aminobenzene-1,2-dicarbonitrile Chemical compound NC1=CC=C(C#N)C(C#N)=C1 RRCAJFYQXKPXOJ-UHFFFAOYSA-N 0.000 description 4
- OOHQHYJZUSXMFD-UHFFFAOYSA-N 4-iodobenzene-1,2-dicarbonitrile Chemical compound IC1=CC=C(C#N)C(C#N)=C1 OOHQHYJZUSXMFD-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229940116333 ethyl lactate Drugs 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical group [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000001007 phthalocyanine dye Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DEQOVKFWRPOPQP-UHFFFAOYSA-N (5-formylthiophen-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)S1 DEQOVKFWRPOPQP-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-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
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- LIKZXCROQGHXTI-UHFFFAOYSA-M acid blue 25 Chemical compound [Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S([O-])(=O)=O)C=C1NC1=CC=CC=C1 LIKZXCROQGHXTI-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000001056 green pigment Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 2
- 229920006391 phthalonitrile polymer Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YKENVNAJIQUGKU-UHFFFAOYSA-N tetraazaporphin Chemical group C=1C(C=N2)=NC2=NC(NN2)=NC2=CC(C=C2)=NC2=CC2=NC=1C=C2 YKENVNAJIQUGKU-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
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- 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
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
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- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- WUICPPBYLKNKNS-UHFFFAOYSA-N benzene-1,2,3-tricarbonitrile Chemical compound N#CC1=CC=CC(C#N)=C1C#N WUICPPBYLKNKNS-UHFFFAOYSA-N 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- IWPATTDMSUYMJV-UHFFFAOYSA-N butyl 2-methoxyacetate Chemical compound CCCCOC(=O)COC IWPATTDMSUYMJV-UHFFFAOYSA-N 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
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- 125000002091 cationic group Chemical group 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
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- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LZCLXQDLBQLTDK-BYPYZUCNSA-N ethyl (2S)-lactate Chemical compound CCOC(=O)[C@H](C)O LZCLXQDLBQLTDK-BYPYZUCNSA-N 0.000 description 1
- WNIHNYUROPJCLW-UHFFFAOYSA-N ethyl 2-ethoxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)OCC WNIHNYUROPJCLW-UHFFFAOYSA-N 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- JLEKJZUYWFJPMB-UHFFFAOYSA-N ethyl 2-methoxyacetate Chemical compound CCOC(=O)COC JLEKJZUYWFJPMB-UHFFFAOYSA-N 0.000 description 1
- WHRLOJCOIKOQGL-UHFFFAOYSA-N ethyl 2-methoxypropanoate Chemical compound CCOC(=O)C(C)OC WHRLOJCOIKOQGL-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- PPFNAOBWGRMDLL-UHFFFAOYSA-N methyl 2-ethoxyacetate Chemical compound CCOCC(=O)OC PPFNAOBWGRMDLL-UHFFFAOYSA-N 0.000 description 1
- YVWPDYFVVMNWDT-UHFFFAOYSA-N methyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OC YVWPDYFVVMNWDT-UHFFFAOYSA-N 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- AKWHOGIYEOZALP-UHFFFAOYSA-N methyl 2-methoxy-2-methylpropanoate Chemical compound COC(=O)C(C)(C)OC AKWHOGIYEOZALP-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- WIVNTNLDTMNDNO-UHFFFAOYSA-N octane-1-sulfonyl chloride Chemical compound CCCCCCCCS(Cl)(=O)=O WIVNTNLDTMNDNO-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
Abstract
본 발명은 컬러필터용 착색 염료 및 이를 포함하는 감광성 수지 조성물에 관한 것이다. 보다 구체적으로, 프탈로시아닌에 용해도를 향상시킬 수 있는 시아노에세틱산기와 같은 특정 이온성 치환기를 도입하고, 또한 용매에 대한 용해도를 향상시킬 수 있는 강한 전자 당김 그룹을 치환시킴으로써, 흡광영역을 블루 영역으로 이동시켜 고휘도를 갖고 내열성, 내광성 및 내화학성이 모두 우수한 컬러필터용 착색 염료와 이를 포함하는 감광성 수지 조성물이 제공된다.The present invention relates to a colored dye for a color filter and a photosensitive resin composition containing the same. More specifically, by introducing a specific ionic substituent group such as cyanoetecetic acid group capable of improving solubility in phthalocyanine and substituting a strong electron withdrawing group capable of improving the solubility in a solvent, To provide a coloring dye for a color filter having high brightness and excellent in heat resistance, light resistance and chemical resistance, and a photosensitive resin composition containing the same.
Description
본 발명은 분자 내에 적어도 1개 이상의 전자 당김 그룹을 갖는 특정 구조의 테트라아자포피린계인 컬러필터용 착색 염료 및 이를 포함하는 감광성 수지 조성물에 관한 것이다.The present invention relates to a colored dye for a color filter, which is a tetraazapopyrin system having a specific structure having at least one electron withdrawing group in a molecule, and a photosensitive resin composition containing the same.
컬러필터는 컬러를 구현하기 위해 액정 위에 빨강, 초록, 파랑(Red, Green, Blue)의 세 가지 색을 띠는 컬러필터를 설치해 통과하는 광의 비율을 조정함으로써 천연의 색을 구현하는 것이다.In order to realize color, a color filter has a color filter having three colors of red, green and blue (liquid crystal) on the liquid crystal, thereby realizing a natural color by adjusting the ratio of light passing through the color filter.
이러한 컬러 필터용 주요 착색제는 안료를 포함하는 착색 감광성 수지 조성물을 이용하여 원하는 착색 패턴을 형성하는 방법으로 제조된다. 그러나 최근 LCD TV의 대형화, 고색재현, 고휘도와 같은 고성능 제품에 대한 요구가 점점 더 커져가고 있으며 이에 색 밝기 및 색 순도가 우수한 청색, 적색 또는 녹색의 각 착색 감광성 조성물에 대한 연구가 다양한 방법으로 이루어지고 있다.The main colorant for such a color filter is prepared by a method of forming a desired coloring pattern using a colored photosensitive resin composition containing a pigment. However, recently, there is a growing demand for high-performance products such as large-sized LCD TVs, high-color reproduction, and high brightness. Thus, research on various colored photosensitive compositions having blue, red or green colors excellent in color brightness and color purity ought.
특히 이러한 착색제 안료는 열과 빛에 대한 견뢰성이 우수하나 용매에 용해되지 않아 색 밝기 및 고휘도 특성을 요구하는 대형 LCD TV 등 고성능 디스플레이에 적용할 수 있는 한계가 있다.Particularly, these colorant pigments have excellent fastness to heat and light, but they are not dissolved in solvents, and thus they can be applied to high-performance displays such as large LCD TVs requiring color brightness and high brightness characteristics.
따라서, 용매에 용해되지 않은 안료에 유기 관능기 그룹을 도입함으로써 용해도를 향상시켜 염료화 시키는 연구가 많이 이루어지고 있다.Therefore, many studies have been made to increase the solubility of dyes by introducing an organic functional group into a pigment not dissolved in a solvent.
예를 들어, 한국특허공개 제2011-0123616호에서는 기존 청색 안료로 사용되는 프탈로시아닌의 말단 그룹에 SO3 - 또는 CO3 -를 도입하여 Na+와 같은 양이온성 물질과 이온결합 형태를 형성하고 트리아릴메탄계 화합물을 혼합하여 착색제로 사용하는 방법을 개시하였다. 하지만, 상기 방법에서 사용되는 프탈로시아닌계 안료는 여전히 용매에 녹지 않은 안료이기 때문에, 용해도를 향상시킬 수 있는 새로운 방법의 개발이 필요한 실정이다.
For example, in Korean Patent Laid-Open Publication No. 2011-0123616, SO 3 - or CO 3 - is introduced into a terminal group of phthalocyanine used as a conventional blue pigment to form an ionic bond with a cationic substance such as Na + Methane-based compounds are mixed and used as a coloring agent. However, since the phthalocyanine-based pigment used in the above method is still a pigment not dissolved in a solvent, it is necessary to develop a new method for improving the solubility.
본 발명의 목적은 용매에 대한 용해도를 향상시키고 강한 전자 당김 그룹을 이용하여 흡광 영역을 블루 영역으로 이동시켜 고휘도를 갖는 컬러필터용 착색 염료 및 그 제조방법을 제공하는 것이다.An object of the present invention is to provide a coloring dye for a color filter having a high luminance by improving the solubility in a solvent and moving the light absorbing region to a blue region by using a strong electron withdrawing group, and a method for producing the same.
또한, 본 발명의 다른 목적은 내열성, 내광성 및 내화학성이 우수한 컬러필터용 착색 염료로 사용하기 적합한 착색 염료를 제공하는 것이다.Another object of the present invention is to provide a coloring dye suitable for use as a coloring dye for a color filter excellent in heat resistance, light resistance and chemical resistance.
본 발명의 또 다른 목적은 상기 착색 염료를 포함하는 감광성 수지 조성물을 제공하는 것이다.
It is still another object of the present invention to provide a photosensitive resin composition containing the above-mentioned colored dye.
본 발명은 하기 화학식 1로 표시되는 컬러필터용 착색 염료를 제공한다:The present invention provides a colored dye for a color filter represented by the following formula (1)
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상을 포함하고, 상기 R1 내지 R4은 각각 독립적으로 수소, 탄소수 1 내지 5의 알킬기, 하기 화학식 2의 치환기, 화학식 3의 치환기를 나타내며, 상기 R1 내지 R4 중 적어도 1개 이상은 하기 화학식 2의 치환기, 화학식 3의 치환기 또는 화학식 2 및 화학식 3의 치환기를 가지고, In Formula 1, R 1 to R include at least one or more of the 4, wherein R 1 to R 4 each independently represent a hydrogen, an alkyl group, a Substituent of Formula 2 having 1 to 5 carbon atoms, the substituent of formula (3) , At least one of R 1 to R 4 is a substituent of the following formula (2), a substituent of the formula (3) or a substituent of the formula (2) and the formula (3)
p는 각각 0~4의 정수이고, 단, p는 동시에 0이 아니며,p is an integer of 0 to 4, provided that p is not 0 at the same time,
M은 Cu 또는 Zn이다.M is Cu or Zn.
[화학식 2](2)
(상기 화학식 2에서, Ar은 탄화수소 방향족기 또는 헤테로고리 방향족기를 하나 이상 포함하고,(Wherein Ar represents a hydrocarbon aromatic group or a heterocyclic aromatic group,
R5는
t는 0 내지 3의 정수이다)and t is an integer of 0 to 3)
[화학식 3](3)
(상기 화학식 3에서, L은 -NH-, -NHCO-, -NHCS-, -S-, -SO2-, -CH-, -CH2- -O-, -CO-, 또는 -CF2- 이고,(In the formula 3, L is -NH-, -NHCO-, -NHCS-, -S-, -SO 2 -, -CH-, -CH 2 - -O-, -CO-, or -CF 2 - ego,
A는 -CH2-, -CF2-, -CO-, -CH2CH2O-, -SO2-, 또는
E는 -CF3, -CH3, -SO3H, -NH2, -OH, OCH3, -SH, -C(CH3)3, -CH(CH3)2 또는 할로겐 원자이고,E is -CF 3, -CH 3, -SO 3 H, -NH 2, -OH, OCH 3, -SH, -C (CH 3) 3, -CH (CH 3) 2 or a halogen atom,
n 및 m은 각각 독립적으로 0~20의 정수이다)n and m are each independently an integer of 0 to 20)
또한, 본 발명은 상술한 염료를 포함하는 컬러필터용 감광성 수지 조성물을 제공한다.
The present invention also provides a photosensitive resin composition for a color filter comprising the above-mentioned dye.
본 발명은 프탈로시아닌계 안료에 유기관능기인 사이아노아세틱산(cyanoacetic acid)으로 치환하여 수지액에 용해도가 우수한 신규한 칼라필터용 염료를 제공하는 효과가 있다. 특히, 본 발명은 유기관능기 중 열과 빛에 견뢰성을 갖는 치환체를 도입하는데, 이중에서 강력한 전자 당김 그룹인 사이아노아세틱산 그룹으로 프탈로시아닌의 말단에서의 1종을 치환하여 프탈로시아닌 염료의 빛 흡수영역 파장대를 단파장영역으로 이동시키고, 동시에 다양한 전자 밀개 그룹을 도입함으로써 흡수영역 파장대를 조절할 수 있고, 일정 영역의 빛을 효과적으로 투과시켜 고휘도, 고투과율 특성을 가지는 우수한 착색 염료를 제공할 수 있다.The present invention provides a novel dye for a color filter excellent in solubility in a resin solution by substituting a cyanoacetic acid which is an organic functional group with a phthalocyanine pigment. In particular, the present invention relates to a method for introducing a substituent having a fastness to heat and light among organic functional groups, wherein a substituent is substituted for a cyanoacetic acid group, which is a strong electron withdrawing group, at the terminal of the phthalocyanine, To a short wavelength region, and at the same time, by introducing various electron confinement groups, an absorption wavelength band can be controlled and an excellent coloring dye having high luminance and high transmittance characteristics can be provided by effectively transmitting light in a certain region.
더욱이, 본 발명은 상기 염료를 칼라필터용 착색 안료조성물에 첨가하여 안료의 단점을 보완하는 보조제로 사용될 수 있다. 또한 본 발명의 염료는 염료감응 태양전지의 염료로서 사용하거나 잉크의 안료 조성물로도 사용될 수 있다.
Moreover, the present invention can be used as an adjunct to supplement the disadvantages of pigments by adding the dye to a color pigment composition for a color filter. The dyes of the present invention can also be used as dyes for dye-sensitized solar cells or as pigment compositions for inks.
도 1은 실시예 1의 감광성 조성물의 파장 영역에 따른 투과율 결과를 나타낸 것이다.
도 2는 실시예 2 의 감광성 조성물의 파장 영역에 따른 투과율 결과를 나타낸 것이다.
도 3은 실시예 3 의 감광성 조성물의 파장 영역에 따른 투과율 결과를 나타낸 것이다.
도 4는 비교예 1의 감광성 조성물의 파장 영역에 따른 투과율 결과를 나타낸 것이다.1 shows the results of the transmittance according to the wavelength region of the photosensitive composition of Example 1. Fig.
Fig. 2 shows the results of the transmittance according to the wavelength range of the photosensitive composition of Example 2. Fig.
Fig. 3 shows the results of the transmittance according to the wavelength region of the photosensitive composition of Example 3. Fig.
4 shows the results of the transmittance according to the wavelength range of the photosensitive composition of Comparative Example 1. Fig.
이하에서 본 발명을 더욱 구체적으로 설명한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
또한 본 발명의 명세서에서 사용되는 "포함하는"의 의미는 특정 특성, 영역, 정수, 단계, 동작, 요소 및/또는 성분을 구체화하며, 다른 특성, 영역, 정수, 단계, 동작, 요소 및/또는 성분의 존재나 부가를 제외시키는 것은 아니다.
Also, " comprising "as used herein should be interpreted as specifying the presence of particular features, integers, steps, operations, elements and / or components, It does not exclude the presence or addition of an ingredient.
이하에서는 본 발명의 바람직한 일 구현예에 따른 저온경화형 감광성 수지 조성물에 관하여 보다 구체적으로 설명하기로 한다.Hereinafter, the low temperature curable photosensitive resin composition according to one preferred embodiment of the present invention will be described in more detail.
본 발명의 일 구현예에 따르면, 하기 화학식 1로 표시되는 컬러필터용 착색 염료가 제공된다.According to one embodiment of the present invention, there is provided a coloring dye for a color filter represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상을 포함하고, 상기 R1 내지 R4은 각각 독립적으로 수소, 탄소수 1 내지 5의 알킬기, 하기 화학식 2의 치환기, 화학식 3의 치환기를 나타내며, 상기 R1 내지 R4 중 적어도 1개 이상은 하기 화학식 2의 치환기, 화학식 3의 치환기 또는 화학식 2 및 화학식 3의 치환기를 가지고,In Formula 1, R 1 to R include at least one or more of the 4, wherein R 1 to R 4 each independently represent a hydrogen, an alkyl group, a Substituent of Formula 2 having 1 to 5 carbon atoms, the substituent of formula (3) , At least one of R 1 to R 4 is a substituent of the following formula (2), a substituent of the formula (3) or a substituent of the formula (2) and the formula (3)
p는 각각 0~4의 정수이고, 단, p는 동시에 0이 아니며,p is an integer of 0 to 4, provided that p is not 0 at the same time,
M은 Cu 또는 Zn이다.M is Cu or Zn.
[화학식 2](2)
(상기 화학식 2에서, Ar은 탄화수소 방향족기 또는 헤테로고리 방향족기를 하나 이상 포함하고,(Wherein Ar represents a hydrocarbon aromatic group or a heterocyclic aromatic group,
R5는
t는 0 내지 3의 정수이다) and t is an integer of 0 to 3)
[화학식 3](3)
(상기 화학식 3에서, L은 -NH-, -NHCO-, -NHCS-, -S-, -SO2-, -CH-, -CH2- -O-, -CO-, 또는 -CF2- 이고,(In the formula 3, L is -NH-, -NHCO-, -NHCS-, -S-, -SO 2 -, -CH-, -CH 2 - -O-, -CO-, or -CF 2 - ego,
A는 -CH2-, -CF2-, -CO-, -CH2CH2O-, -SO2-, 또는
E는 -CF3, -CH3, -SO3H, -NH2, -OH, OCH3, -SH, -C(CH3)3, -CH(CH3)2 또는 할로겐 원자이고,E is -CF 3, -CH 3, -SO 3 H, -NH 2, -OH, OCH 3, -SH, -C (CH 3) 3, -CH (CH 3) 2 or a halogen atom,
n 및 m은 각각 독립적으로 0~20의 정수이다)n and m are each independently an integer of 0 to 20)
본 발명에서는, 특히 청색 및 녹색 화소를 제공하는 안료로서 프탈로시아닌에 사이아노아세틱산 그룹(cyanoacetic acid group) 등을 도입함으로써 수지액에 대한 용해도가 우수할 뿐만 아니라, 강력한 전자 당김 그룹으로 인해 흡수영역을 단파장영역으로 이동시키고 동시에 전자 밀개 그룹을 도입함으로써 이러한 염료의 의한 흡수영역 파장대를 조절함으로써 일정 영역의 빛을 효과적으로 투과시켜 고휘도, 고투과율 특성을 가지며, 열과 빛에 의한 견뢰성이 매우 우수한 착색 염료를 제공하는 것을 특징으로 한다. 이러한 본 발명에서 제공하는 화학식 1의 염료는 청색계열 또는 녹색계열 착색 염료를 포함할 수 있다.In the present invention, by introducing a cyanoacetic acid group or the like into phthalocyanine as a pigment for providing blue and green pixels, not only the solubility in the resin solution is excellent but also the absorption region due to the strong electron withdrawing group By moving to the short wavelength region and introducing the electron confinement group at the same time, it is possible to control the absorption wavelength band of such a dye by effectively transmitting the light of a certain region and thereby to obtain the dye having high brightness, high transmittance characteristic and excellent in fastness due to heat and light . The dye of formula (1) provided by the present invention may include a blue-based or a green-based coloring dye.
또한, 본 발명의 착색 염료는 감광성 수지 조성물에서 염료로 사용될 수 있으며, 컬러필터 제조시 우수한 효과를 나타낼 수 있다.In addition, the coloring dye of the present invention can be used as a dye in a photosensitive resin composition and exhibits excellent effects in the production of a color filter.
따라서, 본 발명에서 합성되는 염료는 청색을 띄거나, 경우에 따라서는 녹색을 띄는 염료로 합성될 수 있다. 또한, 염료가 청색을 띄면 청색 안료를 사용하여 청색 감광성 수지 조성물을 제조할 수 있으며, 염료가 녹색을 띄는 경우에는, 녹색 안료를 사용하여 녹색 감광성 수지 조성물을 제조할 수 있다.
Accordingly, the dyes synthesized in the present invention may be bluish or, in some cases, green dyes. If the dye has a blue color, a blue photosensitive resin composition can be prepared. If the dye is green, a green photosensitive resin composition can be prepared using a green pigment.
그러면, 이하에서 본 발명의 화학식 1의 착색 염료에 대하여 보다 구체적으로 설명한다.Hereinafter, the coloring dye of formula (1) of the present invention will be described in more detail.
상술한 바대로, 본 발명의 착색 염료는 화학식 1로 표시되는 화합물로서, 구조 중에, 테트라아자포르피린계 구조를 가진다. 또한 상기 화학식 1은 R1 내지 R4 중 적어도 1종 이상이 화학식 2의 치환기, 화학식 3의 치환기 또는 화학식 2 및 화학식 3의 치환기를 모두 포함할 수 있다.As described above, the coloring dye of the present invention is a compound represented by the general formula (1) and has a tetraazaporphyrin structure in its structure. In Formula 1, at least one of R 1 to R 4 may include a substituent of Formula 2, a substituent of Formula 3, or a substituent of Formula 2 and Formula 3.
여기서, 상기 화학식 3은 강한 전자당김 그룹으로 흡수영역대의 단파장으로의 이동효과를 극대화시키고 아세틱산기의 산기능으로 인한 용해도 향상을 꾀할 수 있다. 다만, 화학식 3은 짧은 치환기로 인해 특정 용매에 용해도가 떨어질 수 있어 화학식 2와 같은 비교적 긴 치환기로 다양한 용매에 부족한 용해도를 향상시켜 용해도 향상을 꾀할 수 있다. 따라서, 본 발명의 경우 화학식 1의 R1 내지 R4 중 화학식 3만 포함하는 것도 가능하나, 화학식 3의 치환기에 의한 용해도 문제를 보완하기 위해, 화학식 2를 함께 포함하는 것이 더 바람직하다. Here, the formula 3 is a strong electron withdrawing group, maximizing the effect of moving the absorption region to a short wavelength, and improving the solubility due to the acid function of the acetic acid group. However, since the solubility of the compound of formula (3) is short due to the short substituent, solubility of the solvent may be improved by improving the solubility of the compound of formula (2). Accordingly, in the present invention, it is possible to include only the formula 3 of R 1 to R 4 in the formula (1), but it is more preferable to include the formula (2) in order to solve the solubility problem of the formula (3).
예를 들어, 본 발명의 바람직한 일 구현예에 따라, 상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상은 화학식 2의 구조를 포함할 수 있다. 다만, 본원의 R1 내지 R4가 모두 화학식 2의 구조를 포함하지 않으며, 이러한 경우 나머지 치환기는 수소 또는 탄소수 1 내지 5의 알킬기를 포함할 수 있다.For example, according to a preferred embodiment of the present invention, at least one of R 1 to R 4 in Formula 1 may include the structure of Formula 2. However, all of R 1 to R 4 in the present specification do not include the structure of Formula 2, and in this case, the remaining substituents may include hydrogen or an alkyl group having 1 to 5 carbon atoms.
또한 본 발명의 바람직한 다른 구현예에 따르면, 상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상은 화학식 3의 구조를 포함할 수 있다. 이러한 경우 나머지 치환기는 수소 또는 탄소수 1 내지 5의 알킬기를 포함할 수 있다.According to another preferred embodiment of the present invention, at least one of R 1 to R 4 in Formula 1 may include the structure of Formula (3). In this case, the remaining substituents may include hydrogen or an alkyl group having 1 to 5 carbon atoms.
또한, 본 발명의 바람직한 다른 구현예에 따르면, 상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상이 화학식 2의 구조일 때, R1 내지 R4 중의 나머지 치환기 중에서 적어도 하나가 화학식 3의 구조를 가질 수 있다. 또한, 상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상이 화학식 3의 구조일 때, R1 내지 R4 중의 나머지 치환기 중에서 적어도 하나가 화학식 2의 구조를 가질 수 있다.Further, according to another embodiment preferred according to the present invention, the above formula 1, R 1 to R at least one or more of the four are at least one of, R 1 to R 4 the remaining substituents of when the structure of formula (II) of formula (3) Structure. Further, in the above formula 1, R 1 to R at least one of the four is when the structure of Formula 3, R 1 to R 4 at least one of the remaining substituents of the may have a structure of formula (2).
상기 화학식 1의 구조에서, 화학식 2 또는 화학식 3의 특정 유기 관능 치환기 구조를 적어도 1종 이상 포함하지 않을 경우, 용해도 저하 뿐 아니라 파장 이동이 어려워 고휘도를 구현할 수 없다.In the structure of the above formula (1), when at least one specific organic functional group substituent of the formula (2) or (3) is not contained, not only the solubility is lowered but also the wavelength shift is difficult.
또한 상기 화학식 2에서 Ar은 하기 치환기 중에서 선택된 어느 하나일 수 있다.In Formula 2, Ar may be any one selected from the following substituents.
또한, 상기 화학식 3에서, n 및 m은 각각 독립적으로 0 내지 8의 정수인 것이 바람직할 수 있다.In the above formula (3), n and m are each independently preferably an integer of 0 to 8.
그리고, 상기 화학식 1에서, p는 1 내지 4의 정수인 것이 바람직하고, p가 동시에 1인 경우가 더 바람직하다. 또한, 상기 화학식 1에서, p는 1일 때, 나머지 치환기는 수소 또는 탄소수 1 내지 5의 알킬기일 수 있다.In Formula 1, p is preferably an integer of 1 to 4, and more preferably 1 at p. In the above formula (1), when p is 1, the remaining substituents may be hydrogen or an alkyl group having 1 to 5 carbon atoms.
상기 화학식 1은 하기 화학식 중에서 선택된 어느 하나를 포함하는 것이 바람직하다.The formula 1 preferably includes any one selected from the following formulas.
한편, 본 발명의 화학식 1의 착색 안료는 이 분야에 잘 알려진 유기합성 법에 따라, 프탈로시아닌 블루의 구조의 말단에서 치환기를 변형시킴에 따라 제조될 수 있다. The colored pigment of Formula 1 of the present invention may be prepared by modifying a substituent at the terminal of the phthalocyanine blue structure according to an organic synthesis method well known in the art.
한편, 본 발명의 화학식 1의 안료는 일반적인 고리화 반응에 따라, 프탈로시아닌 블루의 구조를 합성할 수 있으며, 이후 프탈로시아닌 블루의 말단에서 치환기를 변형시킴에 따라 제조될 수 있다. In the meantime, the pigment of the formula (1) of the present invention can be synthesized by a general cyclization reaction to synthesize the structure of phthalocyanine blue, and then the substituent is modified at the terminal of the phthalocyanine blue.
상기 치환기 중 적어도 하나는 상술한 화학식 2 또는 3의 치환기를 적어도 하나 포함하도록 하는 것이 바람직하다.It is preferable that at least one of the substituents includes at least one substituent of the above-described formula (2) or (3).
예를 들어, 본 발명은 화학식 a의 프탈로니트릴을 출발물질로 하여, 화학식 2 또는 화학식 3의 치환기 또는 이러한 구조를 유래할 수 있는 전구체 화합물을 각각 제조한 후, 이들을 금속 함유 아세테이트 화합물 및 할로겐 치환된 방향족 화합물과 반응시켜 화학식 2 또는 3의 구조를 1종 이상 갖는 프탈로시아닌 중간체를 제조한 후, 일련의 과정을 거쳐, 화학식 1의 테트라아자포르피린(tetraazaporphyrin) 구조를 포함하는 프탈로시아닌 염료를 제조할 수 있다.For example, the present invention relates to a process for producing a compound represented by the general formula (2) or (3) or a precursor compound derived from such a structure by using the phthalonitrile of the general formula (a) as a starting material, (2) or (3) to produce a phthalocyanine dye having a tetraazaporphyrin structure of formula (1) through a series of steps, .
[화학식 a](A)
(상기 식에서, A는 아미노기 또는 할로겐이다)(Wherein A is an amino group or a halogen)
상기 금속 함유 아세테이트 화합물은 코퍼아세테이트 또는 징크아세테이트가 바람직하다.The metal-containing acetate compound is preferably copper acetate or zinc acetate.
상기 할로겐 치환된 방향족 화합물은 탄소수 6 내지 20의 아릴기를 갖는 탄화수소 방향족기 또는 헤테로고리 방향족기를 하나 이상 포함할 수 있다.The halogen-substituted aromatic compound may include at least one hydrocarbon aromatic group or heterocyclic aromatic group having an aryl group having 6 to 20 carbon atoms.
본 발명의 바람직한 일 구현예에 따른 화학식 1의 제조방법은 다음 반응식 1 내지 5에 따라 진행될 수 있다.The preparation of the compound of formula (1) according to one preferred embodiment of the present invention can be carried out according to the following reaction formulas (1) to (5).
[반응식 1][Reaction Scheme 1]
[반응식 2][Reaction Scheme 2]
[반응식 3][Reaction Scheme 3]
[반응식 4][Reaction Scheme 4]
[반응식 5][Reaction Scheme 5]
반응식 1 및 2에서 보면, 아미노 치환기를 갖는 프탈로니트릴 (화합물 a)에 화학식 2 및 3의 치환기 구조를 포함한 화합물을 각각 반응시켜 화합물 b 및 c를 제조한다.In Schemes 1 and 2, compounds b and c are prepared by reacting phthalonitrile (compound a) having an amino substituent group with a compound having a substituent structure of the formulas 2 and 3, respectively.
그리고, 화합물 b 및 c를 코퍼 아세테이트 및 1-클로로나프탈렌과 함께 반응시켜 프탈로시아닌 구조를 가지며, 방향족 고리 말단에 화학식 2 및 3의 치환기 구조를 포함한 중간체 화합물 d를 제조한다. (반응식 3)Then, the compounds b and c are reacted with copper acetate and 1-chloronaphthalene to prepare an intermediate compound d having a phthalocyanine structure and containing substituent structures of the formulas (2) and (3) at the aromatic ring end. (Scheme 3)
또한, 촉매를 이용하여 중간체 화합물 d의 프탈로시아닌의 말단 중에 포함된 사이아노기를 알데히드기로 치환하여 중간체 화합물 e를 제조하고(반응식 4), 다시 이를 사이아노아세틱산으로부터 유래된 치환기를 갖도록 하는 방법(반응식 5)에 의해, 화학식 1의 화합물이 제조될 수 있다.
Further, a method in which a cyano group contained in the terminal of the phthalocyanine of the intermediate compound d is replaced with an aldehyde group using a catalyst to prepare an intermediate compound e (Scheme 4), and then the intermediate compound e is substituted with a substituent derived from cyanoacetic acid 5), the compound of formula (1) can be prepared.
한편, 본 발명의 다른 구현예에 따르면, 상기 착색 염료를 포함하는 컬러필터용 감광성 수지 조성물이 제공된다.According to another embodiment of the present invention, there is provided a photosensitive resin composition for a color filter comprising the colored dye.
상기 화학식 1의 착색 염료는 감광성 수지 조성물에 첨가되는 바인더 수지 100 중량부를 기준으로 0.5 내지 80 중량부, 보다 바람직하게 0.5 내지 60 중량부, 가장 바람직하게는 0.5 내지 50 중량부가 포함하는 것이 바람직하다. 여기서, 상기 착색 염료의 사용량이 0.5 중량부 미만이면 흡광 영역을 블루 영역으로 이동시킬 수 없어 고휘도를 구현할 수 없고 또한 농도가 낮아 충분한 투과율을 구현할 수 없는 문제가 있다. 또한 그 함량이 80 중량부를 초과하면 고온에서의 후공정시 탈색이나 색변화가 발생하며 또한 재료와의 상용성 부족에 의해 착색층 형성시 이물이 발생할 수 있다.The coloring dye of Formula 1 is preferably contained in an amount of 0.5 to 80 parts by weight, more preferably 0.5 to 60 parts by weight, and most preferably 0.5 to 50 parts by weight based on 100 parts by weight of the binder resin added to the photosensitive resin composition. If the amount of the coloring dye used is less than 0.5 parts by weight, the light absorbing region can not be moved to the blue region, so that a high brightness can not be realized. Also, since the concentration is low, a sufficient transmittance can not be realized. If the content exceeds 80 parts by weight, discoloration or color change occurs at a post-process at a high temperature, and foreign matter may be generated upon formation of a colored layer due to lack of compatibility with a material.
그 밖에, 본 발명의 감광성 수지 조성물은 상술한 화학식 1의 안료 이외에, 이 분야에 잘 알려진 유기 또는 무기 안료를 더 포함할 수 있다.In addition, the photosensitive resin composition of the present invention may further contain an organic or inorganic pigment well known in the art, in addition to the pigment of the above formula (1).
이러한 유기안료의 구체적인 예로는 적색 안료로서 C.I. #177, #202, #209, #242, #254, #255; 옐로우 안료로서 C.I. #150, #138, #128 오렌지 안료로서 C.I. #43; 그린 안료로서 C.I. #7, #36, #58; 블루 안료로서 C.I. #15, #15:3, #15:6; 바이올렛 안료로서 C.I. #23; 블랙 안료로서 C.I. #1, #7;등이 있다. 또한 무기안료로는 산화티탄, 티탄블랙, 카본블랙 등을 들 수 있다. 이들 안료는 색 조합을 하기 위해 1종 또는 2종 이상을 혼합하여 사용할 수 있다.Specific examples of such organic pigments include C.I. # 177, # 202, # 209, # 242, # 254, # 255; As the yellow pigment, C.I. # 150, # 138, # 128 C.I. # 43; C.I. # 7, # 36, # 58; C.I. # 15, # 15: 3, # 15: 6; As a violet pigment, C.I. # 23; C.I. # 1, # 7; and so on. Examples of the inorganic pigments include titanium oxide, titanium black, and carbon black. These pigments may be used alone or in combination of two or more thereof in order to make color combinations.
또한, 본 발명에서는 보조 염료를 더 포함할 수 있다. 이러한 보조 염료는 아조계, 안트라퀴논계, 인디고계, 크산틴계, 트리페닐메탄계, 프탈로시안계, 이민계, 및 퀴나프탈논계 화합물로 이루어진 군에서 선택되는 1종 이상일 수 있다.Further, the present invention may further include an auxiliary dye. These auxiliary dyes may be at least one selected from the group consisting of an azo dye, an anthraquinone dye, an indigo dye, a xanthine dye, a triphenylmethane dye, a phthalocyanine dye, an imine dye, and a quinapthanone dye compound.
또한 본 발명에서 염료는 감광성 수지 조성물에 첨가될 때, 그 자체로 직접적으로 투입되거나, 또는 분산제 또는 용매 등을 포함하는 분산액의 형태로 투입될 수 있다.Also, in the present invention, when the dye is added to the photosensitive resin composition, it may be directly added to itself, or may be added in the form of a dispersion containing a dispersant, a solvent, or the like.
또한, 상기 염료 분산액 조성물에 포함될 수 있는 용매로는 에틸렌글리콜아세테이트, 에틸셀로솔브, 프로필렌글리콜 메틸에테르아세테이트, 에틸락테이트, 폴리에틸렌글리콜, 사이클로헥사논, 프로필렌글리콜메틸에테르 등이 사용될 수 있다. 이때, 상기 용매의 함량은 염료 분산액의 고형분 함량이 5 내지 30 중량%가 되도록 조절되는 것이 바람직하다.As the solvent that can be included in the dye dispersion composition, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used. At this time, it is preferable that the content of the solvent is adjusted so that the solid content of the dye dispersion becomes 5 to 30% by weight.
한편, 본 발명의 감광성 수지 조성물은 알칼리 가용성 바인더 수지, 중합개시제, 및 용매를 더 포함할 수 있다. 또한 본 발명은 필요에 따라, 이 분야에 잘 알려진 광가교제, 열경화제, 첨가제 등을 더 포함할 수 있다.On the other hand, the photosensitive resin composition of the present invention may further comprise an alkali-soluble binder resin, a polymerization initiator, and a solvent. In addition, the present invention may further include a photo-crosslinking agent, a thermosetting agent, an additive, and the like, which are well known in the art, if necessary.
상기 알칼리 가용성 바인더 수지를 비롯하여, 중합개시제, 및 용매 등은 이 분야에 잘 알려진 물질이 사용될 수 있고, 그 종류가 특별히 한정되지는 않는다.As the alkali-soluble binder resin, a polymerization initiator, a solvent and the like, materials well known in the art may be used, and the kind thereof is not particularly limited.
상기 바인더 수지는 후술할 안료 및 염료 등의 분산 안정성을 확보함과 동시에, 현상 과정에서 원하는 해상도의 픽셀이 형성되도록 하는 성분이다.The binder resin is a component that secures dispersion stability of pigments and dyes to be described later, and allows pixels having a desired resolution to be formed in a developing process.
예를 들어, 상기 알카리 가용성 바인더 수지는 1 종 이상의 에틸렌계 산성기를 갖는 단량체와 1종 이상의 (메트)아크릴레이트계 단량체가 중합된 공중합체일 수 있다. 상기 바인더 수지는 에틸렌계 산성기를 갖는 단량체 10 내지 40 중량%와 (메트)아크릴레이트계 단량체 60 내지 90 중량%, 바람직하게는 에틸렌계 산성기를 갖는 단량체 20 내지 40 중량%와 (메트)아크릴레이트계 단량체 60 내지 80 중량%, 보다 바람직하게는 에틸렌계 산성기를 갖는 단량체 25 내지 35 중량%와 (메트)아크릴레이트계 단량체 65 내지 75 중량%가 중합된 공중합체일 수 있다.For example, the alkali-soluble binder resin may be a copolymer of a monomer having at least one ethylenic acid group and at least one (meth) acrylate monomer. The binder resin preferably comprises 10 to 40% by weight of a monomer having an ethylenic acid group and 60 to 90% by weight of a (meth) acrylate monomer, preferably 20 to 40% by weight of a monomer having an ethylenic acid group and a (meth) And 60 to 80% by weight of the monomer, more preferably 25 to 35% by weight of the monomer having an ethylenic acid group and 65 to 75% by weight of the (meth) acrylate monomer.
이와 같은 상기 바인더 수지는 조성물의 전체 중량을 기준으로 5 내지 70 중량%로 포함될 수 있다. 즉, 상기 바인더 수지의 첨가에 따른 최소한도의 분산 안정성, 막강도, 내열성 등을 발현시키기 위하여, 상기 바인더 수지는 5 중량% 이상으로 포함되는 것이 바람직하다. 또한, 상기 바인더 수지를 과량으로 사용할 경우 조성물의 점도가 필요 이상으로 상승하여 조성물의 광학적 물성, 물리적 물성 및 공정 효율이 저하될 수 있는데, 이러한 현상을 방지하기 위하여, 상기 바인더 수지는 70 중량% 이하로 포함되는 것이 바람직하다.Such a binder resin may be contained in an amount of 5 to 70% by weight based on the total weight of the composition. That is, it is preferable that the binder resin is contained in an amount of 5 wt% or more in order to exhibit the minimum dispersion stability, film strength, heat resistance, etc. upon addition of the binder resin. When the binder resin is used in an excessive amount, the viscosity of the composition may be increased excessively, thereby deteriorating the optical properties, physical properties, and process efficiency of the composition. To prevent such a phenomenon, .
상기 중합 개시제는 아세토페논계 화합물, 벤조페논계 화합물, 티오크산톤계 화합물, 벤조인계 화합물, 트리아진계 화합물, 옥심계 화합물 및 이들의 혼합물로 이루어진 군에서 선택되는 것일 수 있다.The polymerization initiator may be selected from the group consisting of acetophenone compounds, benzophenone compounds, thioxanone compounds, benzoin compounds, triazine compounds, oxime compounds, and mixtures thereof.
상기 중합 개시제의 함량은 중합 반응을 충분히 일으킬 수 있으면서도 중합 반응 후 미반응 개시제로 인한 투과율 저하 현상 등을 고려하여 결정할 수 있다. 본 발명에 따르면, 상기 중합 개시제의 함량은 상기 바인더 수지 100 중량부를 기준으로 5 내지 50 중량부, 바람직하게는 10 내지 50 중량부, 보다 바람직하게는 10 내지 40 중량부일 수 있다.The content of the polymerization initiator can sufficiently induce the polymerization reaction and can be determined in consideration of the phenomenon of the decrease in the transmittance due to the unreacted initiator after the polymerization. According to the present invention, the content of the polymerization initiator may be 5 to 50 parts by weight, preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the binder resin.
상기 용매는 상기 조성물에 포함되는 성분들의 용해도 및 점도 등을 조절하기 위하여 첨가되는 성분으로서, 전술한 성분들과의 반응성은 나타내지 않으면서도 상용성을 갖는 것이라면, 당업계에서 통상적인 것을 제한 없이 사용할 수 있다.The solvent is added to control the solubility and viscosity of the components contained in the composition. Any solvent that is compatible with the above-described components may be used without limitation, have.
상기 용매는 전체 감광성 수지 조성물의 총 중량 대비 잔량으로 사용될 수 있으며, 그 범위가 특별히 한정되지는 않는다.The solvent may be used as the balance relative to the total weight of the entire photosensitive resin composition, and the range is not particularly limited.
또한, 본 발명의 일 실시예에 따르면, 상기 용매는 메탄올, 에탄올, 이소프로필알코올, 부틸알코올, 벤질알코오르 디아세톤알코올 등의 알코올류; 디클로로에틸에테르, n-부틸에테르, 디이소아밀에테르, 메틸페닐에테르, 테트라히드로퓨란 등의 에테르류; 에틸렌 글리콜 모노메틸에테르, 에틸렌 글리콜 모노에틸에테르 등의 글리콜 에테르류; 메틸 셀로솔브 아세테이트, 에틸 셀로솔브 아세테이트, 디에틸 셀로솔브 아세테이트 등의 셀로솔브 아세테이트류; 메틸에틸 카르비톨, 디에틸 카르비톨, 디에틸렌 글리콜 모노메틸에테르, 디에틸렌 글리콜 모노에틸에테르, 디에틸렌 글리콜 디메틸에테르, 디에틸렌 글리콜 메틸에틸에테르, 디에틸렌 글리콜 디에틸에테르 등의 카르비톨류; 프로필렌글리콜메틸에틸아세테이트, 프로필렌글리콜 메틸에테르아세테이트, 프로필렌글리콜 프로필에테르 아세테이트 등의 프로필렌글리콜 알킬에테르 아세테이트류; 톨루엔, 자일렌 등의 방향족 탄화수소류; 메틸에틸케톤, 시클로헥사논, 4-히드록시-4-메틸-2-펜타논, 메틸-n-프로필케톤, 메틸-n-부틸케논, 메틸-n-아밀케톤, 2-헵타논 등의 케톤류; 초산 에틸, 초산-n-부틸, 초산 이소부틸 등의 포화 지방족 모노카르복실산 알킬 에스테르류; 젖산 메틸, 젖산 에틸 등의 젖산 에스테르류; 옥시 초산 메틸, 옥시 초산 에틸, 옥시 초산 부틸 등의 옥시 초산 알킬 에스테르류; 메톡시 초산 메틸, 메톡시 초산 에틸, 메톡시 초산 부틸, 에톡시 초산 메틸, 에톡시 초산 에틸 등의 알콕시 초산 알킬 에스테르류; 3-옥시 프로피온산 메틸, 3-옥시 프로피온산 에틸 등의 3-옥시 프로피온산 알킬에스테르류; 3-메톡시 프로피온산 메틸, 3-메톡시 프로피온산 에틸, 3-에톡시 프로피온산 에틸, 3-에톡시 프로피온산 메틸 등의 3-알콕시 프로피온산 알킬 에스테르류; 2-옥시 프로피온산 메틸, 2-옥시 프로피온산 에틸, 2-옥시 프로피온산 프로필 등의 2-옥시 프로피온산 알킬 에스테르류; 2-메톡시 프로피온산 메틸, 2-메톡시 프로피온산 에틸, 2-에톡시 프로피온산 에틸, 2-에톡시 프로피온산 메틸 등의 2-알콕시 프로피온산 알킬 에스테르류; 2-옥시-2-메틸 프로피온산 메틸, 2-옥시-2-메틸 프로피온산 에틸 등의 2-옥시-2-메틸 프로피온산 에스테르류; 2-메톡시-2-메틸 프로피온산 메틸, 2-에톡시-2-메틸 프로피온산 에틸 등의 2-알콕시-2-메틸 프로피온산 알킬류의 모노옥시 모노카르복실산 알킬 에스테르류; 2-히드록시 프로피온산 에틸, 2-히드록시-2-메틸 프로피온산 에틸, 히드록시 초산 에틸, 2-히드록시-3-메틸 부탄산 메틸 등의 에스테르류; 피루빈산 에틸 등의 케톤산 에스테르류; 또는 이들의 혼합물일 수 있다.According to an embodiment of the present invention, the solvent may be at least one selected from the group consisting of alcohols such as methanol, ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol diacetone alcohol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ethyl acetate, propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketonic acid esters such as ethyl pyruvate; Or a mixture thereof.
이 밖에도, 상기 용매는 N-메틸포름아미드, N,N-디메틸포름아미드, N-메틸포름아닐라드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, 디메틸술폭시드, 벤질에틸에테르, 디헥실에테르, 아세트닐아세톤, 이소포론, 카프론산, 카프릴산, 1-옥탄올, 1-노난올, 벤질알코올, 초산 벤질, 안식향산 에틸, 옥살산 디에틸, 말레인산 디에틸, 감마-부티로락톤, 탄산 에틸렌, 탄산 프로필렌, 페닐 셀로솔브 아세테이트, 에틸렌글리콜 아세테이트, 에틸셀로솔브, 에틸락테이트, 폴리에틸렌글리콜 등일 수 있다.In addition, the solvent may be selected from the group consisting of N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, , Gamma-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, ethylene glycol acetate, ethyl cellosolve, ethyl lactate, polyethylene glycol and the like.
또한 본 발명의 감광성 수지 조성물은 이 분야에 잘 알려진 기타 첨가제를 더 포함할 수 있다. 상기 첨가제는 에폭시 화합물, 말론산, 3-아미노-1,2-프로판디올, 실란계 커플링제, 실리콘계 또는 플루오르계 레벨링제, 계면활성제 등일 수 있다. 그리고, 이러한 첨가제들의 함량은 조성물의 물성에 악영향을 미치지 않는 범위 내에서 조절하고자 하는 물성에 따라 결정할 수 있으므로, 특별히 제한하지 않는다.
The photosensitive resin composition of the present invention may further include other additives well known in the art. The additive may be an epoxy compound, malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a silicon or fluorine leveling agent, a surfactant, and the like. The content of such additives is not particularly limited as it can be determined according to the properties to be controlled within a range not adversely affecting the physical properties of the composition.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예들을 제시한다. 그러나 하기의 실시예들은 본 발명을 예시하기 위한 것일 뿐, 본 발명을 이들만으로 한정하는 것은 아니다.
Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.
[ [ 합성예1Synthesis Example 1 ]]
하기 반응식 1 내지 5에 따라, 사이아노아세틱산으로부터 유래된 구조가 1개 치환된 구리 프탈로시아닌 염료(화학식 1)를 합성하였다.
A copper phthalocyanine dye (Formula 1) having one structure derived from cyanoacetic acid was substituted according to the following Reaction Schemes 1 to 5.
1. 벤젠-1,2,3-트리카보나이트릴의 합성(화합물 b)1. Synthesis of benzene-1,2,3-tricarbonitrile (Compound b)
[반응식 1][Reaction Scheme 1]
물 9mL에 1mL의 아세틱산과 4-아미노프탈로나이트릴(4-aminophthalonitrile) (a) (3.0 g, 20.95 mmol)을 혼합한 후, 여기에 황산(12 g, 122.35 mmol)을 천천히 떨어뜨렸다. 그 혼합물을 천천히 교반시킨 후 완전히 용해되면 0℃로 온도를 내려주었다. 그리고, 소디움나이트릴(NaNO2) (1.8 g, 26.09 mmol)를 3 mL 물에 용해시킨 후, 상기 혼합물에 30분에 걸쳐서 천천히 떨어뜨린 후 30분간 교반시켜주었다.To 9 mL of water were mixed 1 mL of acetic acid and 4-aminophthalonitrile (a) (3.0 g, 20.95 mmol), and sulfuric acid (12 g, 122.35 mmol) was slowly dropped thereon. The mixture was stirred slowly and then cooled to 0 < 0 > C when completely dissolved. Sodium nitrite (NaNO 2 ) (1.8 g, 26.09 mmol) was dissolved in 3 mL of water, slowly dropped into the mixture over 30 minutes, and stirred for 30 minutes.
다른 반응용기를 준비한 후 카퍼설페이트펜타하이드레이트(CuSO4?5H2O) (6.3 g, 25.23 mmol)를 물 16 mL에 용해시킨 후 반응기의 온도를 0℃로 내리고, 포타슘사이나이드(KCN)(6.5 g, 99.82 mmol)을 물 16 mL에 용해시켜 넣어주었다. 소디움바이카보네이트(NaHCO3) 14g과 톨루엔 14mL를 같이 넣어주었다. 이렇게 만들어진 혼합물을 앞서 만든 아조니움솔트화된 반응기에 30분에 걸쳐 천천히 떨어뜨린 후 50℃로 온도를 올리고 3시간동안 교반시켰다. 반응 종료 후 톨루엔 100 mL와 물을 첨가하여 추출하고, 무수 Na2SO4로 수분 건조후 여과 및 농축하였다. 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) (Hexane : EtOAc = 4:1) 방법으로 분리하여 화합물 (b)를 0.32 g (20% yield) 얻었다. 합성된 화합물은 1H-NMR을 통해 확인하였다. After preparing the different reaction vessel Copper sulfate pentahydrate (CuSO 4? 5H 2 O) (6.3 g, 25.23 mmol) was dissolved in water 16 mL lower the temperature of the reactor to 0 ℃, potassium among cyanide (KCN) (6.5 g, 99.82 mmol) was dissolved in 16 mL of water. 14 g of sodium bicarbonate (NaHCO 3 ) and 14 mL of toluene were added. The thus-prepared mixture was slowly dropped into the above-prepared azonium-salt-added reactor over 30 minutes, then heated to 50 DEG C and stirred for 3 hours. After the completion of the reaction, 100 mL of toluene and water were added to extract, followed by drying with anhydrous Na 2 SO 4 , followed by filtration and concentration. The mixture was separated by flash column chromatography (Hexane: EtOAc = 4: 1) under SiO 2 to obtain 0.32 g (20% yield) of compound (b). The synthesized compound was confirmed by 1 H-NMR.
1H-NMR (CDCl3, Varian 400 MHz): δ 8.78 (1H, d, J = 1.2 Hz), 8.45-8.43 (1H, dd, J = 8.4 Hz), 8.38-8.36 (1H, d, J = 8 Hz)
1 H-NMR (CDCl 3,
2. N-(3,4-다이사이아노페닐)옥탄-1-설폰아마이드의 합성 (화합물 c)2. Synthesis of N- (3,4-dicyanophenyl) octane-1-sulfonamide (Compound c)
[반응식 2][Reaction Scheme 2]
4-아미노프탈로나이트릴(4-aminophthalonitrile) (a)(10.0 g, 69.85 mmol) 및 피리딘(pyridine) 130 mL를 같이 혼합하고, 상온에서 완전히 용해시켰다. 옥탄설포닐클로라이드(Octanesulfonyl chloride) (27.49 g, 129.22 mmol)를 천천히 떨어뜨린 후 1시간 동안 교반시켰다.4-aminophthalonitrile (a) (10.0 g, 69.85 mmol) and pyridine (130 mL) were mixed together and completely dissolved at room temperature. Octanesulfonyl chloride (27.49 g, 129.22 mmol) was slowly added dropwise and stirred for 1 hour.
얼음 200 mL를 비커에 넣은 후 혼합물을 부어 반응을 종결시켰다. EtOAc 200 mL과 물을 첨가하여 추출한 후, 무수 Na2SO4로 수분 건조후 여과 및 농축하였다. 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) (Hexane : EtOAc = 3:1) 방법으로 분리하여 화합물 (c)를 10.3 g (46% yield) 얻었다. 합성된 화합물은 1H-NMR을 통해 확인하였다.200 mL of ice was added to the beaker, and the mixture was poured to terminate the reaction. After extraction with 200 mL of EtOAc and water, the mixture was dried with anhydrous Na 2 SO 4 , filtered, and concentrated. The mixture was separated by flash column chromatography (Hexane: EtOAc = 3: 1) under SiO 2 to obtain 10.3 g (46% yield) of compound (c). The synthesized compound was confirmed by 1 H-NMR.
1H-NMR (CDCl3, Varian 400 MHz): δ 7.77-7.75 (1H, d, J = 8.4 Hz), 7.59-7.59 (1H, d, J = 2.4 Hz), 7.47-7.54 (1H, d, JJ = 8.4 Hz), 6.90 (1H, s), 3.23-3.19 (2H, t, J = 8 Hz), 1.87-1.81 (2H, q, J = 8 Hz), 1.44-1.25 (12H, m), 0.89-0.86 (3H, t, J = 7.2 Hz
1 H-NMR (CDCl 3,
3. 화합물 d의 합성3. Synthesis of compound d
[반응식 3][Reaction Scheme 3]
화합물 (b)(0.36 g, 2.35 mmol) 및 화합물 (c) (3 g, 9.39 mmol)를 1-클로로나프탈렌(1-Chloronaphthalene) 30mL와 혼합하고, 250℃까지 온도를 올려 30분간 유지한 후 온도를 상온까지 떨어뜨렸다. 이후, 상기 혼합물에 카퍼아세테이트(Cu(CH3COO)2)(0.78 g, 4.32 mmol)를 넣어준 후 다시 250℃까지 온도를 올리고 12시간동안 교반시켜 주었다. 반응 종료 후 여과하며 EtOAc 용매로 여러 차례 씻어주었다. 여과액을 농축시킨 후 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) 방법으로 분리하여 화합물 (d)을 0.3 g (11% yield) 얻었다. 합성된 화합물은 1H-NMR을 통해 확인하였다.Compound (b) (0.36 g, 2.35 mmol) and compound (c) (3 g, 9.39 mmol) were mixed with 30 mL of 1-chloronaphthalene, To room temperature. Then, the mixture was added with capper acetate (Cu (CH 3 COO) 2 ) (0.78 g, 4.32 mmol), and the temperature was then raised to 250 ° C. and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was filtered and washed several times with EtOAc solvent. The filtrate was concentrated and separated by flash column chromatography under SiO 2 to obtain 0.3 g (11% yield) of compound (d). The synthesized compound was confirmed by 1 H-NMR.
1H-NMR (CDCl3, Varian 400 MHz): δ 7.89-6.68 (12H, m), 6.90 (3H, s), 3.42-3.12 (6H, t, J = 8 Hz), 1.88-1.20 (36H, m), 0.86-0.83 (9H, t, J = 7.2 Hz)
1 H-NMR (CDCl 3,
4. 화합물 e의 합성4. Synthesis of Compound e
[반응식 4][Reaction Scheme 4]
화합물 (d) (0.3 g, 0.26 mmol)를 무수벤젠 30 mL에 용해시킨 후 1M의 헥센에 용해되어있는 다이아이소부틸알루미늄 하이드라이드(DIBAL-H)(0.05 mL, 0.29 mmol)을 넣어준 후 그 혼합물을 질소하 상온에서 6시간 동안 교반시켜주었다. 반응 종료 후 10% 황산 50 mL를 넣어준 후 벤젠을 첨가하여 추출하고 소금(brine)으로 세척(washing)하고, 무수 Na2SO4로 수분 건조후 여과 및 농축하였다. 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) 방법으로 분리하여 화합물 (e)를 0.2 g (65% yield) 얻었다. 합성된 화합물은 1H-NMR을 통해 확인하였다. Compound (d) (0.3 g, 0.26 mmol) was dissolved in 30 mL of anhydrous benzene, and diisobutyl aluminum hydride (DIBAL-H) (0.05 mL, 0.29 mmol) dissolved in 1M hexene was added thereto. The mixture was stirred at room temperature under nitrogen for 6 hours. After completion of the reaction, 50 mL of 10% sulfuric acid was added, and benzene was added thereto. The mixture was extracted, washed with brine, dried with anhydrous Na 2 SO 4 , filtered and concentrated. The mixture was separated by flash column chromatography method under SiO 2 to obtain 0.2 g (65% yield) of compound (e). The synthesized compound was confirmed by 1 H-NMR.
1H-NMR (CDCl3, Varian 400 MHz): δ 9.88 (1H, s), 7.89-6.92 (12H, m), 6.88 (3H, s), 3.15 (6H, t, J = 8 Hz), 1.61-1.29 (36H, m), 0.86-0.83 (9H, s, J = 7.2 Hz)
1 H-NMR (CDCl 3,
5. 화합물 1의 합성5. Synthesis of Compound 1
[반응식 5][Reaction Scheme 5]
화합물 (e) (0.2 g, 0.17 mmol), 2-사이아노아세틱산(2-cyanoacetic acid) (0.057 g, 0.68 mmol), 피페리딘(piperidine) (4 mL)을 아세토나이트릴(acetonitrile) 15 mL에 용해시킨다. 질소 충진 하에 80℃에서 4시간동안 교반시켰다. 반응이 종료 된 후 상온으로 온도를 내리고 유기층을 감압하여 제거한다. 2-cyanoacetic acid (0.057 g, 0.68 mmol) and piperidine (4 mL) were added to a solution of compound (e) (0.2 g, 0.17 mmol) mL. And the mixture was stirred at 80 DEG C for 4 hours under nitrogen filling. After the reaction is completed, the temperature is lowered to room temperature and the organic layer is removed by decompression.
침전물을 여과하고 증류수로 세척한 후 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) (EtOH : CH2Cl2 = 1:1) 방법으로 분리하여 화합물 (2)을 0.1 g (48% yield) 얻었다.The precipitate was filtered off and the mixture was flash column chromatography (flash column chromatography) under the SiO 2 washed with distilled water (EtOH: CH 2 Cl 2 = 1: 1) , separated by a method of the compound (2) 0.1 g (48% yield ).
1H-NMR (CDCl3, Varian 400 MHz): δ 11.20 (1H, s), 7.95 (1H, s), 7.89-6.92 (12H, m), 6.88 (3H, s), 3.15 (6H, t, J = 8 Hz), 1.61-1.29 (36H, m), 0.86-0.83 (9H, s, J = 7.2 Hz)
1 H-NMR (CDCl 3,
[[ 합성예Synthetic example 2] 2]
6. 화합물 f의 합성6. Synthesis of Compound f
[반응식 6][Reaction Scheme 6]
4-아미노프탈로나이트릴(4-aminophthalonitrile) (a)(3.0 g, 20.96 mmol) 및 피리딘(pyridine) 32 mL를 같이 혼합하고, 상온에서 완전히 용해시켰다. 트리메틸아세틸클로라이드(trimethylacetyl chloride) (3.54 g, 29.34 mmol)를 천천히 떨어뜨린 후 1시간 동안 교반시켰다.4-aminophthalonitrile (a) (3.0 g, 20.96 mmol) and pyridine (32 mL) were mixed together and completely dissolved at room temperature. Trimethylacetyl chloride (3.54 g, 29.34 mmol) was slowly added dropwise and stirred for 1 hour.
얼음 70 mL를 비커에 넣은 후 혼합물을 부어 반응을 종결시켰다. EtOAc 70 mL를 첨가하여 추출한 후 소금(brine)으로 세척(washing)하고, 무수 Na2SO4로 수분 건조후 여과 및 농축하였다. 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) (Hexane : EtOAc = 3:1) 방법으로 분리하여 화합물 (c)를 10.3 g (46% yield) 얻었다.70 mL of ice was added to the beaker, and the mixture was poured to terminate the reaction. Extracted with 70 mL of EtOAc, washed with brine, dried with anhydrous Na 2 SO 4 , filtered, and concentrated. The mixture was separated by flash column chromatography (Hexane: EtOAc = 3: 1) under SiO 2 to obtain 10.3 g (46% yield) of compound (c).
1H-NMR (CDCl3, Varian 400 MHz): δ 8.19-8.18(1H, d, J = 2.4 Hz), 7.89-7.86 (1H, dd, J = 8.4 Hz), 7.75-7.73 (1H, d, JJ = 8.4 Hz), 7.60 (1H, s), 1.34 (3H, s)
1 H-NMR (CDCl 3,
7. 화합물 g의 합성 7. Synthesis of Compound g
[반응식 7][Reaction Scheme 7]
4-아미노프탈로나이트릴(4-aminophthalonitrile) (a)(3.0 g, 20.96 mmol) 을 2M 황산 (H2SO4) 42 ml 에 용해시킨 후 0 ℃로 온도를 내려준다. 그리고, 소디움나이트릴(NaNO2) (1.93 g, 3.94 mmol)를 55 mL 물에 용해시킨 후, 반응기가 0 ℃를 유지한 채, 상기 혼합물에 30분에 걸쳐서 천천히 떨어뜨린 후 30분간 교반시켜주었다. 그 혼합물을 감압하여 감압된 혼합용액에 물 210 ml 와 포타슘아이오다이드(KI) (3.72 g, 22.42 mmol)을 용해시킨 혼합물을 조금씩 떨어뜨린다. 4-aminophthalonitrile (a) (3.0 g, 20.96 mmol) was dissolved in 42 ml of 2M sulfuric acid (H 2 SO 4 ) and the temperature was lowered to 0 ° C. Sodium nitrite (NaNO 2 ) (1.93 g, 3.94 mmol) was dissolved in 55 mL of water, and the mixture was slowly dropped into the mixture over 30 minutes while maintaining the temperature at 0 ° C, followed by stirring for 30 minutes . The mixture is decompressed, and the mixture obtained by dissolving 210 ml of water and potassium iodide (KI) (3.72 g, 22.42 mmol) in a reduced pressure mixed solution is gradually dropped.
상기 혼합물을 상온으로 천천히 올리며 교반시킨 후 침전된 혼합물을 감압하여 고체 침전물을 얻는다. 이렇게 얻어진 고체 침전물을 다이클로로메탄(CH2Cl2)으로 용해시킨 후 5% 소디움바이카보네이트(NaHCO3)에 세척(washing)하고, 무수 Na2SO4로 수분 건조후 여과 및 농축하였다. 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) (MC) 방법으로 분리하여 화합물 (g)를 2.9 g (59% yield) 얻었다.The mixture is slowly stirred at room temperature and stirred, and the precipitated mixture is reduced in pressure to obtain a solid precipitate. The solid precipitate thus obtained was dissolved in dichloromethane (CH 2 Cl 2 ), washed with 5% sodium bicarbonate (NaHCO 3 ), dried with anhydrous Na 2 SO 4 , filtered, and concentrated. The mixture was separated by flash column chromatography (MC) method under SiO 2 to obtain 2.9 g (59% yield) of compound (g).
1H-NMR (CDCl3, Varian 400 MHz): δ 8.17-8.16 (1H, d, J = 1.2 Hz), 8.12-8.10 (1H, d, J = 8.4 Hz), 7.52-7.50 (1H, d, JJ = 8.4 Hz)
1 H-NMR (CDCl 3 ,
8. 화합물 h의 합성8. Synthesis of Compound h
[반응식 8][Reaction Scheme 8]
화합물 (f)(3.0 g, 12.20 mmol) 및 화합물 (g) (0.71 g, 3.05 mmol)를 1-클로로나프탈렌(1-Chloronaphthalene) 30mL와 혼합하고, 250℃까지 온도를 올려 30분간 유지한 후 온도를 상온까지 떨어뜨렸다. 이후, 상기 혼합물에 카퍼아세테이트(Cu(CH3COO)2)(0.78 g, 4.32 mmol)를 넣어준 후 다시 250℃까지 온도를 올리고 12시간 동안 교반시켜 주었다. 반응 종료 후 여과하며 EtOAc 용매로 여러 차례 씻어주었다. 여과액을 농축시킨 후 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) 방법으로 분리하여 화합물 (h)을 0.5 g (16% yield) 얻었다.Compound (f) (3.0 g, 12.20 mmol) and compound (g) (0.71 g, 3.05 mmol) were mixed with 30 mL of 1-chloronaphthalene, To room temperature. Then, the mixture was added with capper acetate (Cu (CH 3 COO) 2 ) (0.78 g, 4.32 mmol), and the temperature was then raised to 250 ° C. and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was filtered and washed several times with EtOAc solvent. The filtrate was concentrated and separated by flash column chromatography under SiO 2 to obtain 0.5 g (16% yield) of compound (h).
1H-NMR (CDCl3, Varian 400 MHz): δ 7.89-6.68 (12H, m), 6.90 (3H, s), 3.42-3.12 (6H, t, J = 8 Hz), 1.88-1.20 (36H, m), 0.86-0.83 (9H, t, J = 7.2 Hz)
1 H-NMR (CDCl 3,
9. 화합물 j의 합성9. Synthesis of Compound j
[반응식 9][Reaction Scheme 9]
화합물 (h) (1.0 g, 1.00 mmol), 5-포밀-2-싸이에닐보로닉에씨드(5-formylthiophene-2-ylboronic acid)(i) (0.16 g, 1.00 mmol), 테트라키스팔라듐트리페닐포시핀(Pd(PPh3)4) (0.015 g, 0.013 mmol), 포타슘카보네이트(potassium carbonate) (2.60 g, 18.80 mmol)을 톨루엔 20 mL와 물 2 mL에 용해시킨 후 24시간동안 110 ℃에서 교반시켜주었다.Compound (h) (1.0 g, 1.00 mmol), 5-formylthiophene-2-ylboronic acid (i) (0.16 g, 1.00 mmol), tetrakispalladium tri phenyl Posey pin (Pd (PPh 3) 4) (0.015 g, 0.013 mmol), potassium carbonate (potassium carbonate) (2.60 g, 18.80 mmol) was dissolved in 2 mL of
반응 종료 추출하고 EtOAc 70 mL를 첨가하여 추출한 후 소금(brine)으로 세척(washing)하고, 무수 Na2SO4로 수분 건조후 여과 및 농축하였다. 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) 방법으로 분리하여 화합물 (j)를 0.7 g (71% yield) 얻었다.After completion of the reaction, the reaction mixture was extracted and extracted with 70 mL of EtOAc, washed with brine, dried with anhydrous Na 2 SO 4 , filtered and concentrated. The mixture was separated by flash column chromatography method under SiO 2 to obtain 0.7 g (71% yield) of compound (j).
1H-NMR (CDCl3, Varian 400 MHz): δ 9.84 (H, s), 8.45-7.48 (14H, m), 7.03 (3H, s), 1.85-1.23 (27H, m)
1 H-NMR (CDCl 3,
10. 화합물 2의 합성10. Synthesis of Compound 2
[반응식 10][Reaction Scheme 10]
화합물 (j) (1 g, 1.02 mmol), 2-사이아노아세틱산(2-cyanoacetic acid) (0.035 g, 4.08 mmol), 피페리딘(piperidine) (2mL, 20.4 mmol)을 아세토나이트릴(acetonitrile) 15 mL에 용해시켰다. 질소 충진 하에 80℃에서 4시간 동안 교반시켰다. 반응이 종료된 후 상온으로 온도를 내리고 유기층을 감압하여 제거하였다.2-cyanoacetic acid (0.035 g, 4.08 mmol) and piperidine (2 mL, 20.4 mmol) were added to a solution of compound (j) (1 g, 1.02 mmol) in acetonitrile ). ≪ / RTI > And the mixture was stirred at 80 DEG C for 4 hours under nitrogen filling. After the reaction was completed, the temperature was lowered to room temperature and the organic layer was removed under reduced pressure.
침전물을 여과하고 증류수로 세척한 후 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) (EtOH : CH2Cl2 = 1:1) 방법으로 분리하여 화합물 (2)을 0.75 g (70% yield) 얻었다.The precipitate was filtered off and the mixture was flash column chromatography (flash column chromatography) under the SiO 2 washed with distilled water (EtOH: CH 2 Cl 2 = 1: 1) separated by the method to the compound (2) 0.75 g (70% yield ).
1H-NMR (CDCl3, Varian 400 MHz): δ 11.0 (1H, s), 8.35-7.92 (14H, m), 7.23 (3H, s), 1.85-1.23 (27H, m)
1 H-NMR (CDCl 3,
[[ 합성예Synthetic example 3] 3]
11. 화합물 k의 합성11. Synthesis of Compound k
[반응식 11][Reaction Scheme 11]
4-아이오드프탈로나이트릴(4-iodophthalonitrile) (f)(15 g, 59.05 mmol), 4-메톡시페닐보로닉에씨드(4-methoxyphenylboronic acid) (k)(13.46 g, 88.58 mmol), 팔라듐트리페닐포시핀(Pd(PPh3)4) (3.41 g, 2.95 mmol), 포타슘카보네이트(potassium carbonate) (26.93 g, 194.87 mmol)을 톨루엔 18 mL와 물 2 mL에 용해시킨 후 24시간 동안 110℃에서 교반시켜주었다.4-iodophthalonitrile (f) (15 g, 59.05 mmol) and 4-methoxyphenylboronic acid (k) (13.46 g, 88.58 mmol) , palladium triphenyl Posey pin (Pd (PPh 3) 4) (3.41 g, 2.95 mmol), potassium carbonate (potassium carbonate) (26.93 g, 194.87 mmol) was dissolved in 2 mL of toluene 18 mL and water for 24 hours Followed by stirring at 110 ° C.
반응 종료 추출하고 EtOAc 70 mL를 첨가하여 추출한 후 소금(brine)으로 세척(washing)하고, 무수 Na2SO4로 수분 건조후 여과 및 농축하였다. 혼합물을 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) 방법으로 분리하여 화합물 (k)를 8.0 g (℃58% yield) 얻었다.After completion of the reaction, the reaction mixture was extracted and extracted with 70 mL of EtOAc, washed with brine, dried with anhydrous Na 2 SO 4 , filtered and concentrated. The mixture was separated by flash column chromatography method under SiO 2 to obtain 8.0 g (캜 58% yield) of compound (k).
1H-NMR (CDCl3, Varian 400 MHz): δ 7.97(1H, s), 7.89-7.87 (1H, dd, J = 8 Hz), 7.84-7.82 (1H, d, J = 8.4 Hz), 7.55-7.53 (2H, d, J = 8.8 Hz), 7.05-7.03 (2H, d, J = 8.8 Hz), 3.88 (3H, s)
1 H-NMR (CDCl 3,
12. 화합물 3의 합성12. Synthesis of Compound 3
[반응식 12][Reaction Scheme 12]
화합물 (k) (3 g, 11.80 mmol)를 1-클로로나프탈렌(1-Chloronaphthalene) 30mL와 혼합하고, 250℃까지 온도를 올려 30분간 유지한 후 온도를 상온까지 떨어뜨렸다. 이후, 상기 혼합물에 카퍼아세테이트(Cu(CH3COO)2)(0.78 g, 4.32 mmol)를 넣어준 후 다시 250℃까지 온도를 올리고 12시간 동안 교반시켜 주었다. 반응 종료 후 여과하며 EtOAc 용매로 여러 차례 씻어주었다. 여과액을 농축시킨 후 SiO2 하에서 플래시 컬럼 크로마토그래피(flash column chromatography) 방법으로 분리하여 화합물 (3)을 1.5 g (13% yield) 얻었다.Compound (k) (3 g, 11.80 mmol) was mixed with 30 mL of 1-Chloronaphthalene, and the temperature was raised to 250 DEG C for 30 minutes, and then the temperature was dropped to room temperature. Then, the mixture was added with capper acetate (Cu (CH 3 COO) 2 ) (0.78 g, 4.32 mmol), and the temperature was then raised to 250 ° C. and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was filtered and washed several times with EtOAc solvent. The filtrate was concentrated and separated by flash column chromatography under SiO 2 to obtain 1.5 g (13% yield) of the compound (3).
1H-NMR (CDCl3, Varian 400 MHz): δ8.16-7.68 (20H, m), 7.05 (8H, dd, J = 8.4 Hz), 3.83 (12H, s)
1 H-NMR (CDCl 3,
[실시예 1][Example 1]
합성예1의 염료를 사용하여, 일반적인 방법으로 감광성 수지 조성물을 제조하였다. Using the dye of Synthesis Example 1, a photosensitive resin composition was prepared by a general method.
즉, 바인더 수지(수용성아크릴 중합체; 메타크릴산벤질/메타클릴산/벤질메타크릴레이트 공중합체(공중합비[몰비]=60:30:10)의 30% Ethyl-L-lactate 용액, E34102, Aldrich) 100 중량부, 반응성 불포화 화합물(비스페놀 에폭시 아크릴레이트 올리고머 약 60 중량부와 디펜타에리스리톨 헥사아크릴레이트 약 120 중량부의 혼합물) 약 180 중량부; 합성예 1의 청색 염료 분산액 (합성예 1의 염료 10 중량%가 용매인 프로필렌글리콜 모노에틸에테르아세테이트에 분산된 상태) 10 중량부; 청색 안료 분산액 (상품명: DJBLUE-01, 제조사: MIKYNI, 용매: 프로필렌글리콜 메틸에테르아세테이트, 안료 15 중량% 분산액으로서, 안료 함량 환산시 약 93.75 중량부) 50 중량부, 광중합 개시제 (상품명 Irgacure-369(제조사: BASF)) 0.58 중량부, 용매인 프로필렌글리콜 메틸에테르아세테이트 52 중량부; 및 플루오르계 레벨링제(상품명: F-474, 제조사: DIC) 0.01 중량부를 혼합하고, 약 2 시간 동안 상온에서 교반한 후, 1.2 ㎛의 여과필터를 통해 불순물을 제거하였다.
That is, 30% Ethyl-L-lactate solution of a binder resin (water-soluble acrylic polymer; benzyl methacrylate / methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio [molar ratio] = 60:30:10), E34102, Aldrich ), About 180 parts by weight of a reactive unsaturated compound (a mixture of about 60 parts by weight of a bisphenol epoxy acrylate oligomer and about 120 parts by weight of dipentaerythritol hexaacrylate) 10 parts by weight of the blue dye dispersion of Synthesis Example 1 (10% by weight of the dye of Synthesis Example 1 dispersed in propylene glycol monoethyl ether acetate as a solvent) 50 parts by weight of a blue pigment dispersion (trade name: DJBLUE-01, manufactured by MIKYNI, solvent: propylene glycol methyl ether acetate, about 15% by weight of pigment as a dispersion and about 93.75 parts by weight in terms of pigment content), a photopolymerization initiator (trade name: Irgacure- Manufactured by BASF)), 52 parts by weight of propylene glycol methyl ether acetate as a solvent; And 0.01 part by weight of a fluorine leveling agent (trade name: F-474, manufacturer: DIC) were mixed and stirred at room temperature for about 2 hours, and then the impurities were removed through a 1.2 占 퐉 filter.
[실시예 2][Example 2]
합성예 2의 염료를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.
A photosensitive resin composition was prepared in the same manner as in Example 1, except that the dye of Synthesis Example 2 was used.
[실시예 3][Example 3]
합성예 3의 염료를 사용하고 녹색 안료 분산액(C.I. 피그먼트 그린58)을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.
A photosensitive resin composition was prepared in the same manner as in Example 1, except that the dye of Synthesis Example 3 was used and a green pigment dispersion (CI Pigment Green 58) was used.
[비교예 1][Comparative Example 1]
합성예 1의 염료 대신 C. I. acid blue 25 (상품명 : Acid blue 25 (제조사: ALDRICH))를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 감광성 수지 조성물을 제조하였다.
A photosensitive resin composition was prepared in the same manner as in Example 1, except that CI acid blue 25 (trade name: Acid blue 25 (manufacturer: ALDRICH)) was used instead of the dye of Synthesis Example 1.
[평가][evaluation]
상기 실시예 1 내지 3 및 비교예 1에 따른 각각의 감광성 수지 조성물을 유리 기판(10 X 10 cm)에 2 ㎛의 두께로 스핀 코팅하여 90 ?의 핫플레이트에서 2 분 동안 프리-베이크(pre-bake)를 수행한 후, 상온에서 1분 동안 냉각하였다. 이를 노광기를 이용하여 100 mJ/㎠의 노광량(365 nm 기준)으로 노광한 후, 220 ?의 통풍식 오븐에서 약 30 분 동안 포스트-베이크(post-bake)를 수행하였다.Each of the photosensitive resin compositions according to Examples 1 to 3 and Comparative Example 1 was spin-coated on a glass substrate (10 X 10 cm) to a thickness of 2 탆 and pre-baked on a 90 ° hot plate for 2 minutes. bake), followed by cooling at room temperature for 1 minute. This was exposed using an exposure apparatus at an exposure dose of 100 mJ / cm 2 (365 nm standard), and then post-baked for about 30 minutes in a 220 ° ventilated oven.
상기와 같은 방법으로 준비된 각각의 샘플에 대하여 다음과 같은 방법으로 물성을 측정하였다.
The physical properties of each of the samples prepared as described above were measured as follows.
(내열성 측정)(Heat resistance measurement)
포스트-베이크 후의 기판을 약 240 ?의 오븐에서 약 30 분 동안 가열한 후, 색도계 MCPD-3000 장비 (제조사: 오츠카)를 이용하여 조사 전후로의 패턴 상의 상에 있어서의 색도 변화, 즉 색차(△Eab)를 측정하였다. 그리고 다음 판정 기준에 따라, 합성예 1 내지 3 및 비교예 1에서 사용된 염료의 내열성 결과를 표 1에 나타내었다.The post-baked substrate was heated in an oven at about 240 DEG C for about 30 minutes, and then the chromaticity change on the pattern image before and after irradiation, that is, the color difference (DELTA Eab) was measured using a color meter MCPD- ) Were measured. The heat resistance results of the dyes used in Synthesis Examples 1 to 3 and Comparative Example 1 are shown in Table 1 according to the following criteria.
판정기준Criteria
○: △Eab치 < 5○: ΔEab value <5
△: △Eab치 ≤10?:? Eab value? 10
Ⅹ: 10 < △Eab치
Ⅹ: 10 <△ Eab value
(용해도 평가)(Solubility evaluation)
상기 합성예 1 내지 3 및 비교예 1의 염료의 용해도를 PGMEA, PGME, EL 및 DMAc을 용매로 사용하여 측정한 후, 그 결과를 하기 표 1에 나타내었다. 하기 표에서, 용해도 10% 이상은 ○로 표기하였고, 용해도 2%~10%는 △로 표기하였고, 용해도 2% 미만은 Ⅹ로 표기하였고 이를 표 2에 나타내었다. The solubilities of the dyes of Synthesis Examples 1 to 3 and Comparative Example 1 were measured using PGMEA, PGME, EL and DMAc as solvents, and the results are shown in Table 1 below. In the following table, solubility of 10% or more is indicated by o, solubility of 2% to 10% is indicated by △, solubility of less than 2% is indicated by Ⅹ, and it is shown in Table 2.
PGMEA : 프로필렌 글리콜 모노에틸 에테르 아세테이트PGMEA: Propylene glycol monoethyl ether acetate
PGME : 프로필렌 글리콜 모노에틸 에테르PGME: Propylene glycol monoethyl ether
EL : 에틸 락테이트EL: ethyl lactate
DMAc : 디메틸아세트아미드
DMAc: Dimethylacetamide
상기 표 1과 표 2에서와 같이, 본 발명의 실시예 1 내지 3의 염료의 용해도 및 내열성은 비교예 1의 염료와 비교하여 매우 우수하였다.
As shown in Tables 1 and 2, the solubility and heat resistance of the dyes of Examples 1 to 3 of the present invention were superior to those of Comparative Example 1.
(컬러필터에 대한 파장영역별 투과율 측정)(Measurement of transmittance by wavelength region for color filter)
색도 측정 장비(제조사: 오츠카, 모델명: MCPD-3000)를 이용하여, 실시예 1 내지 3 및 비교예 1에 따른 조성물을 사용하여 각각 제조한 컬러필터 샘플에 대하여, 파장영역별 투과율을 비교 측정하였고, 그 결과를 도 1 내지 4에 나타내었다. 이때, 청색은 파장영역 450~460 nm, 녹색은 파장영역 515~550 nm에서의 최대 투과율(Max%)을 측정하였다.The transmittance of each of the color filter samples prepared by using the compositions according to Examples 1 to 3 and Comparative Example 1 was measured using a chromaticity meter (manufacturer: Otsuka, model name: MCPD-3000) , And the results are shown in Figs. At this time, the maximum transmittance (Max%) of blue light in the wavelength region of 450 to 460 nm and green light in the wavelength region of 515 to 550 nm was measured.
그 결과, 실시예 1 내지 3(도 1 내지 3)은 비교예 1(도 4) 보다 투과율이 우수하였다.
As a result, Examples 1 to 3 (Figs. 1 to 3) had better transmittance than Comparative Example 1 (Fig. 4).
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 당 업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.
While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
Claims (11)
[화학식 1]
상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상을 포함하고, 상기 R1 내지 R4은 각각 독립적으로 수소, 탄소수 1 내지 5의 알킬기, 하기 화학식 2의 치환기, 화학식 3의 치환기를 나타내며, 상기 R1 내지 R4 중 적어도 1개 이상은 하기 화학식 2의 치환기, 화학식 3의 치환기 또는 화학식 2 및 화학식 3의 치환기를 가지고,
p는 각각 0~4의 정수이고, 단, p는 동시에 0이 아니며,
M은 Cu 또는 Zn이다.
[화학식 2]
(상기 화학식 2에서, Ar은 탄화수소 방향족기 또는 헤테로고리 방향족기를 하나 이상 포함하고,
R5는
t는 0 내지 3의 정수이다)
[화학식 3]
(상기 화학식 3에서, L은 -NH-, -NHCO-, -NHCS-, -S-, -SO2-, -CH-, -CH2- -O-, -CO-, 또는 -CF2- 이고,
A는 -CH2-, -CF2-, -CO-, -CH2CH2O-, -SO2-, 또는
E는 -CF3, -CH3, -SO3H, -NH2, -OH, OCH3, -SH, -C(CH3)3, -CH(CH3)2 또는 할로겐 원자이고,
n 및 m은 각각 독립적으로 0~20의 정수이다)
A colored dye for a color filter represented by the following formula (1)
[Chemical Formula 1]
In Formula 1, R 1 to R include at least one or more of the 4, wherein R 1 to R 4 each independently represent a hydrogen, an alkyl group, a Substituent of Formula 2 having 1 to 5 carbon atoms, the substituent of formula (3) , At least one of R 1 to R 4 is a substituent of the following formula (2), a substituent of the formula (3) or a substituent of the formula (2) and the formula (3)
p is an integer of 0 to 4, provided that p is not 0 at the same time,
M is Cu or Zn.
(2)
(Wherein Ar represents a hydrocarbon aromatic group or a heterocyclic aromatic group,
R 5 is
and t is an integer of 0 to 3)
(3)
(In the formula 3, L is -NH-, -NHCO-, -NHCS-, -S-, -SO 2 -, -CH-, -CH 2 - -O-, -CO-, or -CF 2 - ego,
A is -CH 2 -, -CF 2 -, -CO-, -CH 2 CH 2 O-, -SO 2 -, or
E is -CF 3, -CH 3, -SO 3 H, -NH 2, -OH, OCH 3, -SH, -C (CH 3) 3, -CH (CH 3) 2 or a halogen atom,
n and m are each independently an integer of 0 to 20)
상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상은 화학식 2의 구조를 포함하는, 컬러필터용 착색 염료.
The method according to claim 1,
In the formula (1), at least one of R 1 to R 4 includes the structure of formula (2).
In the formula (1), at least one of R 1 to R 4 includes the structure of formula (3).
상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상이 화학식 2의 구조일 때, R1 내지 R4 중의 나머지 치환기 중에서 적어도 하나가 화학식 3의 구조를 가지는 컬러필터용 착색 염료.
The method according to claim 1,
In Formula 1, R 1 to R 4 of when the at least the at least one structure represented by the following formula 2, R 1 to R 4 of the color filter for the colored dye is at least one of the remaining substituents have a structure of formula (3).
상기 화학식 1에서, R1 내지 R4 중 적어도 1개 이상이 화학식 3의 구조일 때, R1 내지 R4 중의 나머지 치환기 중에서 적어도 하나가 화학식 2의 구조를 가지는 컬러필터용 착색 염료.
The method according to claim 1,
In Formula 1, R 1 to R 4 of when the at least the at least one structure represented by the following formula 3, R 1 to R 4 of the color filter for the colored dye is at least one of the remaining substituents have a structure of formula (2).
The coloring dye for a color filter according to claim 1, wherein Ar in formula (2) is any one of the following substituents.
상기 화학식 3에서, n 및 m은 각각 독립적으로 0 내지 8의 정수인 컬러필터용 착색 염료.
The method according to claim 1,
In the formula (3), n and m are each independently an integer of from 0 to 8.
상기 화학식 1에서, p는 1일 때, 나머지 치환기는 수소 또는 탄소수 1 내지 5의 알킬기인, 컬러필터용 착색 염료.
The method according to claim 1,
In the above formula (1), when p is 1, the remaining substituent is hydrogen or an alkyl group having 1 to 5 carbon atoms.
The coloring dye for a color filter according to claim 1, wherein the formula (1) comprises any one selected from the following formulas.
10. A photosensitive resin composition for a color filter comprising the coloring dye according to any one of claims 1 to 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190095093A (en) * | 2018-02-06 | 2019-08-14 | 동우 화인켐 주식회사 | Cleaning solution composition |
| KR20210109311A (en) * | 2020-02-27 | 2021-09-06 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same, color filter and cmos image sensor |
| CN113448165A (en) * | 2020-03-25 | 2021-09-28 | 住友化学株式会社 | Colored resin composition |
| CN114545736A (en) * | 2022-03-30 | 2022-05-27 | 苏州华星光电技术有限公司 | Photoresist and display device |
-
2015
- 2015-04-30 KR KR1020150061454A patent/KR20160129385A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190095093A (en) * | 2018-02-06 | 2019-08-14 | 동우 화인켐 주식회사 | Cleaning solution composition |
| KR20210109311A (en) * | 2020-02-27 | 2021-09-06 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same, color filter and cmos image sensor |
| CN113448165A (en) * | 2020-03-25 | 2021-09-28 | 住友化学株式会社 | Colored resin composition |
| CN114545736A (en) * | 2022-03-30 | 2022-05-27 | 苏州华星光电技术有限公司 | Photoresist and display device |
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