WO2013180419A1 - Photoactive compound and light-sensitive resin composition comprising same - Google Patents
Photoactive compound and light-sensitive resin composition comprising same Download PDFInfo
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- WO2013180419A1 WO2013180419A1 PCT/KR2013/004496 KR2013004496W WO2013180419A1 WO 2013180419 A1 WO2013180419 A1 WO 2013180419A1 KR 2013004496 W KR2013004496 W KR 2013004496W WO 2013180419 A1 WO2013180419 A1 WO 2013180419A1
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- Prior art keywords
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- resin composition
- photosensitive resin
- formula
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 100
- 239000011342 resin composition Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 239000003086 colorant Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000006850 spacer group Chemical group 0.000 claims description 5
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000012719 thermal polymerization Methods 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003504 photosensitizing agent Substances 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 57
- 229940048053 acrylate Drugs 0.000 description 57
- -1 oxime ester Chemical class 0.000 description 39
- 238000010586 diagram Methods 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
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- 230000008901 benefit Effects 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000003517 fume Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [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
- 230000007547 defect Effects 0.000 description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- HFNNZEMVTJAKRC-UHFFFAOYSA-N 9-(6-bromohexyl)carbazole Chemical compound C1=CC=C2N(CCCCCCBr)C3=CC=CC=C3C2=C1 HFNNZEMVTJAKRC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229940114077 acrylic acid Drugs 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 235000010187 litholrubine BK Nutrition 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 150000002923 oximes Chemical class 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 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 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 238000005406 washing Methods 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
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- SUDVPELGFZKOMD-UHFFFAOYSA-N 1,2-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C(C)C)C(C(C)C)=CC=C3SC2=C1 SUDVPELGFZKOMD-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- XUIXZBXRQFZHIT-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]-3-methoxypropan-2-ol Chemical compound COCC(O)COC(C)COC(C)CO XUIXZBXRQFZHIT-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-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
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- SRQOBNUBCLPPPH-UHFFFAOYSA-N 1-ethyl-4-phenylbenzene Chemical group C1=CC(CC)=CC=C1C1=CC=CC=C1 SRQOBNUBCLPPPH-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- GBOJZXLCJZDBKO-UHFFFAOYSA-N 2-(2-chlorophenyl)-2-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 GBOJZXLCJZDBKO-UHFFFAOYSA-N 0.000 description 1
- CMCLUJRFBZBVSW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCO CMCLUJRFBZBVSW-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
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- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
Definitions
- the present application relates to a photoactive compound comprising an oxime ester group and a phosphonate group and a photosensitive resin composition comprising the same.
- the present application relates to a photoactive compound comprising an oxime ester group and a phosphonate group and a photosensitive resin composition comprising the same.
- the photosensitive resin composition may be applied to a substrate to form a coating film, and a specific portion of the coating film may be exposed by light irradiation using a photomask or the like, and then used to form a pattern by developing and removing the non-exposed portion. . Since such a photosensitive resin composition can irradiate, superpose
- the transparent photosensitive resin composition is used for column spacers, overcoats, and passivation membranes, and it is generally possible to use an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a solvent without using a colorant such as a pigment. Include.
- the colored photosensitive resin composition is used for a color filter photoresist and a photoresist for a resin black matrix, and is usually a colorant of red, green, blue, and black, an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, and photopolymerization. Initiator and solvent.
- the photosensitive resin composition has been manufactured for the purpose of constituting liquid crystal display devices such as TVs and monitors in addition to the conventional notebooks and mobiles as the use of LCDs has been advanced and diversified, and responds quickly to light for improving productivity and durability.
- the demand for mechanically excellent physical properties is increasing.
- a property that reacts quickly to light that is, light sensitivity becomes a very important factor.
- the overcoat and passivation film serving as a column spacer or a protective film, which serves as a support, to exhibit the original performance without damage to the liquid crystal display device due to an external impact should have excellent mechanical properties.
- a photopolymerization initiator with excellent photosensitivity can solve these problems.
- a photoinitiator with excellent photosensitivity sufficient sensitivity can be realized even with a small amount of photopolymerization initiator, thereby reducing the contamination of liquid crystals, increasing the residual film ratio of the pattern, and increasing the usable width of other raw materials when preparing the composition. It has the advantage of being.
- the problem to be solved by the present application is to overcome all the disadvantages of the conventional photopolymerization initiator, easy to store without degrading sensitivity, chemical resistance, developability, and excellent fume (fume) properties in high temperature process It is to provide a photoactive compound and a photosensitive resin composition comprising the same.
- One embodiment of the present application provides a photoactive compound represented by the following Chemical Formula 1.
- Y is a C 1 to C 15 alkylene group unsubstituted or substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR,
- M 1 is an alkyl group of C 1 ⁇ C 8 ; Or an aryl group of C 6 ⁇ C 12 ,
- R 1 is a C 1 ⁇ C 8 alkyl group; Or an aryl group of C 6 ⁇ C 12 ,
- At least one of R 2 to R 6 is XA, and the others are each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′,
- A is a C 6 -C 20 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ', and CONRR',
- R and R ' are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl group, C 1 -C 10 haloalkyl group and C 7 -C 13 arylalkyl group, wherein R and R' together are a ring Can be formed.
- One embodiment of the present application is a photoactive compound represented by Formula 1; Alkali-soluble binder resins; Polymeric compounds containing ethylenically unsaturated bonds; And it provides a photosensitive resin composition comprising a solvent.
- One embodiment of the present application provides a photosensitive material prepared using the photosensitive resin composition.
- One embodiment of the present application provides an electronic device manufactured using the photosensitive resin composition.
- the compound provided through the present application is easy to store without degrading sensitivity, chemical resistance, and developability, and has excellent fume generation suppression property in a high temperature process. Accordingly, the photosensitive resin composition according to the present application is advantageous not only for curing the column spacer, overcoat and passivation material of the liquid crystal display device, but also in manufacturing the electronic device.
- the inventors of the present application synthesized a compound having a structure containing both an oxime ester group and a phosphonate group in one molecule, and confirmed that the compound absorbs ultraviolet rays more efficiently than other photoinitiators and has excellent sensitivity and high temperature processing characteristics. .
- the compounds initially developed have low photoinitiation efficiency and are not effective in absorbing UV light sources when the color characteristics are good.
- Compounds published after the late 1990s have significantly improved photoinitiation efficiency but do not fully satisfy the recently enhanced process time reductions.
- there is still a difficulty in forming a fine pattern because the pigment concentration is high or the thickness of the coating film is 2.5 ⁇ m or more. Can't satisfy
- Conventionally known oxime derivative compounds have a disadvantage of low photoinitiation efficiency, poor processing time, weak mechanical strength, and poor storage stability.
- the photoactive compound according to the embodiment of the present application has superior photoinitiation efficiency, shorter processing time, superior mechanical strength, superior economical advantages, and improved storage stability compared to the conventional oxime ester photopolymerization initiator. And, there is an advantage in developing. Moreover, it has the advantage of being excellent in sensitivity, having sufficient solubility with respect to the polymeric compound which has an ethylenically unsaturated bond, and being stable also over time. In addition, the efficiency of generating radicals by efficiently absorbing ultraviolet rays of i-line (365 nm), and excellent solubility and compatibility with the binder, has the advantage of excellent high temperature process characteristics.
- One embodiment of the present application provides a photoactive compound represented by the following Chemical Formula 1.
- Chemical Formula 1 may be Chemical Formula 2.
- Y is a C 1 to C 15 alkylene group; Or a C 1 to C 15 alkylene group substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR, and preferably an alkylene group of C 2 to C 6 .
- an ethylene group or a propylene group is more preferable in view of solubility and compatibility.
- M 1 is an alkyl group of C 1 ⁇ C 8 ; Or an aryl group of C 6 to C 12 , preferably an alkyl group of C 1 to C 10 , and more preferably a methyl group or an ethyl group.
- R 1 is an alkyl group of C 1 ⁇ C 8 ; Or a C 6 -C 12 aryl group, preferably a methyl group or a phenyl group.
- R 1 is a part which is decomposed into radicals which are active species at the time of exposure, and is not particularly limited in structure, but the simpler the structure, the better the movement and the photoinitiation efficiency is improved.
- R 2 To R 6 At least one of may be XA, preferably R 4 May be XA.
- R 2 To R 6 Except XA The remainder may be each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
- A may be a C 6 to C 20 aryl group which is unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′. And preferably a phenyl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
- Substituents corresponding to A in Formula 2 are R 7 , R 8 , R 9 , and R 10 to R 11 .
- R 7 , R 8 , R 9 , R 10 and R 11 may be each independently selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
- R and R ' may each be selected from the group consisting of hydrogen, C 1 ⁇ C 10 alkyl group, C 1 ⁇ C 10 haloalkyl group and C 7 ⁇ C 13 arylalkyl group, or R and R' together May form a ring.
- R and R 'together form a ring it may form a 5-membered, 6-membered or 7-membered ring, may be monocyclic or polycyclic, and may be aromatic, aliphatic ring, heteroaromatic or heteroaliphatic ring. have.
- the halogen group may be fluorine, chlorine, bromine or iodine.
- the aryl group may be a monocyclic aryl group or a polycyclic aryl group.
- the aryl group when the aryl group is a monocyclic aryl group, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like, but is not limited thereto.
- the aryl group may be specifically naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perrylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.
- the alkyl group may be straight, branched or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. may be, but is not limited thereto.
- the alkoxy group may be linear, branched or cyclic, and may be substituted or unsubstituted.
- Examples of the alkoxy group may be methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, cyclopentyloxy group and the like, but is not limited thereto.
- the alkylene group may be linear or branched, and may be substituted or unsubstituted. Specific examples of the alkylene group include methylene, ethylene, propylene, isopropylene, butylene, t-butylene, but are not limited thereto.
- substituted or unsubstituted means substituted with one or more substituents or no substituent.
- the substituent is not particularly defined may be hydrogen.
- the photoactive compound of the present application represented by Formula 1 or Formula 2 includes an oxime ester group and a phosphonate group (-Y-PO (OM 1 ) 2 ) in its structure and includes a substituted or unsubstituted phenyl group. There is a characteristic.
- the phosphonate group increases the solubility of the compound represented by Formula 1 or Formula 2, and improves the solubility of the photosensitive resin composition with high compatibility with the binder resin by forming a hydrogen bond with an alkali-soluble binder resin in the photosensitive resin composition. It also lowers volatility.
- the photoactive compound of the present application represented by Formula 1 or Formula 2 has a high melting point and has an advantage of easy storage, and has an effect of preventing generation of fume in a high temperature process.
- a photosensitive resin composition containing a conventional photoactive compound fumes are generated in the exposure process, volatilized into the air, and then adhered to a portion such as a mask, which may cause defects. .
- the fume may be a foreign substance, which may cause a defect.
- One embodiment of the present application is a photoactive compound represented by Formula 1; Alkali-soluble binder resins; Polymeric compounds containing ethylenically unsaturated bonds; And it provides a photosensitive resin composition comprising a solvent.
- the compound of Formula 1 may be a compound of Formula 2.
- the compound of Formula 1 or Formula 2 may be a compound of any one of Formulas 3 to 6.
- the amount of the photoactive compound represented by Formula 1 may be included in 0.1 to 5% by weight of the total photosensitive resin composition, but is not limited thereto. If it is less than 0.1% by weight may not give sufficient sensitivity, if it exceeds 5% by weight high UV absorption may not be able to transmit the UV light to the bottom.
- the photosensitive resin composition according to the exemplary embodiment of the present application has an effect of adjusting the viscosity by including a binder resin, and has an effect of enabling patterning using an alkaline developer.
- a binder resin those generally used in the art such as an alkali-soluble polymer resin may be used.
- the alkali-soluble resin binder is a copolymer of a monomer containing an acid functional group and a monomer giving a film strength copolymerizable with the monomer, or a polymer reaction with an ethylenically unsaturated compound containing an epoxy group. It may be a compound prepared through.
- the alkali-soluble resin binder used in the present application may have an acid value of about 30 to 300 KOH mg / g. If the acid value is less than 30 KOH mg / g is not well developed to obtain a clean pattern, and if it exceeds 300 KOH mg / g, the washing characteristics are excessively improved and the pattern may fall off.
- the weight average molecular weight of the alkali-soluble resin binder is preferably in the range of 1,000 to 200,000, more preferably may be in the range of 5,000 to 100,000. If the weight average molecular weight of the alkali-soluble binder resin is less than 1,000, the heat resistance and chemical resistance deteriorate. If the weight-average molecular weight of the alkali-soluble binder resin is more than 200,000, the solubility in the developing solution is lowered, so that the development is not possible, and the viscosity of the solution is excessively increased, making it difficult to apply uniformly. Can not do it.
- Non-limiting examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, mono 2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, ⁇ -carboxy polycaprolactone mono (meth) acrylate, or mixtures thereof have.
- Non-limiting examples of monomers copolymerizable with the monomer containing the acid group include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) ) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (Meth) acrylate, tetrahydroperpryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, acyloc
- Aromatic vinyls such as styrene, ⁇ -methylstyrene, (o, m, p) -vinyl toluene, (o, m, p) -methoxy styrene, (o, m, p) -chloro styrene;
- Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
- N-vinyl tertiary amines such as N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine
- Unsaturated imides such as N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide
- Maleic anhydrides such as maleic anhydride and methyl maleic anhydride;
- Unsaturated glycidyl compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or mixtures thereof.
- allyl glycidyl ether, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2 One or more selected from the group consisting of -methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene.
- the content of the binder resin may be 1 to 30% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
- the content of the binder resin is 1% by weight or more, the effect of patterning using an alkali aqueous solution is well effected, and the problem of difficulty in forming a pattern due to the lack of solubility in a developer is prevented. There is an effect that can prevent the loss of, and the viscosity of the entire solution is too high to prevent problems that may be difficult to coat.
- the photosensitive resin composition according to the embodiment of the present application may include a crosslinkable compound, and specifically, a polymerizable compound including an ethylenically unsaturated bond may be used. More specifically, a crosslinkable compound including two or more unsaturated acrylic groups and a crosslinkable compound including three or more unsaturated acrylic groups may be used.
- ethylene glycol di (meth) acrylate an ethylene group having 2 to 14 polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene glycol di (meth) acrylate with 2 to 14 propylene groups, dipentaerythritol penta A mixture of an acidic modification of (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate (trade name TO- 2348, TO-2349) compound obtained by
- silica dispersions may be used for these compounds, for example, Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.
- the content of the crosslinkable compound, specifically, the polymerizable compound including an ethylenically unsaturated bond may be 0.5 to 30% by weight based on the total weight of the photosensitive resin composition.
- the present invention is not limited thereto. If the content is less than 0.5% by weight is not preferable because the cross-linking reaction is not progressed by light, when the content exceeds 30% by weight is difficult to form a pattern of the poor solubility in alkali.
- non-limiting examples of the solvent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclo Pentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, and
- the content of the solvent may be 40 to 95 wt% based on the total weight of the photosensitive resin composition, but is not limited thereto.
- Photosensitive resin composition is a transparent photosensitive resin composition, 0.1 to 5% by weight of the photoactive compound represented by the formula (1), 0.5 to 30% by weight of a polymerizable compound containing an ethylenically unsaturated bond, alkali soluble It may include 1 to 30% by weight of the binder resin and 40 to 95% by weight of the solvent.
- the photosensitive resin composition according to the embodiment of the present application may further include a colorant.
- the coloring agent may be used one or more pigments, dyes or mixtures thereof.
- a metal oxide such as carbon black, graphite, titanium black, or the like may be used.
- Examples of carbon black include cysto 5HIISAF-HS, cysto KH, cysto 3HHAF-HS, cysto NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, cysto 116MAF, cysto FMFEF-HS , Sisto SOFEF, Sisto VGPF, Sisto SVHSRF-HS and Sisto SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, MA
- examples of the colorant to be colored are carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086), cyanine black, linole yellow (CI21090), Linol yellow GRO (CI 21090), benzidine yellow 4T-564D, Victoria pure blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I.
- a white pigment, a fluorescent pigment, etc. can also be used.
- a substance containing zinc as the center metal may be used.
- the content of the colorant may be 1 to 20% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
- Photosensitive resin composition is a colored photosensitive resin composition, 0.1 to 5% by weight of the photoactive compound represented by the formula (1), 0.5 to 30% by weight of a polymerizable compound containing an ethylenically unsaturated bond, alkali soluble It may include 1 to 30% by weight of the binder resin, 1 to 20% by weight of the colorant and 40 to 95% by weight of the solvent.
- the photosensitive resin composition according to the exemplary embodiment of the present application may include, as necessary, a second photoactive compound, a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, a UV absorber, a plasticizer, an adhesion promoter, a filler, a surfactant, and the like, as necessary. It may further comprise one or two or more additives of.
- the second photoactive compound is contained in an amount of 0.1 to 5% by weight, and the other additives in amounts of 0.01 to 5% by weight, respectively.
- the second photoactive compound is specifically, a triazine compound, a biimidazole compound, an acetophenone compound, an O-acyl oxime compound, a benzophenone compound, It may be selected from the group consisting of a thioxanthone compound, a phosphine oxide compound and a coumarin compound.
- the second photoactive compound is more specifically 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6 -Triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- ⁇ 4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio ⁇ propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6-tri Triazine compounds such as azine and 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine;
- O-acyl oxime compounds such as Irgacure OXE 01 from BASF, Irgacure OXE 02, N-1919, NCI-831, NCI-930 from ADEKA Corporation;
- Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone;
- Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone;
- 2,4,6-trimethylbenzoyl diphenylphosphine oxide bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide
- Phosphine oxide compounds such as these;
- examples of the curing accelerator, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimer Capto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate ), Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) , Trimethylolethane tris (2-mercaptoacetate), and trimethylolethane tris (3-mercaptopropionate) may include one or more selected from the group
- the thermal polymerization inhibitor p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitroso It may include one or more selected from the group consisting of phenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt and phenothiazine, but are not limited thereto, and those known in the art It may include.
- the dispersant may be a polymer type, nonionic, anionic, or cationic dispersant.
- Non-limiting examples of such dispersants include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, esteralkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxes Acid salts, alkylamide alkylene oxide adducts, alkylamines, and the like, and one or a mixture of two or more selected from these may be used, but is not limited thereto.
- non-limiting examples of the antioxidant are 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-g, t- It may include one or more selected from butylphenol, but is not limited thereto.
- non-limiting examples of the ultraviolet absorber are 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole And it may include one or more selected from alkoxy benzophenone, but is not limited thereto.
- the surfactant may include MCF 350SF, F-475, F-488, F-552 (hereinafter referred to as DIC), but are not limited thereto. no.
- plasticizers adhesion promoters, fillers, and the like can also be used for all compounds that can be included in conventional photosensitive resin compositions.
- One embodiment of the present application provides a photosensitive material including the photosensitive resin composition.
- One embodiment of the present application provides a photosensitive material prepared using the photosensitive resin composition.
- the photosensitive resin composition is present in a state in which at least a part of the solvent is removed or photocured by drying and / or curing in the photosensitive material.
- the photosensitive resin composition according to the present application is used in a roll coater (curtain coater), curtain coater (curtain coater), spin coater (spin coater), slot die coater, various printing, deposition, etc., metal, paper, glass plastic substrate It can be applied on a support such as.
- mercury vapor arc arc
- carbon arc arc
- Xe arc etc. which emit light of 250-450 nm in wavelength, etc. are mentioned, for example.
- the photosensitive resin composition comprising the compound of the present application is a pigment dispersion type photosensitive material for manufacturing a TFT LCD color filter, a photosensitive material for forming a black matrix of a TFT LCD or an organic light emitting diode, a photosensitive material for forming an overcoat layer, a column spacer photosensitive material, a printed circuit board
- a photocurable paint a photocurable ink, a photocurable adhesive agent, a printing plate, and a PDP, and the use is not specifically limited.
- One embodiment of the present application provides an electronic device manufactured using the photosensitive resin composition.
- the photoactive compound containing the phosphonate structure according to the present invention has a higher melting point than the compound of the similar structure (comparative compounds 1 to 2), and is stable and easy to handle.
- PMEA propylene glycol monomethyl ether acetate
- a photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Formula 4 prepared in Synthesis Example 2 was used instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1.
- a photosensitive resin composition was prepared in the same manner as in Example 1, except that BAOX's OXE-02 compound was used instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1.
- a photosensitive resin composition was prepared in the same manner as in Example 1 except for using the compound of Formula 7 shown in the Example of Korean Patent Publication No. 10-2010-0092904 instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1. Prepared.
- the photoactive compound according to the present invention exhibits excellent effects in terms of luminance than when using the conventional photoactive compound because of its good heat resistance without causing yellowing.
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Abstract
The present application relates to: a photoactive compound simultaneously comprising an oxime ester group and a phosphonate group; and a light-sensitive resin composition comprising same, and the compound of the present application has outstanding storage stability and high-temperature processing characteristics.
Description
본 출원은 2012년 5월 30일에 한국특허청에 제출된 한국 특허 출원 제 10-2012-0057757호 및 2013년 5월 14일에 한국특허청에 제출된 한국 특허 출원 제 10-2013-0054473호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This application is subject to the Korean Patent Application No. 10-2012-0057757, filed with the Korean Patent Office on May 30, 2012, and the Korean Patent Application No. 10-2013-0054473, filed with the Korean Patent Office on May 14, 2013. Claiming benefit, the entire contents of which are incorporated herein by reference.
본 출원은 옥심 에스테르기와 포스포네이트기를 포함하는 포함하는 광활성 화합물 및 이를 포함하는 감광성 수지 조성물에 관한 것이다.The present application relates to a photoactive compound comprising an oxime ester group and a phosphonate group and a photosensitive resin composition comprising the same.
본 출원은 옥심 에스테르기와 포스포네이트기를 포함하는 광활성 화합물 및 이를 포함하는 감광성 수지 조성물에 관한 것이다.The present application relates to a photoactive compound comprising an oxime ester group and a phosphonate group and a photosensitive resin composition comprising the same.
감광성 수지 조성물은 기판상에 도포되어 도막을 형성하고, 이 도막의 특정 부분에 포토마스크 등을 이용하여 광조사에 의한 노광을 실시한 후, 비노광부를 현상 처리하여 제거함으로써 패턴을 형성하는데 사용될 수 있다. 이러한 감광성 수지 조성물은 광을 조사하여 중합하고 경화시키는 것이 가능하므로 광경화성 잉크, 감광성 인쇄판, 각종 포토레지스트, LCD용 컬러 필터 포토레지스트, 수지 블랙 매트릭스용 포토레지스트, 또는 투명 감광재 등에 이용되고 있다. The photosensitive resin composition may be applied to a substrate to form a coating film, and a specific portion of the coating film may be exposed by light irradiation using a photomask or the like, and then used to form a pattern by developing and removing the non-exposed portion. . Since such a photosensitive resin composition can irradiate, superpose | polymerize, and harden | cure light, it is used for photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for LCD, photoresists for resin black matrices, transparent photoresists, and the like.
그 중 투명한 감광성 수지 조성물은 컬럼 스페이서, 오버코트 및 패시베이션 막에 이용되는 것으로, 통상적으로 안료와 같은 착색 조제를 사용하지 않고, 알칼리 가용성 수지, 에틸렌성 불포화 결합을 갖는 중합성 화합물, 광중합 개시제 및 용매를 포함한다.Among them, the transparent photosensitive resin composition is used for column spacers, overcoats, and passivation membranes, and it is generally possible to use an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a solvent without using a colorant such as a pigment. Include.
그 중 착색 감광성 수지 조성물은 컬러 필터 포토레지스트와 수지 블랙 매트릭스용 포토레지스트에 이용되는 것으로, 통상적으로 레드, 그린, 블루, 블랙의 착색제, 알칼리 가용성 수지, 에틸렌성 불포화 결합을 갖는 중합성 화합물, 광중합 개시제 및 용매를 포함한다.Among them, the colored photosensitive resin composition is used for a color filter photoresist and a photoresist for a resin black matrix, and is usually a colorant of red, green, blue, and black, an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, and photopolymerization. Initiator and solvent.
감광성 수지 조성물은 LCD의 용도가 고급화, 다양화 됨에 따라 종래의 노트북, 모바일 등의 용도외에 TV, 모니터 등의 액정표시소자를 구성하는 용도로 제작되고 있으며, 생산성 및 내구성 향상을 위해 빛에 빠르게 반응하고, 기계적으로 우수한 물성에 대한 요구가 높아지고 있다. 포토리소그래피(Photo-lithography) 법에 의해 패턴을 형성시키거나, 전면 노광을 통해 절연 보호막을 형성하는 경우에 있어 빛에 빠르게 반응하는 특성, 즉 광감도는 매우 중요한 역할을 하는 요인이 된다. 또한, 외부에서 가한 충격에 의해 액정표시소자가 파손되지 않고 원래의 성능을 발휘하게 하기 위해서 지지대 역할을 하는 컬럼 스페이서 또는 보호막의 역할을 하는 오버코트와 패시베이션 막은 기계적 물성이 우수해야 한다. The photosensitive resin composition has been manufactured for the purpose of constituting liquid crystal display devices such as TVs and monitors in addition to the conventional notebooks and mobiles as the use of LCDs has been advanced and diversified, and responds quickly to light for improving productivity and durability. In addition, the demand for mechanically excellent physical properties is increasing. In the case of forming a pattern by a photo-lithography method or forming an insulating protective film through full exposure, a property that reacts quickly to light, that is, light sensitivity becomes a very important factor. In addition, the overcoat and passivation film serving as a column spacer or a protective film, which serves as a support, to exhibit the original performance without damage to the liquid crystal display device due to an external impact, should have excellent mechanical properties.
따라서, 광감도가 우수한 광중합 개시제를 사용하면 이러한 문제들을 해결할 수 있다. 광감도가 우수한 광중합 개시제를 사용하는 경우, 적은 양의 광중합 개시제로도 충분한 감도를 구현할 수 있어 액정의 오염원이 줄어들고, 패턴의 잔막률이 상승될 뿐만 아니라, 조성물 제조 시 다른 원재료의 가용 폭을 높일 수 있다는 장점을 지니게 된다.Therefore, the use of a photopolymerization initiator with excellent photosensitivity can solve these problems. When using a photoinitiator with excellent photosensitivity, sufficient sensitivity can be realized even with a small amount of photopolymerization initiator, thereby reducing the contamination of liquid crystals, increasing the residual film ratio of the pattern, and increasing the usable width of other raw materials when preparing the composition. It has the advantage of being.
따라서, 소량의 사용으로도 UV 광원을 효율적으로 흡수할 수 있으며, 감도와 고온공정 특성이 우수한 광중합 개시제의 개발이 요구되고 있다.Therefore, development of a photoinitiator which can absorb a UV light source efficiently even with a small amount of use, and is excellent in a sensitivity and a high temperature process characteristic is calculated | required.
본 출원이 해결하고자 하는 과제는 종래의 광중합 개시제들의 단점을 모두 극복할 수 있고, 감도, 내화학성, 현상성을 저하시키지 않으면서도 보관이 용이하며, 고온 공정에서의 퓸(fume) 특성이 우수한 신규 광활성 화합물 및 이를 포함하는 감광성 수지 조성물을 제공하는 것이다.The problem to be solved by the present application is to overcome all the disadvantages of the conventional photopolymerization initiator, easy to store without degrading sensitivity, chemical resistance, developability, and excellent fume (fume) properties in high temperature process It is to provide a photoactive compound and a photosensitive resin composition comprising the same.
본 출원의 일 구현예는 하기 화학식 1로 표시되는 광활성 화합물을 제공한다. One embodiment of the present application provides a photoactive compound represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,
Y는 R, OR, SR, COR 및 OCOR로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 C1~C15의 알킬렌기이고,Y is a C 1 to C 15 alkylene group unsubstituted or substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR,
M1 은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이며,M 1 is an alkyl group of C 1 ~ C 8 ; Or an aryl group of C 6 ~ C 12 ,
R1은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이고,R 1 is a C 1 ~ C 8 alkyl group; Or an aryl group of C 6 ~ C 12 ,
R2 내지 R6 중 적어도 하나는 XA이고, 나머지는 각각 독립적으로 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되며,At least one of R 2 to R 6 is XA, and the others are each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′,
X는 직접 연결이거나; C=O; O; S; S=O; 및 SO2로 이루어진 군으로부터 선택되고,X is a direct link; C = O; O; S; S = O; And SO 2 ,
A는 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되는 하나 이상의 기로 치환 또는 비치환된 C6~C20의 아릴기이며,A is a C 6 -C 20 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ', and CONRR',
R 및 R′는 각각 독립적으로 수소, C1~C10의 알킬기, C1~C10의 할로알킬기 및 C7~C13의 아릴알킬기로 이루어진 군으로부터 선택되거나, 상기 R과 R′는 함께 고리를 형성할 수 있다.R and R 'are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl group, C 1 -C 10 haloalkyl group and C 7 -C 13 arylalkyl group, wherein R and R' together are a ring Can be formed.
본 출원의 일 구현예는 상기 화학식 1 표시되는 광활성 화합물; 알칼리 가용성 바인더 수지; 에틸렌성 불포화 결합을 포함하는 중합성 화합물; 및 용매를 포함하는 감광성 수지 조성물을 제공한다. One embodiment of the present application is a photoactive compound represented by Formula 1; Alkali-soluble binder resins; Polymeric compounds containing ethylenically unsaturated bonds; And it provides a photosensitive resin composition comprising a solvent.
본 출원의 일 구현예는 상기 감광성 수지 조성물을 이용하여 제조된 감광재를 제공한다. One embodiment of the present application provides a photosensitive material prepared using the photosensitive resin composition.
본 출원의 일 구현예는 상기 감광성 수지 조성물을 이용하여 제조된 전자소자를 제공한다.One embodiment of the present application provides an electronic device manufactured using the photosensitive resin composition.
본 출원을 통해 제공되는 화합물은 감도, 내화학성, 현상성을 저하시키지 않으면서도 보관이 용이하며, 고온 공정에서의 퓸(fume) 발생 억제 특성이 우수하다. 따라서, 본 출원에 따른 감광성 수지 조성물은 액정표시소자의 컬럼 스페이서, 오버코트 및 패시베이션 재료의 경화에 유리할 뿐 아니라 전자소자를 제조에 있어서 유리하다.The compound provided through the present application is easy to store without degrading sensitivity, chemical resistance, and developability, and has excellent fume generation suppression property in a high temperature process. Accordingly, the photosensitive resin composition according to the present application is advantageous not only for curing the column spacer, overcoat and passivation material of the liquid crystal display device, but also in manufacturing the electronic device.
본 출원의 이점 및 특징, 그리고 그것들을 달성하는 방법은 상세하게 후술되어 있는 구현예들을 참조하면 명확해질 것이다. 그러나, 본 출원은 이하에서 개시되는 구현예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 구현예들은 본 출원의 개시가 완전하도록 하며, 본 출원이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 출원은 청구항의 범주에 의해 정의될 뿐이다. Advantages and features of the present application, and methods of achieving them will be apparent with reference to the embodiments described below in detail. However, the present application is not limited to the embodiments disclosed below, but will be implemented in various different forms, only the embodiments make the disclosure of the present application complete, and those skilled in the art to which the present application belongs. It is provided to fully inform the person having the scope of the invention, this application is defined only by the scope of the claims.
다른 정의가 없다면, 본 명세서에서 사용되는 모든 용어(기술 및 과학적 용어를 포함)는 본 출원이 속하는 기술분야에서 통상의 지식을 가진 자에게 공통적으로 이해될 수 있는 의미로 사용될 수 있을 것이다. 또한, 일반적으로 사용되는 사전에 정의되어 있는 용어들은 명백하게 특별히 정의되어 있지 않는 한 이상적으로 또는 과도하게 해석되지 않는다.Unless otherwise defined, all terms used in this specification (including technical and scientific terms) may be used as meanings that can be commonly understood by those skilled in the art to which this application belongs. In addition, terms that are defined in a commonly used dictionary are not ideally or excessively interpreted unless they are specifically defined clearly.
이하, 본 출원을 상세히 설명한다.Hereinafter, the present application will be described in detail.
본 출원의 발명자들은 한 분자 내에 옥심 에스테르기 및 포스포네이트기를 함께 포함하는 구조의 화합물을 합성하였으며, 이러한 화합물이 기존 다른 광개시제에 비해 자외선을 효율적으로 흡수하고 감도와 고온공정 특성이 우수함을 확인하였다.The inventors of the present application synthesized a compound having a structure containing both an oxime ester group and a phosphonate group in one molecule, and confirmed that the compound absorbs ultraviolet rays more efficiently than other photoinitiators and has excellent sensitivity and high temperature processing characteristics. .
종래의 옥심 에스테르기를 포함하는 광활성 화합물은 아래와 같은 문제점이 있었다 Conventional photoactive compounds containing oxime ester groups have the following problems
옥심 에스테르 구조의 광개시제로는 α-옥소옥심 유도체(일본공개 특허공보 소61-118423호), β-아미노옥심을 사용한 광개시제(미국특허 제5,776,996호) 등이 개발되었다. As photoinitiators of the oxime ester structure, α-oxo oxime derivatives (JP-A-61-118423), photoinitiators using β-amino oximes (US Pat. No. 5,776,996) and the like have been developed.
그러나 상기와 같이 사용된 옥심 유도체 화합물 중 초기에 개발된 화합물은 광개시 효율이 낮으며, 색 특성이 좋을 경우 UV 광원 흡수에 효율적이지 못하다. 1990년대 후반 이후에 발표된 화합물들은 광개시 효율이 상당히 개선되었으나 최근에 강화된 공정시간 단축을 충분히 만족시키지 못하고 있다. 특히 안료의 농도가 높거나 코팅막의 두께가 2.5 ㎛ 이상이 되는 후막의 경화도를 충분히 만족하지 못하여 여전히 미세 패턴의 형성에 난점이 있고, 형성된 패턴이 제품에서 요구되는 CD (critical dimension)나 기계적 강도를 만족시킬 수 없다.However, among the oxime derivative compounds used as described above, the compounds initially developed have low photoinitiation efficiency and are not effective in absorbing UV light sources when the color characteristics are good. Compounds published after the late 1990s have significantly improved photoinitiation efficiency but do not fully satisfy the recently enhanced process time reductions. In particular, there is still a difficulty in forming a fine pattern because the pigment concentration is high or the thickness of the coating film is 2.5 µm or more. Can't satisfy
종래 알려진 옥심 유도체 화합물은 광개시 효율이 낮으며, 공정시간 면에서 좋지 않고, 기계적 강도가 약하거나, 보관 안정성이 떨어지는 단점이 있다.Conventionally known oxime derivative compounds have a disadvantage of low photoinitiation efficiency, poor processing time, weak mechanical strength, and poor storage stability.
최근에 상용화되고 있는 BASF 社의 옥심 에스테르계 광중합 개시제 Irgacure OXE 01, Irgacure OXE 02는 감도가 상당히 개선되어 감광성 수지 조성물의 용도로 각광받고 있다. 그러나 이 광중합 개시제들은 상당히 고가여서 경제적 측면에서 충분한 감도를 낼 정도로 사용할 수 없고, 광중합 개시제 자체의 보관 안정성이 떨어지는 단점이 있다.The recently commercialized oxime ester photopolymerization initiators Irgacure OXE 01 and Irgacure OXE 02 from BASF Co., Ltd. have been significantly improved in sensitivity, and are being spotlighted for use in photosensitive resin compositions. However, these photopolymerization initiators are considerably expensive and cannot be used to give sufficient sensitivity in terms of economics, and the photopolymerization initiator itself has a disadvantage in poor storage stability.
본 출원의 일 구현예에 따른 광활성 화합물은 종래의 옥심 에스테르계 광중합 개시제에 비하여 광개시 효율이 우수하고, 공정시간이 단축되며, 기계적 강도가 우수하고, 경제적인 장점도 우수하며, 보관 안정성도 개선되며, 현상성이 우수한 장점이 있다. 또한, 감도가 우수하고, 에틸렌성 불포화 결합을 갖는 중합성 화합물에 대해 용해성이 충분하여 시간 경과에 따라서도 안정한 장점이 있다. 또한, i-line(365 ㎚)의 자외선을 효율적으로 흡수하여 라디칼을 생성하는 효율이 우수하고, 용해도 및 바인더와의 상용성이 우수하며, 고온공정 특성이 우수한 장점이 있다. The photoactive compound according to the embodiment of the present application has superior photoinitiation efficiency, shorter processing time, superior mechanical strength, superior economical advantages, and improved storage stability compared to the conventional oxime ester photopolymerization initiator. And, there is an advantage in developing. Moreover, it has the advantage of being excellent in sensitivity, having sufficient solubility with respect to the polymeric compound which has an ethylenically unsaturated bond, and being stable also over time. In addition, the efficiency of generating radicals by efficiently absorbing ultraviolet rays of i-line (365 nm), and excellent solubility and compatibility with the binder, has the advantage of excellent high temperature process characteristics.
본 출원의 일 구현예는 하기 화학식 1로 표시되는 광활성 화합물을 제공한다. One embodiment of the present application provides a photoactive compound represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
본 출원의 일 구현예에 따른 화합물에 있어서, 상기 화학식 1은 화학식 2 일 수 있다. In the compound according to the embodiment of the present application, Chemical Formula 1 may be Chemical Formula 2.
[화학식 2][Formula 2]
본 출원의 일 구현예에 따른 화합물에 있어서, 상기 화학식 1 또는 화학식 2 의 치환기들을 보다 구체적으로 설명하면 하기와 같다.In the compound according to the exemplary embodiment of the present application, the substituents of Chemical Formula 1 or Chemical Formula 2 will be described in more detail below.
상기 Y는 C1~C15의 알킬렌기이거나; 또는 R, OR, SR, COR 및 OCOR로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환된 C1~C15의 알킬렌기일 수 있고, 바람직하게는 C2~C6의 알킬렌기일 수 있다. 그리고, 에틸렌기 또는 프로필렌기인 것이 용해도 및 상용성 면에서 더욱 바람직하다. Y is a C 1 to C 15 alkylene group; Or a C 1 to C 15 alkylene group substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR, and preferably an alkylene group of C 2 to C 6 . In addition, an ethylene group or a propylene group is more preferable in view of solubility and compatibility.
상기 M1 은 C1~C8의 알킬기; 또는 C6~C12의 아릴기일 수 있고, 바람직하게는 C1~C10의 알킬기일 수 있고, 더욱 바람직하게는 메틸기 또는 에틸기일 수 있다. M 1 is an alkyl group of C 1 ~ C 8 ; Or an aryl group of C 6 to C 12 , preferably an alkyl group of C 1 to C 10 , and more preferably a methyl group or an ethyl group.
상기 R1은 C1~C8의 알킬기; 또는 C6~C12의 아릴기일 수 있고, 바람직하게는 메틸기 또는 페닐기일 수 있다. R1 은 노광 시에 활성종인 라디칼로 분해가 되는 부분으로, 특별히 구조상의 제약은 받지 않으나 구조가 단순할수록 움직임이 좋아 광개시 효율이 향상된다.R 1 is an alkyl group of C 1 ~ C 8 ; Or a C 6 -C 12 aryl group, preferably a methyl group or a phenyl group. R 1 is a part which is decomposed into radicals which are active species at the time of exposure, and is not particularly limited in structure, but the simpler the structure, the better the movement and the photoinitiation efficiency is improved.
상기 R2 내지 R6 중 적어도 하나는 XA일 수 있고, 바람직하게는 R4가 XA일 수 있다. R2 내지 R6 중 XA를 제외한 나머지는 각각 독립적으로 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되는 것일 수 있다.R2 To R6At least one of may be XA, preferably R4May be XA. R2 To R6Except XA The remainder may be each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
상기 X는 직접 연결이거나; C=O; O; S; S=O; 및 SO2로 이루어진 군으로부터 선택되는 것일 수 있고, 바람직하게는 O 또는 S일 수 있다.X is a direct link; C = O; O; S; S = O; And it may be selected from the group consisting of SO 2 , preferably may be O or S.
상기 화학식 1에서 상기 A는 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되는 하나 이상의 기로 치환 또는 비치환된 C6~C20의 아릴기일 수 있고, 바람직하게는 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되는 하나 이상의 기로 치환 또는 비치환된 페닐기일 수 있다. In Formula 1, A may be a C 6 to C 20 aryl group which is unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′. And preferably a phenyl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
상기 화학식 2에서 A에 대응되는 부분의 치환기는 R7, R8, R9, R10 내지 R11이다. R7, R8, R9, R10 및 R11 은 각각 독립적으로 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되는 것일 수 있다. Substituents corresponding to A in Formula 2 are R 7 , R 8 , R 9 , and R 10 to R 11 . R 7 , R 8 , R 9 , R 10 and R 11 may be each independently selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
상기 R 및 R′는 각각 수소, C1~C10의 알킬기, C1~C10의 할로알킬기 및 C7~C13의 아릴알킬기로 이루어진 군으로부터 선택될 수 있거나, 상기 R과 R′는 함께 고리를 형성할 수 있다. 상기 R과 R′가 함께 고리를 형성하는 경우, 5원, 6원 또는 7원 고리를 형성할 수 있고, 단환 또는 다환의 형태일 수 있으며, 방향족, 지방족환, 헤테로 방향족 또는 헤테로지방족환이 될 수 있다. R and R 'may each be selected from the group consisting of hydrogen, C 1 ~ C 10 alkyl group, C 1 ~ C 10 haloalkyl group and C 7 ~ C 13 arylalkyl group, or R and R' together May form a ring. When R and R 'together form a ring, it may form a 5-membered, 6-membered or 7-membered ring, may be monocyclic or polycyclic, and may be aromatic, aliphatic ring, heteroaromatic or heteroaliphatic ring. have.
상기 할로겐기는 불소, 염소, 브롬 또는 요오드가 될 수 있다.The halogen group may be fluorine, chlorine, bromine or iodine.
상기 아릴기는 단환식 아릴기 또는 다환식 아릴기일 수 있다. The aryl group may be a monocyclic aryl group or a polycyclic aryl group.
상기 아릴기가 단환식 아릴기일 경우 구체적으로, 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기, 스틸베닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. Specifically, when the aryl group is a monocyclic aryl group, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like, but is not limited thereto.
상기 아릴기가 다환식 아릴기의 경우 구체적으로 나프틸기, 안트릴기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. In the case of the polycyclic aryl group, the aryl group may be specifically naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perrylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.
상기 알킬기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 상기 알킬기의 구체적인 예로는 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, sec-부틸기, t-부틸기, n-펜틸기, iso-펜틸기, neo-펜틸기, n-헥실기, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기 등이 될 수 있으나, 이에 한정되는 것은 아니다. The alkyl group may be straight, branched or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. may be, but is not limited thereto.
상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있고, 치환 또는 비치환된 것일 수 있다. 알콕시기의 예로는 메톡시기, 에톡시기, n-프로필옥시기, iso-프로필옥시기, n-부틸옥시기, 시클로펜틸옥시기 등이 될 수 있으나, 이에 한정되는 것은 아니다. The alkoxy group may be linear, branched or cyclic, and may be substituted or unsubstituted. Examples of the alkoxy group may be methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, cyclopentyloxy group and the like, but is not limited thereto.
상기 알킬렌기는 직쇄 또는 분지쇄일 수 있고, 치환 또는 비치환된 것일 수 있다. 상기 알킬렌기의 구체적인 예로는 메틸렌, 에틸렌, 프로필렌, 이소프로필렌, 부틸렌, t-부틸렌 등이 있으나, 이에만 한정되는 것은 아니다. The alkylene group may be linear or branched, and may be substituted or unsubstituted. Specific examples of the alkylene group include methylene, ethylene, propylene, isopropylene, butylene, t-butylene, but are not limited thereto.
본 명세서에서 상기 "치환 또는 비치환"이란 1개 이상의 치환기로 치환되었거나, 어떠한 치환기도 갖지 않는 것을 의미한다. As used herein, the term "substituted or unsubstituted" means substituted with one or more substituents or no substituent.
상기 화학식 1 또는 화학식 2에서 치환기가 특별히 정의되지 않은 부분은 수소일 수 있다.In the general formula (1) or (2), the substituent is not particularly defined may be hydrogen.
상기 화학식 1 또는 화학식 2 로 표시되는 본 출원의 광활성 화합물은 그 구조 내에 옥심 에스테르기 및 포스포네이트기(-Y-PO(OM1)2)를 포함하고 치환 또는 비치환된 페닐기를 포함하는 데 특징이 있다.The photoactive compound of the present application represented by Formula 1 or Formula 2 includes an oxime ester group and a phosphonate group (-Y-PO (OM 1 ) 2 ) in its structure and includes a substituted or unsubstituted phenyl group. There is a characteristic.
상기 포스포네이트기는 화학식 1 또는 화학식 2 로 표시되는 화합물의 용해도를 높여주며, 감광성 수지 조성물에서 알칼리 가용성 바인더 수지와 수소 결합 등을 형성함으로써 바인더 수지와 높은 상용성으로 감광성 수지 조성물의 용해도를 개선시키고, 휘발성을 낮추어주는 역할을 한다. The phosphonate group increases the solubility of the compound represented by Formula 1 or Formula 2, and improves the solubility of the photosensitive resin composition with high compatibility with the binder resin by forming a hydrogen bond with an alkali-soluble binder resin in the photosensitive resin composition. It also lowers volatility.
상기 화학식 1 또는 화학식 2 로 표시되는 본 출원의 광활성 화합물은 녹는 점이 높아서 보관이 용이한 장점이 있고, 고온 공정에서 퓸(fume) 발생을 방지하는 효과가 있다. 컬러필터를 제조할 때를 예로 들면, 종래의 광활성 화합물을 포함하는 감광성 수지 조성물을 사용하는 경우, 노광 공정에서 퓸이 발생되어 공기 중으로 휘발되었다가 마스크와 같은 부분에 부착되어 불량 발생이 있을 수 있다. 또한, 베이킹 공정에서 퓸이 발생되어 오븐 벽에 달라붙었다가 떨어지면 이물질이 될 수 있어, 불량 발생이 있을 수 있다. 그러나, 본 출원의 광활성 화합물을 포함하는 감광성 수지 조성물을 사용하는 경우, 고온 공정에서 퓸 발생을 방지하는 효과가 있으므로, 노광 공정이나 베이킹 공정 등에서 불량 발생을 억제할 수 있는 장점이 있다.The photoactive compound of the present application represented by Formula 1 or Formula 2 has a high melting point and has an advantage of easy storage, and has an effect of preventing generation of fume in a high temperature process. For example, when manufacturing a color filter, when using a photosensitive resin composition containing a conventional photoactive compound, fumes are generated in the exposure process, volatilized into the air, and then adhered to a portion such as a mask, which may cause defects. . In addition, if fume is generated in the baking process and sticks to the oven wall, the fume may be a foreign substance, which may cause a defect. However, in the case of using the photosensitive resin composition containing the photoactive compound of the present application, since there is an effect of preventing the generation of fume in the high temperature process, there is an advantage that can suppress the occurrence of defects in the exposure process, baking process and the like.
본 출원의 일 구현예에 따른 화합물에 있어서, 상기 화학식 1 또는 화학식 2 로 표시되는 화합물의 구체적인 예는 아래와 같으나, 이에만 한정되는 것은 아니다.In the compound according to the exemplary embodiment of the present application, specific examples of the compound represented by Formula 1 or Formula 2 are as follows, but are not limited thereto.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
본 출원의 일 구현예는 상기 화학식 1로 표시되는 광활성 화합물; 알칼리 가용성 바인더 수지; 에틸렌성 불포화 결합을 포함하는 중합성 화합물; 및 용매를 포함하는 감광성 수지 조성물을 제공한다.One embodiment of the present application is a photoactive compound represented by Formula 1; Alkali-soluble binder resins; Polymeric compounds containing ethylenically unsaturated bonds; And it provides a photosensitive resin composition comprising a solvent.
본 출원의 일 구현예에서 상기 화학식 1의 화합물은 화학식 2의 화합물일 수 있다. 또한, 본 출원의 일 구현예에서 상기 화학식 1 또는 화학식 2의 화합물은 화학식 3 내지 화학식 6 중의 어느 하나의 화합물일 수 있다.In one embodiment of the present application, the compound of Formula 1 may be a compound of Formula 2. In addition, in one embodiment of the present application, the compound of Formula 1 or Formula 2 may be a compound of any one of Formulas 3 to 6.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 화학식 1로 표시되는 광활성 화합물의 첨가량은 전체 감광성 수지 조성물 중 0.1 내지 5중량%로 포함될 수 있으나, 이에만 한정되는 것은 아니다. 0.1중량% 미만인 경우 충분한 감도를 내지 못할 수 있고, 5중량%를 초과하는 경우 높은 UV 흡수로 인해 UV 빛이 바닥까지 전달되지 못할 수 있다.In the photosensitive resin composition according to the embodiment of the present application, the amount of the photoactive compound represented by Formula 1 may be included in 0.1 to 5% by weight of the total photosensitive resin composition, but is not limited thereto. If it is less than 0.1% by weight may not give sufficient sensitivity, if it exceeds 5% by weight high UV absorption may not be able to transmit the UV light to the bottom.
본 출원의 일 구현예에 따른 감광성 수지 조성물은 바인더 수지를 포함함으로써, 점도를 조절하는 효과가 있고, 알칼리 현상액을 이용한 패터닝을 가능하게 하는 효과가 있다. 상기 바인더로는 알칼리 가용성 고분자 수지 등 당업계에서 일반적으로 사용되는 것들이 사용될 수 있다. 구체적으로 상기 알칼리 가용성 수지 바인더는 산기(acid functional group)를 포함하는 모노머와 이 모노머와 공중합 가능한 필름강도를 주는 모노머의 공중합체, 또는 이 공중합체가 에폭시기를 함유한 에틸렌성 불포화 화합물과 고분자 반응을 통하여 제조되는 화합물일 수 있다.The photosensitive resin composition according to the exemplary embodiment of the present application has an effect of adjusting the viscosity by including a binder resin, and has an effect of enabling patterning using an alkaline developer. As the binder, those generally used in the art such as an alkali-soluble polymer resin may be used. Specifically, the alkali-soluble resin binder is a copolymer of a monomer containing an acid functional group and a monomer giving a film strength copolymerizable with the monomer, or a polymer reaction with an ethylenically unsaturated compound containing an epoxy group. It may be a compound prepared through.
본 출원에서 사용된 알칼리 가용성 수지 바인더는 산가가 30 내지 300 KOH mg/g 정도일 수 있다. 산가가 30 KOH mg/g 미만인 경우 현상이 잘 이루어지지 않아 깨끗한 패턴을 얻을 수 없고, 또한 300 KOH mg/g을 초과하는 경우는 씻김 특성이 과도하게 향상되어 패턴이 떨어져 나갈 수 있다.The alkali-soluble resin binder used in the present application may have an acid value of about 30 to 300 KOH mg / g. If the acid value is less than 30 KOH mg / g is not well developed to obtain a clean pattern, and if it exceeds 300 KOH mg / g, the washing characteristics are excessively improved and the pattern may fall off.
상기 알칼리 가용성 수지 바인더의 중량평균 분자량은 1,000 내지 200,000의 범위인 것이 바람직하며, 더욱 바람직하게는 분자량이 5,000 내지 100,000의 범위일 수 있다. 알칼리 가용성 바인더 수지의 중량평균분자량이 1,000 미만인 경우 내열성 및 내화학성이 악화되며, 또한 200,000을 초과하는 경우 현상액에 대한 용해도가 낮아져 현상이 되지 않으며 용액의 점도가 지나치게 증가하여 균일한 도포가 어려워 바람직하지 못하다.The weight average molecular weight of the alkali-soluble resin binder is preferably in the range of 1,000 to 200,000, more preferably may be in the range of 5,000 to 100,000. If the weight average molecular weight of the alkali-soluble binder resin is less than 1,000, the heat resistance and chemical resistance deteriorate. If the weight-average molecular weight of the alkali-soluble binder resin is more than 200,000, the solubility in the developing solution is lowered, so that the development is not possible, and the viscosity of the solution is excessively increased, making it difficult to apply uniformly. Can not do it.
상기 산기를 포함하는 모노머의 비제한적인 예로는, (메타)아크릴산, 크로톤산, 이타콘산, 말레인산, 푸마르산, 모노메틸 말레인산, 이소프렌 술폰산, 스티렌 술폰산, 5-노보넨-2-카르복실산, 모노-2-((메타)아크릴로일옥시)에틸 프탈레이트, 모노-2-((메타)아크릴로일옥시)에틸 숙시네이트, ω-카르복시 폴리카프로락톤 모노(메타)아크릴레이트 또는 이들의 혼합물 등이 있다.Non-limiting examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, mono 2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, ω-carboxy polycaprolactone mono (meth) acrylate, or mixtures thereof have.
상기 산기를 포함하는 모노머와 공중합가능한 모노머의 비제한적인 예로는, 벤질(메타)아크릴레이트, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 에틸헥실(메타)아크릴레이트, 2-페녹시에틸(메타)아크릴레이트, 테트라히드로퍼프릴(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시-3-클로로프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 아실옥틸옥시-2-히드록시프로필(메타)아크릴레이트, 글리세롤(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 3-메톡시부틸(메타)아크릴레이트, 에톡시디에틸렌글리콜(메타)아크릴레이트, 메톡시트리에틸렌글리콜(메타)아크릴레이트, 메톡시트리프로필렌글리콜(메타)아크릴레이트, 폴리(에틸렌 글리콜) 메틸에테르(메타)아크릴레이트, 페녹시디에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리프로필렌글리콜(메타)아크릴레이트, 테트라플루오로프로필(메타)아크릴레이트, 1,1,1,3,3,3-헥사플루오로이소프로필(메타)아크릴레이트, 옥타플루오로펜틸(메타)아크릴레이트, 헵타데카플루오로데실(메타)아크릴레이트, 트리브로모페닐(메타)아크릴레이트, 메틸 α-히드록시메틸 아크릴레이트, 에틸 α-히드록시메틸 아크릴레이트, 프로필 α-히드록시메틸 아크릴레이트, 부틸 α-히드록시메틸 아크릴레이트, 디시클로펜타닐 (메타)아크릴레이트, 디시클로펜테닐 (메타)아크릴레이트, 디시클로펜타닐 옥시에틸 (메타)아크릴레이트, 디시클로펜테닐 옥시에틸 (메타)아크릴레이트와 같은 불포화 카르복시산 에스테르류; Non-limiting examples of monomers copolymerizable with the monomer containing the acid group include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) ) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (Meth) acrylate, tetrahydroperpryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) acrylate Methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol ( Meta) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3, 3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl α-hydride Hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, dicyclopentanyl (meth) acrylate, disc Pentenyl (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) unsaturated carboxylic acid esters such as acrylate;
스티렌, α-메틸스티렌, (o,m,p)-비닐 톨루엔, (o,m,p)-메톡시 스티렌, (o,m,p)-클로로 스티렌과 같은 방향족 비닐류; Aromatic vinyls such as styrene, α-methylstyrene, (o, m, p) -vinyl toluene, (o, m, p) -methoxy styrene, (o, m, p) -chloro styrene;
비닐 메틸 에테르, 비닐 에틸 에테르, 알릴 글리시딜 에테르와 같은 불포화 에테르류;Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
N-비닐 피롤리돈, N-비닐 카바졸, N-비닐 모폴린과 같은 N-비닐 삼차아민류; N-페닐 말레이미드, N-(4-클로로페닐) 말레이미드, N-(4-히드록시페닐) 말레이미드, N-시클로헥실 말레이미드와 같은 불포화 이미드류; 무수 말레인산, 무수 메틸 말레인산과 같은 무수 말레인산류; N-vinyl tertiary amines, such as N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine; Unsaturated imides such as N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide; Maleic anhydrides such as maleic anhydride and methyl maleic anhydride;
알릴 글리시딜 에테르, 글리시딜 (메타)아크릴레이트, 3,4-에폭시시클로헥실메틸 (메타)아크릴레이트와 같은 불포화 글리시딜 화합물류 또는 이들의 혼합물 등이 있다.Unsaturated glycidyl compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or mixtures thereof.
상기 에폭시기를 함유한 에틸렌성 불포화 화합물로는, 알릴 글리시딜 에테르, 글리시딜 (메타)아크릴레이트, 3,4-에폭시시클로헥실메틸 (메타)아크릴레이트, 글리시딜 5-노보넨-2-메틸-2-카복실레이트(엔도, 엑소 혼합물), 1,2-에폭시-5-헥센, 및 1,2-에폭시-9-데센으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.As an ethylenically unsaturated compound containing the said epoxy group, allyl glycidyl ether, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2 One or more selected from the group consisting of -methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 바인더 수지의 함량은 감광성 수지 조성물 총 중량을 기준으로 1 ~ 30 중량%일 수 있으나, 이에만 한정되는 것은 아니다. 바인더 수지의 함량이 1 중량% 이상이면 알칼리 수용액을 이용한 패터닝이 잘 되는 효과가 있고, 현상액에 대한 가용성이 나타나지 않아 패턴 형성이 어려워지는 문제를 방지할 수 있으며, 30 중량% 이하면 현상 공정 때 패턴의 유실이 발생하는 것을 방지하고, 전체 용액의 점도가 너무 높아지게 되어 코팅에 어려움이 있을 수 있는 문제를 방지할 수 있는 효과가 있다.In the photosensitive resin composition according to the embodiment of the present application, the content of the binder resin may be 1 to 30% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto. When the content of the binder resin is 1% by weight or more, the effect of patterning using an alkali aqueous solution is well effected, and the problem of difficulty in forming a pattern due to the lack of solubility in a developer is prevented. There is an effect that can prevent the loss of, and the viscosity of the entire solution is too high to prevent problems that may be difficult to coat.
본 출원의 일 구현예에 따른 감광성 수지 조성물은 가교성 화합물을 포함할 수 있고, 구체적으로, 에틸렌성 불포화 결합을 포함하는 중합성 화합물을 사용할 수 있다. 더욱 구체적으로, 두 개 이상의 불포화 아크릴기를 포함하는 가교성 화합물, 세 개 이상의 불포화 아크릴기를 포함하는 가교성 화합물을 사용할 수 있다. 구체적인 예로서, 에틸렌글리콜 디(메타)아크릴레이트, 에틸렌기의 수가 2 내지 14인 폴리에틸렌 글리콜 디(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 트리메틸올프로판 트리(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 2-트리스아크릴로일옥시메틸에틸프탈산, 프로필렌기의 수가 2 내지 14인 프로필렌 글리콜 디(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트의 산성 변형물과 디펜타에리스리톨 헥사(메타)아크릴레이트의 혼합물(상품명으로 일본 동아합성사의 TO-2348, TO-2349) 등의 다가 알콜을 α,β-불포화 카르복실산으로 에스테르화하여 얻어지는 화합물; 트리메틸올프로판 트리글리시딜에테르아크릴산 부가물, 비스페놀 A 디글리시딜에테르아크릴산 부가물 등의 글리시딜기를 함유하는 화합물에 (메타)아크릴산을 부가하여 얻어지는 화합물; β-히드록시에틸(메타)아크릴레이트의 프탈산디에스테르, β-히드록시에틸 (메타)아크릴레이트의 톨루엔 디이소시아네이트 부가물 등의 수산기 또는 에틸렌성 불포화 결합을 갖는 화합물과 다가 카르복실산과의 에스테르 화합물, 또는 폴리이소시아네이트와의 부가물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트 등의 (메타)아크릴산 알킬에스테르; 및 9,9'-비스[4-(2-아크릴로일옥시에톡시)페닐]플루오렌으로 이루어지는 군으로부터 선택되는 1종 이상을 포함할 수 있으며, 이들로만 한정되지 않고 당 기술 분야에 알려져 있는 화합물들을 사용할 수 있다. 또한 경우에 따라서는 이들 화합물에 실리카 분산체를 사용할 수 있는데, 예를 들면 Hanse Chemie 社제 Nanocryl XP series(0596, 1045, 21/1364)와 Nanopox XP series(0516, 0525) 등이 있다.The photosensitive resin composition according to the embodiment of the present application may include a crosslinkable compound, and specifically, a polymerizable compound including an ethylenically unsaturated bond may be used. More specifically, a crosslinkable compound including two or more unsaturated acrylic groups and a crosslinkable compound including three or more unsaturated acrylic groups may be used. As a specific example, ethylene glycol di (meth) acrylate, an ethylene group having 2 to 14 polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene glycol di (meth) acrylate with 2 to 14 propylene groups, dipentaerythritol penta A mixture of an acidic modification of (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate (trade name TO- 2348, TO-2349) compound obtained by esterifying polyhydric alcohols, such as (alpha), (beta)-unsaturated carboxylic acid; Compounds obtained by adding (meth) acrylic acid to a compound containing glycidyl groups such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Ester compound of the compound which has hydroxyl group or ethylenically unsaturated bond, such as phthalic acid diester of (beta) -hydroxyethyl (meth) acrylate and toluene diisocyanate adduct of (beta) -hydroxyethyl (meth) acrylate, and polyhydric carboxylic acid Or adducts with polyisocyanates; (Meth) acrylic-acid alkylesters, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; And 9,9'-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, and may include one or more selected from the group consisting of, but are not limited to, those known in the art. Compounds can be used. In some cases, silica dispersions may be used for these compounds, for example, Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 가교성 화합물, 구체적으로 에틸렌성 불포화 결합을 포함하는 중합성 화합물의 함량은 감광성 수지 조성물 총 중량을 기준으로 0.5 내지 30 중량% 일 수 있으나, 이에만 한정되는 것은 아니다. 함량이 0.5 중량% 미만인 경우 빛에 의한 가교반응이 진행되지 않아 바람직하지 못하며, 30 중량%를 초과하면 알칼리에 대한 가용성이 떨어져 패턴 형성이 어려운 단점이 있다.In the photosensitive resin composition according to the embodiment of the present application, the content of the crosslinkable compound, specifically, the polymerizable compound including an ethylenically unsaturated bond may be 0.5 to 30% by weight based on the total weight of the photosensitive resin composition. However, the present invention is not limited thereto. If the content is less than 0.5% by weight is not preferable because the cross-linking reaction is not progressed by light, when the content exceeds 30% by weight is difficult to form a pattern of the poor solubility in alkali.
본 출원의 일 구현예에 따른 감광성 수지 조성물에서, 상기 용매의 비제한적인 예로는 메틸 에틸 케톤, 메틸셀로솔브, 에틸셀로솔브, 에틸렌글리콜 디메틸 에테르, 에틸렌글리콜 디에틸 에테르, 프로필렌글리콜 디메틸 에테르, 프로필렌글리콜 디에틸 에테르, 디에틸렌글리콜 디메틸에테르, 디에틸렌글리콜 디에틸에테르, 디에틸렌글리콜 메틸 에틸에테르, 2-에톡시 프로판올, 2-메톡시 프로판올, 3-메톡시 부탄올, 시클로헥사논, 시클로펜타논, 프로필렌글리콜 메틸 에테르 아세테이트, 프로필렌글리콜 에틸 에테르 아세테이트, 3-메톡시부틸 아세테이트, 에틸 3-에톡시 프로피오네이트, 에틸 셀로솔브아세테이트, 메틸 셀로솔브아세테이트, 부틸 아세테이트, 및 디프로필렌글리콜 모노메틸 에테르로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.In the photosensitive resin composition according to the embodiment of the present application, non-limiting examples of the solvent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclo Pentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, and dipropylene glycol monomethyl May contain one or more selected from the group consisting of ethers .
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 용매의 함량은 감광성 수지 조성물 총 중량을 기준으로 40 내지 95 중량% 일 수 있으나, 이에만 한정되는 것은 아니다.In the photosensitive resin composition according to the embodiment of the present application, the content of the solvent may be 40 to 95 wt% based on the total weight of the photosensitive resin composition, but is not limited thereto.
본 출원의 일 구현예에 따른 감광성 수지 조성물은 투명 감광성 수지 조성물이고, 상기 화학식 1로 표시되는 광활성 화합물 0.1 내지 5 중량%, 에틸렌성 불포화 결합을 포함하는 중합성 화합물 0.5 내지 30 중량%, 알칼리 가용성 바인더 수지 1 내지 30 중량% 및 용매 40 내지 95 중량%로 포함할 수 있다.Photosensitive resin composition according to an embodiment of the present application is a transparent photosensitive resin composition, 0.1 to 5% by weight of the photoactive compound represented by the formula (1), 0.5 to 30% by weight of a polymerizable compound containing an ethylenically unsaturated bond, alkali soluble It may include 1 to 30% by weight of the binder resin and 40 to 95% by weight of the solvent.
본 출원의 일 구현예에 따른 감광성 수지 조성물은 착색제를 더 포함할 수 있다. The photosensitive resin composition according to the embodiment of the present application may further include a colorant.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 착색제로는 1종 이상의 안료, 염료 또는 이들의 혼합물을 사용할 수 있다. 구체적으로 예시하면, 흑색 안료로는 카본 블랙, 흑연, 티탄 블랙 등과 같은 금속산화물 등을 사용할 수 있다. 카본 블랙의 예로는 시스토 5HIISAF-HS, 시스토 KH, 시스토 3HHAF-HS, 시스토 NH, 시스토 3M, 시스토 300HAF-LS, 시스토 116HMMAF-HS, 시스토 116MAF, 시스토 FMFEF-HS, 시스토 SOFEF, 시스토 VGPF, 시스토 SVHSRF-HS 및 시스토 SSRF(동해카본 ㈜) ; 다이어그램 블랙 II, 다이어그램 블랙 N339, 다이어그램 블랙 SH, 다이어그램 블랙 H, 다이어그램 LH, 다이어그램 HA, 다이어그램 SF, 다이어그램 N550M, 다이어그램 M, 다이어그램 E, 다이어그램 G, 다이어그램 R, 다이어그램 N760M, 다이어그램 LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B 및 OIL31B(미쯔비시화학㈜) ; PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, 및 LAMP BLACK-101(대구사㈜); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170(콜롬비아 카본㈜) 또는 이들의 혼합물 등이 있다. 또한, 색깔을 띄는 착색제의 예로는 카민 6B(C.I.12490), 프탈로시아닌 그린(C.I. 74260), 프탈로시아닌 블루(C.I. 74160), 페릴렌 블랙(BASF K0084. K0086), 시아닌 블랙, 리놀옐로우(C.I.21090), 리놀 옐로우GRO(C.I. 21090), 벤지딘 옐로우4T-564D, 빅토리아 퓨어 블루(C.I.42595), C.I. PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36, 58; C.I. PIGMENT blue 15:1, 15:3, 15:4, 15:6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37 등이 있고, 이 밖에 백색 안료, 형광 안료 등도 이용할 수 있다. 안료로 사용되는 프탈로시아닌 계 착화합물로는 구리 외에 아연을 중심 금속으로 하는 물질도 사용 가능하다.In the photosensitive resin composition according to the embodiment of the present application, the coloring agent may be used one or more pigments, dyes or mixtures thereof. Specifically, as the black pigment, a metal oxide such as carbon black, graphite, titanium black, or the like may be used. Examples of carbon black include cysto 5HIISAF-HS, cysto KH, cysto 3HHAF-HS, cysto NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, cysto 116MAF, cysto FMFEF-HS , Sisto SOFEF, Sisto VGPF, Sisto SVHSRF-HS and Sisto SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Daegu Corporation); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 (Colombia Carbon, Inc.) or mixtures thereof. In addition, examples of the colorant to be colored are carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086), cyanine black, linole yellow (CI21090), Linol yellow GRO (CI 21090), benzidine yellow 4T-564D, Victoria pure blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36, 58; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37, etc. In addition, a white pigment, a fluorescent pigment, etc. can also be used. As the phthalocyanine-based compound used as a pigment, in addition to copper, a substance containing zinc as the center metal may be used.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 착색제의 함량은 감광성 수지 조성물 총 중량을 기준으로 1 내지 20 중량%일 수 있으나, 이에만 한정되는 것은 아니다.In the photosensitive resin composition according to the embodiment of the present application, the content of the colorant may be 1 to 20% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
본 출원의 일 구현예에 따른 감광성 수지 조성물은 착색 감광성 수지 조성물이고, 상기 화학식 1로 표시되는 광활성 화합물 0.1 내지 5 중량%, 에틸렌성 불포화 결합을 포함하는 중합성 화합물 0.5 내지 30 중량%, 알칼리 가용성 바인더 수지 1 내지 30 중량%, 착색제 1~20중량% 및 용매 40 내지 95 중량%로 포함할 수 있다.Photosensitive resin composition according to an embodiment of the present application is a colored photosensitive resin composition, 0.1 to 5% by weight of the photoactive compound represented by the formula (1), 0.5 to 30% by weight of a polymerizable compound containing an ethylenically unsaturated bond, alkali soluble It may include 1 to 30% by weight of the binder resin, 1 to 20% by weight of the colorant and 40 to 95% by weight of the solvent.
본 출원의 일 구현예에 따른 감광성 수지 조성물은, 상기 구성성분 외에 필요에 따라 제 2 광활성 화합물, 경화촉진제, 열 중합억제제, 분산제, 산화방지제, 자외선흡수제, 가소제, 접착 촉진제, 충전제 또는 계면활성제 등의 첨가제를 하나 또는 둘 이상 추가로 포함할 수 있다.The photosensitive resin composition according to the exemplary embodiment of the present application may include, as necessary, a second photoactive compound, a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, a UV absorber, a plasticizer, an adhesion promoter, a filler, a surfactant, and the like, as necessary. It may further comprise one or two or more additives of.
본 출원의 일 구현예에서 상기 첨가제를 첨가할 경우, 제 2 광활성 화합물은 0.1 내지 5 중량%, 그 외 나머지 첨가제는 각각 0.01 내지 5 중량%로 함유되는 것이 바람직하다.When the additive is added in one embodiment of the present application, it is preferable that the second photoactive compound is contained in an amount of 0.1 to 5% by weight, and the other additives in amounts of 0.01 to 5% by weight, respectively.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 제 2 광활성 화합물은 구체적으로, 트리아진계 화합물, 비이미다졸계 화합물, 아세토페논계 화합물, O-아실옥심계 화합물, 벤조페논계 화합물, 티옥산톤계 화합물, 포스핀 옥사이드계 화합물 및 쿠마린계 화합물로 이루어진 군에서 선택될 수 있다. 상기 제 2 광활성 화합물은 더욱 구체적으로 2,4-트리클로로메틸-(4'-메톡시페닐)-6-트리아진, 2,4-트리클로로메틸-(4'-메톡시스티릴)-6-트리아진, 2,4-트리클로로메틸-(피플로닐)-6-트리아진, 2,4-트리클로로메틸-(3',4'-디메톡시페닐)-6-트리아진, 3-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오} 프로판산, 2,4-트리클로로메틸-(4'-에틸비페닐)-6-트리아진, 2,4-트리클로로메틸-(4'-메틸비페닐)-6-트리아진 등의 트리아진계 화합물; In the photosensitive resin composition according to the embodiment of the present application, the second photoactive compound is specifically, a triazine compound, a biimidazole compound, an acetophenone compound, an O-acyl oxime compound, a benzophenone compound, It may be selected from the group consisting of a thioxanthone compound, a phosphine oxide compound and a coumarin compound. The second photoactive compound is more specifically 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6 -Triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6-tri Triazine compounds such as azine and 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine;
2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐 비이미다졸, 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸 등의 비이미다졸 화합물; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole compounds such as 5′-tetraphenylbiimidazole;
2-히드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 4-(2-히드록시에톡시)-페닐 (2-히드록시)프로필 케톤, 1-히드록시시클로헥실 페닐 케톤, 2,2-디메톡시-2-페닐 아세토페논, 2-메틸-(4-메틸티오페닐)-2-몰폴리노-1-프로판-1-온(Irgacure-907), 2-벤질-2-디메틸아미노-1-(4-몰폴리노페닐)-부탄-1-온(Irgacure-369) 등의 아세토페논계 화합물; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-mol Acetope such as polyno-1-propane-1-one (Irgacure-907) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure-369) Non-based compounds;
BASF 社의 Irgacure OXE 01, Irgacure OXE 02, ADEKA 社의 N-1919, NCI-831, NCI-930과 같은 O-아실옥심계 화합물;O-acyl oxime compounds such as Irgacure OXE 01 from BASF, Irgacure OXE 02, N-1919, NCI-831, NCI-930 from ADEKA Corporation;
4,4'-비스(디메틸아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논 등의 벤조페논계 화합물; 2,4-디에틸 티옥산톤, 2-클로로 티옥산톤, 이소프로필 티옥산톤, 디이소프로필 티옥산톤 등의 티옥산톤계 화합물; 2,4,6-트리메틸벤조일 디페닐포스핀 옥사이드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸 포스핀 옥사이드, 비스(2,6-디클로로벤조일) 프로필 포스핀 옥사이드 등의 포스핀 옥사이드계 화합물; Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these;
3,3'-카르보닐비닐-7-(디에틸아미노)쿠마린, 3-(2-벤조티아졸일)-7-(디에틸아미노)쿠마린, 3-벤조일-7-(디에틸아미노)쿠마린, 3-벤조일-7-메톡시-쿠마린, 10,10'-카르보닐비스[1,1,7,7-테트라메틸-2,3,6,7-테트라하이드로-1H,5H,11H-Cl]-벤조피라노[6,7,8-ij]-퀴놀리진-11-온 등의 쿠마린계 화합물 등이 있다.3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] Coumarin-based compounds such as -benzopyrano [6,7,8-ij] -quinolizin-11-one; and the like.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 경화촉진제의 예로는, 2-머캡토벤조이미다졸, 2-머캡토벤조티아졸, 2-머캡토벤조옥사졸, 2,5-디머캡토-1,3,4-티아디아졸, 2-머캡토-4,6-디메틸아미노피리딘, 펜타에리스리톨 테트라키스(3-머캡토프로피오네이트), 펜타에리스리톨 트리스(3-머캡토프로피오네이트), 펜타에리스리톨 테트라키스(2-머캡토아세테이트), 펜타에리스리톨 트리스(2-머캡토아세테이트), 트리메틸올프로판 트리스(2-머캡토아세테이트), 트리메틸올프로판 트리스(3-머캡토프로피오네이트), 트리메틸올에탄 트리스(2-머캡토아세테이트), 및 트리메틸올에탄 트리스(3-머캡토프로피오네이트)로 이루어진 군으로부터 선택된 1 종 이상을 포함할 수 있으나, 이들로만 한정되는 것은 아니며 당 기술 분야에 알려져 있는 것들을 포함할 수 있다.In the photosensitive resin composition according to an embodiment of the present application, examples of the curing accelerator, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimer Capto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate ), Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) , Trimethylolethane tris (2-mercaptoacetate), and trimethylolethane tris (3-mercaptopropionate) may include one or more selected from the group consisting of, but are not limited thereto. Known things for Pho Can.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 열 중합 억제제로는, p-아니솔, 히드로퀴논, 피로카테콜(pyrocatechol), t-부틸카테콜(t-butylcatechol), N-니트로소페닐히드록시아민 암모늄염, N-니트로소페닐히드록시아민 알루미늄염 및 페노티아진(phenothiazine)으로 이루어진 군으로부터 선택된 1 종 이상을 포함할 수 있으나, 이들로만 한정되는 것은 아니며 당 기술 분야에 알려져 있는 것들을 포함할 수 있다.In the photosensitive resin composition according to the embodiment of the present application, the thermal polymerization inhibitor, p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitroso It may include one or more selected from the group consisting of phenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt and phenothiazine, but are not limited thereto, and those known in the art It may include.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 분산제로는 고분자형, 비이온성, 음이온성, 또는 양이온성 분산제를 사용할 수 있다. 이러한 분산제의 비제한적인 예로는 폴리알킬렌글리콜 및 이의 에스테르, 폴리옥시알킬렌 다가알콜, 에스테르알킬렌 옥사이드 부가물, 알코올알킬렌옥사이드 부가물, 설폰산 에스테르, 설폰산염, 카르복실산에스테르, 카르복실산염, 알킬아미드 알킬렌옥사이드 부가물, 알킬아민 등을 포함할 수 있으며, 이들 중에서 선택된 1종 또는 2종 이상의 혼합물을 사용할 수 있으나, 이들에만 한정하는 것은 아니다.In the photosensitive resin composition according to the embodiment of the present application, the dispersant may be a polymer type, nonionic, anionic, or cationic dispersant. Non-limiting examples of such dispersants include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, esteralkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxes Acid salts, alkylamide alkylene oxide adducts, alkylamines, and the like, and one or a mixture of two or more selected from these may be used, but is not limited thereto.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 산화방지제의 비제한적인 예로는 2,2-티오비스(4-메틸-6-t-부틸페놀) 및 2,6-g,t-부틸페놀 중에서 선택된 1종 이상을 포함할 수 있으나, 이들에만 한정하는 것은 아니다.In the photosensitive resin composition according to the embodiment of the present application, non-limiting examples of the antioxidant are 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-g, t- It may include one or more selected from butylphenol, but is not limited thereto.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 자외선흡수제의 비제한적인 예로는 2-(3-t-부틸-5-메틸-2-히드록시페닐)-5-클로로-벤조트리아졸 및 알콕시 벤조페논 중에서 선택된 1종 이상을 포함할 수 있으나, 이들에만 한정하는 것은 아니다.In the photosensitive resin composition according to the embodiment of the present application, non-limiting examples of the ultraviolet absorber are 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole And it may include one or more selected from alkoxy benzophenone, but is not limited thereto.
본 출원의 일 구현예에 따른 감광성 수지 조성물에 있어서, 상기 계면 활성제로는 MCF 350SF, F-475, F-488, F-552(이하 DIC 사)등을 포함할 수 있으나, 이들에만 한정하는 것은 아니다.In the photosensitive resin composition according to the embodiment of the present application, the surfactant may include MCF 350SF, F-475, F-488, F-552 (hereinafter referred to as DIC), but are not limited thereto. no.
기타 가소제, 접착 촉진제 또는 충전제 등도 종래의 감광성 수지 조성물에 포함될 수 있는 모든 화합물이 사용될 수 있다.Other plasticizers, adhesion promoters, fillers, and the like can also be used for all compounds that can be included in conventional photosensitive resin compositions.
본 출원의 일 구현예는 상기 감광성 수지 조성물을 포함하는 감광재를 제공한다. One embodiment of the present application provides a photosensitive material including the photosensitive resin composition.
본 출원의 일 구현예는 상기 감광성 수지 조성물을 이용하여 제조된 감광재를 제공한다. One embodiment of the present application provides a photosensitive material prepared using the photosensitive resin composition.
상기 감광성 수지 조성물은 감광재에서 건조 및/또는 경화에 의하여 용매의 적어도 일부가 제거된 상태 또는 광경화된 상태로 존재한다. The photosensitive resin composition is present in a state in which at least a part of the solvent is removed or photocured by drying and / or curing in the photosensitive material.
한편, 본 출원에 따른 감광성 수지 조성물은 롤 코터(roll coater), 커튼 코터(curtain coater), 스핀 코터(spin coater), 슬롯 다이 코터, 각종 인쇄, 침적 등에 사용되며, 금속, 종이, 유리 플라스틱 기판 등의 지지체 상에 적용될 수 있다. On the other hand, the photosensitive resin composition according to the present application is used in a roll coater (curtain coater), curtain coater (curtain coater), spin coater (spin coater), slot die coater, various printing, deposition, etc., metal, paper, glass plastic substrate It can be applied on a support such as.
또한 필름 등의 지지체 상에 도포한 후 기타 지지체 상에 전사하거나 제1의 지지체에 도포한 후 블랭킷 등에 전사하고, 다시 제2의 지지체에 전사하는 것도 가능하며, 그 적용 방법은 특별히 한정되지 않는다.Moreover, after apply | coating on support bodies, such as a film, it is also possible to transfer on another support body, or to apply | coat it to a 1st support body, to transfer to a blanket etc., and to transfer to a 2nd support body again, The application method is not specifically limited.
본 출원의 감광성 수지 조성물을 경화시키기 위한 광원으로는, 예컨대 파장이 250 내지 450 ㎚의 광을 발산하는 수은 증기 아크(arc), 탄소 아크 또는 Xe 아크 등이 있다.As a light source for hardening the photosensitive resin composition of this application, mercury vapor arc (arc), carbon arc, or Xe arc etc. which emit light of 250-450 nm in wavelength, etc. are mentioned, for example.
본 출원의 화합물을 포함하는 감광성 수지 조성물은 TFT LCD 컬러필터 제조용 안료분산형 감광재, TFT LCD 또는 유기발광다이오드의 블랙 매트릭스 형성용 감광재, 오버코트층 형성용 감광재, 컬럼 스페이서 감광재, 인쇄배선반용 감광재, 기타 투명 감광재에 사용되는 것이 바람직하나, 광경화성 도료, 광경화성 잉크, 광경화성 접착제, 인쇄판, 및 PDP 제조 등에도 사용할 수 있으며, 그 용도에 특별히 제한을 두지는 않는다.The photosensitive resin composition comprising the compound of the present application is a pigment dispersion type photosensitive material for manufacturing a TFT LCD color filter, a photosensitive material for forming a black matrix of a TFT LCD or an organic light emitting diode, a photosensitive material for forming an overcoat layer, a column spacer photosensitive material, a printed circuit board Although it is preferable to be used for the photosensitive material for a photoresist and other transparent photosensitive materials, it can also be used for manufacture of a photocurable paint, a photocurable ink, a photocurable adhesive agent, a printing plate, and a PDP, and the use is not specifically limited.
본 출원의 일 구현예는 상기 감광성 수지 조성물을 이용하여 제조된 전자소자를 제공한다. One embodiment of the present application provides an electronic device manufactured using the photosensitive resin composition.
본 출원이 속한 분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 출원의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.Those skilled in the art to which this application belongs will be able to perform various applications and modifications within the scope of the present application based on the above contents.
이상으로 본 출원의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 출원의 범위가 제한되는 것이 아닌 점은 명백하다. 따라서, 본 출원의 실질적인 범위는 첨부된 청구항과 그의 등가물에 의하여 정의된다고 할 것이다.As described above in detail a specific part of the present application, it is apparent to those skilled in the art that such a specific technique is only a preferred embodiment, and the scope of the present application is not limited thereto. Accordingly, the substantial scope of the present application will be defined by the appended claims and equivalents thereof.
이하, 본 발명을 실시예를 들어 상세하게 설명한다. 하기 실시예는 본 발명을 설명하기 위한 것으로, 본 발명의 범위는 하기의 특허청구범위에 기재된 범위 및 그 치환 및 변경을 포함하며, 실시예의 범위로 한정되지 않는다.Hereinafter, an Example is given and this invention is demonstrated in detail. The following examples are provided to illustrate the present invention, and the scope of the present invention includes the ranges described in the following claims, their substitutions and changes, and is not limited to the examples.
<실시예><Example>
<합성예 1> Synthesis Example 1
화학식3 화합물의 제조Preparation of Compound
(1) 9-(6-브로모헥실)-카바졸(9-(6-bromohexyl)-carbazole, 1a)의 제조(1) Preparation of 9- (6-bromohexyl) -carbazole (9- (6-bromohexyl) -carbazole, 1a)
디페닐설파이드 55.9g(300 mmol)를 디클로로메탄 500 mL에 녹인 후 염화알루미늄 42g(315 mmol)과 3-클로로프로피오닐클로라이드 40g(315 mmol)을 0 내지 10℃의 범위에서 천천히 나누어 첨가하였다. 이 온도에서 30분 동안 더 교반시킨 후 상온으로 올려서 2시간 더 교반시켰다. 상기 반응물을 얼음물이 든 비이커에 부어준 후 유기층을 추출하고 포화 NaHCO3 수용액으로 세정한 후 무수 소듐설페이트로 물을 제거하고 용매를 진공하에서 제거하고 에틸아세테이트/헥산(1/5)에서 재결정을 수행하여 아실화물 1a 64.5g을 얻었다. (수율 : 78 %) 상기 1a의 1H-NMR을 이용한 측정 결과는 다음과 같다.After dissolving 55.9 g (300 mmol) of diphenylsulfide in 500 mL of dichloromethane, 42 g (315 mmol) of aluminum chloride and 40 g (315 mmol) of 3-chloropropionyl chloride were slowly added in portions ranging from 0 to 10 ° C. After further stirring at this temperature for 30 minutes, the mixture was stirred at room temperature for 2 hours. The reaction was poured into a beaker of ice water, followed by extracting the organic layer, washing with saturated aqueous NaHCO3 solution, removing water with anhydrous sodium sulfate, removing the solvent under vacuum, and recrystallization from ethyl acetate / hexane (1/5). 64.5 g of Acylate 1a was obtained. (Yield: 78%) The measurement results using the 1H-NMR of 1a are as follows.
1H NMR (500 MHz, CDCl3, ppm) : 7.85-7.80 (2H, d, ArH), 7.55-7.48 (2H, m, ArH), 7.45-7.37 (3H, m, ArH), 7.23-7.18 (2H, d, ArH), 3.91 (2H, t, CH2), 3.39 (2H, t, CH2).1 H NMR (500 MHz, CDCl 3 , ppm): 7.85-7.80 (2H, d, ArH), 7.55-7.48 (2H, m, ArH), 7.45-7.37 (3H, m, ArH), 7.23-7.18 (2H , d, ArH), 3.91 (2H, t, CH 2), 3.39 (2H, t, CH 2 ).
(2) 1b의 제조(2) Preparation of 1b
상기 (1)에서 얻은 화합물(1a) 64.3 g(232 mmol)와 테트라부틸암모늄브로마이드 0.23g(7mmol)을 트리에틸포스파이트 231g에 녹인 후 150℃, 질소기류 하에서 1 시간 동안 교반시켰다. 상기 혼합물을 상온으로 식힌 후 진공으로 잔류용매를 제거하였다. 잔류물을 디클로로메탄 600mL에 녹인 후 아이소아밀나이트라이트 35g과 트리메틸클로로실란 32.8g을 0 내지 10℃의 범위에서 천천히 나누어 첨가하였다. 이 온도에서 30분 동안 더 교반시킨 후 상온으로 올려서 2시간 더 교반시켰다. 상기 반응물을 포화 NaHCO3 수용액으로 세정한 후 유기층을 무수 마그네슘설페이트로 물을 제거하고 용매를 진공하에서 제거하고 에틸아세테이트/헥산(1/3)에서 재결정을 수행하여 옥심화합물(1b) 68.9g을 얻었다. (수율 : 73 %) 상기 1b의 1H-NMR을 이용한 측정 결과는 다음과 같다. 64.3 g (232 mmol) of compound (1a) and 0.23 g (7 mmol) of tetrabutylammonium bromide obtained in (1) were dissolved in 231 g of triethylphosphite, and stirred at 150 ° C. for 1 hour under a nitrogen stream. After cooling the mixture to room temperature, the residual solvent was removed by vacuum. The residue was dissolved in 600 mL of dichloromethane, and 35 g of isoamyl nitrite and 32.8 g of trimethylchlorosilane were added slowly in the range of 0 to 10 ° C. After further stirring at this temperature for 30 minutes, the mixture was stirred at room temperature for 2 hours. The reaction was washed with a saturated NaHCO 3 aqueous solution, the organic layer was dried with anhydrous magnesium sulfate, the solvent was removed under vacuum, and recrystallized from ethyl acetate / hexane (1/3) to give 68.9 g of oxime compound (1b). . (Yield: 73%) The measurement results using the 1H-NMR of 1b are as follows.
1H NMR (500 MHz, CDCl3, ppm) : 11.4 (1H, s, NOH), 7.85-7.80 (2H, d, ArH), 7.88-7.80 (2H, m, ArH), 7.50-7.44 (2H, m, ArH), 7.40-7.35 (3H, m, ArH), 7.13-7.08 (2H, d, ArH), 4.16-4.00 (4H, m, 2OCH2), 3.47 (2H, d, CH2), 1.26-1.15 (6H, m, 2CH3).1 H NMR (500 MHz, CDCl 3 , ppm): 11.4 (1H, s, NOH), 7.85-7.80 (2H, d, ArH), 7.88-7.80 (2H, m, ArH), 7.50-7.44 (2H, m , ArH), 7.40-7.35 (3H, m, ArH), 7.13-7.08 (2H, d, ArH), 4.16-4.00 (4H, m, 20CH 2 ), 3.47 (2H, d, CH 2 ), 1.26- 1.15 (6H, m, 2 CH 3 ).
(3) 화학식 3 화합물의 제조(3) Preparation of Compound of Formula 3
상기 (2)에서 얻은 화합물(1b) 67.8 g(167 mmol)와 트리에틸아민 (22g, 217 mmol)을 500 mL의 디클로로메탄에 녹인 용액에 벤조일클로라이드 (28g, 200 mmol)을 첨가하여 상온에서 1 시간 동안 교반시켰다. 상기 반응물을 포화 NaHCO3 수용액으로 2회 세정한 후 유기층을 무수 마그네슘설페이트로 물을 제거하고 용매를 진공하에서 제거하고 에틸아세테이트/헥산(1/3)에서 재결정을 수행하여 화학식 3의 화합물 77.7g을 얻었다. (수율 : 91 %) 상기 화학식 3의 1H-NMR을 이용한 측정 결과는 다음과 같다. 67.8 g (167 mmol) of compound (1b) obtained in (2) and triethylamine (22 g, 217 mmol) were dissolved in 500 mL of dichloromethane, and benzoyl chloride (28 g, 200 mmol) was added thereto. Stir for hours. The reaction was washed twice with saturated NaHCO 3 aqueous solution, and then the organic layer was removed with anhydrous magnesium sulfate, the solvent was removed under vacuum, and recrystallized from ethyl acetate / hexane (1/3) to obtain 77.7 g of Compound 3. Got it. (Yield: 91%) The measurement results using the 1H-NMR of Chemical Formula 3 are as follows.
1H NMR (500 MHz, CDCl3, ppm) : 8.20-8.11 (2H, d, ArH), 8.09-8.03 (2H, d, ArH), 7.69-7.62 (1H, m, ArH), 7.55-7.44 (4H, m, ArH), 7.44-7.39 (3H, m, ArH), 7.25-7.19 (2H, d, ArH), 4.10-4.00 (4H, m, 2OCH2), 3.70 (2H, d, CH2), 1.18-1.11 (6H, m, 2CH3).1 H NMR (500 MHz, CDCl 3 , ppm): 8.20-8.11 (2H, d, ArH), 8.09-8.03 (2H, d, ArH), 7.69-7.62 (1H, m, ArH), 7.55-7.44 (4H , m, ArH), 7.44-7.39 (3H, m, ArH), 7.25-7.19 (2H, d, ArH), 4.10-4.00 (4H, m, 2OCH 2 ), 3.70 (2H, d, CH2), 1.18 -1.11 (6H, m, 2CH 3 ).
<합성예 2> Synthesis Example 2
화학식 4 화합물의 제조Preparation of Compound of Formula 4
합성예 1의 (3) 단계에서 벤조일 클로라이드 대신에 아세틸클로라이드를 사용한 것을 제외하고는 동일한 방법으로 반응시켜 하기 화학식 4로 표시되는 광활성 화합물을 얻었다. 하기 화학식 4로 표시되는 광활성 화합물의 1H-NMR을 이용한 측정 결과는 다음과 같다.Except for using acetyl chloride instead of benzoyl chloride in step (3) of Synthesis Example 1 was reacted in the same manner to obtain a photoactive compound represented by the formula (4). Measurement results using 1 H-NMR of the photoactive compound represented by the formula (4) are as follows.
[화학식 4][Formula 4]
1H NMR (500 MHz, CDCl3, ppm) : 8.00-7.92 (2H, d, ArH), 7.56-7.50 (2H, m, ArH), 7.45-7.40 (3H, m, ArH), 7.20-7.15 (2H, d, ArH), 4.10-4.00 (4H, m, 2OCH2), 3.57 (2H, d, CH2), 2.26 (3H, s, OCH3), 1.18-1.09 (6H, m, 2CH3).1 H NMR (500 MHz, CDCl 3 , ppm): 8.00-7.92 (2H, d, ArH), 7.56-7.50 (2H, m, ArH), 7.45-7.40 (3H, m, ArH), 7.20-7.15 (2H , d, ArH), 4.10-4.00 (4H, m, 20CH 2 ), 3.57 (2H, d, CH 2 ), 2.26 (3H, s, OCH 3 ), 1.18-1.09 (6H, m, 2CH 3 ).
<합성예 3> Synthesis Example 3
화학식 5 화합물의 제조Preparation of Compound of Formula 5
합성예 1의 (1) 단계에서 디페닐설파이드 대신에 4-벤조일디페닐설파이드를 사용한 것을 제외하고는 동일한 방법으로 반응시켜 하기 화학식 5으로 표시되는 광활성 화합물을 얻었다. 하기 화학식 5으로 표시되는 광활성 화합물의 1H-NMR을 이용한 측정 결과는 다음과 같다.Except for using 4-benzoyldiphenyl sulfide instead of diphenyl sulfide in step (1) of Synthesis Example 1 was reacted in the same manner to obtain a photoactive compound represented by the formula (5). Measurement results using 1 H-NMR of the photoactive compound represented by the formula (5) are as follows.
[화학식 5][Formula 5]
1H NMR (500 MHz, CDCl3, ppm) : 8.20-8.12 (4H, m, ArH), 7.84-7.77 (4H, m, ArH), 7.68-7.58 (2H, m, ArH), 7.56-7.40 (8H, m, ArH), 4.10-4.00 (4H, m, 2OCH2), 3.72 (2H, d, CH2), 1.15-1.06 (6H, m, 2CH3).1 H NMR (500 MHz, CDCl 3 , ppm): 8.20-8.12 (4H, m, ArH), 7.84-7.77 (4H, m, ArH), 7.68-7.58 (2H, m, ArH), 7.56-7.40 (8H , m, ArH), 4.10-4.00 (4H, m, 20CH 2 ), 3.72 (2H, d, CH 2 ), 1.15-1.06 (6H, m, 2CH 3 ).
<합성예 4> Synthesis Example 4
화학식6 화합물의 제조Preparation of Compound of Formula 6
합성예 2의 (1) 단계에서 디페닐설파이드 대신에 4-벤조일디페닐설파이드를 사용한 것을 제외하고는 동일한 방법으로 반응시켜 하기 화학식 6으로 표시되는 광활성 화합물을 얻었다. 하기 화학식 6으로 표시되는 광활성 화합물의 1H-NMR을 이용한 측정 결과는 다음과 같다.Except for using 4-benzoyldiphenyl sulfide instead of diphenyl sulfide in step (1) of Synthesis Example 2 was reacted in the same manner to obtain a photoactive compound represented by the formula (6). Measurement results using 1 H-NMR of the photoactive compound represented by the formula (6) are as follows.
[화학식 6][Formula 6]
1H NMR (500 MHz, CDCl3, ppm) : 8.05-7.99 (2H, d, ArH), 7.82-7.74 (4H, m, ArH), 7.62-7.56 (1H, m, ArH), 7.53-7.44 (4H, m, ArH), 7.38-7.33 (2H, d, ArH), 4.15-4.00 (4H, m, 2OCH2), 3.57 (2H, d, CH2), 2.25 (3H, s, OCH3), 1.18-1.07 (6H, m, 2CH3).1 H NMR (500 MHz, CDCl 3 , ppm): 8.05-7.99 (2H, d, ArH), 7.82-7.74 (4H, m, ArH), 7.62-7.56 (1H, m, ArH), 7.53-7.44 (4H , m, ArH), 7.38-7.33 (2H, d, ArH), 4.15-4.00 (4H, m, 20CH 2 ), 3.57 (2H, d, CH 2 ), 2.25 (3H, s, OCH 3 ), 1.18 -1.07 (6H, m, 2CH 3 ).
<실험예 1> Experimental Example 1
하기 표 1의 화합물의 녹는점을 DSC 장비를 이용하여 측정하였으며, 그 결과를 다음 표 1에 나타내었다.Melting points of the compounds of Table 1 were measured using a DSC instrument, and the results are shown in Table 1 below.
표 1 
Table 1
상기 표 1에서 나타낸 바와 같이, 본 발명에 따른 포스포네이트 구조를 포함하고 있는 광활성 화합물이 기존 유사한 구조의 화합물 (비교화합물1~2)보다 녹는점이 높아 안정적이며, 취급도 쉬운 것을 알 수 있다.As shown in Table 1, it can be seen that the photoactive compound containing the phosphonate structure according to the present invention has a higher melting point than the compound of the similar structure (comparative compounds 1 to 2), and is stable and easy to handle.
<실시예 1> <Example 1>
착색 감광성 수지 조성물의 제조Preparation of colored photosensitive resin composition
알칼리 가용성 아크릴계 바인더{벤질메타아크릴레이트/N-페닐말레이미드/스티렌/메타아크릴산(몰비 60/10/12/18, Mw = 10000, 80 KOH ㎎/g)} 8중량부, C. I. 피그먼트 그린 58과 C. I. 피그먼트 옐로우 139로이루어진 그린 밀베이스 43-49 중량부, 중합성 화합물로 디펜타에리스리톨 헥사 아크릴레이트 16중량부, 광중합 개시제로 합성예 1에서 제조된 화학식 3 화합물 2.0 중량부 및 유기 용매로 프로필렌글리콜 모노메틸에테르 아세테이트(PGMEA) 27 내지 33 중량부를 쉐이커를 이용하여 3시간 동안 혼합시켜 감광성 수지 조성물을 제조하였다.Alkali-soluble acrylic binder {benzyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid (molar ratio 60/10/12/18, Mw = 10000, 80 KOH mg / g)} 8 parts by weight, CI pigment green 58 43-49 parts by weight of a green mill base consisting of CI pigment yellow and 139, 16 parts by weight of dipentaerythritol hexa acrylate as a polymerizable compound, 2.0 parts by weight of the compound of formula 3 prepared in Synthesis Example 1 as a photopolymerization initiator, and an organic solvent. 27-33 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was mixed for 3 hours using a shaker to prepare a photosensitive resin composition.
<실시예 2> <Example 2>
착색 감광성 수지 조성물의 제조Preparation of colored photosensitive resin composition
상기 실시예 1에서 합성예 1에서 제조된 화학식3 화합물 대신 합성예 2에서 제조된 화학식 4 화합물을 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 compound of Formula 4 prepared in Synthesis Example 2 was used instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1.
<비교예 1>Comparative Example 1
상기 실시예 1에서 합성예 1에서 제조된 화학식3 화합물 대신 BASF사의 OXE-02 화합물을 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 BAOX's OXE-02 compound was used instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1.
<비교예 2>Comparative Example 2
상기 실시예 1에서 합성예 1에서 제조된 화학식3 화합물 대신 한국공개특허 제10-2010-0092904의 실시예에 나오는 화학식 7의 화합물을 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 for using the compound of Formula 7 shown in the Example of Korean Patent Publication No. 10-2010-0092904 instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1. Prepared.
<실험예 2>Experimental Example 2
상기 제조된 감광성 수지 조성물을 유리 위에 스핀 코팅한 후, 100℃에서 100초간 프리베이크(pre-bake 혹은 soft bake)하는 과정을 통해, 용매를 적당량 제거한다. 코팅된 유리를 i-line 노광기를 통해 노광한 후, 수산화 칼륨(KOH)을 희석한 현상액에 현상하고, 230℃ 오븐에서 20분간 포스트 베이크(postbake 혹은 hardbake) 한 후, 형성된 패턴의 컬러 및 휘도를 측정하여 하기 표 2에 나타내었다.After spin-coating the prepared photosensitive resin composition on glass, a suitable amount of the solvent is removed by prebaking at 100 ° C. for 100 seconds. The coated glass was exposed through an i-line exposure machine, then developed in a developer diluted with potassium hydroxide (KOH), postbaked or hardbake in a 230 ° C. oven for 20 minutes, and then the color and luminance of the formed pattern was measured. The measurement is shown in Table 2 below.
표 2 
TABLE 2
상기 표 2에 나타낸 바와 같이 본 발명에 따른 광활성 화합물은 황변을 일으키지 않고 내열특성이 좋아 기존의 광활성 화합물을 사용했을 때보다 휘도면에서 우수한 효과를 나타냈다.As shown in Table 2, the photoactive compound according to the present invention exhibits excellent effects in terms of luminance than when using the conventional photoactive compound because of its good heat resistance without causing yellowing.
Claims (21)
- 하기 화학식 1로 표시되는 광활성 화합물:A photoactive compound represented by the following formula (1):[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,Y는 R, OR, SR, COR 및 OCOR로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 C1~C15의 알킬렌기이고,Y is a C 1 to C 15 alkylene group unsubstituted or substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR,M1 은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이며,M 1 is an alkyl group of C 1 ~ C 8 ; Or an aryl group of C 6 ~ C 12 ,R1은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이고,R 1 is a C 1 ~ C 8 alkyl group; Or an aryl group of C 6 ~ C 12 ,R2 내지 R6 중 적어도 하나는 XA이고, 나머지는 각각 독립적으로 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되며,At least one of R 2 to R 6 is XA, and the others are each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′,X는 직접 연결이거나; C=O; O; S; S=O; 및 SO2로 이루어진 군으로부터 선택되고,X is a direct link; C = O; O; S; S = O; And SO 2 ,A는 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되는 하나 이상의 기로 치환 또는 비치환된 C6~C20의 아릴기이며,A is a C 6 -C 20 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ', and CONRR',R 및 R′는 각각 독립적으로 수소, C1~C10의 알킬기, C1~C10의 할로알킬기 및 C7~C13의 아릴알킬기로 이루어진 군으로부터 선택되거나, 상기 R과 R′는 함께 고리를 형성할 수 있다.R and R 'are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl group, C 1 -C 10 haloalkyl group and C 7 -C 13 arylalkyl group, wherein R and R' together are a ring Can be formed. - 청구항 1에 있어서, The method according to claim 1,상기 화학식 1은 화학식 2인 것을 특징으로 하는 광활성 화합물:Formula 1 is a photoactive compound, characterized in that:[화학식 2][Formula 2]
상기 화학식 2 에서,In Chemical Formula 2,Y는 R, OR, SR, COR 및 OCOR로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 C1~C15의 알킬렌기이고,Y is a C 1 to C 15 alkylene group unsubstituted or substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR,M1 은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이며,M 1 is an alkyl group of C 1 ~ C 8 ; Or an aryl group of C 6 ~ C 12 ,R1은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이고,R 1 is a C 1 ~ C 8 alkyl group; Or an aryl group of C 6 ~ C 12 ,X는 직접 연결이거나; C=O; O; S; S=O; 및 SO2로 이루어진 군으로부터 선택되며, X is a direct link; C = O; O; S; S = O; And SO 2 ,R2, R3, R5, R6, R7, R8, R9, R10 및 R11 은 각각 독립적으로 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되고,R 2 , R 3 , R 5 , R 6, R 7 , R 8 , R 9 , R 10 and R 11 are each independently a halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′ Selected from the group consisting ofR 및 R′는 각각 독립적으로 수소, C1~C10의 알킬기, C1~C10의 할로알킬기 및 C7~C13의 아릴알킬기로 이루어진 군으로부터 선택되거나, 상기 R과 R′는 함께 고리를 형성할 수 있다.R and R 'are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl group, C 1 -C 10 haloalkyl group and C 7 -C 13 arylalkyl group, wherein R and R' together are a ring Can be formed. - 청구항 1에 있어서, The method according to claim 1,상기 화학식 1은 하기 화학식 3 내지 화학식 6 중에 어느 하나인 것을 특징으로 하는 광활성 화합물: Formula 1 is a photoactive compound, characterized in that any one of the following formulas (3) to:[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
- 하기 화학식 1로 표시되는 광활성 화합물;A photoactive compound represented by Formula 1;알칼리 가용성 바인더 수지;Alkali-soluble binder resins;에틸렌성 불포화 결합을 포함하는 중합성 화합물; 및Polymeric compounds containing ethylenically unsaturated bonds; And용매를 포함하는 감광성 수지 조성물:Photosensitive resin composition comprising a solvent:[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,Y는 R, OR, SR, COR 및 OCOR로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 C1~C15의 알킬렌기이고,Y is a C 1 to C 15 alkylene group unsubstituted or substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR,M1 은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이며,M 1 is an alkyl group of C 1 ~ C 8 ; Or an aryl group of C 6 ~ C 12 ,R1은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이고,R 1 is a C 1 ~ C 8 alkyl group; Or an aryl group of C 6 ~ C 12 ,R2 내지 R6 중 적어도 하나는 XA이고, 나머지는 각각 독립적으로 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되며,At least one of R 2 to R 6 is XA, and the others are each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′,X는 직접 연결이거나; C=O; O; S; S=O; 및 SO2로 이루어진 군으로부터 선택되고,X is a direct link; C = O; O; S; S = O; And SO 2 ,A는 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되는 하나 이상의 기로 치환 또는 비치환된 C6~C20의 아릴기이며,A is a C 6 -C 20 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ', and CONRR',R 및 R′는 각각 독립적으로 수소, C1~C10의 알킬기, C1~C10의 할로알킬기 및 C7~C13의 아릴알킬기로 이루어진 군으로부터 선택되거나, 상기 R과 R′는 함께 고리를 형성할 수 있다.R and R 'are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl group, C 1 -C 10 haloalkyl group and C 7 -C 13 arylalkyl group, wherein R and R' together are a ring Can be formed. - 청구항 4에 있어서, The method according to claim 4,상기 화학식 1은 화학식 2인 것을 특징으로 하는 특징으로 하는 감광성 수지 조성물: Formula 1 is a photosensitive resin composition, characterized in that:[화학식 2] [Formula 2]
상기 화학식 2 에서,In Chemical Formula 2,Y는 R, OR, SR, COR 및 OCOR로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 C1~C15의 알킬렌기이고,Y is a C 1 to C 15 alkylene group unsubstituted or substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR,M1 은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이며,M 1 is an alkyl group of C 1 ~ C 8 ; Or an aryl group of C 6 ~ C 12 ,R1은 C1~C8의 알킬기; 또는 C6~C12의 아릴기이고,R 1 is a C 1 ~ C 8 alkyl group; Or an aryl group of C 6 ~ C 12 ,X는 직접 연결이거나; C=O; O; S; S=O; 및 SO2로 이루어진 군으로부터 선택되며, X is a direct link; C = O; O; S; S = O; And SO 2 ,R2, R3, R5, R6, R7, R8, R9, R10 및 R11 은 각각 독립적으로 할로겐기, CN, R, OR, SR, COR, OCOR, NRR′ 및 CONRR′로 이루어진 군으로부터 선택되고,R 2 , R 3 , R 5 , R 6, R 7 , R 8 , R 9 , R 10 and R 11 are each independently a halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′ Selected from the group consisting ofR 및 R′는 각각 독립적으로 수소, C1~C10의 알킬기, C1~C10의 할로알킬기 및 C7~C13의 아릴알킬기로 이루어진 군으로부터 선택되거나, 상기 R과 R′는 함께 고리를 형성할 수 있다.R and R 'are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl group, C 1 -C 10 haloalkyl group and C 7 -C 13 arylalkyl group, wherein R and R' together are a ring Can be formed. - 청구항 4에 있어서, The method according to claim 4,상기 화학식 1은 하기 화학식 3 내지 화학식 6 중에 어느 하나인 것을 특징으로 하는 감광성 수지 조성물: Formula 1 is a photosensitive resin composition, characterized in that any one of the following formula (3) to:[화학식 3] [Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
- 청구항 4에 있어서, The method according to claim 4,상기 알칼리 가용성 바인더 수지는 산가 30 내지 300 KOH mg/g 인 것을 특징으로 하는 감광성 수지 조성물.The alkali-soluble binder resin has an acid value of 30 to 300 KOH mg / g photosensitive resin composition, characterized in that.
- 청구항 4에 있어서,The method according to claim 4,상기 알칼리 가용성 바인더 수지는 중량평균 분자량이 1,000 내지 200,000인 것을 특징으로 하는 감광성 수지 조성물.The alkali-soluble binder resin has a weight average molecular weight of 1,000 to 200,000, the photosensitive resin composition.
- 청구항 4에 있어서,The method according to claim 4,상기 화학식 1의 광활성 화합물의 함량은 감광성 수지 조성물 총 중량을 기준으로 0.1 내지 5중량% 인 것을 특징으로 하는 감광성 수지 조성물.Content of the photoactive compound of Formula 1 is a photosensitive resin composition, characterized in that 0.1 to 5% by weight based on the total weight of the photosensitive resin composition.
- 청구항 4에 있어서,The method according to claim 4,상기 알칼리 가용성 바인더 수지의 함량은 감광성 수지 조성물 총 중량을 기준으로 1 내지 30 중량% 인 것을 특징으로 하는 감광성 수지 조성물.The content of the alkali-soluble binder resin is 1 to 30% by weight based on the total weight of the photosensitive resin composition, the photosensitive resin composition.
- 청구항 4에 있어서,The method according to claim 4,상기 에틸렌성 불포화 결합을 포함하는 중합성 화합물의 함량은 감광성 수지 조성물 총 중량을 기준으로 0.5 내지 30 중량% 인 것을 특징으로 하는 감광성 수지 조성물.The content of the polymerizable compound including the ethylenically unsaturated bond is a photosensitive resin composition, characterized in that 0.5 to 30% by weight based on the total weight of the photosensitive resin composition.
- 청구항 4에 있어서,The method according to claim 4,상기 용매의 함량은 감광성 수지 조성물 총 중량을 기준으로 40 내지 95중량% 인 것을 특징으로 하는 감광성 수지 조성물.The content of the solvent is a photosensitive resin composition, characterized in that 40 to 95% by weight based on the total weight of the photosensitive resin composition.
- 청구항 4에 있어서, The method according to claim 4,상기 감광성 수지 조성물은 착색제를 더 포함하는 것을 특징으로 하는 감광성 수지 조성물.The photosensitive resin composition further comprises a colorant.
- 청구항 13에 있어서, The method according to claim 13,상기 착색제의 함량은 감광성 수지 조성물 총 중량을 기준으로 1 내지 20 중량%인 것을 특징으로 하는 감광성 수지 조성물.The content of the colorant is a photosensitive resin composition, characterized in that 1 to 20% by weight based on the total weight of the photosensitive resin composition.
- 청구항 4에 있어서, The method according to claim 4,상기 감광성 수지 조성물은 제2 광활성 화합물을 더 포함하는 것을 특징으로 하는 감광성 수지 조성물.The photosensitive resin composition further comprises a second photoactive compound.
- 청구항 15에 있어서, The method according to claim 15,상기 제2 광활성 화합물의 함량은 감광성 수지 조성물 총 중량을 기준으로 0.1 내지 5중량%인 것을 특징으로 하는 감광성 수지 조성물.The content of the second photoactive compound is a photosensitive resin composition, characterized in that 0.1 to 5% by weight based on the total weight of the photosensitive resin composition.
- 청구항 4에 있어서, The method according to claim 4,상기 감광성 수지 조성물은 경화촉진제, 열 중합 억제제, 분산제, 산화방지제, 자외선흡수제, 레벨링제, 광증감제, 가소제, 접착 촉진제, 충전제 및 계면활성제로 이루어진 군에서 선택되는 하나 또는 둘 이상의 첨가제를 더 포함하는 것을 특징으로 하는 감광성 수지 조성물.The photosensitive resin composition further includes one or two or more additives selected from the group consisting of curing accelerators, thermal polymerization inhibitors, dispersants, antioxidants, ultraviolet absorbers, leveling agents, photosensitizers, plasticizers, adhesion promoters, fillers and surfactants. The photosensitive resin composition characterized by the above-mentioned.
- 청구항 17에 있어서, The method according to claim 17,상기 첨가제의 함량은 감광성 수지 조성물 총 중량을 기준으로 각각 0.01 내지 5 중량% 인 것을 특징으로 하는 감광성 수지 조성물.The content of the additive is a photosensitive resin composition, characterized in that 0.01 to 5% by weight, respectively, based on the total weight of the photosensitive resin composition.
- 청구항 4 내지 청구항 18 중 어느 한 항의 감광성 수지 조성물을 이용하여 제조된 감광재.The photosensitive material manufactured using the photosensitive resin composition of any one of Claims 4-18.
- 청구항 19에 있어서, The method according to claim 19,상기 감광재는 TFT LCD 컬러필터 제조용 안료분산형 감광재, TFT LCD 또는 유기발광다이오드의 블랙 매트릭스 형성용 감광재, 오버코트층 형성용 감광재, 컬럼 스페이서 감광재 및 인쇄배선반용 감광재로 이루어진 군으로부터 선택되는 것을 특징으로 하는 감광재.The photosensitive material is selected from the group consisting of pigment dispersion type photosensitive material for manufacturing TFT LCD color filter, photosensitive material for forming black matrix of TFT LCD or organic light emitting diode, photosensitive material for forming overcoat layer, column spacer photosensitive material and photosensitive material for printed wiring board. Photosensitive material characterized in that.
- 청구항 4 내지 청구항 18 중 어느 한 항의 감광성 수지 조성물을 이용하여 제조된 전자소자.An electronic device manufactured using the photosensitive resin composition of claim 4.
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| KR20130054473A KR101489067B1 (en) | 2012-05-30 | 2013-05-14 | Photoactive compound and photosensitive resin composition comprising the same |
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| KR20080104287A (en) * | 2006-03-28 | 2008-12-02 | 후지필름 가부시키가이샤 | Photopolymerization initiator, photosensitive composition, photosensitive film, photosensitive laminate, method of forming permanent pattern and printed board |
| KR20110059525A (en) * | 2009-11-27 | 2011-06-02 | 가부시키가이샤 아데카 | Oxime ester compound and photopolymerization initiator comprising the compound |
| JP2011141413A (en) * | 2010-01-07 | 2011-07-21 | Toppan Printing Co Ltd | Blue photosensitive resin composition and color filter |
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| WO2005080337A1 (en) * | 2004-02-23 | 2005-09-01 | Mitsubishi Chemical Corporation | Oxime ester compound, photopolymerizable composition and color filter utilizing the same |
| KR20080104287A (en) * | 2006-03-28 | 2008-12-02 | 후지필름 가부시키가이샤 | Photopolymerization initiator, photosensitive composition, photosensitive film, photosensitive laminate, method of forming permanent pattern and printed board |
| KR20110059525A (en) * | 2009-11-27 | 2011-06-02 | 가부시키가이샤 아데카 | Oxime ester compound and photopolymerization initiator comprising the compound |
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