TWI376571B - Photo-sensitive resin composition for black matrix, black matrix produced by the composition and liquid crystal display including the black matrix - Google Patents
Photo-sensitive resin composition for black matrix, black matrix produced by the composition and liquid crystal display including the black matrix Download PDFInfo
- Publication number
- TWI376571B TWI376571B TW097106080A TW97106080A TWI376571B TW I376571 B TWI376571 B TW I376571B TW 097106080 A TW097106080 A TW 097106080A TW 97106080 A TW97106080 A TW 97106080A TW I376571 B TWI376571 B TW I376571B
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- TW
- Taiwan
- Prior art keywords
- acrylate
- meth
- black matrix
- acid
- group
- Prior art date
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- 239000011159 matrix material Substances 0.000 title claims description 81
- 239000011342 resin composition Substances 0.000 title claims description 45
- 239000000203 mixture Substances 0.000 title claims description 14
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 81
- -1 bicyclic fluorene compound Chemical class 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- 239000000049 pigment Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 11
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical group C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000052 vinegar Substances 0.000 claims description 8
- 235000021419 vinegar Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- FFOPEPMHKILNIT-UHFFFAOYSA-N Isopropyl butyrate Chemical compound CCCC(=O)OC(C)C FFOPEPMHKILNIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- FYYZTOOGFNLGII-UHFFFAOYSA-N (1,6-dihydroxy-1-prop-2-enoyloxyhexyl) prop-2-enoate Chemical compound OCCCCCC(O)(OC(=O)C=C)OC(=O)C=C FYYZTOOGFNLGII-UHFFFAOYSA-N 0.000 claims description 2
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 claims description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- SFAMKDPMPDEXGH-UHFFFAOYSA-N 2-hydroxyethyl propanoate Chemical compound CCC(=O)OCCO SFAMKDPMPDEXGH-UHFFFAOYSA-N 0.000 claims description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HSZUHSXXAOWGQY-UHFFFAOYSA-N [2-methyl-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)COC(=O)C=C HSZUHSXXAOWGQY-UHFFFAOYSA-N 0.000 claims description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000006226 butoxyethyl group Chemical group 0.000 claims description 2
- LSURRKWOANERMF-UHFFFAOYSA-N butyl 2-(hydroxymethyl)prop-2-enoate Chemical compound CCCCOC(=O)C(=C)CO LSURRKWOANERMF-UHFFFAOYSA-N 0.000 claims description 2
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims 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 claims description 2
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- SYGAXBISYRORDR-UHFFFAOYSA-N ethyl 2-(hydroxymethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CO SYGAXBISYRORDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940117360 ethyl pyruvate Drugs 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229940117955 isoamyl acetate Drugs 0.000 claims description 2
- RFUCOAQWQVDBEU-UHFFFAOYSA-N methyl 2-(hydroxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CO RFUCOAQWQVDBEU-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001054 red pigment Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001052 yellow pigment Substances 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims 2
- UHWZHMJNTNPTGP-QXMHVHEDSA-N (z)-2-decylbut-2-enedioic acid Chemical compound CCCCCCCCCC\C(C(O)=O)=C\C(O)=O UHWZHMJNTNPTGP-QXMHVHEDSA-N 0.000 claims 1
- FMQPBWHSNCRVQJ-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C(F)(F)F)C(F)(F)F FMQPBWHSNCRVQJ-UHFFFAOYSA-N 0.000 claims 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 claims 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims 1
- XYRRJTMWSSGQGR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO.OCC(CO)(CO)CO XYRRJTMWSSGQGR-UHFFFAOYSA-N 0.000 claims 1
- FRWZCZGRCTVLKW-UHFFFAOYSA-N 2-(1H-inden-1-yl)prop-2-enoic acid Chemical compound C1(C=CC2=CC=CC=C12)C(C(=O)O)=C FRWZCZGRCTVLKW-UHFFFAOYSA-N 0.000 claims 1
- WZKHBEGQWSEAJI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound OCCOCCO.COCCOCCOC WZKHBEGQWSEAJI-UHFFFAOYSA-N 0.000 claims 1
- LPWLBMUEYCGYCH-UHFFFAOYSA-N 2-ethylhexanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCC(CC)C(O)=O LPWLBMUEYCGYCH-UHFFFAOYSA-N 0.000 claims 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims 1
- YSIKHBWUBSFBRZ-UHFFFAOYSA-N 3-methoxypropanoic acid Chemical compound COCCC(O)=O YSIKHBWUBSFBRZ-UHFFFAOYSA-N 0.000 claims 1
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 claims 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims 1
- SNLNZQSPGQPTDW-UHFFFAOYSA-N acetic acid;2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound CC(O)=O.OCC(CO)(CO)CO SNLNZQSPGQPTDW-UHFFFAOYSA-N 0.000 claims 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical group CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims 1
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 claims 1
- 239000001530 fumaric acid Substances 0.000 claims 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims 1
- 150000002848 norbornenes Chemical group 0.000 claims 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims 1
- 229940090181 propyl acetate Drugs 0.000 claims 1
- 239000001057 purple pigment Substances 0.000 claims 1
- 230000001235 sensitizing effect Effects 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 238000011161 development Methods 0.000 description 13
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920005596 polymer binder Polymers 0.000 description 5
- 239000002491 polymer binding agent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
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Classifications
-
- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Description
1376571 九、發明說明: 【發明所屬之技術領域】 本發明係有關於一種用於液晶顯示器(下文中表示為 LCD)之黑色矩陣之感錢脂組絲,—種由該組成物^製 5造之黑色矩陣以及一種包括此黑色矩陣之液晶顯示器。更 明確地’本發明係關於一種黑色矩陣用之樹脂組成物其 包括有一以葬基為主體之樹脂,因此具有高敏感性及光密 度與極佳顯影附著性。 • 本申凊主張源自2007年2月21日申請於韓國智慧局 H)之韓國專利申請第1〇_2〇〇7_17486號之優先權,其所揭露 之内容於此合併作為本發明之參考。 【先前技術】 為了滿足LCD所要求特性,例如高影像品質及高對 • 比,需要形成一種具有絕佳遮光性質之黑色矩陣(BM卜一 15般需要如下之多階段製程來形成黑色矩陣:以真空沈積製 程形成如鉻之金屬膜,塗佈光阻於金屬膜上,曝光、顯影、 % 蝕刻,然後光阻由金屬膜上移除,此製程所製造之黑色矩 陣具有薄及高遮光特性之優點。然而,因為此黑色矩陣具 有高的光反射性,則需要一額外製程。再者,因為黑色矩 °陣疋由多階段製程所製造,生產成本增加,且會因使用金 屬而有環保的問題。再者,在IPS (In_piain Switching)形 式中需要具低體積電阻之黑色矩陣,因此而廣泛使用樹脂 黑色矩陣。樹脂黑色矩陣由一遮光物質、一黏結樹脂、一 夕S旎單體、一光起始劑、一溶劑或其相似物所組成。 5 1376571 為了具有足夠的光遮蔽性質,習知的黑色矩陣需要充 足量的遮光顏料。然而’使用高濃度之遮光顏料,已成為 劣化顯影之感光性及敏感性的主要因素。 已進行很多研究開發各式的黑色矩陣用之黏結劑樹 5 脂,以解決這些問題。例如,韓國專利公開第2003-0093514 號,建議一種具有反應性基團且以丙烯酸為主體之黏結 劑’以及韓國專利公開第2005-0088119號,建議一種具有 缓基之丙烯酸共聚物黏結劑樹脂,日本未審查公開第 ^ 5-339356及8-278630號,以及韓國專利公開第2000-55255 10號,都揭露一種酚酞(card〇)為主體之黏結劑樹脂。近來, 酚酞為主體之黏結劑樹脂,已廣泛使用作為具有高敏感 度'極佳抗熱性與抗化學性或其相似性質之黑色矩陣的成 . 分。然而,習知的酚酞為主體之黏結劑樹脂是藉由二醇化 • α物與酸二酐反應製得。因此,當黏結劑高分子量提高 15時,其酸質相對變高,導致顯影時圖案邊緣大量受損,= 此很難得到穩定之圖案,且魔大的分子結構亦會導致附著 t 性劣化。 【發明内容】 技術問題 、因此,為了改善上述習知技術之問題,本發明之—目 ^係提供—種具有足夠的遮光性質、以及高敏感度與附著 之黑色矩陣用的感光樹脂組成物,—種該組成物所製造 之黑色矩陣,以及一種包括此黑色矩陣之液晶顯示器。 20 1376571 技術方案 為達到上述目的,本發明提供一種黑色矩陣用之感光 樹脂組成物,包括 a) 1至70重量百分比之包含一顏料劑之遮光物質; b) l至30重量百分比之具有如下式1之重複單元之樹 脂黏結劑; c) l至30重量百分比之具有乙烯不飽和鍵之多官能單
d) 1至30重量百分比之光聚合起始劑;以及 e) 剩餘量之溶劑。 [式1]
其中X係選自由:具有1至3個碳原子之亞烷基 (alkylene)、J衣氧乙烧(ethyiene 〇xide)以及氧化丙烯 (propylene oxide)所組群組之其中之一者,以及 Y係選自由:環己烷(cycl〇hexane)、環己烯 (CyCl〇hexene)、苯以及具有i至3個碳原子之亞烷基所組 群組之其中之一者。 再者,本發明提供一種由該感光樹脂組成物所製造之 黑色矩陣。 7 20 1376571 種包括有該黑色矩陣之彩色濾光 再者,本發明提供_ 片及液晶顯示器。 、根據本發月色矩陣用之感光樹脂組成物具有足夠 5 的遮光性質、穩;^之圖案形狀及^夠的顯影限度,因此形 成具有製程性改善的黑色矩陣。 【實施方式】 下文中,將詳述本發明。 , 式1可如下式2所不’當X是亞曱基,及γ是環己烯 10 [式 2]
黑色矩陣用之感光樹脂組成物中,包含於遮光物質之 # 顏料劑可為選自一或多種有機顏料,例如黑色顏料、紅色 顏料、黃色顏料、藍色顏料及紫色顏料。黑色顏料之例子 15 包括碳黑及泰坦黑(titan black) ’而碳黑之例子包括例如 SAF、ISAF、HAF、FEF、SRF、及 GPF 之爐黑(furnace black);例如FT及MT之熱黑(thermal black);及乙炔 黑(acetylene black),就遮光特性及經濟效率而言,較佳 為碳黑顏料。 20 基於黑色矩陣用之感光樹脂組成物總重量,遮光物質 8 1376571 較佳含量為1至70重量百分比。遮光物質之含量影響光 學密度(OD)。據此,較佳為高的光學密度,因此,若遮光 物質含量太低,使光學密度下降,造成遮光性質變差。若 遮光物質含量太高,雖然光學密度較佳,然而卻會造成製 5 程性變差。 包3於黑色矩陣用之感光樹脂組成物之樹脂黏結劑 為具有式1之重複單元的第基主體樹脂聚合物,可將含有
10 第基之二環氧化合物(如下式3所示),以及二酸化合物之 縮合反應而製備,該二酸化合物具有兩端皆取代有兩酸之 結構,該結構選自苯'環己院、環己稀、降冰片稀及具有 3至1〇碳原子之烧烴。 [式3]
15 其中X係選自具有1至3個維房工 芏J個石厌原子之亞烷基、環氧乙 燒及氧化丙歸之一者。 具體而言,當式3中之+ 入為氧化丙烯時,其可表示如 下式4所示。 [式4] 9
再者,根據本發明,包含在第基主體樹脂聚合物中之 二酸化合物,其具有一結構,此結構為選自苯、環己烷、 環己稀、降冰片炼(norbornene)及具有3至10碳原子之烧 烴之其一者的兩端受兩酸取代,且其可包括以下化合物, 較佳為具有一環基之化合物,以在圖案進行顯影製程時改 善基板上之附著力。 二酸化合物之例子,較佳地包括順-4-環己烯-1,2-二羧 酸(cis-4-cyclohexene-l,2-dicarboxylic acid)、順式-5-降冰 片稀-内型-2,3-二緩酸(cis-5-norbornene-endo-2,3-dicarboxylic acid)、丁二酸(succinic acid)、間苯二甲酸 (isophthalic acid)、苯二甲酸(phthalic acid)、1,2-環己烧二 曱酸(1,2-cyclohexanedicarboxylic acid)、1,2-亞苯基雙乙酸 (1,2-phenylene diacetic acid)、1,2-亞苯基二氧雙乙酸 (1,2-phenylene dioxy diacetic acid)、1,4-環己二叛酸 (1,4-cyclohexanedicarboxylic acid),其可表示為以下化合 物。
1376571
COOH
COOH
COOH
CO OH COOH
H 02C —
10
15 基於黑色矩陣用感光樹脂組成物之總重量,苐基主體 樹脂聚合物較佳具有重量平均分子量為1,000至50,000, 且其含量為1至30重量百分比。若其含量低於1重量百 分比,則損害形成膜的附著性,若含量高於30重量百分 比,所形成的影像之敏感性及強度則會受損。 為了改善本發明黑色矩陣用之感光樹脂組成物之鹼 顯影,樹脂黏結劑可額外與可溶於鹼之樹脂黏結劑混合。 作為可溶於鹼之黏結劑時,則可使用單體含酸官能基之均 質共聚物,或該單體與能增加膜強度之另一單體所形成之 共聚物。再者,所形成之共聚物與含有環氧基之乙烯不飽 和化合物,進行聚合反應所製備的聚合物化合物也可使 用。 含有酸官能基之單體,其非限定之例子包括(曱基)丙 浠酸、丁烯酸(crotonic acid)、亞甲基 丁二酸(itaconic aicd)、順丁稀二酸、反丁烯二酸、單甲基馬來酸 20 (monomethyl maleic acid)、異戍二稀續酸(isoprene sulfonic acid)、苯乙稀確酸(styrene sulfonic acid)、5-降冰片烯-2- 11 1376571
10 15
20 曱酸,且可自上述選擇一者或多者使用。 能夠與該含有酸官能基單體進行共聚合之單體,其非 限定之例子包括苯乙烯、氯苯乙烯、α-甲基苯乙烯、乙烯 基甲基苯、(甲基)丙烯酸-2-乙基己基酯、(甲基)丙烯酸甲 酯、(曱基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸 苄酯(benzyl(meth)acrylate)、甲基丙烯酸二甲胺基乙酯 (dimethylaminoethyl(meth)acrylate)、(曱基)丙稀酸異丁 酯、(曱基)丙烯酸第三丁酯、曱基丙烯酸環己酯 (cyclohexyl(meth)acrylate)、甲基丙烯酸二環戊酯 (dicyclopentanyl(meth)acrylate)、.甲基丙稀酸異冰片基酯 (isobornyl(meth)acrylate)、(甲基)丙浠酸 2-笨氧基乙酯、 曱 基 丙烯酸 四氫0夫喃酯 (tetrahydrofurfuryl(meth)acrylate)、(甲基)丙稀酸經乙基 酯、(甲基)丙烯酸-2-羥乙基酯、(甲基)丙烯酸-2-羥丙基酯、 (曱基)丙烯酸 -2-羥基 -3-氯丙基酯 (2-hydroxy-3-chloropropyl(meth)acrylate)、(曱基)丙烯酸-2-羥丁基酯、(甲基)丙烯酸-4-羥丁基酯、(甲基)丙烯酸二甲 基甲胺基酉旨(dimethylaminomethyl(meth)acrylate)、二乙基 氨基(曱基)丙稀酸乙酯(diethylamino(meth)acrylate)、(甲基) 丙稀酸酿基癸氧基-2-經丙基酯(acyloctyloxy-2-hydroxypropyl(meth)acrylate)、丙稀酸乙基己酉旨、(曱基) 丙稀酸-2-曱氧基乙基酯(2-methoxyethyl(meth)acrylate)、 (曱基)丙烯酸-3-甲氧基丁基酯(3-methoxybutyl-(meth)acrylate)、(曱基)丙浠酸丁氧基乙基醋 12 1376571 5
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20 (butoxyethyl(meth)acrylate)、(甲基)丙稀酸二乙二醇醋 (ethoxydiethyleneglycol(meth)acrylate)、(甲基)丙稀酸曱氧 基三乙二醇醋(methoxytriethyleneglycol(meth)acrylate)、 (曱基)丙烯酸曱氧基三丙二醇酯(methoxy-tripropyleneglycol(meth)acrylate)、(曱基)丙烯酸曱氧基聚 乙二醇醋(methoxypolyethyleneglycol(meth)acrylate)、(甲 基)丙稀酸苯氧基二乙二醇酯(phenoxydiethyleneglycol-(meth)acrylate)、(甲基)丙烯酸對壬基苯氧基聚乙二醇酯 (p-nonylphenoxypolyethylenegiycol(meth)acrylate)、(曱基) 丙婦酸對壬基苯氧基聚丙二醇酯(p-nonylphenoxy-polypropyleneglycol(meth)acrylate)、四氟丙基曱基丙烯酸 酯(tetrafluoropropyl(meth)acrylate)、1,1,1,3,3,3-六氣異丙 基曱基丙稀酸酉旨(l,l,l,3,3,3-hexafluoroisopropyl(meth)-acrylate)、(甲基)丙稀酸八氟戊烧基醋 (octafluoropentyl(meth)acrylate)、(甲基)丙稀酸十七敗癸基 酉旨(heptadecafluorodecyl(meth)acrylate)、甲基丙烯酸三溴 苯酉旨(tribromophenyl(meth)acrylate)、β-甲基酿氧基乙基氫 琥 ί白酸醋(p-(meth)acyloloxyethylhydrogen succinate)、丙稀 酸甲基 α-經曱基酉旨(methyl α-hydroxymethyl acrylate)、丙 稀酸乙基 α-經曱基醋(ethyl α-hydroxymethyl acrylate)、丙 烯酸丙基 α-經曱基酯(propyl α-hydroxymethyl acrylate)、 丙稀酸丁基 α-經曱基酉旨(butyl α-hydroxymethyl acrylate)、 N-苯基馬來醯亞胺以及N-(4-氣苯基)馬來醯亞胺 (N-(4-chlorophenyl)maleimide),且可自上述選擇一者或多 13 1376571
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者使用。 再者,含有環氧基(能夠與共聚物(其含有能與含酸官 能基單體共聚合之單體)進行聚合反應)之乙烯不飽和化合 物,其非限定例子包括(曱基)丙烯酸缩水甘油基酯 (glycidyl (meth)acrylate)、乙烯苄基缩水甘油基謎(vinyl benzylglycidyl ether)、乙婶缩水甘油基醚(vinyl glycidyl ether)、稀丙基縮水甘油醚(allylglycidyl ether)、4-曱基-4,5-環氧戊稀(4-methyl-4,5-epoxypentene)、τ ·縮水甘油謎氧基 丙基三曱氡基石夕烧(γ -glycidoxy propyl trimethoxy silane)、7·-縮水甘油醚氧基丙基甲基二乙氧基 石夕烧(7 -glycidoxy propyl methyldiethoxysilane)、7 -縮水 甘油醚氧基丙基三乙氧基石夕烧(7 -glycidoxy propyl triethoxy silane)以及降冰片稀(nobornyl)衍生物,且可自上 述選擇一者或多者使用。 可溶於鹼之樹脂黏結劑較佳具有酸值為50至300 KOH mg/g,及重量平均分子量為1,000至200,000。 包含於黑色矩陣用之感光樹脂組成物中,具有乙烯不 飽和鍵之多官能單體,其非限定例子包括單(甲基)丙烯酸 聚乙二醇醋(polyethylene glycolmono(meth)acrylate)、單 (甲基)丙稀酸聚丙二醇酯 (polypropylene glycolmono(meth)acrylate)、(甲基)丙稀酸苯氧基乙醋 (phenoxyethyl(meth)acrylate)、甲基丙稀酸聚乙二醇醋 (polyethylene glycol(meth)acrylate)、曱基丙稀酸聚丙二醇 醋(polypropylene glycol(meth)acrylate)、二丙稀酸-1,4-丁 20 1376571
10 15 二 g旨、二丙稀酸-1,6-己二醇龍(l,6-hexandiol diacrylate)、 二丙稀酸雙齡A酷(bisphenolA diacrylate)、丙稀酸紛搭環 氧基酯(novolacepoxy acrylate)、三丙烯酸三經曱基乙烧基 酯(trimethylol ethane triacrylate)、三丙稀酸三經曱基丙烧 基酯、(曱基)丙稀酸新戊二酵酯(neopentyl glycol(meth)acrylate)、季戊四醇三丙稀酸酯、季戊四醇四 丙浠酸S旨、季戊四醇六丙稀酸醋(pentaerythritol hexaacrylate)、雙季戊四醇二丙稀酸醋(dipentaerythritol diacrylate)、雙季戊四醇五丙烯酸酯以及雙季戊四醇六丙 烯酸酯,且可自上述選擇一者或多者使用。 基於黑色矩陣用之感光樹脂組成物之總重量,具有乙 烯不飽和鍵之多官能單體較佳含量為1至30重量百分 比。若其含量低於1重量百分比,黑色矩陣之感光性或強 度將劣化。若其含量高於30重量百分比,感光樹脂層之 附著性過大,因此黑色矩陣之強度不足,於顯影時會使圖 案發生損失。
20 包含於黑色矩陣用感光樹脂組成物中之光聚合起始 劑,因光而產生自由基。其非限定例子包括苯乙酮主體之 ^(匕合物(acetophenone based compound) 、 # 口米0坐 (non-imidazole)主體之化合物、三嗓主體之化合物 (triazine-based compound)、以及肪基(oxime)主體之化合 物,且可自上述選擇一者或多者使用。再者,光聚合起始 劑較佳含量為1至30重量百分比,基於感光樹脂組成物 之總重。 15 1376571 5
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苯乙酮主體之化合物的例子可包括2-羥基-2-甲基-1-苯丙烧-1-酮(DAROCURE 1173, 2-hydroxy-2-methyl-l-phenylpropane-1-on)、1-(4-異丙苯基)-2-經基-2-甲基丙燒 -1(DAROCURE 1116, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-l-on)、l-[4-(2-經乙氧基)-苯基]-2·經基· 二-2-曱 基-1-丙烧-1- _ (Irgacure 2959, l-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-di-2-methyl-l-propane-l-on)、1-經基環己基苯基曱酮(1-11乂(11*〇乂7-cyclohexylphenylketone, IRGACURE 184)、二乙氧基苯乙 酮(diethoxyacetophenone,first DEAP)、2,2-二曱氧基-2-笨 基 苯乙嗣 (2,2-dimethoxy-2-phenylacetophenone, 111〇入(:111^651)、2,2-二乙氧基-苯基苯乙酮(1;¥八1'0^£ 8302, 2,2-diethoxy-2-phenylacetophenone)、2-甲基-(4-甲硫 基)苯基-2-嗎啉基-1-丙烷-1-酮(IRGACURE907,2-methyl-(4-methylthio)phenyl-2-morpholino-1-propane-1-on) ' 2-苯 曱基-2-二曱胺基-1-(4-嗎啉基苯基)-丁烷-1-酮(IRGACURE 369, 2-benzyl-2-dimethyl amino-1 -(4-morpholinophenyl)- butane-l-on)、安息香乙醚(benzoinethyl ether)、安息香異 丁基醚(benzoinisobutyl ether, esacure EB3)、及安息香丁基 20 醚(benzoinbutyl ether, BIPE)。 非°米e坐(non-imidazole)主體之化合物的例子可包括 2,2-雙(2-氣笨基)-4,4·,5,5·-四苯基聯咪唑 (2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole)、2,2'-雙(〇-氣苯基)_4,4',5,5·-四(3,4,5-三甲氧苯基)-1,2’-聯咪唑 25 (2,2’-bis(o-chlorophenyl)-4,4',5,5’-tetrakis(3,4,5-tri- 16 1376571 5
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20 methoxyphenyl)-l,2'-biimidazole)、2,2'-雙(2,3-二氯笨 基)-4,4·,5,5,-四苯基聯咪唑(2,2'-1^3(2,3-(^〇111〇1*〇?1161^1)· ^tJJ’-tetraphenyl biimidazole)、以及 2,2'-雙(鄰氯笨 基)-4,4,5,5’-四苯基-1,2'-聯 eiK^pj'-bish-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole) 〇 三。秦(triazine)主體之化合物可包括3-{4-[2,4-雙(三氣 曱基)-s-三嗪-6-基]苯硫基}丙酸(3-{4-[2,4-bis(trichl〇r〇-methyl)-s-triazine-6-yl]phenylthio} propionic acid)、 1,1,1,3,3,3-六氟異丙基-3-{4-[2,4-雙(三氣曱基)-8-三嗪-6-基]苯疏基}丙酸 g|(l,l,l,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio} propionate)、乙基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯 硫基}醋酸醋 (ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate)、. 2-環氧乙基-2-{4-[2,4-雙(三氣甲基)-s-三嗪-6-基]苯硫基}醋酸Sl(2-epoxyethyl- 2- {4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio} acetate)、環己基-2-{4-[2,4-雙(三氣甲基)-s-三嗓-6-基]苯硫 基}醋酸醋(cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s· triazine-6-yl]phenylthio}acetate)、苯甲基-2-{4-[2,4-雙(三 氯曱基)-s-三嗪-6-基]苯硫基}醋酸酯卬61^乂1-2-{4-[2,4-bi s(trichlorome thy l)-s-triazine-6-yl]phenylthio} acetate) 、 3- {氣-4-[2,4-雙(三氣曱基)-s-三嗪-6-基]苯硫基}丙酸 (3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine-6-yl] phenylthio}propionic acid)、3-{4-[2,4-雙(三氣曱基)-s-三嗪 -6-基]苯硫基}丙醯胺(3-{4-[2,4-bis(trichloromethyl)-s- 17 25 1376571 5
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triazine-6-yl]phenylthio}propionamide)、2,4-雙(三氣甲 基)-6-p-甲氧基苯乙婦基-s-三嗪(2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine)、2,4-雙(三氯甲基)-6-(l-p-二 甲胺基苯基)-1,3,-丁間二烯基-s-S,(2,4-bis(trichloro-methyl)-6-(l-p-dimethylaminophenyl)-l ,3,-butadienyl-s-triazine)、以及2 -二亂甲基-4-胺基- 6-ρ·甲乳基本乙稀基- s-三嗪 (2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine) ° 肟基(oxime)主體之化合物可包括l-[9-乙基-6-(2-曱基 苯曱醯基)-9H-咔唑-3-基]-1-(0-乙醯基肟)乙酮 (1 - [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -1 -(O-ac etyloximee)ethanon,CGI-242)、以及 1-[4-(苯基硫醇)苯 基]-2-(0-苯甲醯基肟)-1,2-辛二酮(1-[4-(?1^1^1仆1〇1)-phenyl]-2-(0-benzoyloxime) -1,2-octanedione, CGI-124, ciba,曰本)》 基於黑色矩陣用之感光樹脂組成物之總重,光聚合起 始劑可更包含〇·〇 1至5重量百分比之感光交聯敏感劑以促 進自由基之產生,或0.01至5重量百分比之硬化加速劑, 作為輔助成分。 20 感光交聯敏感劑之例子包括苯甲酮主體之化合物,例 如笨甲酮、4,4-雙(二甲基胺基)苯甲酮 (4,4-bis(dimethylamino)benzophenone)、4,4-雙(二乙基胺基) 苯曱酮(4,4-bis(diethylamino)benzophenone) ' 2,4,6-三甲基 胺基苯曱酮(2,4,6-trimethylaminobenzophenone)、曱基鄰苯 25 甲醢苯甲酸(methyl-o-benzoylbenzoate)、3,3·二甲基-4-甲 18 1376571 5
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氧基苯曱鋼(3,3-dimethyl-4-methoxybenzophenone)、及 3,3,4,4-四(第三丁基過氧羰基)苯甲酮 (3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone);芴嗣 主體之化合物,例如9-芴銅(9-fluorenone)、2-氯-9-芴酿I (2-chloro-9-fluorenone)、以及 2-曱基-9-芴酮 (2-methyl-9-fluorenone);嗟嘲酮主體(thioxanthone-based) 之化合物,例如嘆嘲酮(thioxanthone)、2,4-二乙基嘆嘲酮 (2,4-diethyl thioxanthone) 、2-氯嗟"頓 _ (2-chloro thioxanthone)、1 -氯-4-丙氧基嗟嘲鲷(1-chloro-4-propyloxy thioxanthone)、異丙基嗟 °頓酮(isopropylthioxanthone)以及 二異丙基°塞α頓鋼(diisopropylthioxanthone);雜氧蔥酮主體 (xanthone-based)之化合物,例如雜氧蔥_(xanthone)以2-甲基雜氧蔥網(2-methylxanthone);蒽酿主體之化合物 (anthraquinone-based compounds),例如蒽酿i、2-甲基蒽醒 (2-methyl anthraquinone) 、 2-乙基蒽酿(2-ethyl anthraquinone)、第三丁基蒽酿(t-butyl anthraquinone)以及 2,6-二氣-9,10-蒽醒(2,6-出<:111〇1*〇-9,10-3111:1^391^11〇116);〇丫〇定 主體之化合物(acridine-based compounds),例如9-苯基0丫 唆(9-phenylacridine) 、 1,7-二(9- 0丫咳)-庚院 (l,7-bis(9-acridinyl)heptane)、1,5-二(9- 0丫0定)-戊烧 (l,5-bis(9-acridinylpentane))、以及 1,3-二(9-°丫咬)-丙烧 (1,3-bis(9-acridinyl)propane);雙幾基主體之化合物 (dicarbonyl-based compounds) ’ 例如苯曱基(benzyl)、1,7,7-三甲基-二環[2,2,1]庚烧-2,3-二酮(l,7,7-trimethyl· 20 1376571 5
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20 bicyclo[2,2,l]heptane-2,3-dione)、以及 9,10-菲醒 (9,10-phenanthrenequinone);氧化腺主體之化合物,例如 2,4,6-三曱基笨甲酿二苯基氧化膦(2,4,6-trimethylbenzoyl diphenyl phosphine oxide)、以及雙(2,6-二甲氧基苯甲酿 -2,4,4-三甲基戊基氧化腾(1^(2,6-<111116111〇\)^)6112〇丫1)· 2,4,4-trimethylpentyl phosphine oxide);胺基增效劑(amino synergists),例如2,5-雙(4-二乙基胺基苯亞甲基)環戊酮 (2,5-bis(4-diethylaminobenzal)cyclopentanone)、2,6-雙(4-二乙基胺基苯亞甲基)環己酮(2,6-bis(4-diethylaminobenzal) cyclohexanone )以及2,6-雙(4-二乙基胺基苯亞曱基)-4-甲 基環戊鲷(2,6-bis(4-diethylaminobenzal)-4-methyl-cyclo-pentanone);香豆素主體之化合物(coumarin-based compounds),例如3,3-幾基乙稀基-7-(二乙胺基)香豆素 (3,3-carbonylvinyl-7-(diethylamino)coumarin)、3-(2-苯並嗔 0全)-7-(二乙胺基)香豆素(3-(2-benzothiazolyl)-7-(diethyl-amino)coumarin)、3-苯甲醯基-7-(二乙胺基)香豆素 (3-benzoyl-7-(diethylamino)coumarin)、 3-苯曱酿基-7-曱 氧基-香豆素(3-benzoyl-7-methoxy-coumarin)以及 10,10-叛 基雙[1,1,7,7-四甲基-2,3,6,7-四氫-111,511,1111-(:1]-苯並°比 喃[6,7,8-ij]-嗤-11-_(10,10-。&1_15〇11711^3[1,1,7,7-161^8-methyl-2,3,6,7-tetrahydro- 1H,5H, 11H-C1 ]-benzopyrano[6,7 ,8-ij]-quinolizine-11-on);查耳酮化合物(chalcone compounds),例如 4-二乙胺基查耳酮(4-diethylamino chalcone) 及 4- 疊氮苯亞甲基苯乙酮 25 (4-azidebenzalacetophenone);以及 2-苯甲醯亞甲烧 20 1376571
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20 (2-benzoyl methylene)及 3-曱基-b·萘嚷吐啦 (3-methyl-b-naphthothiazoline),且可自上述選擇—者或多 者使用。 硬化加速劑的例子包括 2-硫醇基苯並咪吐 (2-mercaptobenzoimidazole) 、 2-疏基笨並嗟吐 (2-mercaptobenzothiazole) 、 2-魏基苯 並惡峻 (2-mercaptobenzooxazole)、2,5-二疏基-1,3,4-嘆二嗤 (2,5-dimercapto-l,3,4-thiadiazole)、2-疏基-4,6-二甲氨基。比 咬(2-mercapto-4,6-dimethylaminopyridine)、季戊四醇-四 (3-疏基丙 酸酯) (pentaerythrit〇Ktetrakis(3-mercaptopropionate))、 季戊四醇-三(3-巯基丙酸酯) (pentaerythritol-tris(3-mercaptopropionate))、爾基乙酸 _2,2 -雙[[(疏基乙酿基)-氧]曱基]-1,3-丙二醇S旨、季戍四醇_ 四(2-巯基醋酸酯)(pentaerythritol-tetrakis(2-mercaptoacetate))、季戊四醇-三(2-酼基醋酸酯) (pentaerythritol-tris(2-mercaptoacetate))、三經甲基丙烧三 (2-疏基乙酸醋)(trimethylolpropane-tris(2-mercaptoacetate)) 以及三羟曱基丙烷-三(3-酼基丙酸酯) (trimethylolpropane-tris(3-mercaptopropionate)),且可自上 述選擇一者或多者使用。 包含於黑色矩陣用之感光樹脂組成物之溶劑之例 子,在考慮溶解度及顏料分散性下,包括1-甲氧基-2-丙醇 (propyleneglycol monomethyl ether)、乙二醇甲醚乙酸醋 (ethyleneglycol monomethyl ether acetate)·、乙酸-1-甲氧基 21 1376571 5
•15 -2-丙基 S旨(propyleneglycol monomethyl ether acetate)、丙 二醇曱謎酷酸 i旨(propyleneglycol monoethyl ether acetate)、二甘醇雙甲醚(diethyleneglycol dimethyl ether)、 環己酮、2-庚酮' 3-庚酮、2-羟基乙基丙酸酯 (2-hydroxyethylpropionate)、3·甲基-3-曱氧基丁基丙酸酉旨 (3-methyl-3-methoxy butylpropionate)、3-曱氧基丙酸乙醋 (ethyl-3-methoxypropionate) > 3-乙氧基丙酸曱醋 (methyl-3-ethoxypropionate) 、3-乙氧基丙酸乙醋 (ethyl-3-ethoxypropionate)、乙酸丁 S旨、戊酸戊醋 (amvlpermeate、、乙酸異戊酯(isoamylacetate)、乙酸異丁酯 (isobutylacetate)、正丁 基丙酸 g旨(butylpropionate)、丁酸異 丙 @旨(isopropylbutyrate)、丁酸乙酉旨(ethylbutyrate)、丁酸丁 S旨(butylbutyrate)、丙 _ 酸乙 S旨(ethylpyruvate)以及 γ -丁酿 基醋酸S旨(γ -butyrolacetate),且可自上述選擇一者或多者 使用。
20 可包含於黑色矩陣用之感光樹脂組成物中之剩餘量 之溶劑及溶劑含量,隨著包含於黑色矩陣用之感光樹脂組 成物之成分含量而變化。例如,基於黑色矩陣用之感光樹 脂組成物之總重,可使用溶劑含量為1 〇至95重量百分比。 黑色矩陣用之感光樹脂組成物可更包括一或多添加 劑’其選自分散劑、黏著促進劑、抗氧化劑、UV吸收劑、 抗熱聚合劑劑以及平坦劑,且可以使用相關技術之習知物 質。 特別地,經由預先以分散劑為顏料表面處理,分散劑 22 1376571 5
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20 可添加於顏料外部或内部。 分散劑的例子可包括高分子型、非離子、陽離子、陰 離子分散劑。分散劑的例子包括但不限於混合聚氧化烷撐 (polyalkyleneglycol)及其酯類、聚氧化烯多元醇 (polyoxyalkylene polyol)、酉旨院樓氧化物(esteralkylene oxide)添加物、醇環氧烧烴(alcoholalkyleneoxide)添加 物、續酸醋(sulfonic acid ester) ' 績酸鹽(sulfonate)、叛酸 醋(carboxylic acid ester)、叛酸鹽(carboxylate)、烧基酿胺 烧撐氧化物(alkylamidealkyleneoxide)添加物、以及烧基胺 (alkylamine),且可自上述選擇一者或多者使用。 黏著促進劑之例子包括但不限於乙烯基三甲氧基矽 炫> (vinyltrimethoxysilane) ' 乙稀基三乙氧石夕烧 (vinyltriethoxysilane)、乙稀基-三(2-甲氧基乙氧基)-石夕烧 (vinyltris(2-methoxyethoxy)-silane)、氣-(2-氨乙基)-3-氨基 丙基曱基二曱氧基矽烷(N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane)、It -(2-氨乙基)-3-氨基 丙基甲基二甲氧基石夕院(N-(2-aminoethyl)-3-aminopropylmethylirimethoxysilane)、3-三乙氧基甲石夕烧基 -1 -丙胺(3-aminopropyltriethoxysilane)、3-縮水甘油醚氧基 丙基三乙氧基石夕烧(3-glycidoxypropyltriethoxysilane)、3-縮水甘油醚氧基丙基甲基二甲氧基矽烷 (3-glycidoxypropylmethyldimethoxysilane)、2-(3,4-乙氧基 環已基)乙基三甲氧基矽烷(2-(3,4-ethoxy cyclohexyl)ethyltrimethoxysilane)、3-氯化丙基二曱氧基曱 23 1376571 5
基石夕烧(3-chloropropyl methyldimethoxysilane)、3-氯丙基 三曱氧石夕烧(3-chloropropyl trimethoxy silane)、3·曱基丙稀 酸氧丙 基三曱 氧基石夕烧 (3-methacryl oxypropyltrimethoxysilane)、及3-魏丙基三乙氧基梦烧 (3-mercaptopropyltrimethoxysilane),且可自上述選擇一者 或多者使用。 抗氧化劑的例子包括但不限於2,2-硫代雙(4-甲基-6-t-丁 基苯盼)(2,2-thiobis(4-methyl-6-t-butylphenol))及 2,6-§,1>丁基苯龄(2,6-£,卜1)1^)^11611〇1),且可自上述選擇一 者或多者使用。 UV吸收劑的例子包括但不限於2-(3-t-丁基-5-曱基 -2-羟基苯基)-5-氣-苯并三唑(2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole)及烧氧基二苯曱酮 (alkoxy benzophenone),且可自上述選擇一者或多者使用。 15 抗熱聚合劑劑的例子包括但不限於氫醌 (hydroquinone)、對-甲氧基苯盼(p-methoxyphenol)、二叔 丁 基對曱基苯盼(di-t-butyl-p-cresol)、焦倍酸(pyrogallol)、 • 對叔丁基鄰苯二盼(t-butylcatechol)、對苯西昆 (benzoquinone)、4,4-硫代雙(3-甲基-6-t- 丁基苯酷) 20 (4,4-化1〇1^(3-1116化71-6小1)111>^11611〇1)、2,2-亞甲基雙(4-曱 基-6-t- 丁基苯盼)(2,2-methylenebis(4-methyl-6-t-butylphenol))、及 2-疏基口*«^(2-mercaptoimidazole),且可 自上述選擇一者或多者使用。 為了製備本發明之黑色矩陣用之感光樹脂組成物,能 24 1376571 * 純用為遮光物質之顏料分散溶液首先製備。關於此,可 以使用商業性可得到之分散溶液形式之顏料。樹脂黏結劑 與顏料分散溶液及具有乙烯不飽和鍵之多官能單體混 合,然後光聚合起始劑及溶劑加入其中。進行攪拌而製成 5 黑色矩陣用之感光樹脂組成物。 再者本發明供一黑色矩陣,其該由黑色矩陣用之 感光树知組成物所製造·》該黑色矩陣可以下列方式製造。 黑色矩陣用之感光樹脂組成物塗佈於一基板表面,然 ^ 後預烤以移除溶劑,形成一膜。塗佈方式的例子可以包括 1〇喷塗法、滾筒塗佈法、旋轉塗佈法、橫條塗佈法及狹縫塗 佈法。預烤一般可在70至15(TC下進行〇.5至3〇分鐘, 根據成分組成及組成比例而定。 . 接著,已預烤完之塗佈膜經由一預定圖案光罩進行 UV照射,然後以鹼性溶液顯影而去除不需要的部分形 '15成一圖案。對於顯影,可以應用沈浸法、噴灑法或其相^ 方法而無任何限制。顯影通常進行30至180秒。 顯影溶液的例子包括,如鹼性溶液,無機鹼例如氫氧 響化鈉、氫氧化鉀、石夕酸鈉、石夕酸二納及氨;例如乙胺及正丙 胺之一級氨;例如二乙胺及二丙胺之二級氨;例如三甲 20胺、N,N_二乙基甲胺及n,n-二甲基乙胺之三級氨;例如二 甲基乙醇胺、曱氨基二乙醇、及氨基三乙醇之三級醇氨; 例如。比咯' 氮雜環己烷、^曱基呱啶' Ν·甲基四氫〇比哈、 1,8-二氮雜二環[5.4.0]·7-十一碳场氧 (l’8-diazabicyclo[5.4.0]-7-undecene)及 15-二氮雜二環 25 1376571 [4·3.0]-5-壬烯(l,5-diazabicyclo[4.3.0]-5-nonene)之環狀三 級氨;例如础咬(pyridine)、三曱基0比咬(collidine)、二曱 基。比咬(lutidine)及啥啦(quinolin)之芳香三級氨;例如四甲 基氫氧化銨及氫氧化四乙基銨之四級銨鹽。 5 顯影後,以水進行清洗約30至90秒,然後以空氣或 氮氣進行乾燥以形成圖案。使用熱板或烤箱硬烤圖案而形 成黑色矩陣。關於此,較佳在150至230°C下進行硬烤1〇
10 15
20 至90分鐘。 所製造之黑色矩陣具有足夠之遮光性質,且在厚度為 1.2 μιη時,其光學密度(OD)為3.5或更高,較佳為於厚度 1.2 μπι,光學密度(OD)為4.0或更高。 本發明提供一包括此黑色矩陣之彩色濾光片。 再者,本發明提供一包括此黑色矩陣之液晶顯示器。 下文,將以實施例詳述本發明。然而,本發明可以許 多不同形式實現,在此之實施例不應被解釋為本發明之限 制。反之,提供這些實施例係為完整及全部揭露,並將本 發明之觀念傳遞給本技術領域之人。 <製備例1> 122 克之 9,9-雙酚芴二缩水甘油醚 (9,9-bisphenolfluorenediglycidylether)及 45 克之 4-環己稀 -1,2-二叛酸(4-cyclohexene-l,2-dicarboxylic acid)與 150 克 之丙二醇甲 _醋酸酉旨(propyleneglycol methyl ether acetate) 一起攪拌。當反應器加熱到110°C時,供給氧氣進入反應 器。10小時後,反應完全,200克之反應溶劑加入其中而 26 1376571 為本發明之樹脂黏結劑(固含量:29.19% ’酸值:25,分子 量:13000)〇 <製備例2> 5
10 124 克之 9,9-雙酚芴二缩水甘油醚 (9,9-bisphenolfluoreneciiglycidylether)及 44g 之苯二曱酸與 150g之丙二醇曱醚醋酸酯一起攪拌。當反應器加熱到11〇 °C時,供給氧氣進入反應器。10小時後,反應完全,200 克之反應溶劑加入其中而為本發明之樹脂黏結劑(固含 量:28.80%,酸值:32,分子量:10300)。 <製備例3> 107 克之 9,9-雙酚芴二缩水甘油醚 (9,9-bisphenolfluorenediglycidylether)及 42g 之 5-雙環庚 烯-2,3-雙梭酸(5-norbornene-2,3-dicarboxylic acid)與 I50g 之丙二醇甲醚醋酸酯一起攪拌。當反應器加熱到n〇〇c 15 時’供給氧氣進入反應器。10小時後,反應完全,200克 之反應溶劑加入其中而為本發明之樹脂黏結劑(固含量: 31.65%,酸值:25,分子量:4000)。 • <製備例4> 90 克之 9,9-雙酚芴二缩水甘油醚 20 (9,9-bisphenolfluorenediglycidylether)及 30 克之 丁二酸 (succinic acid)與180克之丙二醇甲醚醋酸酯一起搜拌。當 反應器加熱到1 l〇°C時,供給氧氣進入反應器。10小時後, 反應完全而為本發明比較例之樹脂黏結劑(固含量: 40.91%,酸值:95,分子量:2400)。 27 1376571
10 15
20 以下實施例1之重量份是基於1000重量份之黑色矩 陣用之感光樹脂組成物。 <實施例1>黑色矩陣用之感光樹脂組成物之製備 30重量份之苐基主體樹脂聚合物黏結劑(固含量:30 重量百分比,70重量百分比之丙二醇甲醚醋酸酯)如製備 例1之樹脂,60重量份之聚合物(莫耳比:73/19/8, Mw = 22.000) ,其中甲基丙烯酸縮水甘油酯(glycidyl methacrylate)加入於(曱基)丙烯酸苄酯/(曱基)丙烯酸之共 聚物,作為可溶於鹼之樹脂黏結劑(固含量:30重量百分 比,70重量百分比之丙二醇曱醚醋酸酯),80重量份之二 季戊四醇六丙烯酸酯(dipentaerythritolhexaacrylate)(固含 量:50重量百分比,50重量百分比之丙二醇甲醚醋酸酯) 為單體,與375重量份之碳黑分散溶液(固含量:20重量 百分比之碳黑,3重量百分比之分散劑,4重量百分比之(甲 基)丙烯酸苄酯/(甲基)丙烯酸共聚物,莫耳比:70/30,Mw = 23.000) 及73重量百分比之丙二醇甲醚醋酸酯混合,然後 與4重量份之2-苄基-2-(二甲胺基)-1-(4-嗎啉基苯基)丁基 -1-1¾ (2-benzyl-2-(dimethylamino)-l -(4-morpholinophenyl)-butyl-1 - on)(商業名稱:Irgacure 369)、5 重量份之 l-[9 -乙 基-6-(2-曱基笨曱醯基)-9H-咔唑-3-基]-1-(0-乙醯基肟)乙 酮 (1 - [9-ethyl-6-(2-methylbenzoyl)-9H-carbazo 卜3-yl] -1 -(O-acetyloxime)ethanon)(商業名稱:CGI-242)、4 重量份之 2,2·-雙(〇-氣苯基)-4,4,5,5匕四苯基-1,2匕聯咪唑 (2,2'-bis(o-chlorophenyl)-4,4,5,5’-tetraphenyl-1,2'-biimidaz ole) , 4 重量份之四乙基米氏酮 28 25 1376571 5
10 15
20 (4,4_bis(diethylamino)benzophenone),及 2 重量份之 2-疏 基笨並嗟唾(mercaptobenzothiazole)光聚合起始劑混合。5 重量份之3 -甲基丙稀酸氧丙基三甲氧基碎烧(3-me thacryl oxypropyltrimethoxysilane)為黏著促進劑及1重量份之平 坦劑混合其中。作為溶劑,150重量份之丙二醇甲醚醋酸 酯(propylene glycol monomethyl ether acetate),140 重量份 之3-甲氧基丁基乙酸醋(3-methoxy butyl acetate)及140重 量份之二丙二醇單甲醚(dipropylene glycol monomethyl ether)混合其中。然後,混合物攪拌5小時而製備黑色矩陣 用之感光樹脂組成物。 <實施例2> 如實施例1之相同組成及方式,製備一黑色矩陣用之 感光樹脂組成物,除了使用製備例2之苐基主體樹脂聚合 物黏結劑。 <實施例3> 如實施例1之相同組成及方式,製備一黑色矩陣用之 感光樹脂組成物,除了使用製備例3之苐基主體樹脂聚合 物黏結劑。 <實施例4> 如實施例1之相同組成及方式,製備一黑色矩陣用之 感光樹脂組成物,除了使用製備例4之苐基主體樹脂聚合 物黏結劑。 <比較例1> 如實施例1之相同組成及方式,製備一黑色矩陣用之 29 1376571 感光樹脂組成物’除了使用(甲基)丙烯酸苄酯/(甲基)丙烯 酸之共聚物(莫耳比:73/27, Mw = 23 〇〇〇)代替苐基主體樹 脂聚合物黏結劑。 5
10 〈實驗例1>黑色矩陣圖案之形成 每一實施例1至4及比較例1之黑色矩陣用之感光樹 脂組成物,以旋轉塗佈之方式塗佈於一玻璃玻璃上然後 在110 C預烤2分鐘而形成一具有厚度約13μπι之膜。接 著,膜冷卻到室溫,^後於高Μ汞燈,曝光間距100叫、 能量6〇mJ/cm2下,經由一光罩曝光。已曝光之基材於25 C下,使用〇.〇4%K〇H水溶液以喷麗之方式顯影然後以 純水清洗。乾燥該基板,以及在22代下以烤箱硬烤扣 分鐘而形成黑色矩陣圖案。 15 20 敏威她夕吾泪,丨 在形成之黑色矩陣中,於驗液顯影前使用膜 量測其厚度。光劑量由20mJ逐漸增加到10mJ,』 進行顯影。然後在量測-次厚度,並根據曝 劑=算殘膜率而得到最小曝光劑量,於此 和。其結果呈現於表―。再者,使用光學密度儀 值(Macbeth D200-H),其結果呈現於下表1中。-顯影附著,夕f〒丨 =性量測所得之最小曝光劑量下進行照射。使用 7 ‘在預&時間下進行㈣,根 最小圖案尺寸呈現於表2中。 B間所侍之 25 【表1】 30 1376571
厚度 (μηι) 遮光性質 (0D) 直線性 錐形角 敏感度 (mJ/απΓ) 實施例1 1.2 4.5 ◎ 40或更小 60 實施例2 1.2 4.5 '〇 50或更小 60 實施例3 1.2 4.5 〇 50或更小 60 實施例4 1.2 4.5 Δ 70或更小 60 比較例1 1.2 4.5 △ 70或更小 80 (g).極佳◦:佳△:普通χ•差 【表2】 殘留最小尺寸 根據顯影時間 實施例1 60秒 70秒 80秒 90秒 實施例1 3 4 7 10 實施例2 3 5 8 11 實施例3 4 6 9 13 實施例4 7 11 15 20 比較例1 8 11 16 25 如上述本發明所得到之黑色矩陣圖案具有1.2㈣之 厚度,且無圖案損失,未曝光部分無殘留,並且由光學顯 微鏡(OLYMPUS BX60F-3)證實極佳的直線性與表面平整 性。 【圖式簡單說明】 圖1係實施例1之黑色矩陣用之感光樹脂組成物所製 造之黑色矩陣圖案之光學顯微鏡相片。 圖2係比較例!之黑色矩陣用之感光樹脂組成物所製 造之黑色矩陣圖案之光學顯微鏡相片。 31 1376571 【主要元件符號說明】
Claims (1)
1376571 第ΜΠΟΜΟΙ號,101年s月修正頁 十、申請專利範圍: 1 ·種’’’、色矩陣用之感光樹脂組成物,包括: 1至70重2:百分比之包含一顏料劑之一遮光物質; 1至30重量百分比夕目士, 刀比之具有如下式i之重複單元之一樹 5 脂黏結劑; 1至30重里百分比之具有乙缔不飽和鍵之一多官能單 體;
年《^月2日修正本 1至30重量百分比之—光聚合起始劑;以及 剩餘量之一溶劑; 10 [式1] OH
其中X係選自由·具有1至3個碳原子之亞烷基、環 氧乙炫以及氡化丙稀所組群組之其中之一者,且_ Y係選自由·環己烧、環己稀以及降冰片稀所組群組 之其中之一者。 2. 如申請專利㈣第1項所述之黑色矩陣用之感光 樹脂組成物,其中該顏料劑包括至少一者選自由:含有碳 黑或泰坦黑之黑色顏料、紅色顏料、黃色顏料、藍色顏料 及紫色顏料所組群組之有機顏料。 3. 如申§青專利範圍第1項所述之黑色矩陣用之感光 33 20 1376571 樹月曰組成物,其中該樹脂黏結劑係以一如下式3所示含有 i基之二環氡化合物,以及一二酸化合物進行縮合反應而 製備,該一酸化合物為選自於環己烷'環己烯以及降冰片 烯中至少一者之兩端取代有兩酸之結構; [式3]
其中X係選自具有1至3個碳原子之稀烴基、環氧乙 烧及氧化丙晞之其中之一者。 10 15 4. 如申睛專利範圍第3項所述之黑色矩陣用之感光 樹脂組成物’其中該樹脂黏結劑係額外與一可溶於驗之樹 脂黏結劑混合’該可溶於鹼之樹脂黏結劑包括之一含有酸 官能基之單體及一能與該單體共聚合之單體之共聚合 物;或是一聚合物化合物,其藉由結合一含有環氧基之乙 烯不飽和化合物與該共聚物所形成。 5. 如申請專利範圍第4項所述之黑色矩陣用之感光 樹脂組成物,其中該含有酸官能基之單體係為一者或多者 選自(甲基)丙烯酸、α-丁烯酸、亞曱基丁二酸、順丁稀二 酸、反丁烯二酸、單曱基馬來酸、異戊二烯磺酸、笨乙稀 續酸、5-降冰片稀-2 -曱酸之一混合物。 6. 如申請專利範圍第4項所述之黑色矩陣用之感光 樹脂組成物’其中該能夠與該含有酸官能基單體共聚人之 34 20 1376571 5
10 15
20 單體係至少一者選自苯乙烯、氣笨乙烯、α-甲基苯乙烯、 乙烯基甲基笨、(甲基)丙烯酸-2-乙基己基酯、(甲基)丙烯 酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基) 丙烯酸苄醋(benzyl(meth)acrylate)、甲基丙稀酸二曱胺基 乙醋(dimethylaminoethyl(meth)acrylate)、(甲基)丙稀酸異 丁酯、(曱基)丙烯酸第三丁酯、甲基丙烯酸環己酯 (cyclohexyl(meth)acrylate)、曱基丙稀酸二環戊醋 (dicyclopentanyl(meth)acrylate)、曱基丙稀酸異冰片基酷 (isobornyl(meth)acrylate)、(曱基)丙稀酸 2-苯氧基乙 6旨、 曱 基丙烯 酸四氫 呋喃酯 (tetrahydrofurfuryl(meth)acrylate)、(甲基)丙稀酸經乙基 酯、(甲基)丙烯酸-2-羥乙基酯、(曱基)丙烯酸-2-羥丙基酯、 (甲基)丙烯酸-2-羥基-3-氣丙基酯 (2-hydroxy-3-chloropropyl(meth)acrylate)、(甲基)丙稀酸-2-羥丁基酯、(甲基)丙烯酸-4-羥丁基酯、(甲基)丙烯酸二甲 基甲胺基醋(dimethylaminomethyl(meth)acrylate)、二乙基 氨基(甲基)丙烯睃乙醋(diethylamino(meth)acrylate)、(甲基) 丙稀酸酿基癸氧基-2-經丙基醋(acyloctyloxy-2-hydroxypropyl(meth)acrylate)、丙稀酸乙基己醋、(甲基) 丙稀酸-2-甲氧基乙基 g| (2-methoxyethyl(meth)acrylate)、 (甲基)丙稀酸-3-曱氧基丁基酯(3-methoxybutyl-(meth)acrylate)、(甲基)丙稀酸丁氧基乙基酯 (butoxyethyl(meth)acrylate)、(甲基)丙稀酸二乙二醇醋 (ethoxydiethyleneglycol(meth)acrylate)、(曱基)丙稀酸甲氧 35 1376571 5
10 15
20 基三乙二醇酯(methoxytriethyleneglycol(meth)acrylate)、 (甲基)丙烯酸甲氧基三丙二醇酯(〇^11〇乂丫-tripropyleneglycol(meth)acrylate)、(甲基)丙炼酸甲氧基聚 乙二醇 S旨(methoxypolyethyleneglycol(meth)acrylate)、(甲 基)丙稀酸笨氧基二乙二醇酯(phenoxydiethyleneglycol-(meth)acrylate)、(曱基)丙炼酸對壬基苯氧基聚乙二醇醋 (p-nonylphenoxypolyethyleneglycol(meth)acrylate)、(曱基) 丙稀酸對壬基笨氧基聚丙二醇酯(p-nonylphenoxy-polypropyleneglycol(meth)acrylate)、四氟丙基甲基丙稀酸 醋(tetrafluoropropyl(meth)acrylate)、1,1,1,3,3,3-六氟異丙 基曱基丙烯酸酯(l,l,l,3,3,3-hexafluoroisopropyl(meth)-acrylate)、(曱基)丙稀酸八氟戊炫基醋 (octafluoropentyl(meth)acrylate)、(曱基)丙稀酸十七氣癸基 δ 旨(heptadecafluorodecyl(meth)acrylate)、甲基丙稀酸三漠 苯醋(tribromophenyl(meth)acrylate)、β-甲基酿氧基乙基氫 破 J6 酸醋(p-(meth)acyloloxyethylhydrogen succinate)、丙烯 酸甲基 a-經甲基酯(methyl α-hydroxymethyl acrylate)、丙 稀酸乙基 α-經甲基醋(ethyl α-hydroxymethyl acrylate)、丙 稀酸丙基 α-經甲基醋(propyl α-hydroxymethyl acrylate)、 丙稀酸丁基 α-經曱基醋(butyl α-hydroxymethyl acrylate)、 N-笨基馬來醯亞胺以及N-(4-氣苯基)馬來醯亞胺 (N-(4-chlorophenyl)maleimide)酿。 7.如申請專利範圍第4項所述之黑色矩陣用之感光 樹脂組成物,其中該可溶於鹼之樹脂黏結劑具有一酸值為 36 1376571 50至300 KOH mg/g,及一重量平均分子量為1,〇〇〇至200,000 - 5
10 15
20 8. 如申請專利範圍第1項所述之黑色矩陣用之感光 樹脂組成物,其中該具有乙烯不飽和鍵之多官能單體包括 至少一者選自單(曱基)丙烯酸聚乙二醇酯(polyethylene glycolmono(meth)acrylate)、單(甲基)丙稀酸聚丙二醇酯 (polypropylene glycolmono(meth)acrylate)、(甲基)丙稀酸 苯氧基乙醋(phenoxyethyl(meth)acrylate)、曱基丙稀酸聚乙 二醇醋(polyethylene glycol(meth)acrylate)、甲基丙稀酸聚 丙二醇醋(polypropylene glycol(meth)acrylate)、二丙稀酸 -1,4- 丁二酯、二丙稀酸-1,6-己二醇醋(1,6-hexandiol diacrylate)、二丙缔酸雙酌 A 醋(bisphenolA diacrylate)、 丙稀酸紛搭環氧基醋(novolacepoxy acrylate)、三丙稀酸三 經甲基乙烧基醋(trimethylol ethane triacrylate)、三丙烯酸 三經甲基丙院基酯、(甲基)丙稀酸新戊二醇酯(neopentyl glycol(meth)acrylate)、季戊四醇三丙稀酸醋、季戊四醇四 丙稀酸醋、季戊四醇六丙烤酸醋(pentaerythritol hexaacrylate)、雙季戊四醇二丙烯酸 δ| (dipentaerythritol diacrylate)、雙季戊四醇五丙稀酸酯以及雙季戊四醇六丙 烯酸酯。 9. 如申請專利範圍第1項所述之黑色矩陣用之感光 樹脂組成物,其中該黑色矩陣用之感光樹脂組成物更包括 有至少一選自感光交聯敏感劑、硬化加速分散劑、黏著促 進劑、抗氧化劑、UV吸收劑、抗熱聚合劑劑以及平坦劑。 37 1376571 5
15
20 10. 如申請專利範圍第1項所述之黑色矩陣用之感光 樹脂組成物,其中該溶劑係為一者或多者選自1-甲氧基-2-丙醇(propyleneglycol monomethyl ether)、乙二醇甲鍵乙酸 SI (ethyleneglycol monomethyl ether acetate)、乙酸-1-甲氧 基-2-丙基醋(propyleneglycol monomethyl ether acetate)、 丙二醇甲謎醋酸醋(propyleneglycol monoethyl ether acetate)、二甘醇雙甲越(diethyleneglycol dimethyl ether)、 環己酮、2-庚酮、3-庚酮、2-羟基乙基丙酸酯 (2-hydroxyethylpropionate)、3-曱基-3-曱氧基丁基丙酸酯 (3-methyl-3-methoxy butylpropionate)、3-曱氧基丙酸乙酯 (ethyl-3-methoxypropionate) 、3-乙氧基丙酸甲醋 (methyl-3-ethoxypropionate) 、3-乙氧基丙酸乙醋 (ethyl-3-ethoxypropionate)、乙酸丁醋、戊酸戊酷 (amvlpermeate)、乙酸異戊 S旨(isoamylacetate)、乙酸異丁 S旨 (isolputylacetate)、正丁 基丙酸 S旨(butylpropionate)、丁酸異 丙醋(isopropylbutyrate)、丁酸乙 S旨(ethylbutyrate)、丁酸丁 醋(butylbutyrate)、丙酮酸乙醋(ethylpyruvate)以及 7 -丁酿 基醋酸醋(7 -butyrolacetate)之混合物。 11. 一種黑色矩陣,其由申請專利範圍第1至10項中 任一項所述之感光樹脂組成物所製造。 12. —種彩色濾光片,其包括申請專利範圍第11項之 黑色矩陣》 13. —種液晶顯示器,其包括申請專利範圍第11項之 黑色矩陣。 38
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| TWI781550B (zh) * | 2020-03-18 | 2022-10-21 | 南韓商三星Sdi股份有限公司 | 感光性樹脂組成物、使用其的感光性樹脂層及顯示裝置 |
| CN111574656B (zh) * | 2020-06-01 | 2022-04-22 | 江苏博砚电子科技有限公司 | 一种用于黑色矩阵光刻胶的含氟感光树脂及其树脂组合物 |
| KR102787025B1 (ko) * | 2022-08-30 | 2025-03-25 | 삼성에스디아이 주식회사 | 감광성 수지 조성물, 이를 이용하여 제조된 감광성 수지막 및 컬러필터 |
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| JP2849021B2 (ja) * | 1993-04-12 | 1999-01-20 | 日本ペイント株式会社 | 体積ホログラム記録用感光性組成物 |
| JP3998797B2 (ja) * | 1998-02-10 | 2007-10-31 | 東京応化工業株式会社 | 光重合性樹脂組成物及び該光重合性樹脂組成物を用いたカラーフィルターの製造方法 |
| JP2002221786A (ja) * | 2001-01-29 | 2002-08-09 | Sumitomo Chem Co Ltd | カラーフィルター用着色感光性樹脂組成物 |
| JP2003057845A (ja) * | 2001-08-16 | 2003-02-28 | Sumitomo Chem Co Ltd | 着色パターンの形成方法 |
| JP2003107693A (ja) * | 2001-09-27 | 2003-04-09 | Sumitomo Chem Co Ltd | 樹脂組成物 |
| JP2003107702A (ja) * | 2001-09-27 | 2003-04-09 | Sumitomo Chem Co Ltd | 樹脂組成物 |
| JP3943883B2 (ja) * | 2001-10-02 | 2007-07-11 | 新日鐵化学株式会社 | 絶縁用樹脂組成物及びこれを用いた積層体 |
| JP4019726B2 (ja) * | 2002-02-07 | 2007-12-12 | 三菱化学株式会社 | カラーフィルタ用感光性組成物およびカラーフィルタ |
| JP4400025B2 (ja) * | 2002-07-10 | 2010-01-20 | 住友化学株式会社 | ポリカルボン酸樹脂の製造方法 |
| JP4830310B2 (ja) * | 2004-02-23 | 2011-12-07 | 三菱化学株式会社 | オキシムエステル系化合物、光重合性組成物及びこれを用いたカラーフィルター |
| JP2006208835A (ja) * | 2005-01-28 | 2006-08-10 | Hitachi Chem Co Ltd | 感光性樹脂組成物及び感光性エレメント |
| JP4508924B2 (ja) * | 2005-03-29 | 2010-07-21 | 新日鐵化学株式会社 | 感光性樹脂組成物及びそれを用いたカラーフィルター |
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| JP4804577B2 (ja) | 2011-11-02 |
| KR20080077815A (ko) | 2008-08-26 |
| CN101617272B (zh) | 2012-06-20 |
| KR100961818B1 (ko) | 2010-06-08 |
| CN101617272A (zh) | 2009-12-30 |
| JP2010519592A (ja) | 2010-06-03 |
| TW200846826A (en) | 2008-12-01 |
| US20100085518A1 (en) | 2010-04-08 |
| WO2008102990A1 (en) | 2008-08-28 |
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